+

US20030175535A1 - Plasma curing process for porous silica thin film - Google Patents

Plasma curing process for porous silica thin film Download PDF

Info

Publication number
US20030175535A1
US20030175535A1 US10/384,141 US38414103A US2003175535A1 US 20030175535 A1 US20030175535 A1 US 20030175535A1 US 38414103 A US38414103 A US 38414103A US 2003175535 A1 US2003175535 A1 US 2003175535A1
Authority
US
United States
Prior art keywords
coating
plasma
cured coating
sio
plasma cured
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/384,141
Inventor
Ivan Berry
Todd Bridgewater
Wei Chen
Qingyuan Han
Eric Moyer
Michael Spaulding
Carlo Waldfried
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Corp
Original Assignee
Dow Corning Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/681,332 external-priority patent/US6558755B2/en
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Priority to US10/384,141 priority Critical patent/US20030175535A1/en
Assigned to DOW CORNING CORPORATION reassignment DOW CORNING CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AXCELIS TECHNOLOGIES, INC.
Publication of US20030175535A1 publication Critical patent/US20030175535A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312—Organic layers, e.g. photoresist
    • H01L21/3121—Layers comprising organo-silicon compounds
    • H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/126—Preparation of silica of undetermined type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H01L21/02134—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material comprising hydrogen silsesquioxane, e.g. HSQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • H01L21/0234—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31695—Deposition of porous oxides or porous glassy oxides or oxide based porous glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02203—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being porous
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • This invention relates generally to coatings for use in electronic devices. More particularly, the invention relates to coatings having an improved elastic modulus and a low dielectric constant and to methods of making such coatings.
  • Thin film dielectric coatings on electric devices are known in the art.
  • U.S. Pat. Nos. 4,749,631 and 4,756,977, to Haluska et al. disclose silica based coatings produced by applying solutions of silicon alkoxides or hydrogen silsesquioxane, respectively, to substrates and then heating the coated substrates to a temperature between 200 and 1000° C.
  • the dielectric constant of these coatings is often too high for certain electronic devices and circuits.
  • U.S. Pat. No. 4,636,440 discloses a method of reducing the drying time for a sol-gel coated substrate comprising exposing the substrate to aqueous quaternary ammonium hydroxide and/or alkanol amine compounds. Jada requires that the coating be dried prior to heating. It is specifically limited to hydrolyzed or partially hydrolyzed silicon alkoxides and does not teach the utility of the process on coatings having Si—H bonds.
  • U.S. Pat. No. 5,547,703 to Camilletti et al. teaches a method for forming low dielectric constant Si—O containing coatings on substrates comprising heating a hydrogen silsesquioxane resin successively under wet ammonia, dry ammonia, and oxygen.
  • the resultant coatings have dielectric constants as low as 2.42 at 1 MHz.
  • This reference teaches the removal of solvent before converting the coating to a ceramic.
  • U.S. Pat. No. 5,523,163, to Balance et al. teaches a method for forming Si—O containing coatings on substrates comprising heating a hydrogen silsesquioxane resin to convert it to a Si—O containing ceramic coating and then exposing the coating to an annealing atmosphere containing hydrogen gas.
  • the resultant coatings have dielectric constants as low as 2.773.
  • the reference teaches the removal of solvent before converting the coating to a ceramic.
  • U.S. Pat. No. 5,618,878, to Syktich et al. discloses coating compositions containing hydrogen silsesquioxane resin dissolved in saturated alkyl hydrocarbons useful for forming thick ceramic coatings.
  • the alkyl hydrocarbons disclosed are those up to dodecane.
  • the reference does not teach exposure of the coated substrates to basic catalysts before solvent removal.
  • U.S. Pat. No. 6,231,989 discloses a method of making porous network coatings with low dielectric constants.
  • the method comprises depositing a coating on a substrate with a solution comprising a resin containing at least 2 Si—H groups and a solvent in a manner in which at least 5 volume % of the solvent remains in the coating after deposition.
  • the coating is then exposed to an environment comprising a basic catalyst and water.
  • the solvent is evaporated from the coating to form a porous network.
  • the coating can be cured by heating to form a ceramic.
  • Films made by this process have dielectric constants in the range of 1.5 to 2.4 with an elastic modulus of about 2-3 GPa.
  • porous network coatings can be plasma cured, eliminating the need for prior furnace curing.
  • the present invention produces a coating with a low dielectric constant and an improved elastic modulus.
  • the method of making the coating involves providing a porous network coating produced from a resin containing at least 2 Si—H groups. The coating is plasma cured to reduce the amount of Si—H bonds remaining in the coating. Plasma curing of the porous network coating yields a high elastic modulus of greater than or about 4 GPa.
  • the plasma cured coating can optionally be annealed. Thermal annealing of the plasma cured coating reduces the dielectric constant of the coating while maintaining the increase in the elastic modulus as compared to the elastic modulus before the anneal.
  • the annealing temperature is typically less than or about 475° C., and the annealing time is typically no more than or about 180 seconds.
  • the annealed, plasma cured coating has a dielectric constant in the range of from about 1.1 to about 3.5 and an elastic modulus that is generally greater than or about 4 GPa, and typically in the range of from about 4 GPa to about 10 GPa.
  • Plasma curing can generate a notable amount of polar species in the film, which can be undesirable in some applications.
  • the present invention is also based on the discovery that applying thermal annealing to plasma cured coatings produces a low dielectric constant, improved modulus material.
  • the methods of the present invention are particularly applicable to the deposition of coatings on electronic devices or electronic circuits where they can serve as interlevel dielectric layers, doped dielectric layers to produce transistor like devices, pigment loaded binder systems containing silicon to produce capacitor and capacitor like devices, multilayer devices, 3-D devices, silicon on insulator devices, super lattice devices, and the like.
  • the choice of substrates and devices to be coated by the instant invention is limited only by the need for thermal and chemical stability of the substrate at the temperature and pressure used in the present invention.
  • the coatings of the present invention can be used on substrates such as plastics including, for example, polyimides, epoxies, polytetrafluoroethylene and copolymers thereof, polycarbonates, acrylics and polyesters, ceramics, leather, textiles, metals, and the like.
  • plastics including, for example, polyimides, epoxies, polytetrafluoroethylene and copolymers thereof, polycarbonates, acrylics and polyesters, ceramics, leather, textiles, metals, and the like.
  • the expression “ceramic” includes ceramics such as amorphous silica and ceramic-like materials such as amorphous silica-like materials that are not fully free of carbon and/or hydrogen but are otherwise ceramic in character.
  • the expressions “electronic device” or “electronic circuit” include, but are not limited to, silica-based devices, gallium arsenide based devices, silicon carbide based devices, focal plane arrays, opto-electronic devices, photovoltaic cells and optical devices.
  • a porous network coating is needed as a starting material for the present invention.
  • One method of making such a porous network coating is disclosed in U.S. Pat. No. 6,231,989, which is described below.
  • the method of producing the porous network coating starts with depositing a coating on a substrate with a solution comprising a resin molecule containing at least 2 Si—H groups and a solvent.
  • the resin molecules containing at least 2 Si—H groups are repeating units, which form the silicate backbone of the resin.
  • the resins containing at least 2 Si—H groups are not particularly limited as long as the Si—H bonds can be hydrolyzed and at least partially condensed by the basic catalyst and water to form a crosslinked network that serves as the structure for the porous network.
  • such materials have the formula:
  • each R is independently selected from the group consisting of hydrogen, alkyl, alkenyl, or aryl groups, or alkyl, alkenyl, or aryl groups substituted with a hetero atom such as a halogen, nitrogen, sulfur, oxygen, or silicon, and a, b, c, and d are mole fractions of the particular unit and their total is 1, with the proviso that at least 2 R groups per molecule are hydrogen and the material is sufficiently resinous in structure to form the desired network.
  • alkyl groups are methyl, ethyl, propyl, butyl, and the like, with alkyls of 1-6 carbons being typical.
  • alkenyl groups include vinyl, allyl, and hexenyl.
  • aryls include phenyl.
  • each R′ is independently selected from the group consisting of alkyl, alkenyl, or aryl groups, or alkyl, alkenyl, or aryl groups substituted with a hetero atom such as a halogen, nitrogen, sulfur, oxygen, or silicon.
  • alkyl groups are methyl, ethyl, propyl, butyl, and the like, with alkyls of 1-6 carbons being typical.
  • alkenyl groups include vinyl, allyl, and hexenyl.
  • aryls include phenyl.
  • These resins may be essentially fully condensed (HSiO 3/2 ) n where n is 8 or greater, or they may be only partially hydrolyzed (i.e., containing some Si—OR′), and/or partially condensed (i.e., containing some Si—OH).
  • the structure of the resin containing at least 2 Si—H groups is not limited.
  • the structure may be what is generally known as ladder-type, cage-type, or mixtures thereof.
  • the HSQ resins may contain endgroups such as hydroxyl groups, triorganosiloxy groups, diorganohydrogensiloxy groups, trialkoxy groups, dialkoxy groups and others.
  • the HSQ resin may also contain a small number (e.g., less than 10%) of the silicon atoms which have either 0 or 2 hydrogen atoms attached thereto and/or a small number of Si-C groups, such as CH 3 SiO 3/2 or HCH 3 SiO 2/2 groups.
  • hydridosiloxane resins such as those described in U.S. Pat. No. 4,999,397, to Frye, and U.S. Pat. No. 5,210,160, to Bergstrom, those produced by hydrolyzing an alkoxy or acyloxy silane in an acidic, alcoholic hydrolysis medium, those described in Japanese Kokai Patent Nos. 59-178749, 60-086017, and 63-107122, or any other equivalent hydridosiloxanes, will also function herein.
  • a typical fraction comprises material wherein at least 75% of the polymeric species have a number average molecular weight above about 1200, and a more typical fraction comprises material wherein at least 75% of the polymeric species have a number average molecular weight between about 1200 and about 100,000.
  • the Si—H containing resins may contain other components as long as these components do not interfere with the integrity of the coating. It should be noted, however, that certain materials may increase the dielectric constant of the coating.
  • Ceramic oxide precursors may also be used in combination with the Si—H containing resins.
  • the ceramic oxide precursors useful herein include compounds of various metals such as aluminum, titanium, zirconium, tantalum, niobium and/or vanadium, as well as various non-metallic compounds, such as those of boron or phosphorus, which may be dissolved in solution, hydrolyzed and subsequently pyrolyzed at relatively low temperature to form ceramic oxides. Ceramic oxide precursors useful herein are described in U.S. Pat. Nos. 4,808,653, 5,008,320, and 5,290,394.
  • Si—H containing resins are applied to the substrates as solvent dispersions to form a coating on the substrate (“SiH resin coating”).
  • Solvents that may be used include any agent or mixture of agents that will dissolve or disperse the resin to form a homogeneous liquid mixture without affecting the resulting coating or the substrate.
  • solvents can include alcohols, such as ethyl alcohol or isopropyl alcohol; aromatic hydrocarbons, such as benzene or toluene; branched or linear alkanes, such as n-heptane, dodecane, or nonane; branched or linear alkenes, such as n-heptene, dodecene or tetradecene; ketones, such as methyl isobutyl ketone; esters; ethers, such as glycol ethers; or linear or cyclic siloxanes, such as hexamethyldisiloxane, octamethyldisiloxane, and mixtures thereof, or cyclic dimethylpolysiloxanes; or mixtures of any of the above solvents.
  • alcohols such as ethyl alcohol or isopropyl alcohol
  • aromatic hydrocarbons such as benzene or toluene
  • branched or linear alkanes such as
  • the solvent is generally present in an amount sufficient to dissolve/disperse the resin to the concentration desired for application. Typically, the solvent is present in an amount of about 20 to about 99.9 wt %, and more typically from about 70 to about 95 wt %, based on the weight of the resin and solvent.
  • the dispersion can include fillers, colorants, adhesion promoters, and the like.
  • Specific methods for application of the resin dispersion to the substrate include, but are not limited to, spin coating, dip coating, spray coating, flow coating, screen printing, or others.
  • a typical method is spin coating.
  • At least about 5 volume % of the solvent should remain in the SiH resin coating until the resin is contacted with the basic catalyst and water. This solvent forms the pores of the porous network coating as the Si—H bonds are hydrolyzed and condensed. In some embodiments, it may be typical that at least about 10 volume % solvent remains, while in others, it may be typical that at least about 15 volume % solvent remains, and in still others, it may be typical that at least about 25 volume % solvent remains.
  • a high boiling point solvent can be used alone or as a co-solvent with one of the solvents described above. In this manner, processing the resin dispersion as described above under normal conditions allows for at least about 5% residual solvent remaining.
  • Typical high boiling solvents in this embodiment are those with boiling points above about 175° C. including hydrocarbons, aromatic hydrocarbons, esters, ethers, and the like.
  • the above processing i.e., primarily deposition of the SiH resin coating solution
  • the spin coating can be performed in a closed environment such that the subsequent steps (i.e., contact with the basic catalyst and water) can occur before the solvent is completely evaporated.
  • the SiH resin coating containing at least about 5 volume % solvent is then contacted with a basic catalyst and water.
  • basic catalysts include ammonia, ammonium hydroxide, as well as amines.
  • the amines useful herein may include primary amines (RNH 2 ), secondary amines (R 2 NH), and/or tertiary amines (R 3 N) in which R is independently a saturated or unsaturated aliphatic, such as methyl, ethyl, propyl, vinyl, allyl, ethynyl, etc.; an alicyclic, such as cyclohexylmethyl; an aromatic, such as phenyl; a substituted hetero atom, such as oxygen, nitrogen, sulfur, etc.; or compounds in which the nitrogen atom is a member of a heterocyclic ring such as quinoline, pyrrolidine, or pyridine.
  • any of the above amine compounds may be substituted with other hydrocarbon and/or hetero containing groups to form compounds such as diamines, amides, etc.
  • compounds, which are converted to amines under the reactions conditions used would function in an equivalent manner.
  • a compound such as an ammonium salt that yields an amine upon dissolution would provide the desired catalytic effect.
  • Examples of the amines that may used herein include methylamine, ethylamine, butylamine, allylamine, cyclohexylamine, aniline, dimethylamine, diethylamide, dioctylamine, dibutylamine, methylethylamine, saccharin, piperidine, trimethylamine, triethylamine, pyridine, diethyl toluidene ethylmethylpropylamine, imidazole, choline acetate, triphenyl phosphene analine, trimethylsilylimidazole, ethylenediamine, diethylhydroxylamine, triethylenediamine, n-methylpyrolidone, etc.
  • the basic catalyst can generally be used at any concentration sufficient to catalyze hydrolysis of the Si—H bonds. Generally, concentrations of the basic catalyst can be from about 1 ppm to about 100 wt % based on the weight of the resin, depending on the basic catalyst.
  • the water used can be that present in the ambient environment (e.g., > about 25% relative humidity), the ambient environment can be supplemented with additional water vapor (e.g., relative humidity up to about 100%), water can be used as a liquid, or a compound which generates water under the reaction conditions can be used.
  • the SiH resin coating can be accomplished by any means practical or desirable.
  • the SiH resin coating can be contacted with vapors of the basic catalyst and water vapor.
  • the SiH resin coating can be contacted with the basic catalyst and water in the liquid state, such as by immersing the coating in an ammonium hydroxide solution.
  • the SiH resin coating is typically exposed to an environment comprising the basic catalyst and water in the vapor state, more typically ammonia and water vapor.
  • the SiH resin coated substrate may be placed in a container and the appropriate environment introduced therein, or a stream of the basic catalyst and water may be directed at the SiH resin coating.
  • the method used to generate the basic catalyst and water environment is generally not significant in the present embodiment.
  • Methods such as bubbling the basic catalyst (e.g., ammonia gas) through water or ammonium hydroxide solutions (to control the amount of water vapor present), heating a basic catalyst and water, or heating water and introducing the basic catalyst gas (e.g., ammonia gas) are all functional herein.
  • methods, which generate basic catalyst vapors in situ such as the addition of water to amine salts, or the addition of water to a silazane such as hexamethyldisilazane, will also be effective.
  • the basic catalyst used may be at any concentration desired.
  • the concentration may be from about 1 ppm up to a saturated atmosphere.
  • the exposure can be at any temperature desired from room temperature up to about 300° C.
  • a temperature in the range of from about 20° C. to about 200° C. is typical, with a range of from about 20° C. to about 100° C. being more typical.
  • the SiH resin coating should be exposed to the basic catalyst and water environment for the time necessary to hydrolyze the Si—H groups to form silanols (Si—OH) and for the silanols to at least partially condense to form Si—O—Si bonds. Generally, exposures of up to about 20 minutes are typical, with exposures of at least about 1 second up to about 5 minutes being more typical. If the coatings are to be used as a dielectric layer, it is generally typical to have a shorter exposure, as longer exposures tend to increase the dielectric constant of the coating.
  • the coating When the coating is exposed to the basic catalyst and water in the liquid state, the exposure is usually conducted by immersing the coated substrate in a solution. Other equivalent methods can be used, such as flushing the coating with a basic catalyst and water solution. In addition, vacuum infiltration may also be used to increase penetration of the basic catalyst and water into the coating.
  • the basic catalyst solution used in this embodiment may be at any concentration desired. Generally when ammonium hydroxide is used, a concentrated aqueous solution of between about 28 and about 30% is typical since the duration of exposure is thereby shortened. When dilute solutions are used, the diluent is generally water.
  • Exposure to the basic catalyst and water solution in this embodiment may be conducted at any temperature and pressure desired. Temperatures from about room temperature (20-30° C.) up to about the boiling point of the basic catalyst solution, and pressures from below to above atmospheric are all contemplated herein. From a practical standpoint, it is typical that the exposure occur at about room temperature and at about atmospheric pressure.
  • the resin coating is exposed to the basic catalyst solution in this embodiment for the time necessary to hydrolyze the Si—H groups to form silanols (Si—OH) and for the silanols to at least partially condense to form Si—O—Si bonds.
  • exposures of up to about 2 hours are typical, with exposures of at least about 1 second up to about 15 minutes being more typical.
  • the coating may be exposed to both a liquid basic catalyst and water environment (e.g., ammonium hydroxide) and a gaseous basic catalyst and water vapor environment (ammonia gas and water vapor).
  • a liquid basic catalyst and water environment e.g., ammonium hydroxide
  • a gaseous basic catalyst and water vapor environment ammonia gas and water vapor.
  • the exposures may be either sequential or simultaneous, and are generally under the same conditions as those described above.
  • the solvent is then removed from the coating. This can be accomplished by any desired means, including but not limited to, heating the coating, and by vacuum. When the solvent is removed by heating the coating, condensation of the remaining silanols may be facilitated.
  • the coating produced by this process can be used as the starting material (“porous network coating”) in the present invention.
  • a substrate is coated with the Si—H containing resin and solvent in a manner which ensures that at least about 5 volume % of the solvent remains in the coating.
  • the coating is then exposed to the basic catalyst and water, and the solvent is evaporated.
  • the method comprises contacting a hydridosilicon containing resin with a 1-alkene comprising about 8 to about 28 carbon atoms in the presence of a platinum group metal-containing hydrosilation catalyst, effecting formation of an alkylhydridosiloxane resin where at least about 5 percent of the silicon atoms are substituted with at least one hydrogen atom and heating the alkylhydridosiloxane prepared at a temperature sufficient to effect curing and thermolysis of alkyl groups from the silicon atoms, thereby forming a nanoporous silicone resin.
  • porous network coatings having low dielectric constants are desirable, it would be advantageous to have a coating with a higher elastic modulus.
  • the plasma cure can be done by radio frequency (RF), inductive coupled, RF capacitive coupled, helical resinator, microwave downstream, and microwave electron cyclotron resonance (ECR) plasma.
  • RF radio frequency
  • ECR microwave electron cyclotron resonance
  • the wafer is quickly heated in a rapid temperature ramp-up step to the desired temperature, and the wafer is plasma cured.
  • Microwave Plasma Power 1000 W-2000 W Wafer Temperature: 80° C.-350° C.
  • Process Pressure 1.0 torr-6.0 torr Plasma Cure Time: >15 seconds
  • Plasma Gases H 2 /N 2 /CF 4 /O 2 O 2 flow rate: 0-4000 sccm CF 4 flow rate: 0-400 sccm H 2 /N 2 Gas Mixture flow rate: >0-4000 sccm
  • the plasma cured porous network coatings of the present invention have improved chemical stability and improved dimensional stability.
  • improved chemical stability we mean that the coatings are more resistant to chemicals, such as cleaning solutions and chemical polishing solutions, and plasma damaging during photoresist ashing and dry etching processes.
  • plasma cure can generate a notable amount of polar species in the film.
  • the plasma cured coatings can be annealed using any type of thermal exposure to reduce the dielectric constant, if desired.
  • the plasma cured coatings can be placed in a conventional oven until the polar species are removed, such as at 450° C. for 30 minutes.
  • Another process which can be used involves annealing the plasma cured coatings in a Rapid Thermal Processing (RTP) chamber in order to reduce the dielectric constant.
  • RTP Rapid Thermal Processing
  • the plasma cured coating is annealed at a typical temperature for a sufficient time, and cooled to about 100° C.
  • the dielectric constant of the annealed, plasma cured coatings is reduced as compared to the plasma cured porous network coatings.
  • the dielectric constant of the annealed, plasma cured coatings is typically in the range of from about 1.1 to about 3.5 and more typically in the range of from about 2 to about 2.5.
  • the elastic modulus of the annealed, plasma cured coatings is increased as compared to a furnace (thermally) cured coating which would have an elastic modulus of between about 2.0 and about 3.0 when the dielectric constant is about 2.0. This increase in the elastic modulus is typically greater than or about 50%, and more typically greater than or about 100%. Typically, the elastic modulus of the annealed, plasma cured coating is greater than or about 4 GPa, and more typically between about 4 GPa and about 10 GPa.
  • Porous network coatings were produced from hydrogen silsesquioxane resin by spinning onto silicon wafers and treating with NH 3 followed by 1 minute 150° C. hotplate thermal treatments. The plasma conversion was done in an Axcelis Fusion Gemini® ES plasma asher. After the plasma conversion, porous silica films with low dielectric constant and high modulus have been obtained. The results are shown in Table 1.
  • the plasma conditions were 2-4 torr in pressure. The temperatures were controlled between 195-230° C.
  • the forming gas was N 2 /H 2 /CF 4 .
  • the plasma power and gas flow data are listed in Table 1.
  • the dielectric constants are in a range of 2.0 to 2.8.
  • the plasma conditions at 210° C. yielded films of lower dielectric constants, lower than 2.4.
  • the films processed at 195, 225, and 230° C. showed dielectric constants higher than 2.4.
  • the modulus of the plasma cured films are from 6 to 9 GPa.
  • the plasma curing process took off approximately 10% of the film thickness.
  • the uniformity of the plasma cured film is typically within 2%.
  • the FTIR spectra suggest that Si—H bonds were completely removed from the films during the plasma curing at pressures of 2-3 torr, implying that porous silica films were made from the plasma curing process.
  • the films with the dielectric constants of 2.0-2.3 include less than 1% Si—OH.
  • TABLE 1 Plasma Cure of Films (Example 1) Pre-Plasma Heating Plasma Cure Conditions Time Pressure Temperature Time Pressure Temperature Power H 2 N 2 CF 4 Modulus Refractive Thickness Wafer (sec) (torr) (° C.) (sec) (torr) (° C.) (W) (sccm) (sccm) Dk (GPa) Index ( ⁇ ) 1 120 2.0 210 90 2.0 210 1800 2000 100 2.30 7.3 1.202 4302 2 120 3.0 210 90 3.0 210 1800 2000 100 2.13 7.0 1.196 4265 3 120 3.0 210 90 3.0 210 1800 2000 100 2.27 8.2 1.258 3628 4 120 2.5 210 90 2.5 210 1800 2000 100 2.29 7.9 1.247 3671 5 120 4.0 210 90 4.0 210 1800 2000 100 2.16 6.7 1.205 3676 6 120 4.0 210 90 4.0 210 1800 2000 100 2.24 6.5
  • Porous network coatings were produced from hydrogen silsesquioxane by spinning onto silicon wafers and treating with NH 3 followed by 1 minute 150° C. hotplate thermal treatments.
  • the NH 3 aging time was 1 ⁇ 2 to 2 ⁇ 3 of standard recipes specified in both the TEL spin tool and the DNS spin tool.
  • the plasma conversion was done in an Axcelis Fusion Gemini® ES plasma asher. After the plasma conversion, porous silica films with low dielectric constant and high modulus have been obtained. The results are shown in Table 2.
  • the plasma conditions were 2-4 torr in pressure. The temperatures were controlled at 210° C.
  • the forming gas was N 2 /H 2 /CF 4 .
  • the plasma power and gas flow data are listed in Table 2.
  • the plasma curing can also convert the initial films into porous silica films even if the initial films were aged for a short time under moist NH 3 .
  • the plasma cured films with less than standard aging time show dielectric constants under 2.3.
  • the modulus values are from 5.7 to 9 GPa.
  • Si—H bonds were removed during the plasma curing so that porous silica films were obtained.
  • the Si—OH level in these films is typically less than 1%.
  • Porous network coatings were produced from hydrogen silsesquioxane by spinning onto silicon wafers and treating with excessive NH 3 followed by 1 minute 150° C. hotplate thermal treatments.
  • the NH 3 aging time was twice as long as that specified in the standard recipes for both the TEL spin tool and the DNS spin tool.
  • the plasma conversion was done in an Axcelis Fusion Gemini® ES plasma asher. The results are shown in Tables 3A and 3B.
  • the plasma conditions were 2.5-3 torr in pressure. The temperatures were controlled at 210° C.
  • the forming gas was N 2 /H 2 /CF 4 .
  • the plasma power and gas flow data are listed in Tables 3A and 3B.
  • the dielectric constants of the plasma cured porous films are 2.5 or higher, and the moduli are approximately 7-8 GPa.
  • the Si—OH content is typically around 1.5-2.5%, as calculated from FTIR spectra. The Si—H bonds were completely removed.
  • the infrared spectra of the annealed, plasma cured coatings that were thermally annealed by heating using RTP are virtually identical to those coatings that were thermally annealed by other heating methods.
  • the features in the spectra indicate that this plasma cured film is silica in nature.
  • the SiOH content is less than 1 weight percent as calculated from the infrared spectra.
  • the refractive index (RI) of the RTP annealed coatings (1.20 to 1.22) is consistent with the RI value of coatings that were thermally annealed by other heating methods.
  • the elastic modulus of the plasma cured coatings that were thermally annealed by RTP can be two or three times higher (as high as 7-8 GPa) than the initial elastic modulus.
  • the dielectric constants of these coatings range from 2.1 to 2.3.
  • a thin (less than 5 microns) SiO 2 containing coating is produced on the substrate.
  • the coating has an improved elastic modulus. Furthermore, with the annealing step, the coating can have an improved elastic modulus and a low dielectric constant.
  • the coating smooths the irregular surfaces of various substrates and has excellent adhesion.
  • the coating may be covered by other coatings, such as further SiO 2 coatings, SiO 2 /modifying ceramic oxide layers, silicon containing coatings, carbon containing coatings, and/or diamond like coatings.
  • These coatings posses low defect density and are useful on electronic devices as dielectric layers in, for example, multilayer devices.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Formation Of Insulating Films (AREA)
  • Paints Or Removers (AREA)
  • Silicon Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Low dielectric constant films with improved elastic modulus. An SiO2-containing plasma cured coating having a first dielectric constant and having a first elastic modulus is provided, the coating being formed by providing a porous network coating produced from a resin molecule containing at least 2 Si—H groups, and plasma curing the porous network coating to reduce an amount of Si—H bonds. Plasma curing of the network coating yields a coating with improved modulus, but with a higher dielectric constant. Accordingly, an SiO2-containing plasma cured coating is also provided, the coating being formed by annealing the plasma cured coating to produce an annealed, plasma cured coating having a second dielectric constant which is less than the first dielectric constant and having a second elastic modulus which is comparable to the first elastic modulus. The annealed, SiO2-containing plasma cured coating can have a dielectric constant between about 1.1 and about 3.5 and an elastic modulus greater than or about 4 GPa. It is emphasized that this abstract is provided to comply with the rules requiring an abstract which will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. 37 CFR §1.72(b).

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a division of application Ser. No. 09/681,332, filed Mar. 19, 2001 entitled “PLASMA CURING PROCESS FOR POROUS SILICA THIN FILM”, which is a continuation-in-part of application Ser. No. 09/528,835, filed Mar. 20, 2000 entitled “High Modulus, Low Dielectric Constant Coatings”.[0001]
    • BACKGROUND OF THE INVENTION
  • This invention relates generally to coatings for use in electronic devices. More particularly, the invention relates to coatings having an improved elastic modulus and a low dielectric constant and to methods of making such coatings. [0002]
  • Thin film dielectric coatings on electric devices are known in the art. For instance, U.S. Pat. Nos. 4,749,631 and 4,756,977, to Haluska et al., disclose silica based coatings produced by applying solutions of silicon alkoxides or hydrogen silsesquioxane, respectively, to substrates and then heating the coated substrates to a temperature between 200 and 1000° C. The dielectric constant of these coatings is often too high for certain electronic devices and circuits. [0003]
  • U.S. Pat. Nos. 4,847,162 and 4,842,888, to Haluska et al., teach the formation of nitrided silica coatings by heating hydrogen silsesquioxane resin and silicate esters, respectively, to a temperature between 200 and 1000° C. in the presence of ammonia. These references teach the use of anhydrous ammonia so that the resulting coating has about 1 to 2% by weight nitrogen incorporated therein. [0004]
  • Glasser et al., Journal of Non-Crystalline Solids, 64 (1984) pp. 209-221, teaches the formation of ceramic coatings by heating tetraethoxysilane in the presence of ammonia. This reference teaches the use of anhydrous ammonia and that the resulting silica coatings are nitrided. [0005]
  • U.S. Pat. No. 4,636,440, to Jada, discloses a method of reducing the drying time for a sol-gel coated substrate comprising exposing the substrate to aqueous quaternary ammonium hydroxide and/or alkanol amine compounds. Jada requires that the coating be dried prior to heating. It is specifically limited to hydrolyzed or partially hydrolyzed silicon alkoxides and does not teach the utility of the process on coatings having Si—H bonds. [0006]
  • U.S. Pat. Nos. 5,262,201, to Chandra, and 5,116,637, to Baney et al., teach the use of basic catalysts to lower the temperature necessary for the conversion of various preceramic materials, all involving hydrogen silsesquioxane, to ceramic coatings. These references teach the removal of solvent before the coating is exposed to the basic catalysts. [0007]
  • U.S. Pat. No. 5,547,703, to Camilletti et al., teaches a method for forming low dielectric constant Si—O containing coatings on substrates comprising heating a hydrogen silsesquioxane resin successively under wet ammonia, dry ammonia, and oxygen. The resultant coatings have dielectric constants as low as 2.42 at 1 MHz. This reference teaches the removal of solvent before converting the coating to a ceramic. [0008]
  • U.S. Pat. No. 5,523,163, to Balance et al., teaches a method for forming Si—O containing coatings on substrates comprising heating a hydrogen silsesquioxane resin to convert it to a Si—O containing ceramic coating and then exposing the coating to an annealing atmosphere containing hydrogen gas. The resultant coatings have dielectric constants as low as 2.773. The reference teaches the removal of solvent before converting the coating to a ceramic. [0009]
  • U.S. Pat. No. 5,618,878, to Syktich et al., discloses coating compositions containing hydrogen silsesquioxane resin dissolved in saturated alkyl hydrocarbons useful for forming thick ceramic coatings. The alkyl hydrocarbons disclosed are those up to dodecane. The reference does not teach exposure of the coated substrates to basic catalysts before solvent removal. [0010]
  • U.S. Pat. No. 6,231,989, to Chung et al., entitled METHOD OF FORMING COATINGS, discloses a method of making porous network coatings with low dielectric constants. The method comprises depositing a coating on a substrate with a solution comprising a resin containing at least 2 Si—H groups and a solvent in a manner in which at least 5 volume % of the solvent remains in the coating after deposition. The coating is then exposed to an environment comprising a basic catalyst and water. Finally, the solvent is evaporated from the coating to form a porous network. If desired, the coating can be cured by heating to form a ceramic. Films made by this process have dielectric constants in the range of 1.5 to 2.4 with an elastic modulus of about 2-3 GPa. [0011]
  • It has now been discovered that instead of plasma treating, porous network coatings can be plasma cured, eliminating the need for prior furnace curing. [0012]
  • However, there remains a need for a method of making a porous network coating having an improved elastic modulus. [0013]
    • SUMMARY OF THE INVENTION
  • The present invention produces a coating with a low dielectric constant and an improved elastic modulus. The method of making the coating involves providing a porous network coating produced from a resin containing at least 2 Si—H groups. The coating is plasma cured to reduce the amount of Si—H bonds remaining in the coating. Plasma curing of the porous network coating yields a high elastic modulus of greater than or about 4 GPa. [0014]
  • The plasma cured coating can optionally be annealed. Thermal annealing of the plasma cured coating reduces the dielectric constant of the coating while maintaining the increase in the elastic modulus as compared to the elastic modulus before the anneal. The annealing temperature is typically less than or about 475° C., and the annealing time is typically no more than or about 180 seconds. [0015]
  • The annealed, plasma cured coating has a dielectric constant in the range of from about 1.1 to about 3.5 and an elastic modulus that is generally greater than or about 4 GPa, and typically in the range of from about 4 GPa to about 10 GPa. [0016]
  • Accordingly, it is an object of the present invention to produce coatings having improved elastic modulus and low dielectric constant. [0017]
    • DETAILED DESCRIPTION OF THE INVENTION
  • The manufacture of ultra low dielectric constant coatings having a dielectric constant of about 1.5 to about 2.4 is described in U.S. Pat. No. 6,231,989, which is incorporated herein by reference for its teaching on how to produce coatings having ultra low dielectric constants. This patent describes a process in which pores are introduced into hydrogen silsesquioxane (HSQ) based films. HSQ based films produced according to the method taught in U.S. Pat. No. 6,231,989, which have been cured under thermal conditions, contain about 20 to about 60% Si—H bonds density. When the dielectric constant of the coating is about 2.0, the coating has an elastic modulus of between about 2 and about 3 GPa. The present invention is based on the discovery that plasma curing porous HSQ based films increases the elastic modulus of the film without the necessity of thermally curing the film. Plasma curing reduces the amount of Si—H bonds remaining without losing the low density structure of the film. [0018]
  • Plasma curing can generate a notable amount of polar species in the film, which can be undesirable in some applications. The present invention is also based on the discovery that applying thermal annealing to plasma cured coatings produces a low dielectric constant, improved modulus material. [0019]
  • The methods of the present invention are particularly applicable to the deposition of coatings on electronic devices or electronic circuits where they can serve as interlevel dielectric layers, doped dielectric layers to produce transistor like devices, pigment loaded binder systems containing silicon to produce capacitor and capacitor like devices, multilayer devices, 3-D devices, silicon on insulator devices, super lattice devices, and the like. However, the choice of substrates and devices to be coated by the instant invention is limited only by the need for thermal and chemical stability of the substrate at the temperature and pressure used in the present invention. As such, the coatings of the present invention can be used on substrates such as plastics including, for example, polyimides, epoxies, polytetrafluoroethylene and copolymers thereof, polycarbonates, acrylics and polyesters, ceramics, leather, textiles, metals, and the like. [0020]
  • As used in the present invention, the expression “ceramic” includes ceramics such as amorphous silica and ceramic-like materials such as amorphous silica-like materials that are not fully free of carbon and/or hydrogen but are otherwise ceramic in character. The expressions “electronic device” or “electronic circuit” include, but are not limited to, silica-based devices, gallium arsenide based devices, silicon carbide based devices, focal plane arrays, opto-electronic devices, photovoltaic cells and optical devices. [0021]
  • A porous network coating is needed as a starting material for the present invention. One method of making such a porous network coating is disclosed in U.S. Pat. No. 6,231,989, which is described below. [0022]
  • The method of producing the porous network coating starts with depositing a coating on a substrate with a solution comprising a resin molecule containing at least 2 Si—H groups and a solvent. Those skilled in the art will understand that the resin molecules containing at least 2 Si—H groups are repeating units, which form the silicate backbone of the resin. The resins containing at least 2 Si—H groups are not particularly limited as long as the Si—H bonds can be hydrolyzed and at least partially condensed by the basic catalyst and water to form a crosslinked network that serves as the structure for the porous network. Generally, such materials have the formula: [0023]
  • {R3SiO1/2}a{R2SiO2/2}b{RSiO3/2}c{SiO4/2}d
  • wherein each R is independently selected from the group consisting of hydrogen, alkyl, alkenyl, or aryl groups, or alkyl, alkenyl, or aryl groups substituted with a hetero atom such as a halogen, nitrogen, sulfur, oxygen, or silicon, and a, b, c, and d are mole fractions of the particular unit and their total is 1, with the proviso that at least 2 R groups per molecule are hydrogen and the material is sufficiently resinous in structure to form the desired network. Examples of alkyl groups are methyl, ethyl, propyl, butyl, and the like, with alkyls of 1-6 carbons being typical. Examples of alkenyl groups include vinyl, allyl, and hexenyl. Examples of aryls include phenyl. Examples of substituted groups include CF[0024] 3(CF2)nCH2CH2, where n=0-6.
  • Useful in the present invention are various hydridosiloxane resins, known as hydrogen silsesquioxane resins, comprising units of the formula HSi(OH)[0025] x(OR′)yOz/2. In this formula, each R′ is independently selected from the group consisting of alkyl, alkenyl, or aryl groups, or alkyl, alkenyl, or aryl groups substituted with a hetero atom such as a halogen, nitrogen, sulfur, oxygen, or silicon. Examples of alkyl groups are methyl, ethyl, propyl, butyl, and the like, with alkyls of 1-6 carbons being typical. Examples of alkenyl groups include vinyl, allyl, and hexenyl. Examples of aryls include phenyl. Examples of substituted groups include CF3(CF2)nCH2CH2, where n=0-6. When these R′ groups are bonded to silicon through the oxygen atom, they form a hydrolyzable substituent. In the above formula, x=0 to 2, y=0 to 2, z=1 to 3, an x+y+z=3. These resins may be essentially fully condensed (HSiO3/2)n where n is 8 or greater, or they may be only partially hydrolyzed (i.e., containing some Si—OR′), and/or partially condensed (i.e., containing some Si—OH).
  • The structure of the resin containing at least 2 Si—H groups is not limited. The structure may be what is generally known as ladder-type, cage-type, or mixtures thereof. The HSQ resins may contain endgroups such as hydroxyl groups, triorganosiloxy groups, diorganohydrogensiloxy groups, trialkoxy groups, dialkoxy groups and others. The HSQ resin may also contain a small number (e.g., less than 10%) of the silicon atoms which have either 0 or 2 hydrogen atoms attached thereto and/or a small number of Si-C groups, such as CH[0026] 3SiO3/2 or HCH3SiO2/2 groups.
  • The resins containing at least 2 Si—H groups and methods for their production are known in the art. For example, U.S. Pat. No. 3,615,272, to Collins, teaches the production of an essentially fully condensed hydrogen silsesquioxane resin (which may contain up to 100-300 ppm silanol) by a process comprising hydrolyzing trichlorosilane in a benzenesulfonic acid hydrate hydrolysis medium, and then washing the resulting resin with water or aqueous sulfuric acid. Similarly, U.S. Pat. No. 5,010,159 to Bank, teaches a method comprising hydrolyzing hydridosilanes in an arylsulfonic acid hydrate hydrolysis medium to form a resin which is then contacted with a neutralizing agent. [0027]
  • Other hydridosiloxane resins, such as those described in U.S. Pat. No. 4,999,397, to Frye, and U.S. Pat. No. 5,210,160, to Bergstrom, those produced by hydrolyzing an alkoxy or acyloxy silane in an acidic, alcoholic hydrolysis medium, those described in Japanese Kokai Patent Nos. 59-178749, 60-086017, and 63-107122, or any other equivalent hydridosiloxanes, will also function herein. [0028]
  • Specific molecular weight fractions of the Si—H containing resins may also be used. Such fractions and methods for their preparation are taught in U.S. Pat. No. 5,063,267, to Hanneman, and U.S. Pat. No. 5,416,190, to Mine. A typical fraction comprises material wherein at least 75% of the polymeric species have a number average molecular weight above about 1200, and a more typical fraction comprises material wherein at least 75% of the polymeric species have a number average molecular weight between about 1200 and about 100,000. [0029]
  • The Si—H containing resins may contain other components as long as these components do not interfere with the integrity of the coating. It should be noted, however, that certain materials may increase the dielectric constant of the coating. [0030]
  • Ceramic oxide precursors may also be used in combination with the Si—H containing resins. The ceramic oxide precursors useful herein include compounds of various metals such as aluminum, titanium, zirconium, tantalum, niobium and/or vanadium, as well as various non-metallic compounds, such as those of boron or phosphorus, which may be dissolved in solution, hydrolyzed and subsequently pyrolyzed at relatively low temperature to form ceramic oxides. Ceramic oxide precursors useful herein are described in U.S. Pat. Nos. 4,808,653, 5,008,320, and 5,290,394. [0031]
  • The Si—H containing resins are applied to the substrates as solvent dispersions to form a coating on the substrate (“SiH resin coating”). Solvents that may be used include any agent or mixture of agents that will dissolve or disperse the resin to form a homogeneous liquid mixture without affecting the resulting coating or the substrate. These solvents can include alcohols, such as ethyl alcohol or isopropyl alcohol; aromatic hydrocarbons, such as benzene or toluene; branched or linear alkanes, such as n-heptane, dodecane, or nonane; branched or linear alkenes, such as n-heptene, dodecene or tetradecene; ketones, such as methyl isobutyl ketone; esters; ethers, such as glycol ethers; or linear or cyclic siloxanes, such as hexamethyldisiloxane, octamethyldisiloxane, and mixtures thereof, or cyclic dimethylpolysiloxanes; or mixtures of any of the above solvents. The solvent is generally present in an amount sufficient to dissolve/disperse the resin to the concentration desired for application. Typically, the solvent is present in an amount of about 20 to about 99.9 wt %, and more typically from about 70 to about 95 wt %, based on the weight of the resin and solvent. [0032]
  • If desired, other materials can be included in the resin dispersion. For instance, the dispersion can include fillers, colorants, adhesion promoters, and the like. [0033]
  • Specific methods for application of the resin dispersion to the substrate include, but are not limited to, spin coating, dip coating, spray coating, flow coating, screen printing, or others. A typical method is spin coating. [0034]
  • At least about 5 volume % of the solvent should remain in the SiH resin coating until the resin is contacted with the basic catalyst and water. This solvent forms the pores of the porous network coating as the Si—H bonds are hydrolyzed and condensed. In some embodiments, it may be typical that at least about 10 volume % solvent remains, while in others, it may be typical that at least about 15 volume % solvent remains, and in still others, it may be typical that at least about 25 volume % solvent remains. [0035]
  • The method of retaining the solvent is not particularly restricted. In a typical embodiment, a high boiling point solvent can be used alone or as a co-solvent with one of the solvents described above. In this manner, processing the resin dispersion as described above under normal conditions allows for at least about 5% residual solvent remaining. Typical high boiling solvents in this embodiment are those with boiling points above about 175° C. including hydrocarbons, aromatic hydrocarbons, esters, ethers, and the like. Examples of specific solvents which can be used in this embodiment include saturated hydrocarbons, such as dodecane, tetradecane, hexadecane, etc., unsaturated hydrocarbons such as dodecene, tetradecene, etc., xylenes, mesitylene, 1-heptanol, dipentene, d-limonene, tetrahydrofurfuryl alcohol, mineral spirits, 2-octanol, stoddard solvent, Isopar H™, diethyl oxalate, diamyl ether, tetrahydropyran-2-methanol, lactic acid butyl ester, isooctyl alcohol, propylene glycol, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, dimethyl sulfoxide, 2,5-hexanedione, 2-butoxyethanol acetate, diethylene glycol monomethyl ether, 1-octanol, ethylene glycol, Isopar L™, dipropylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, N-methylpyrrolidone, ethylene glycol dibutyl ether, gamma-butyrolactone, 1,3-butanediol, diethylene glycol monomethyl ether acetate, trimethylene glycol, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, alpha-terpineol, n-hexyl ether, kerosene, 2-(2-n-butoxyethoxy)ethanol, dibutyl oxalate, propylene carbonate, propylene glycol monophenyl ether, diethylene glycol, catechol, diethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether, diethylene glycol dibutyl ether, diphenyl ether, ethylene glycol monobenzyl ether, hydroquinone, sulfolane, and triethylene glycol. Hydrocarbon solvents are particularly preferred. [0036]
  • The above processing (i.e., primarily deposition of the SiH resin coating solution) can be done in an environment that inhibits solvent evaporation prior to contact with the basic catalyst and water. For example, the spin coating can be performed in a closed environment such that the subsequent steps (i.e., contact with the basic catalyst and water) can occur before the solvent is completely evaporated. [0037]
  • The SiH resin coating containing at least about 5 volume % solvent is then contacted with a basic catalyst and water. Examples of basic catalysts include ammonia, ammonium hydroxide, as well as amines. The amines useful herein may include primary amines (RNH[0038] 2), secondary amines (R2NH), and/or tertiary amines (R3N) in which R is independently a saturated or unsaturated aliphatic, such as methyl, ethyl, propyl, vinyl, allyl, ethynyl, etc.; an alicyclic, such as cyclohexylmethyl; an aromatic, such as phenyl; a substituted hetero atom, such as oxygen, nitrogen, sulfur, etc.; or compounds in which the nitrogen atom is a member of a heterocyclic ring such as quinoline, pyrrolidine, or pyridine. In addition, any of the above amine compounds may be substituted with other hydrocarbon and/or hetero containing groups to form compounds such as diamines, amides, etc. Finally, it is also contemplated that compounds, which are converted to amines under the reactions conditions used, would function in an equivalent manner. For example, a compound such as an ammonium salt that yields an amine upon dissolution would provide the desired catalytic effect.
  • Examples of the amines that may used herein include methylamine, ethylamine, butylamine, allylamine, cyclohexylamine, aniline, dimethylamine, diethylamide, dioctylamine, dibutylamine, methylethylamine, saccharin, piperidine, trimethylamine, triethylamine, pyridine, diethyl toluidene ethylmethylpropylamine, imidazole, choline acetate, triphenyl phosphene analine, trimethylsilylimidazole, ethylenediamine, diethylhydroxylamine, triethylenediamine, n-methylpyrolidone, etc. [0039]
  • The basic catalyst can generally be used at any concentration sufficient to catalyze hydrolysis of the Si—H bonds. Generally, concentrations of the basic catalyst can be from about 1 ppm to about 100 wt % based on the weight of the resin, depending on the basic catalyst. [0040]
  • The water used can be that present in the ambient environment (e.g., > about 25% relative humidity), the ambient environment can be supplemented with additional water vapor (e.g., relative humidity up to about 100%), water can be used as a liquid, or a compound which generates water under the reaction conditions can be used. [0041]
  • Contact of the SiH resin coating with the basic catalyst and water can be accomplished by any means practical or desirable. For instance, the SiH resin coating can be contacted with vapors of the basic catalyst and water vapor. Alternatively, the SiH resin coating can be contacted with the basic catalyst and water in the liquid state, such as by immersing the coating in an ammonium hydroxide solution. [0042]
  • The SiH resin coating is typically exposed to an environment comprising the basic catalyst and water in the vapor state, more typically ammonia and water vapor. For instance, the SiH resin coated substrate may be placed in a container and the appropriate environment introduced therein, or a stream of the basic catalyst and water may be directed at the SiH resin coating. [0043]
  • The method used to generate the basic catalyst and water environment is generally not significant in the present embodiment. Methods such as bubbling the basic catalyst (e.g., ammonia gas) through water or ammonium hydroxide solutions (to control the amount of water vapor present), heating a basic catalyst and water, or heating water and introducing the basic catalyst gas (e.g., ammonia gas) are all functional herein. It is also contemplated that methods, which generate basic catalyst vapors in situ, such as the addition of water to amine salts, or the addition of water to a silazane such as hexamethyldisilazane, will also be effective. [0044]
  • The basic catalyst used may be at any concentration desired. For example, the concentration may be from about 1 ppm up to a saturated atmosphere. [0045]
  • The exposure can be at any temperature desired from room temperature up to about 300° C. A temperature in the range of from about 20° C. to about 200° C. is typical, with a range of from about 20° C. to about 100° C. being more typical. [0046]
  • The SiH resin coating should be exposed to the basic catalyst and water environment for the time necessary to hydrolyze the Si—H groups to form silanols (Si—OH) and for the silanols to at least partially condense to form Si—O—Si bonds. Generally, exposures of up to about 20 minutes are typical, with exposures of at least about 1 second up to about 5 minutes being more typical. If the coatings are to be used as a dielectric layer, it is generally typical to have a shorter exposure, as longer exposures tend to increase the dielectric constant of the coating. [0047]
  • When the coating is exposed to the basic catalyst and water in the liquid state, the exposure is usually conducted by immersing the coated substrate in a solution. Other equivalent methods can be used, such as flushing the coating with a basic catalyst and water solution. In addition, vacuum infiltration may also be used to increase penetration of the basic catalyst and water into the coating. [0048]
  • The basic catalyst solution used in this embodiment may be at any concentration desired. Generally when ammonium hydroxide is used, a concentrated aqueous solution of between about 28 and about 30% is typical since the duration of exposure is thereby shortened. When dilute solutions are used, the diluent is generally water. [0049]
  • Exposure to the basic catalyst and water solution in this embodiment may be conducted at any temperature and pressure desired. Temperatures from about room temperature (20-30° C.) up to about the boiling point of the basic catalyst solution, and pressures from below to above atmospheric are all contemplated herein. From a practical standpoint, it is typical that the exposure occur at about room temperature and at about atmospheric pressure. [0050]
  • The resin coating is exposed to the basic catalyst solution in this embodiment for the time necessary to hydrolyze the Si—H groups to form silanols (Si—OH) and for the silanols to at least partially condense to form Si—O—Si bonds. Generally, exposures of up to about 2 hours are typical, with exposures of at least about 1 second up to about 15 minutes being more typical. [0051]
  • Alternatively, the coating may be exposed to both a liquid basic catalyst and water environment (e.g., ammonium hydroxide) and a gaseous basic catalyst and water vapor environment (ammonia gas and water vapor). The exposures may be either sequential or simultaneous, and are generally under the same conditions as those described above. [0052]
  • After the resin is exposed to one of the above environments, the solvent is then removed from the coating. This can be accomplished by any desired means, including but not limited to, heating the coating, and by vacuum. When the solvent is removed by heating the coating, condensation of the remaining silanols may be facilitated. [0053]
  • The coating produced by this process can be used as the starting material (“porous network coating”) in the present invention. In a typical procedure to produce a porous network coating, a substrate is coated with the Si—H containing resin and solvent in a manner which ensures that at least about 5 volume % of the solvent remains in the coating. The coating is then exposed to the basic catalyst and water, and the solvent is evaporated. [0054]
  • Another method of making such a porous network coating is disclosed in U.S. Pat. No. 6,143,360 to Zhong, entitled METHOD FOR MAKING NANOPOROUS SILICONE RESINS FROM ALKYLHYDRIDOSILOXANE RESINS. The method comprises contacting a hydridosilicon containing resin with a 1-alkene comprising about 8 to about 28 carbon atoms in the presence of a platinum group metal-containing hydrosilation catalyst, effecting formation of an alkylhydridosiloxane resin where at least about 5 percent of the silicon atoms are substituted with at least one hydrogen atom and heating the alkylhydridosiloxane prepared at a temperature sufficient to effect curing and thermolysis of alkyl groups from the silicon atoms, thereby forming a nanoporous silicone resin. [0055]
  • Although porous network coatings having low dielectric constants are desirable, it would be advantageous to have a coating with a higher elastic modulus. [0056]
  • In order to raise the elastic modulus of the porous network coating, it is exposed to a plasma cure. The plasma cure can be done by radio frequency (RF), inductive coupled, RF capacitive coupled, helical resinator, microwave downstream, and microwave electron cyclotron resonance (ECR) plasma. [0057]
  • In a typical plasma curing process, the wafer is quickly heated in a rapid temperature ramp-up step to the desired temperature, and the wafer is plasma cured. [0058]
  • The exact conditions for the plasma cure depend upon what type of plasma cure is being used. Examples of typical microwave plasma cure conditions for a 200 mm wafer are shown below. [0059]
    Microwave Plasma Power: 1000 W-2000 W
    Wafer Temperature: 80° C.-350° C.
    Process Pressure: 1.0 torr-6.0 torr
    Plasma Cure Time: >15 seconds
    Plasma Gases: H2/N2/CF4/O2
    O2 flow rate: 0-4000 sccm
    CF4 flow rate: 0-400 sccm
    H2/N2 Gas Mixture flow rate: >0-4000 sccm
  • The plasma cured porous network coatings of the present invention have improved chemical stability and improved dimensional stability. By improved chemical stability, we mean that the coatings are more resistant to chemicals, such as cleaning solutions and chemical polishing solutions, and plasma damaging during photoresist ashing and dry etching processes. [0060]
  • However, plasma cure can generate a notable amount of polar species in the film. [0061]
  • The plasma cured coatings can be annealed using any type of thermal exposure to reduce the dielectric constant, if desired. For example, the plasma cured coatings can be placed in a conventional oven until the polar species are removed, such as at 450° C. for 30 minutes. Another process which can be used involves annealing the plasma cured coatings in a Rapid Thermal Processing (RTP) chamber in order to reduce the dielectric constant. The plasma cured coating is annealed at a typical temperature for a sufficient time, and cooled to about 100° C. [0062]
  • Typical operating conditions for the RTP process are shown below. [0063]
    Ramp rate: 150° C./sec
    Wafer Temperature: 350-450° C.
    Annealing Time: <180 seconds
  • The dielectric constant of the annealed, plasma cured coatings is reduced as compared to the plasma cured porous network coatings. The dielectric constant of the annealed, plasma cured coatings is typically in the range of from about 1.1 to about 3.5 and more typically in the range of from about 2 to about 2.5. [0064]
  • The elastic modulus of the annealed, plasma cured coatings is increased as compared to a furnace (thermally) cured coating which would have an elastic modulus of between about 2.0 and about 3.0 when the dielectric constant is about 2.0. This increase in the elastic modulus is typically greater than or about 50%, and more typically greater than or about 100%. Typically, the elastic modulus of the annealed, plasma cured coating is greater than or about 4 GPa, and more typically between about 4 GPa and about 10 GPa. [0065]
  • In order that the invention may be more readily understood, reference is made to the following examples, which are intended to illustrate the invention, but not limit the scope thereof.[0066]
    • EXAMPLE 1
  • Porous network coatings were produced from hydrogen silsesquioxane resin by spinning onto silicon wafers and treating with NH[0067] 3 followed by 1 minute 150° C. hotplate thermal treatments. The plasma conversion was done in an Axcelis Fusion Gemini® ES plasma asher. After the plasma conversion, porous silica films with low dielectric constant and high modulus have been obtained. The results are shown in Table 1.
  • The plasma conditions were 2-4 torr in pressure. The temperatures were controlled between 195-230° C. The forming gas was N[0068] 2/H2/CF4. The plasma power and gas flow data are listed in Table 1.
  • The results indicate that, after plasma curing, the dielectric constants are in a range of 2.0 to 2.8. The plasma conditions at 210° C. yielded films of lower dielectric constants, lower than 2.4. The films processed at 195, 225, and 230° C. showed dielectric constants higher than 2.4. The modulus of the plasma cured films are from 6 to 9 GPa. The plasma curing process took off approximately 10% of the film thickness. However, the uniformity of the plasma cured film is typically within 2%. The FTIR spectra suggest that Si—H bonds were completely removed from the films during the plasma curing at pressures of 2-3 torr, implying that porous silica films were made from the plasma curing process. Typically, the films with the dielectric constants of 2.0-2.3 include less than 1% Si—OH. [0069]
    TABLE 1
    Plasma Cure of Films (Example 1)
    Pre-Plasma Heating Plasma Cure Conditions
    Time Pressure Temperature Time Pressure Temperature Power H2N2 CF4 Modulus Refractive Thickness
    Wafer (sec) (torr) (° C.) (sec) (torr) (° C.) (W) (sccm) (sccm) Dk (GPa) Index (Å)
    1 120 2.0 210 90 2.0 210 1800 2000 100 2.30 7.3 1.202 4302
    2 120 3.0 210 90 3.0 210 1800 2000 100 2.13 7.0 1.196 4265
    3 120 3.0 210 90 3.0 210 1800 2000 100 2.27 8.2 1.258 3628
    4 120 2.5 210 90 2.5 210 1800 2000 100 2.29 7.9 1.247 3671
    5 120 4.0 210 90 4.0 210 1800 2000 100 2.16 6.7 1.205 3676
    6 120 4.0 210 90 4.0 210 1800 2000 100 2.24 6.5 1.182 4403
    7 120 2.5 230 90 2.5 230 1800 2000 100 2.80 8.8 1.244 3652
    8 120 2.0 225 90 2.0 225 1800 2000 100 2.88 7.6 1.203 4442
    9 120 2.5 225 90 2.5 225 1800 2000 100 2.57 7.2 1.212 4315
    10 120 3.0 225 90 3.0 225 1800 2000 100 2.43 7.2 1.197 4400
    11 120 2.0 195 90 2.0 195 1800 2000 100 2.59 6.8 1.215 4351
    12 120 2.5 195 90 2.5 195 1800 2000 100 2.74 7.3 1.216 4315
    13 120 3.0 195 90 3.0 195 1800 2000 100 2.73 7.0 1.203 4296
    14 0 2.5 210 90 2.5 210 1800 2000 100 2.10 6.9 1.216 3733
    15 0 3.0 210 90 3.0 210 1800 2000 100 2.02 6.6 1.212 3766
    • EXAMPLE 2
  • Porous network coatings were produced from hydrogen silsesquioxane by spinning onto silicon wafers and treating with NH[0070] 3 followed by 1 minute 150° C. hotplate thermal treatments. The NH3 aging time was ½ to ⅔ of standard recipes specified in both the TEL spin tool and the DNS spin tool. The plasma conversion was done in an Axcelis Fusion Gemini® ES plasma asher. After the plasma conversion, porous silica films with low dielectric constant and high modulus have been obtained. The results are shown in Table 2.
  • The plasma conditions were 2-4 torr in pressure. The temperatures were controlled at 210° C. The forming gas was N[0071] 2/H2/CF4. The plasma power and gas flow data are listed in Table 2.
  • The plasma curing can also convert the initial films into porous silica films even if the initial films were aged for a short time under moist NH[0072] 3. The plasma cured films with less than standard aging time show dielectric constants under 2.3. The modulus values are from 5.7 to 9 GPa. Again, from FTIR spectra, Si—H bonds were removed during the plasma curing so that porous silica films were obtained. The Si—OH level in these films is typically less than 1%.
    TABLE 2
    Plasma Cure of Films (Example 2)
    Pre-Plasma Heating Plasma Cure Conditions
    Time Pressure Temperature Time Pressure Temperature Power H2N2 CF4 Modulus Refractive Thickness
    Wafer (sec) (torr) (° C.) (sec) (torr) (° C.) (W) (sccm) (sccm) Dk (GPa) Index (Å)
    2/3 NH3 Treatment in TEL
    1 120 3.0 210 90 3.0 210 1800 2000 100 2.60 8.8 1.258 3521
    2 120 2.5 210 90 2.5 210 1800 2000 100 2.32 9.0 1.261 3577
    3 120 2.5 210 90 2.5 210 1800 2000 100 2.27 8.2 1.258 3628
    4 120 4.0 210 90 4.0 210 1800 2000 100 2.23 5.7 1.214 3570
    5 120 2.5 230 90 2.5 230 1800 2000 100 2.24 8.5 1.257 3654
    6 60 2.5 210 90 2.5 210 1800 2000 100 2.21 9.1 1.254 4599
    7 0 2.5 210 90 2.5 210 1800 2000 100 2.24 9.0 1.270 3550
    1/2 NH3 Treatment in DNS
    8 120 2.5 210 90 2.5 210 1800 2000 100 2.27 8.4 1.219 4269
    9 120 3.0 210 90 3.0 210 1800 2000 100 2.39 8.0 1.218 4186
    • EXAMPLE 3
  • Porous network coatings were produced from hydrogen silsesquioxane by spinning onto silicon wafers and treating with excessive NH[0073] 3 followed by 1 minute 150° C. hotplate thermal treatments. The NH3 aging time was twice as long as that specified in the standard recipes for both the TEL spin tool and the DNS spin tool. The plasma conversion was done in an Axcelis Fusion Gemini® ES plasma asher. The results are shown in Tables 3A and 3B.
  • The plasma conditions were 2.5-3 torr in pressure. The temperatures were controlled at 210° C. The forming gas was N[0074] 2/H2/CF4. The plasma power and gas flow data are listed in Tables 3A and 3B.
  • After longer NH[0075] 3 aging, the dielectric constants of the plasma cured porous films are 2.5 or higher, and the moduli are approximately 7-8 GPa. The Si—OH content is typically around 1.5-2.5%, as calculated from FTIR spectra. The Si—H bonds were completely removed.
  • In Examples 1-3, the infrared spectra of the annealed, plasma cured coatings that were thermally annealed by heating using RTP are virtually identical to those coatings that were thermally annealed by other heating methods. The features in the spectra indicate that this plasma cured film is silica in nature. The SiOH content is less than 1 weight percent as calculated from the infrared spectra. The refractive index (RI) of the RTP annealed coatings (1.20 to 1.22) is consistent with the RI value of coatings that were thermally annealed by other heating methods. The elastic modulus of the plasma cured coatings that were thermally annealed by RTP can be two or three times higher (as high as 7-8 GPa) than the initial elastic modulus. The dielectric constants of these coatings range from 2.1 to 2.3. [0076]
    TABLE 3A
    Long Aging Time 2 × Standard Time on the DNS Tool (Example 3)
    Pre-Plasma Heating Plasma Cure Conditions
    Time Pressure Temperature Time Pressure Temperature Power H2N2 CF4 Modulus Refractive Thickness
    Wafer (sec) (torr) (° C.) (sec) (torr) (° C.) (W) (sccm) (sccm) Dk (GPa) Index (Å)
    1 120 3.0 210 90 3.0 210 1800 2000 100 2.63 8.0 1.197 4369
    2 120 2.5 210 90 2.5 210 1800 2000 100 2.53 8.2 1.197 4685
  • [0077]
    TABLE 3B
    Long Aging Time 1.5 × Standard Time on the DNS Tool (Example 3)
    Pre-Plasma Heating Plasma Cure Conditions
    Time Pressure Temperature Time Pressure Temperature Power H2N2 CF4 Modulus Refractive Thickness
    Wafer (sec) (torr) (° C.) (sec) (torr) (° C.) (W) (sccm) (sccm) Dk (GPa) Index (Å)
    3 120 3.0 210 90 3.0 210 1800 2000 100 2.54 8.4 1.200 4429
    4 120 2.5 210 90 2.5 210 1800 2000 100 2.53 8.7 1.199 4454
  • By the above methods, a thin (less than 5 microns) SiO[0078] 2 containing coating is produced on the substrate. The coating has an improved elastic modulus. Furthermore, with the annealing step, the coating can have an improved elastic modulus and a low dielectric constant.
  • The coating smooths the irregular surfaces of various substrates and has excellent adhesion. In addition, the coating may be covered by other coatings, such as further SiO[0079] 2 coatings, SiO2/modifying ceramic oxide layers, silicon containing coatings, carbon containing coatings, and/or diamond like coatings.
  • These coatings posses low defect density and are useful on electronic devices as dielectric layers in, for example, multilayer devices. [0080]
  • While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the compositions and methods disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims.[0081]

Claims (28)

What is claimed is:
1. An SiO2-containing plasma cured coating having a first dielectric constant and having a first elastic modulus, the coating being formed by
providing a porous network coating produced from a resin molecule containing at least 2 Si—H groups; and
plasma curing the porous network coating to reduce an amount of Si—H bonds.
2. The SiO2-containing plasma cured coating of claim 1 being formed by plasma curing the porous network coating for between about 15 and about 120 seconds.
3. The SiO2-containing plasma cured coating of claim 1 being formed by plasma curing the porous network coating at a temperature less than or about 350° C.
4. The SiO2-containing plasma cured coating of claim 1 being formed by plasma curing the porous network coating at a temperature between about 80 and about 280° C.
5. The SiO2-containing plasma cured coating of claim 1 being formed by plasma curing the porous network coating at a temperature between about 195 and about 230° C.
6. The SiO2-containing plasma cured coating of claim 1 being formed by annealing the plasma cured coating to produce an annealed, plasma cured coating having a second dielectric constant which is less than the first dielectric constant and having a second elastic modulus which is comparable to the first elastic modulus.
7. The SiO2-containing plasma cured coating of claim 6 being formed by annealing the plasma cured coating at a temperature less than or about 475° C.
8. The SiO2-containing plasma cured coating of claim 6 being formed by annealing the plasma cured coating at a temperature between about 350 and about 450° C.
9. The SiO2-containing plasma cured coating of claim 6 being formed by annealing the plasma cured coating for no more than or about 180 seconds.
10. The SiO2-containing plasma cured coating of claim 6 wherein the second elastic modulus of the annealed, plasma cured coating is greater than or about 4 GPa.
11. The SiO2-containing plasma cured coating of claim 6 wherein the second elastic modulus of the annealed, plasma cured coating is between about 4 and about 10 GPa.
12. The SiO2-containing plasma cured coating of claim 6 wherein the second dielectric constant of the annealed, plasma cured coating is between about 1.1 and about 3.5.
13. The SiO2-containing plasma cured coating of claim 6 wherein the second dielectric constant of the annealed, plasma cured coating is between about 2 and about 2.5.
14. An annealed, SiO2-containing plasma cured coating having a dielectric constant between about 1.1 and about 3.5 and an elastic modulus greater than or about 4 GPa, the coating being formed by
providing a porous network coating produced from a resin molecule containing at least 2 Si—H groups;
plasma curing the porous network coating to reduce an amount of Si—H bonds and to produce a plasma cured coating; and
annealing the plasma cured coating.
15. The annealed, SiO2-containing plasma cured coating of claim 14 having an elastic modulus between about 4 and about 10 GPa.
16. The annealed, SiO2-containing plasma cured coating of claim 14 having a dielectric constant between about 2 and about 2.5.
17. An electronic device containing a plasma cured coating, the coating being formed by
providing a porous network coating produced from a resin molecule containing at least 2 Si—H groups; and
plasma curing the porous network coating to reduce an amount of Si—H bonds.
18. An electronic device containing an annealed, plasma cured coating, the coating being formed by
providing a porous network coating produced from a resin molecule containing at least 2 Si—H groups;
plasma curing the porous network coating to reduce an amount of Si—H bonds and to produce a plasma cured coating; and
annealing the plasma cured coating.
19. An electronic circuit containing a plasma cured coating, the coating being formed by
providing a porous network coating produced from a resin molecule containing at least 2 Si—H groups; and
plasma curing the porous network coating to reduce an amount of Si—H bonds.
20. An electronic circuit containing an annealed, plasma cured coating, the coating being formed by
providing a porous network coating produced from a resin molecule containing at least 2 Si—H groups;
plasma curing the porous network coating to reduce an amount of Si—H bonds and to produce a plasma cured coating; and
annealing the plasma cured coating.
21. A substrate having a plasma cured coating, the coating being formed by
providing a porous network coating produced from a resin molecule containing at least 2 Si—H groups; and
plasma curing the porous network coating to reduce an amount of Si—H bonds.
22. A substrate having an annealed, plasma cured coating, the coating being formed by
providing a porous network coating produced from a resin molecule containing at least 2 Si—H groups;
plasma curing the porous network coating to reduce an amount of Si—H bonds and to produce a plasma cured coating; and
annealing the plasma cured coating.
23. A porous SiO2-containing plasma cured coating having a dielectric constant between about 1.1 and about 3.5 and an elastic modulus between about 4 and about 10 GPa.
24. A porous SiO2-containing plasma cured coating having a dielectric constant between about 2 and about 2.9 and an elastic modulus between about 5.7 and about 9.1 GPa.
25. A porous SiO2-containing plasma cured coating produced from a resin molecule containing at least 2 Si—H groups, the coating having a dielectric constant between about 1.1 and about 3.5 and an elastic modulus between about 4 and about 10 GPa.
26. A porous SiO2-containing plasma cured coating produced from a resin molecule containing at least 2 Si—H groups, the coating having a dielectric constant between about 2 and about 2.9 and an elastic modulus between about 5.7 and about 9.1 GPa.
27. The porous SiO2-containing plasma cured coating of claim 25 wherein the resin molecule has the formula:
{R3SiO1/2}a{R2SiO2/2}b{RSiO3/2}c{SiO4/2}d
wherein each R is independently selected from the group consisting of hydrogen, alkyl, alkenyl, and aryl groups or alkyl, alkenyl, and aryl groups substituted with halogen, nitrogen, oxygen sulfur or silicon atoms, with the proviso that at least 2 R groups are hydrogen.
28. The porous SiO2-containing plasma cured coating of claim 25 wherein the resin molecule comprises a hydrogen silsesquioxane resin molecule of the structure selected from (HSiO3/2)n, a polymer having units of the formula HSi(OH)aO3-x/2 and a polymer having units of the formula HSi(OH)x(OR)yOz/2, wherein each R is independently an organic group which, when bonded to silicon through the oxygen atom, forms a hydrolyzable substituent, a=0-2, x=0-2, y=0-2, z=1-3, x+y+z=3, n is an integer greater than 3 and the average value of y over all of the units of the polymer is greater than 0.
US10/384,141 2000-03-20 2003-03-07 Plasma curing process for porous silica thin film Abandoned US20030175535A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/384,141 US20030175535A1 (en) 2000-03-20 2003-03-07 Plasma curing process for porous silica thin film

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/528,835 US6576300B1 (en) 2000-03-20 2000-03-20 High modulus, low dielectric constant coatings
US09/681,332 US6558755B2 (en) 2000-03-20 2001-03-19 Plasma curing process for porous silica thin film
US10/384,141 US20030175535A1 (en) 2000-03-20 2003-03-07 Plasma curing process for porous silica thin film

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/681,332 Division US6558755B2 (en) 2000-03-20 2001-03-19 Plasma curing process for porous silica thin film

Publications (1)

Publication Number Publication Date
US20030175535A1 true US20030175535A1 (en) 2003-09-18

Family

ID=24107386

Family Applications (3)

Application Number Title Priority Date Filing Date
US09/528,835 Expired - Fee Related US6576300B1 (en) 2000-03-20 2000-03-20 High modulus, low dielectric constant coatings
US10/384,141 Abandoned US20030175535A1 (en) 2000-03-20 2003-03-07 Plasma curing process for porous silica thin film
US10/413,034 Expired - Fee Related US6759133B2 (en) 2000-03-20 2003-04-14 High modulus, low dielectric constant coatings

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US09/528,835 Expired - Fee Related US6576300B1 (en) 2000-03-20 2000-03-20 High modulus, low dielectric constant coatings

Family Applications After (1)

Application Number Title Priority Date Filing Date
US10/413,034 Expired - Fee Related US6759133B2 (en) 2000-03-20 2003-04-14 High modulus, low dielectric constant coatings

Country Status (8)

Country Link
US (3) US6576300B1 (en)
EP (1) EP1265813B1 (en)
JP (1) JP2003528021A (en)
AT (1) ATE299475T1 (en)
AU (1) AU2001245905A1 (en)
DE (1) DE60111926T2 (en)
TW (1) TW524773B (en)
WO (1) WO2001070628A2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070269610A1 (en) * 2004-12-28 2007-11-22 Haruyo Fukui Coated Cutting Tool and Manufacturing Method Thereof
CN100375248C (en) * 2003-12-31 2008-03-12 台湾积体电路制造股份有限公司 Heterogeneous low dielectric constant material and method for forming the same
TWI747084B (en) * 2018-11-30 2021-11-21 日商國際電氣股份有限公司 Semiconductor device manufacturing method, substrate processing method, substrate processing apparatus and program

Families Citing this family (434)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6800571B2 (en) * 1998-09-29 2004-10-05 Applied Materials Inc. CVD plasma assisted low dielectric constant films
US6759098B2 (en) * 2000-03-20 2004-07-06 Axcelis Technologies, Inc. Plasma curing of MSQ-based porous low-k film materials
US7011868B2 (en) 2000-03-20 2006-03-14 Axcelis Technologies, Inc. Fluorine-free plasma curing process for porous low-k materials
US6913796B2 (en) 2000-03-20 2005-07-05 Axcelis Technologies, Inc. Plasma curing process for porous low-k materials
CN1197134C (en) * 2000-05-08 2005-04-13 电气化学工业株式会社 SiOx film with low relative permittivity, manufacturing method and semiconductor device using same
US20030054115A1 (en) * 2001-09-14 2003-03-20 Ralph Albano Ultraviolet curing process for porous low-K materials
US6756085B2 (en) * 2001-09-14 2004-06-29 Axcelis Technologies, Inc. Ultraviolet curing processes for advanced low-k materials
US7307343B2 (en) 2002-05-30 2007-12-11 Air Products And Chemicals, Inc. Low dielectric materials and methods for making same
US7569497B2 (en) 2002-07-30 2009-08-04 Tokyo Electron Limited Method and apparatus for forming insulating layer
AU2003252352A1 (en) * 2002-07-30 2004-02-16 Tokyo Electron Limited Method for forming insulating layer
EP1535290A4 (en) * 2002-08-15 2006-06-14 Honeywell Int Inc NANOPORROSIVE MATERIALS AND METHOD FOR THE PRODUCTION THEREOF
US6825130B2 (en) 2002-12-12 2004-11-30 Asm Japan K.K. CVD of porous dielectric materials
US6699797B1 (en) * 2002-12-17 2004-03-02 Intel Corporation Method of fabrication of low dielectric constant porous metal silicate films
US6787453B2 (en) * 2002-12-23 2004-09-07 Intel Corporation Barrier film integrity on porous low k dielectrics by application of a hydrocarbon plasma treatment
US6914014B2 (en) * 2003-01-13 2005-07-05 Applied Materials, Inc. Method for curing low dielectric constant film using direct current bias
JP2004235548A (en) * 2003-01-31 2004-08-19 Nec Electronics Corp Semiconductor device and its fabricating method
JP4092220B2 (en) * 2003-01-31 2008-05-28 Ｎｅｃエレクトロニクス株式会社 Semiconductor device and manufacturing method thereof
US7208389B1 (en) 2003-03-31 2007-04-24 Novellus Systems, Inc. Method of porogen removal from porous low-k films using UV radiation
US20050260420A1 (en) * 2003-04-01 2005-11-24 Collins Martha J Low dielectric materials and methods for making same
JP4358563B2 (en) * 2003-07-02 2009-11-04 東京エレクトロン株式会社 Method for forming low dielectric constant insulating film of semiconductor device
US7390537B1 (en) 2003-11-20 2008-06-24 Novellus Systems, Inc. Methods for producing low-k CDO films with low residual stress
US7341761B1 (en) 2004-03-11 2008-03-11 Novellus Systems, Inc. Methods for producing low-k CDO films
US7781351B1 (en) 2004-04-07 2010-08-24 Novellus Systems, Inc. Methods for producing low-k carbon doped oxide films with low residual stress
US7253125B1 (en) 2004-04-16 2007-08-07 Novellus Systems, Inc. Method to improve mechanical strength of low-k dielectric film using modulated UV exposure
US9659769B1 (en) 2004-10-22 2017-05-23 Novellus Systems, Inc. Tensile dielectric films using UV curing
US7790633B1 (en) 2004-10-26 2010-09-07 Novellus Systems, Inc. Sequential deposition/anneal film densification method
US7695765B1 (en) 2004-11-12 2010-04-13 Novellus Systems, Inc. Methods for producing low-stress carbon-doped oxide films with improved integration properties
US20060125102A1 (en) * 2004-12-15 2006-06-15 Zhen-Cheng Wu Back end of line integration scheme
US7166531B1 (en) 2005-01-31 2007-01-23 Novellus Systems, Inc. VLSI fabrication processes for introducing pores into dielectric materials
US7510982B1 (en) 2005-01-31 2009-03-31 Novellus Systems, Inc. Creation of porosity in low-k films by photo-disassociation of imbedded nanoparticles
US8454750B1 (en) 2005-04-26 2013-06-04 Novellus Systems, Inc. Multi-station sequential curing of dielectric films
US8137465B1 (en) 2005-04-26 2012-03-20 Novellus Systems, Inc. Single-chamber sequential curing of semiconductor wafers
US8980769B1 (en) 2005-04-26 2015-03-17 Novellus Systems, Inc. Multi-station sequential curing of dielectric films
US8889233B1 (en) 2005-04-26 2014-11-18 Novellus Systems, Inc. Method for reducing stress in porous dielectric films
US8282768B1 (en) 2005-04-26 2012-10-09 Novellus Systems, Inc. Purging of porogen from UV cure chamber
US7405168B2 (en) * 2005-09-30 2008-07-29 Tokyo Electron Limited Plural treatment step process for treating dielectric films
US7662714B2 (en) * 2005-10-05 2010-02-16 Dongbu Electronics Co., Ltd. Method for forming metal line of semiconductor device
JP5006203B2 (en) * 2005-10-19 2012-08-22 パナソニック株式会社 Method for forming metal oxide film, metal oxide film and optical electronic device
US7892985B1 (en) 2005-11-15 2011-02-22 Novellus Systems, Inc. Method for porogen removal and mechanical strength enhancement of low-k carbon doped silicon oxide using low thermal budget microwave curing
US7851232B2 (en) * 2006-10-30 2010-12-14 Novellus Systems, Inc. UV treatment for carbon-containing low-k dielectric repair in semiconductor processing
US10037905B2 (en) 2009-11-12 2018-07-31 Novellus Systems, Inc. UV and reducing treatment for K recovery and surface clean in semiconductor processing
US8465991B2 (en) * 2006-10-30 2013-06-18 Novellus Systems, Inc. Carbon containing low-k dielectric constant recovery using UV treatment
US7906174B1 (en) 2006-12-07 2011-03-15 Novellus Systems, Inc. PECVD methods for producing ultra low-k dielectric films using UV treatment
US8242028B1 (en) 2007-04-03 2012-08-14 Novellus Systems, Inc. UV treatment of etch stop and hard mask films for selectivity and hermeticity enhancement
US7622162B1 (en) 2007-06-07 2009-11-24 Novellus Systems, Inc. UV treatment of STI films for increasing tensile stress
US8211510B1 (en) 2007-08-31 2012-07-03 Novellus Systems, Inc. Cascaded cure approach to fabricate highly tensile silicon nitride films
US9050623B1 (en) 2008-09-12 2015-06-09 Novellus Systems, Inc. Progressive UV cure
US10378106B2 (en) 2008-11-14 2019-08-13 Asm Ip Holding B.V. Method of forming insulation film by modified PEALD
US9394608B2 (en) 2009-04-06 2016-07-19 Asm America, Inc. Semiconductor processing reactor and components thereof
US8802201B2 (en) 2009-08-14 2014-08-12 Asm America, Inc. Systems and methods for thin-film deposition of metal oxides using excited nitrogen-oxygen species
CN103596896A (en) * 2011-05-31 2014-02-19 费罗公司 Low volatile organic component medium
US9312155B2 (en) 2011-06-06 2016-04-12 Asm Japan K.K. High-throughput semiconductor-processing apparatus equipped with multiple dual-chamber modules
US9793148B2 (en) 2011-06-22 2017-10-17 Asm Japan K.K. Method for positioning wafers in multiple wafer transport
US10364496B2 (en) 2011-06-27 2019-07-30 Asm Ip Holding B.V. Dual section module having shared and unshared mass flow controllers
US10854498B2 (en) 2011-07-15 2020-12-01 Asm Ip Holding B.V. Wafer-supporting device and method for producing same
US20130023129A1 (en) 2011-07-20 2013-01-24 Asm America, Inc. Pressure transmitter for a semiconductor processing environment
US9017481B1 (en) 2011-10-28 2015-04-28 Asm America, Inc. Process feed management for semiconductor substrate processing
US8946830B2 (en) 2012-04-04 2015-02-03 Asm Ip Holdings B.V. Metal oxide protective layer for a semiconductor device
US8785215B2 (en) * 2012-05-31 2014-07-22 Asm Ip Holding B.V. Method for repairing damage of dielectric film by cyclic processes
US9558931B2 (en) 2012-07-27 2017-01-31 Asm Ip Holding B.V. System and method for gas-phase sulfur passivation of a semiconductor surface
US9659799B2 (en) 2012-08-28 2017-05-23 Asm Ip Holding B.V. Systems and methods for dynamic semiconductor process scheduling
US9021985B2 (en) 2012-09-12 2015-05-05 Asm Ip Holdings B.V. Process gas management for an inductively-coupled plasma deposition reactor
US9324811B2 (en) 2012-09-26 2016-04-26 Asm Ip Holding B.V. Structures and devices including a tensile-stressed silicon arsenic layer and methods of forming same
US10714315B2 (en) 2012-10-12 2020-07-14 Asm Ip Holdings B.V. Semiconductor reaction chamber showerhead
JP6096470B2 (en) * 2012-10-29 2017-03-15 東京エレクトロン株式会社 Plasma processing method and plasma processing apparatus
US9640416B2 (en) 2012-12-26 2017-05-02 Asm Ip Holding B.V. Single-and dual-chamber module-attachable wafer-handling chamber
US20160376700A1 (en) 2013-02-01 2016-12-29 Asm Ip Holding B.V. System for treatment of deposition reactor
US9484191B2 (en) 2013-03-08 2016-11-01 Asm Ip Holding B.V. Pulsed remote plasma method and system
US9589770B2 (en) 2013-03-08 2017-03-07 Asm Ip Holding B.V. Method and systems for in-situ formation of intermediate reactive species
US8993054B2 (en) 2013-07-12 2015-03-31 Asm Ip Holding B.V. Method and system to reduce outgassing in a reaction chamber
US9018111B2 (en) 2013-07-22 2015-04-28 Asm Ip Holding B.V. Semiconductor reaction chamber with plasma capabilities
US9793115B2 (en) 2013-08-14 2017-10-17 Asm Ip Holding B.V. Structures and devices including germanium-tin films and methods of forming same
US9240412B2 (en) 2013-09-27 2016-01-19 Asm Ip Holding B.V. Semiconductor structure and device and methods of forming same using selective epitaxial process
US9556516B2 (en) 2013-10-09 2017-01-31 ASM IP Holding B.V Method for forming Ti-containing film by PEALD using TDMAT or TDEAT
US10179947B2 (en) 2013-11-26 2019-01-15 Asm Ip Holding B.V. Method for forming conformal nitrided, oxidized, or carbonized dielectric film by atomic layer deposition
US10683571B2 (en) 2014-02-25 2020-06-16 Asm Ip Holding B.V. Gas supply manifold and method of supplying gases to chamber using same
US9447498B2 (en) 2014-03-18 2016-09-20 Asm Ip Holding B.V. Method for performing uniform processing in gas system-sharing multiple reaction chambers
US10167557B2 (en) 2014-03-18 2019-01-01 Asm Ip Holding B.V. Gas distribution system, reactor including the system, and methods of using the same
US11015245B2 (en) 2014-03-19 2021-05-25 Asm Ip Holding B.V. Gas-phase reactor and system having exhaust plenum and components thereof
US9404587B2 (en) 2014-04-24 2016-08-02 ASM IP Holding B.V Lockout tagout for semiconductor vacuum valve
US10858737B2 (en) 2014-07-28 2020-12-08 Asm Ip Holding B.V. Showerhead assembly and components thereof
US9543180B2 (en) 2014-08-01 2017-01-10 Asm Ip Holding B.V. Apparatus and method for transporting wafers between wafer carrier and process tool under vacuum
US9890456B2 (en) 2014-08-21 2018-02-13 Asm Ip Holding B.V. Method and system for in situ formation of gas-phase compounds
US9657845B2 (en) 2014-10-07 2017-05-23 Asm Ip Holding B.V. Variable conductance gas distribution apparatus and method
US10941490B2 (en) 2014-10-07 2021-03-09 Asm Ip Holding B.V. Multiple temperature range susceptor, assembly, reactor and system including the susceptor, and methods of using the same
KR102300403B1 (en) 2014-11-19 2021-09-09 에이에스엠 아이피 홀딩 비.브이. Method of depositing thin film
KR102263121B1 (en) 2014-12-22 2021-06-09 에이에스엠 아이피 홀딩 비.브이. Semiconductor device and manufacuring method thereof
US9478415B2 (en) 2015-02-13 2016-10-25 Asm Ip Holding B.V. Method for forming film having low resistance and shallow junction depth
US10529542B2 (en) 2015-03-11 2020-01-07 Asm Ip Holdings B.V. Cross-flow reactor and method
US10276355B2 (en) 2015-03-12 2019-04-30 Asm Ip Holding B.V. Multi-zone reactor, system including the reactor, and method of using the same
US10458018B2 (en) 2015-06-26 2019-10-29 Asm Ip Holding B.V. Structures including metal carbide material, devices including the structures, and methods of forming same
US10600673B2 (en) 2015-07-07 2020-03-24 Asm Ip Holding B.V. Magnetic susceptor to baseplate seal
US9899291B2 (en) 2015-07-13 2018-02-20 Asm Ip Holding B.V. Method for protecting layer by forming hydrocarbon-based extremely thin film
US10043661B2 (en) 2015-07-13 2018-08-07 Asm Ip Holding B.V. Method for protecting layer by forming hydrocarbon-based extremely thin film
US10083836B2 (en) 2015-07-24 2018-09-25 Asm Ip Holding B.V. Formation of boron-doped titanium metal films with high work function
US10087525B2 (en) 2015-08-04 2018-10-02 Asm Ip Holding B.V. Variable gap hard stop design
US9647114B2 (en) 2015-08-14 2017-05-09 Asm Ip Holding B.V. Methods of forming highly p-type doped germanium tin films and structures and devices including the films
US9711345B2 (en) 2015-08-25 2017-07-18 Asm Ip Holding B.V. Method for forming aluminum nitride-based film by PEALD
US9960072B2 (en) 2015-09-29 2018-05-01 Asm Ip Holding B.V. Variable adjustment for precise matching of multiple chamber cavity housings
US9909214B2 (en) 2015-10-15 2018-03-06 Asm Ip Holding B.V. Method for depositing dielectric film in trenches by PEALD
US10211308B2 (en) 2015-10-21 2019-02-19 Asm Ip Holding B.V. NbMC layers
US10322384B2 (en) 2015-11-09 2019-06-18 Asm Ip Holding B.V. Counter flow mixer for process chamber
US9455138B1 (en) 2015-11-10 2016-09-27 Asm Ip Holding B.V. Method for forming dielectric film in trenches by PEALD using H-containing gas
US9905420B2 (en) 2015-12-01 2018-02-27 Asm Ip Holding B.V. Methods of forming silicon germanium tin films and structures and devices including the films
US9607837B1 (en) 2015-12-21 2017-03-28 Asm Ip Holding B.V. Method for forming silicon oxide cap layer for solid state diffusion process
US9735024B2 (en) 2015-12-28 2017-08-15 Asm Ip Holding B.V. Method of atomic layer etching using functional group-containing fluorocarbon
US9627221B1 (en) 2015-12-28 2017-04-18 Asm Ip Holding B.V. Continuous process incorporating atomic layer etching
US11139308B2 (en) 2015-12-29 2021-10-05 Asm Ip Holding B.V. Atomic layer deposition of III-V compounds to form V-NAND devices
US10468251B2 (en) 2016-02-19 2019-11-05 Asm Ip Holding B.V. Method for forming spacers using silicon nitride film for spacer-defined multiple patterning
US9754779B1 (en) 2016-02-19 2017-09-05 Asm Ip Holding B.V. Method for forming silicon nitride film selectively on sidewalls or flat surfaces of trenches
US10529554B2 (en) 2016-02-19 2020-01-07 Asm Ip Holding B.V. Method for forming silicon nitride film selectively on sidewalls or flat surfaces of trenches
US10501866B2 (en) 2016-03-09 2019-12-10 Asm Ip Holding B.V. Gas distribution apparatus for improved film uniformity in an epitaxial system
US10343920B2 (en) 2016-03-18 2019-07-09 Asm Ip Holding B.V. Aligned carbon nanotubes
US9892913B2 (en) 2016-03-24 2018-02-13 Asm Ip Holding B.V. Radial and thickness control via biased multi-port injection settings
US10865475B2 (en) 2016-04-21 2020-12-15 Asm Ip Holding B.V. Deposition of metal borides and silicides
US10190213B2 (en) 2016-04-21 2019-01-29 Asm Ip Holding B.V. Deposition of metal borides
US10087522B2 (en) 2016-04-21 2018-10-02 Asm Ip Holding B.V. Deposition of metal borides
US10032628B2 (en) 2016-05-02 2018-07-24 Asm Ip Holding B.V. Source/drain performance through conformal solid state doping
US10367080B2 (en) 2016-05-02 2019-07-30 Asm Ip Holding B.V. Method of forming a germanium oxynitride film
KR102592471B1 (en) 2016-05-17 2023-10-20 에이에스엠 아이피 홀딩 비.브이. Method of forming metal interconnection and method of fabricating semiconductor device using the same
US11453943B2 (en) 2016-05-25 2022-09-27 Asm Ip Holding B.V. Method for forming carbon-containing silicon/metal oxide or nitride film by ALD using silicon precursor and hydrocarbon precursor
US10388509B2 (en) 2016-06-28 2019-08-20 Asm Ip Holding B.V. Formation of epitaxial layers via dislocation filtering
US10612137B2 (en) 2016-07-08 2020-04-07 Asm Ip Holdings B.V. Organic reactants for atomic layer deposition
US9859151B1 (en) 2016-07-08 2018-01-02 Asm Ip Holding B.V. Selective film deposition method to form air gaps
US9793135B1 (en) 2016-07-14 2017-10-17 ASM IP Holding B.V Method of cyclic dry etching using etchant film
US10714385B2 (en) 2016-07-19 2020-07-14 Asm Ip Holding B.V. Selective deposition of tungsten
KR102354490B1 (en) 2016-07-27 2022-01-21 에이에스엠 아이피 홀딩 비.브이. Method of processing a substrate
KR102532607B1 (en) 2016-07-28 2023-05-15 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus and method of operating the same
US10177025B2 (en) 2016-07-28 2019-01-08 Asm Ip Holding B.V. Method and apparatus for filling a gap
US10395919B2 (en) 2016-07-28 2019-08-27 Asm Ip Holding B.V. Method and apparatus for filling a gap
US9812320B1 (en) 2016-07-28 2017-11-07 Asm Ip Holding B.V. Method and apparatus for filling a gap
US9887082B1 (en) 2016-07-28 2018-02-06 Asm Ip Holding B.V. Method and apparatus for filling a gap
US10090316B2 (en) 2016-09-01 2018-10-02 Asm Ip Holding B.V. 3D stacked multilayer semiconductor memory using doped select transistor channel
US9847221B1 (en) 2016-09-29 2017-12-19 Lam Research Corporation Low temperature formation of high quality silicon oxide films in semiconductor device manufacturing
US10410943B2 (en) 2016-10-13 2019-09-10 Asm Ip Holding B.V. Method for passivating a surface of a semiconductor and related systems
US10643826B2 (en) 2016-10-26 2020-05-05 Asm Ip Holdings B.V. Methods for thermally calibrating reaction chambers
US11532757B2 (en) 2016-10-27 2022-12-20 Asm Ip Holding B.V. Deposition of charge trapping layers
US10714350B2 (en) 2016-11-01 2020-07-14 ASM IP Holdings, B.V. Methods for forming a transition metal niobium nitride film on a substrate by atomic layer deposition and related semiconductor device structures
US10229833B2 (en) 2016-11-01 2019-03-12 Asm Ip Holding B.V. Methods for forming a transition metal nitride film on a substrate by atomic layer deposition and related semiconductor device structures
US10435790B2 (en) 2016-11-01 2019-10-08 Asm Ip Holding B.V. Method of subatmospheric plasma-enhanced ALD using capacitively coupled electrodes with narrow gap
US10643904B2 (en) 2016-11-01 2020-05-05 Asm Ip Holdings B.V. Methods for forming a semiconductor device and related semiconductor device structures
US10134757B2 (en) 2016-11-07 2018-11-20 Asm Ip Holding B.V. Method of processing a substrate and a device manufactured by using the method
KR102546317B1 (en) 2016-11-15 2023-06-21 에이에스엠 아이피 홀딩 비.브이. Gas supply unit and substrate processing apparatus including the same
US10340135B2 (en) 2016-11-28 2019-07-02 Asm Ip Holding B.V. Method of topologically restricted plasma-enhanced cyclic deposition of silicon or metal nitride
KR102762543B1 (en) 2016-12-14 2025-02-05 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
US9916980B1 (en) 2016-12-15 2018-03-13 Asm Ip Holding B.V. Method of forming a structure on a substrate
US11447861B2 (en) 2016-12-15 2022-09-20 Asm Ip Holding B.V. Sequential infiltration synthesis apparatus and a method of forming a patterned structure
US11581186B2 (en) 2016-12-15 2023-02-14 Asm Ip Holding B.V. Sequential infiltration synthesis apparatus
KR102700194B1 (en) 2016-12-19 2024-08-28 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
US10269558B2 (en) 2016-12-22 2019-04-23 Asm Ip Holding B.V. Method of forming a structure on a substrate
US10867788B2 (en) 2016-12-28 2020-12-15 Asm Ip Holding B.V. Method of forming a structure on a substrate
US11390950B2 (en) 2017-01-10 2022-07-19 Asm Ip Holding B.V. Reactor system and method to reduce residue buildup during a film deposition process
US10655221B2 (en) 2017-02-09 2020-05-19 Asm Ip Holding B.V. Method for depositing oxide film by thermal ALD and PEALD
US10468261B2 (en) 2017-02-15 2019-11-05 Asm Ip Holding B.V. Methods for forming a metallic film on a substrate by cyclical deposition and related semiconductor device structures
US11313040B2 (en) * 2017-03-24 2022-04-26 Embraco Indústria De Compressores E Soluçôes Em Refrigeraçâo Ltda. Plasma-assisted process of ceramization of polymer precursor on surface, surface comprising ceramic polymer
US10283353B2 (en) 2017-03-29 2019-05-07 Asm Ip Holding B.V. Method of reforming insulating film deposited on substrate with recess pattern
US10529563B2 (en) 2017-03-29 2020-01-07 Asm Ip Holdings B.V. Method for forming doped metal oxide films on a substrate by cyclical deposition and related semiconductor device structures
US10103040B1 (en) 2017-03-31 2018-10-16 Asm Ip Holding B.V. Apparatus and method for manufacturing a semiconductor device
USD830981S1 (en) 2017-04-07 2018-10-16 Asm Ip Holding B.V. Susceptor for semiconductor substrate processing apparatus
KR102457289B1 (en) 2017-04-25 2022-10-21 에이에스엠 아이피 홀딩 비.브이. Method for depositing a thin film and manufacturing a semiconductor device
US10770286B2 (en) 2017-05-08 2020-09-08 Asm Ip Holdings B.V. Methods for selectively forming a silicon nitride film on a substrate and related semiconductor device structures
US10892156B2 (en) 2017-05-08 2021-01-12 Asm Ip Holding B.V. Methods for forming a silicon nitride film on a substrate and related semiconductor device structures
US10446393B2 (en) 2017-05-08 2019-10-15 Asm Ip Holding B.V. Methods for forming silicon-containing epitaxial layers and related semiconductor device structures
US10504742B2 (en) 2017-05-31 2019-12-10 Asm Ip Holding B.V. Method of atomic layer etching using hydrogen plasma
US10886123B2 (en) 2017-06-02 2021-01-05 Asm Ip Holding B.V. Methods for forming low temperature semiconductor layers and related semiconductor device structures
US12040200B2 (en) 2017-06-20 2024-07-16 Asm Ip Holding B.V. Semiconductor processing apparatus and methods for calibrating a semiconductor processing apparatus
US11306395B2 (en) 2017-06-28 2022-04-19 Asm Ip Holding B.V. Methods for depositing a transition metal nitride film on a substrate by atomic layer deposition and related deposition apparatus
US10685834B2 (en) 2017-07-05 2020-06-16 Asm Ip Holdings B.V. Methods for forming a silicon germanium tin layer and related semiconductor device structures
KR20190009245A (en) 2017-07-18 2019-01-28 에이에스엠 아이피 홀딩 비.브이. Methods for forming a semiconductor device structure and related semiconductor device structures
US11018002B2 (en) 2017-07-19 2021-05-25 Asm Ip Holding B.V. Method for selectively depositing a Group IV semiconductor and related semiconductor device structures
US11374112B2 (en) 2017-07-19 2022-06-28 Asm Ip Holding B.V. Method for depositing a group IV semiconductor and related semiconductor device structures
US10541333B2 (en) 2017-07-19 2020-01-21 Asm Ip Holding B.V. Method for depositing a group IV semiconductor and related semiconductor device structures
US10590535B2 (en) 2017-07-26 2020-03-17 Asm Ip Holdings B.V. Chemical treatment, deposition and/or infiltration apparatus and method for using the same
US10605530B2 (en) 2017-07-26 2020-03-31 Asm Ip Holding B.V. Assembly of a liner and a flange for a vertical furnace as well as the liner and the vertical furnace
US10312055B2 (en) 2017-07-26 2019-06-04 Asm Ip Holding B.V. Method of depositing film by PEALD using negative bias
TWI815813B (en) 2017-08-04 2023-09-21 荷蘭商Ａｓｍ智慧財產控股公司 Showerhead assembly for distributing a gas within a reaction chamber
US10692741B2 (en) 2017-08-08 2020-06-23 Asm Ip Holdings B.V. Radiation shield
US10770336B2 (en) 2017-08-08 2020-09-08 Asm Ip Holding B.V. Substrate lift mechanism and reactor including same
US11139191B2 (en) 2017-08-09 2021-10-05 Asm Ip Holding B.V. Storage apparatus for storing cassettes for substrates and processing apparatus equipped therewith
US11769682B2 (en) 2017-08-09 2023-09-26 Asm Ip Holding B.V. Storage apparatus for storing cassettes for substrates and processing apparatus equipped therewith
US10249524B2 (en) 2017-08-09 2019-04-02 Asm Ip Holding B.V. Cassette holder assembly for a substrate cassette and holding member for use in such assembly
US10236177B1 (en) 2017-08-22 2019-03-19 ASM IP Holding B.V.. Methods for depositing a doped germanium tin semiconductor and related semiconductor device structures
USD900036S1 (en) 2017-08-24 2020-10-27 Asm Ip Holding B.V. Heater electrical connector and adapter
US11830730B2 (en) 2017-08-29 2023-11-28 Asm Ip Holding B.V. Layer forming method and apparatus
US11056344B2 (en) 2017-08-30 2021-07-06 Asm Ip Holding B.V. Layer forming method
US11295980B2 (en) 2017-08-30 2022-04-05 Asm Ip Holding B.V. Methods for depositing a molybdenum metal film over a dielectric surface of a substrate by a cyclical deposition process and related semiconductor device structures
KR102491945B1 (en) 2017-08-30 2023-01-26 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
KR102401446B1 (en) 2017-08-31 2022-05-24 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
US10607895B2 (en) 2017-09-18 2020-03-31 Asm Ip Holdings B.V. Method for forming a semiconductor device structure comprising a gate fill metal
KR102630301B1 (en) 2017-09-21 2024-01-29 에이에스엠 아이피 홀딩 비.브이. Method of sequential infiltration synthesis treatment of infiltrateable material and structures and devices formed using same
US10844484B2 (en) 2017-09-22 2020-11-24 Asm Ip Holding B.V. Apparatus for dispensing a vapor phase reactant to a reaction chamber and related methods
US10658205B2 (en) 2017-09-28 2020-05-19 Asm Ip Holdings B.V. Chemical dispensing apparatus and methods for dispensing a chemical to a reaction chamber
US10403504B2 (en) 2017-10-05 2019-09-03 Asm Ip Holding B.V. Method for selectively depositing a metallic film on a substrate
US10319588B2 (en) 2017-10-10 2019-06-11 Asm Ip Holding B.V. Method for depositing a metal chalcogenide on a substrate by cyclical deposition
US10923344B2 (en) 2017-10-30 2021-02-16 Asm Ip Holding B.V. Methods for forming a semiconductor structure and related semiconductor structures
US10910262B2 (en) 2017-11-16 2021-02-02 Asm Ip Holding B.V. Method of selectively depositing a capping layer structure on a semiconductor device structure
KR102443047B1 (en) 2017-11-16 2022-09-14 에이에스엠 아이피 홀딩 비.브이. Method of processing a substrate and a device manufactured by the same
US11022879B2 (en) 2017-11-24 2021-06-01 Asm Ip Holding B.V. Method of forming an enhanced unexposed photoresist layer
KR102597978B1 (en) 2017-11-27 2023-11-06 에이에스엠 아이피 홀딩 비.브이. Storage device for storing wafer cassettes for use with batch furnaces
JP7206265B2 (en) 2017-11-27 2023-01-17 エーエスエム アイピー ホールディング ビー．ブイ． Equipment with a clean mini-environment
US10290508B1 (en) 2017-12-05 2019-05-14 Asm Ip Holding B.V. Method for forming vertical spacers for spacer-defined patterning
US10872771B2 (en) 2018-01-16 2020-12-22 Asm Ip Holding B. V. Method for depositing a material film on a substrate within a reaction chamber by a cyclical deposition process and related device structures
TWI799494B (en) 2018-01-19 2023-04-21 荷蘭商Ａｓｍ 智慧財產控股公司 Deposition method
WO2019142055A2 (en) 2018-01-19 2019-07-25 Asm Ip Holding B.V. Method for depositing a gap-fill layer by plasma-assisted deposition
USD903477S1 (en) 2018-01-24 2020-12-01 Asm Ip Holdings B.V. Metal clamp
US11018047B2 (en) 2018-01-25 2021-05-25 Asm Ip Holding B.V. Hybrid lift pin
US10535516B2 (en) 2018-02-01 2020-01-14 Asm Ip Holdings B.V. Method for depositing a semiconductor structure on a surface of a substrate and related semiconductor structures
USD880437S1 (en) 2018-02-01 2020-04-07 Asm Ip Holding B.V. Gas supply plate for semiconductor manufacturing apparatus
US11081345B2 (en) 2018-02-06 2021-08-03 Asm Ip Holding B.V. Method of post-deposition treatment for silicon oxide film
US10896820B2 (en) 2018-02-14 2021-01-19 Asm Ip Holding B.V. Method for depositing a ruthenium-containing film on a substrate by a cyclical deposition process
EP3737779A1 (en) 2018-02-14 2020-11-18 ASM IP Holding B.V. A method for depositing a ruthenium-containing film on a substrate by a cyclical deposition process
US10731249B2 (en) 2018-02-15 2020-08-04 Asm Ip Holding B.V. Method of forming a transition metal containing film on a substrate by a cyclical deposition process, a method for supplying a transition metal halide compound to a reaction chamber, and related vapor deposition apparatus
US10658181B2 (en) 2018-02-20 2020-05-19 Asm Ip Holding B.V. Method of spacer-defined direct patterning in semiconductor fabrication
KR102636427B1 (en) 2018-02-20 2024-02-13 에이에스엠 아이피 홀딩 비.브이. Substrate processing method and apparatus
US10975470B2 (en) 2018-02-23 2021-04-13 Asm Ip Holding B.V. Apparatus for detecting or monitoring for a chemical precursor in a high temperature environment
US11473195B2 (en) 2018-03-01 2022-10-18 Asm Ip Holding B.V. Semiconductor processing apparatus and a method for processing a substrate
US11629406B2 (en) 2018-03-09 2023-04-18 Asm Ip Holding B.V. Semiconductor processing apparatus comprising one or more pyrometers for measuring a temperature of a substrate during transfer of the substrate
US11114283B2 (en) 2018-03-16 2021-09-07 Asm Ip Holding B.V. Reactor, system including the reactor, and methods of manufacturing and using same
KR102646467B1 (en) 2018-03-27 2024-03-11 에이에스엠 아이피 홀딩 비.브이. Method of forming an electrode on a substrate and a semiconductor device structure including an electrode
US11088002B2 (en) 2018-03-29 2021-08-10 Asm Ip Holding B.V. Substrate rack and a substrate processing system and method
US11230766B2 (en) 2018-03-29 2022-01-25 Asm Ip Holding B.V. Substrate processing apparatus and method
US10510536B2 (en) 2018-03-29 2019-12-17 Asm Ip Holding B.V. Method of depositing a co-doped polysilicon film on a surface of a substrate within a reaction chamber
KR102501472B1 (en) 2018-03-30 2023-02-20 에이에스엠 아이피 홀딩 비.브이. Substrate processing method
KR102600229B1 (en) 2018-04-09 2023-11-10 에이에스엠 아이피 홀딩 비.브이. Substrate supporting device, substrate processing apparatus including the same and substrate processing method
US12025484B2 (en) 2018-05-08 2024-07-02 Asm Ip Holding B.V. Thin film forming method
KR102709511B1 (en) 2018-05-08 2024-09-24 에이에스엠 아이피 홀딩 비.브이. Methods for depositing an oxide film on a substrate by a cyclical deposition process and related device structures
US12272527B2 (en) 2018-05-09 2025-04-08 Asm Ip Holding B.V. Apparatus for use with hydrogen radicals and method of using same
TWI816783B (en) 2018-05-11 2023-10-01 荷蘭商Ａｓｍ 智慧財產控股公司 Methods for forming a doped metal carbide film on a substrate and related semiconductor device structures
KR102596988B1 (en) 2018-05-28 2023-10-31 에이에스엠 아이피 홀딩 비.브이. Method of processing a substrate and a device manufactured by the same
TWI840362B (en) 2018-06-04 2024-05-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Wafer handling chamber with moisture reduction
US11718913B2 (en) 2018-06-04 2023-08-08 Asm Ip Holding B.V. Gas distribution system and reactor system including same
US11286562B2 (en) 2018-06-08 2022-03-29 Asm Ip Holding B.V. Gas-phase chemical reactor and method of using same
KR102568797B1 (en) 2018-06-21 2023-08-21 에이에스엠 아이피 홀딩 비.브이. Substrate processing system
US10797133B2 (en) 2018-06-21 2020-10-06 Asm Ip Holding B.V. Method for depositing a phosphorus doped silicon arsenide film and related semiconductor device structures
WO2020003000A1 (en) 2018-06-27 2020-01-02 Asm Ip Holding B.V. Cyclic deposition methods for forming metal-containing material and films and structures including the metal-containing material
US11492703B2 (en) 2018-06-27 2022-11-08 Asm Ip Holding B.V. Cyclic deposition methods for forming metal-containing material and films and structures including the metal-containing material
US10612136B2 (en) 2018-06-29 2020-04-07 ASM IP Holding, B.V. Temperature-controlled flange and reactor system including same
KR102686758B1 (en) 2018-06-29 2024-07-18 에이에스엠 아이피 홀딩 비.브이. Method for depositing a thin film and manufacturing a semiconductor device
US10388513B1 (en) 2018-07-03 2019-08-20 Asm Ip Holding B.V. Method for depositing silicon-free carbon-containing film as gap-fill layer by pulse plasma-assisted deposition
US10755922B2 (en) 2018-07-03 2020-08-25 Asm Ip Holding B.V. Method for depositing silicon-free carbon-containing film as gap-fill layer by pulse plasma-assisted deposition
US10767789B2 (en) 2018-07-16 2020-09-08 Asm Ip Holding B.V. Diaphragm valves, valve components, and methods for forming valve components
US10483099B1 (en) 2018-07-26 2019-11-19 Asm Ip Holding B.V. Method for forming thermally stable organosilicon polymer film
US11053591B2 (en) 2018-08-06 2021-07-06 Asm Ip Holding B.V. Multi-port gas injection system and reactor system including same
US10883175B2 (en) 2018-08-09 2021-01-05 Asm Ip Holding B.V. Vertical furnace for processing substrates and a liner for use therein
US10829852B2 (en) 2018-08-16 2020-11-10 Asm Ip Holding B.V. Gas distribution device for a wafer processing apparatus
US11430674B2 (en) 2018-08-22 2022-08-30 Asm Ip Holding B.V. Sensor array, apparatus for dispensing a vapor phase reactant to a reaction chamber and related methods
KR102707956B1 (en) 2018-09-11 2024-09-19 에이에스엠 아이피 홀딩 비.브이. Method for deposition of a thin film
US11024523B2 (en) 2018-09-11 2021-06-01 Asm Ip Holding B.V. Substrate processing apparatus and method
US11049751B2 (en) 2018-09-14 2021-06-29 Asm Ip Holding B.V. Cassette supply system to store and handle cassettes and processing apparatus equipped therewith
CN110970344B (en) 2018-10-01 2024-10-25 Asmip控股有限公司 Substrate holding apparatus, system comprising the same and method of using the same
US11232963B2 (en) 2018-10-03 2022-01-25 Asm Ip Holding B.V. Substrate processing apparatus and method
KR102592699B1 (en) 2018-10-08 2023-10-23 에이에스엠 아이피 홀딩 비.브이. Substrate support unit and apparatuses for depositing thin film and processing the substrate including the same
US10847365B2 (en) 2018-10-11 2020-11-24 Asm Ip Holding B.V. Method of forming conformal silicon carbide film by cyclic CVD
US10811256B2 (en) 2018-10-16 2020-10-20 Asm Ip Holding B.V. Method for etching a carbon-containing feature
KR102546322B1 (en) 2018-10-19 2023-06-21 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus and substrate processing method
KR102605121B1 (en) 2018-10-19 2023-11-23 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus and substrate processing method
USD948463S1 (en) 2018-10-24 2022-04-12 Asm Ip Holding B.V. Susceptor for semiconductor substrate supporting apparatus
US10381219B1 (en) 2018-10-25 2019-08-13 Asm Ip Holding B.V. Methods for forming a silicon nitride film
US11087997B2 (en) 2018-10-31 2021-08-10 Asm Ip Holding B.V. Substrate processing apparatus for processing substrates
KR102748291B1 (en) 2018-11-02 2024-12-31 에이에스엠 아이피 홀딩 비.브이. Substrate support unit and substrate processing apparatus including the same
US11572620B2 (en) 2018-11-06 2023-02-07 Asm Ip Holding B.V. Methods for selectively depositing an amorphous silicon film on a substrate
US11031242B2 (en) 2018-11-07 2021-06-08 Asm Ip Holding B.V. Methods for depositing a boron doped silicon germanium film
US10818758B2 (en) 2018-11-16 2020-10-27 Asm Ip Holding B.V. Methods for forming a metal silicate film on a substrate in a reaction chamber and related semiconductor device structures
US10847366B2 (en) 2018-11-16 2020-11-24 Asm Ip Holding B.V. Methods for depositing a transition metal chalcogenide film on a substrate by a cyclical deposition process
US10559458B1 (en) 2018-11-26 2020-02-11 Asm Ip Holding B.V. Method of forming oxynitride film
US12040199B2 (en) 2018-11-28 2024-07-16 Asm Ip Holding B.V. Substrate processing apparatus for processing substrates
US11217444B2 (en) 2018-11-30 2022-01-04 Asm Ip Holding B.V. Method for forming an ultraviolet radiation responsive metal oxide-containing film
KR102636428B1 (en) 2018-12-04 2024-02-13 에이에스엠 아이피 홀딩 비.브이. A method for cleaning a substrate processing apparatus
US11158513B2 (en) 2018-12-13 2021-10-26 Asm Ip Holding B.V. Methods for forming a rhenium-containing film on a substrate by a cyclical deposition process and related semiconductor device structures
JP7504584B2 (en) 2018-12-14 2024-06-24 エーエスエム・アイピー・ホールディング・ベー・フェー Method and system for forming device structures using selective deposition of gallium nitride - Patents.com
TWI866480B (en) 2019-01-17 2024-12-11 荷蘭商Ａｓｍ Ｉｐ 私人控股有限公司 Methods of forming a transition metal containing film on a substrate by a cyclical deposition process
KR102727227B1 (en) 2019-01-22 2024-11-07 에이에스엠 아이피 홀딩 비.브이. Semiconductor processing device
CN111524788B (en) 2019-02-01 2023-11-24 Asm Ip私人控股有限公司 Method for forming topologically selective films of silicon oxide
US11482533B2 (en) 2019-02-20 2022-10-25 Asm Ip Holding B.V. Apparatus and methods for plug fill deposition in 3-D NAND applications
JP7603377B2 (en) 2019-02-20 2024-12-20 エーエスエム・アイピー・ホールディング・ベー・フェー Method and apparatus for filling recesses formed in a substrate surface - Patents.com
TWI845607B (en) 2019-02-20 2024-06-21 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Cyclical deposition method and apparatus for filling a recess formed within a substrate surface
KR102626263B1 (en) 2019-02-20 2024-01-16 에이에스엠 아이피 홀딩 비.브이. Cyclical deposition method including treatment step and apparatus for same
TWI842826B (en) 2019-02-22 2024-05-21 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing apparatus and method for processing substrate
KR102762833B1 (en) 2019-03-08 2025-02-04 에이에스엠 아이피 홀딩 비.브이. STRUCTURE INCLUDING SiOCN LAYER AND METHOD OF FORMING SAME
KR102782593B1 (en) 2019-03-08 2025-03-14 에이에스엠 아이피 홀딩 비.브이. Structure Including SiOC Layer and Method of Forming Same
KR20200108242A (en) 2019-03-08 2020-09-17 에이에스엠 아이피 홀딩 비.브이. Method for Selective Deposition of Silicon Nitride Layer and Structure Including Selectively-Deposited Silicon Nitride Layer
KR20200116033A (en) 2019-03-28 2020-10-08 에이에스엠 아이피 홀딩 비.브이. Door opener and substrate processing apparatus provided therewith
KR102809999B1 (en) 2019-04-01 2025-05-19 에이에스엠 아이피 홀딩 비.브이. Method of manufacturing semiconductor device
US11447864B2 (en) 2019-04-19 2022-09-20 Asm Ip Holding B.V. Layer forming method and apparatus
KR20200125453A (en) 2019-04-24 2020-11-04 에이에스엠 아이피 홀딩 비.브이. Gas-phase reactor system and method of using same
KR20200130121A (en) 2019-05-07 2020-11-18 에이에스엠 아이피 홀딩 비.브이. Chemical source vessel with dip tube
KR20200130118A (en) 2019-05-07 2020-11-18 에이에스엠 아이피 홀딩 비.브이. Method for Reforming Amorphous Carbon Polymer Film
KR20200130652A (en) 2019-05-10 2020-11-19 에이에스엠 아이피 홀딩 비.브이. Method of depositing material onto a surface and structure formed according to the method
JP7612342B2 (en) 2019-05-16 2025-01-14 エーエスエム・アイピー・ホールディング・ベー・フェー Wafer boat handling apparatus, vertical batch furnace and method
JP7598201B2 (en) 2019-05-16 2024-12-11 エーエスエム・アイピー・ホールディング・ベー・フェー Wafer boat handling apparatus, vertical batch furnace and method
USD975665S1 (en) 2019-05-17 2023-01-17 Asm Ip Holding B.V. Susceptor shaft
USD947913S1 (en) 2019-05-17 2022-04-05 Asm Ip Holding B.V. Susceptor shaft
USD935572S1 (en) 2019-05-24 2021-11-09 Asm Ip Holding B.V. Gas channel plate
USD922229S1 (en) 2019-06-05 2021-06-15 Asm Ip Holding B.V. Device for controlling a temperature of a gas supply unit
KR20200141003A (en) 2019-06-06 2020-12-17 에이에스엠 아이피 홀딩 비.브이. Gas-phase reactor system including a gas detector
KR20200141931A (en) 2019-06-10 2020-12-21 에이에스엠 아이피 홀딩 비.브이. Method for cleaning quartz epitaxial chambers
KR20200143254A (en) 2019-06-11 2020-12-23 에이에스엠 아이피 홀딩 비.브이. Method of forming an electronic structure using an reforming gas, system for performing the method, and structure formed using the method
USD944946S1 (en) 2019-06-14 2022-03-01 Asm Ip Holding B.V. Shower plate
USD931978S1 (en) 2019-06-27 2021-09-28 Asm Ip Holding B.V. Showerhead vacuum transport
KR20210005515A (en) 2019-07-03 2021-01-14 에이에스엠 아이피 홀딩 비.브이. Temperature control assembly for substrate processing apparatus and method of using same
JP7499079B2 (en) 2019-07-09 2024-06-13 エーエスエム・アイピー・ホールディング・ベー・フェー Plasma device using coaxial waveguide and substrate processing method
CN112216646A (en) 2019-07-10 2021-01-12 Asm Ip私人控股有限公司 Substrate supporting assembly and substrate processing device comprising same
KR20210010307A (en) 2019-07-16 2021-01-27 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
KR20210010820A (en) 2019-07-17 2021-01-28 에이에스엠 아이피 홀딩 비.브이. Methods of forming silicon germanium structures
KR20210010816A (en) 2019-07-17 2021-01-28 에이에스엠 아이피 홀딩 비.브이. Radical assist ignition plasma system and method
US11643724B2 (en) 2019-07-18 2023-05-09 Asm Ip Holding B.V. Method of forming structures using a neutral beam
KR20210010817A (en) 2019-07-19 2021-01-28 에이에스엠 아이피 홀딩 비.브이. Method of Forming Topology-Controlled Amorphous Carbon Polymer Film
TWI839544B (en) 2019-07-19 2024-04-21 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming topology-controlled amorphous carbon polymer film
TWI851767B (en) 2019-07-29 2024-08-11 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Methods for selective deposition utilizing n-type dopants and/or alternative dopants to achieve high dopant incorporation
KR20210015655A (en) 2019-07-30 2021-02-10 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus and method
CN112309900A (en) 2019-07-30 2021-02-02 Asm Ip私人控股有限公司 Substrate processing apparatus
CN112309899A (en) 2019-07-30 2021-02-02 Asm Ip私人控股有限公司 Substrate processing apparatus
US11227782B2 (en) 2019-07-31 2022-01-18 Asm Ip Holding B.V. Vertical batch furnace assembly
US11587814B2 (en) 2019-07-31 2023-02-21 Asm Ip Holding B.V. Vertical batch furnace assembly
US11587815B2 (en) 2019-07-31 2023-02-21 Asm Ip Holding B.V. Vertical batch furnace assembly
KR20210018759A (en) 2019-08-05 2021-02-18 에이에스엠 아이피 홀딩 비.브이. Liquid level sensor for a chemical source vessel
CN112342526A (en) 2019-08-09 2021-02-09 Asm Ip私人控股有限公司 Heater assembly including cooling device and method of using same
USD965044S1 (en) 2019-08-19 2022-09-27 Asm Ip Holding B.V. Susceptor shaft
USD965524S1 (en) 2019-08-19 2022-10-04 Asm Ip Holding B.V. Susceptor support
JP2021031769A (en) 2019-08-21 2021-03-01 エーエスエム アイピー ホールディング ビー．ブイ． Production apparatus of mixed gas of film deposition raw material and film deposition apparatus
USD930782S1 (en) 2019-08-22 2021-09-14 Asm Ip Holding B.V. Gas distributor
USD940837S1 (en) 2019-08-22 2022-01-11 Asm Ip Holding B.V. Electrode
KR20210024423A (en) 2019-08-22 2021-03-05 에이에스엠 아이피 홀딩 비.브이. Method for forming a structure with a hole
USD949319S1 (en) 2019-08-22 2022-04-19 Asm Ip Holding B.V. Exhaust duct
USD979506S1 (en) 2019-08-22 2023-02-28 Asm Ip Holding B.V. Insulator
US11286558B2 (en) 2019-08-23 2022-03-29 Asm Ip Holding B.V. Methods for depositing a molybdenum nitride film on a surface of a substrate by a cyclical deposition process and related semiconductor device structures including a molybdenum nitride film
KR20210024420A (en) 2019-08-23 2021-03-05 에이에스엠 아이피 홀딩 비.브이. Method for depositing silicon oxide film having improved quality by peald using bis(diethylamino)silane
KR102806450B1 (en) 2019-09-04 2025-05-12 에이에스엠 아이피 홀딩 비.브이. Methods for selective deposition using a sacrificial capping layer
KR102733104B1 (en) 2019-09-05 2024-11-22 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
US11562901B2 (en) 2019-09-25 2023-01-24 Asm Ip Holding B.V. Substrate processing method
CN112593212B (en) 2019-10-02 2023-12-22 Asm Ip私人控股有限公司 Method for forming topologically selective silicon oxide film by cyclic plasma enhanced deposition process
TWI846953B (en) 2019-10-08 2024-07-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing device
KR20210042810A (en) 2019-10-08 2021-04-20 에이에스엠 아이피 홀딩 비.브이. Reactor system including a gas distribution assembly for use with activated species and method of using same
TWI846966B (en) 2019-10-10 2024-07-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming a photoresist underlayer and structure including same
US12009241B2 (en) 2019-10-14 2024-06-11 Asm Ip Holding B.V. Vertical batch furnace assembly with detector to detect cassette
TWI834919B (en) 2019-10-16 2024-03-11 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of topology-selective film formation of silicon oxide
US11637014B2 (en) 2019-10-17 2023-04-25 Asm Ip Holding B.V. Methods for selective deposition of doped semiconductor material
KR20210047808A (en) 2019-10-21 2021-04-30 에이에스엠 아이피 홀딩 비.브이. Apparatus and methods for selectively etching films
KR20210050453A (en) 2019-10-25 2021-05-07 에이에스엠 아이피 홀딩 비.브이. Methods for filling a gap feature on a substrate surface and related semiconductor structures
US11646205B2 (en) 2019-10-29 2023-05-09 Asm Ip Holding B.V. Methods of selectively forming n-type doped material on a surface, systems for selectively forming n-type doped material, and structures formed using same
KR20210054983A (en) 2019-11-05 2021-05-14 에이에스엠 아이피 홀딩 비.브이. Structures with doped semiconductor layers and methods and systems for forming same
US11501968B2 (en) 2019-11-15 2022-11-15 Asm Ip Holding B.V. Method for providing a semiconductor device with silicon filled gaps
KR20210062561A (en) 2019-11-20 2021-05-31 에이에스엠 아이피 홀딩 비.브이. Method of depositing carbon-containing material on a surface of a substrate, structure formed using the method, and system for forming the structure
CN112951697A (en) 2019-11-26 2021-06-11 Asm Ip私人控股有限公司 Substrate processing apparatus
KR20210065848A (en) 2019-11-26 2021-06-04 에이에스엠 아이피 홀딩 비.브이. Methods for selectivley forming a target film on a substrate comprising a first dielectric surface and a second metallic surface
CN112885693B (en) 2019-11-29 2025-06-10 Asmip私人控股有限公司 Substrate processing apparatus
CN112885692A (en) 2019-11-29 2021-06-01 Asm Ip私人控股有限公司 Substrate processing apparatus
JP7527928B2 (en) 2019-12-02 2024-08-05 エーエスエム・アイピー・ホールディング・ベー・フェー Substrate processing apparatus and substrate processing method
KR20210070898A (en) 2019-12-04 2021-06-15 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
JP2021097227A (en) 2019-12-17 2021-06-24 エーエスエム・アイピー・ホールディング・ベー・フェー Method of forming vanadium nitride layer and structure including vanadium nitride layer
KR20210080214A (en) 2019-12-19 2021-06-30 에이에스엠 아이피 홀딩 비.브이. Methods for filling a gap feature on a substrate and related semiconductor structures
KR20210089079A (en) 2020-01-06 2021-07-15 에이에스엠 아이피 홀딩 비.브이. Channeled lift pin
TW202140135A (en) 2020-01-06 2021-11-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Gas supply assembly and valve plate assembly
US11993847B2 (en) 2020-01-08 2024-05-28 Asm Ip Holding B.V. Injector
KR20210093163A (en) 2020-01-16 2021-07-27 에이에스엠 아이피 홀딩 비.브이. Method of forming high aspect ratio features
KR102675856B1 (en) 2020-01-20 2024-06-17 에이에스엠 아이피 홀딩 비.브이. Method of forming thin film and method of modifying surface of thin film
TWI871421B (en) 2020-02-03 2025-02-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Devices and structures including a vanadium or indium layer and methods and systems for forming the same
TW202146882A (en) 2020-02-04 2021-12-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of verifying an article, apparatus for verifying an article, and system for verifying a reaction chamber
US11776846B2 (en) 2020-02-07 2023-10-03 Asm Ip Holding B.V. Methods for depositing gap filling fluids and related systems and devices
KR20210103956A (en) 2020-02-13 2021-08-24 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus including light receiving device and calibration method of light receiving device
US11781243B2 (en) 2020-02-17 2023-10-10 Asm Ip Holding B.V. Method for depositing low temperature phosphorous-doped silicon
TW202203344A (en) 2020-02-28 2022-01-16 荷蘭商Ａｓｍ Ｉｐ控股公司 System dedicated for parts cleaning
KR20210113043A (en) 2020-03-04 2021-09-15 에이에스엠 아이피 홀딩 비.브이. Alignment fixture for a reactor system
KR20210116240A (en) 2020-03-11 2021-09-27 에이에스엠 아이피 홀딩 비.브이. Substrate handling device with adjustable joints
KR20210116249A (en) 2020-03-11 2021-09-27 에이에스엠 아이피 홀딩 비.브이. lockout tagout assembly and system and method of using same
CN113394086A (en) 2020-03-12 2021-09-14 Asm Ip私人控股有限公司 Method for producing a layer structure having a target topological profile
US12173404B2 (en) 2020-03-17 2024-12-24 Asm Ip Holding B.V. Method of depositing epitaxial material, structure formed using the method, and system for performing the method
KR102755229B1 (en) 2020-04-02 2025-01-14 에이에스엠 아이피 홀딩 비.브이. Thin film forming method
TW202146689A (en) 2020-04-03 2021-12-16 荷蘭商Ａｓｍ Ｉｐ控股公司 Method for forming barrier layer and method for manufacturing semiconductor device
TW202145344A (en) 2020-04-08 2021-12-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Apparatus and methods for selectively etching silcon oxide films
US11821078B2 (en) 2020-04-15 2023-11-21 Asm Ip Holding B.V. Method for forming precoat film and method for forming silicon-containing film
KR20210128343A (en) 2020-04-15 2021-10-26 에이에스엠 아이피 홀딩 비.브이. Method of forming chromium nitride layer and structure including the chromium nitride layer
US11996289B2 (en) 2020-04-16 2024-05-28 Asm Ip Holding B.V. Methods of forming structures including silicon germanium and silicon layers, devices formed using the methods, and systems for performing the methods
KR20210130646A (en) 2020-04-21 2021-11-01 에이에스엠 아이피 홀딩 비.브이. Method for processing a substrate
JP2021172585A (en) 2020-04-24 2021-11-01 エーエスエム・アイピー・ホールディング・ベー・フェー Methods and equipment for stabilizing vanadium compounds
TW202208671A (en) 2020-04-24 2022-03-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Methods of forming structures including vanadium boride and vanadium phosphide layers
KR20210132600A (en) 2020-04-24 2021-11-04 에이에스엠 아이피 홀딩 비.브이. Methods and systems for depositing a layer comprising vanadium, nitrogen, and a further element
TW202146831A (en) 2020-04-24 2021-12-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Vertical batch furnace assembly, and method for cooling vertical batch furnace
JP2021172884A (en) 2020-04-24 2021-11-01 エーエスエム・アイピー・ホールディング・ベー・フェー Method of forming vanadium nitride-containing layer and structure comprising vanadium nitride-containing layer
KR102783898B1 (en) 2020-04-29 2025-03-18 에이에스엠 아이피 홀딩 비.브이. Solid source precursor vessel
KR20210134869A (en) 2020-05-01 2021-11-11 에이에스엠 아이피 홀딩 비.브이. Fast FOUP swapping with a FOUP handler
JP2021177545A (en) 2020-05-04 2021-11-11 エーエスエム・アイピー・ホールディング・ベー・フェー Substrate processing system for processing substrates
KR20210137395A (en) 2020-05-07 2021-11-17 에이에스엠 아이피 홀딩 비.브이. Apparatus and methods for performing an in-situ etch of reaction chambers with fluorine-based radicals
KR102788543B1 (en) 2020-05-13 2025-03-27 에이에스엠 아이피 홀딩 비.브이. Laser alignment fixture for a reactor system
TW202146699A (en) 2020-05-15 2021-12-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming a silicon germanium layer, semiconductor structure, semiconductor device, method of forming a deposition layer, and deposition system
TW202147383A (en) 2020-05-19 2021-12-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing apparatus
KR20210145079A (en) 2020-05-21 2021-12-01 에이에스엠 아이피 홀딩 비.브이. Flange and apparatus for processing substrates
KR102795476B1 (en) 2020-05-21 2025-04-11 에이에스엠 아이피 홀딩 비.브이. Structures including multiple carbon layers and methods of forming and using same
KR102702526B1 (en) 2020-05-22 2024-09-03 에이에스엠 아이피 홀딩 비.브이. Apparatus for depositing thin films using hydrogen peroxide
TWI876048B (en) 2020-05-29 2025-03-11 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing device
TW202212620A (en) 2020-06-02 2022-04-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Apparatus for processing substrate, method of forming film, and method of controlling apparatus for processing substrate
TW202208659A (en) 2020-06-16 2022-03-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method for depositing boron containing silicon germanium layers
TW202218133A (en) 2020-06-24 2022-05-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method for forming a layer provided with silicon
TWI873359B (en) 2020-06-30 2025-02-21 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing method
TW202202649A (en) 2020-07-08 2022-01-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing method
KR20220010438A (en) 2020-07-17 2022-01-25 에이에스엠 아이피 홀딩 비.브이. Structures and methods for use in photolithography
KR20220011093A (en) 2020-07-20 2022-01-27 에이에스엠 아이피 홀딩 비.브이. Method and system for depositing molybdenum layers
KR20220011092A (en) 2020-07-20 2022-01-27 에이에스엠 아이피 홀딩 비.브이. Method and system for forming structures including transition metal layers
TW202219303A (en) 2020-07-27 2022-05-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Thin film deposition process
KR20220021863A (en) 2020-08-14 2022-02-22 에이에스엠 아이피 홀딩 비.브이. Method for processing a substrate
US12040177B2 (en) 2020-08-18 2024-07-16 Asm Ip Holding B.V. Methods for forming a laminate film by cyclical plasma-enhanced deposition processes
TW202228863A (en) 2020-08-25 2022-08-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method for cleaning a substrate, method for selectively depositing, and reaction system
TWI874701B (en) 2020-08-26 2025-03-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming metal silicon oxide layer and metal silicon oxynitride layer
TW202229601A (en) 2020-08-27 2022-08-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming patterned structures, method of manipulating mechanical property, device structure, and substrate processing system
TW202217045A (en) 2020-09-10 2022-05-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Methods for depositing gap filing fluids and related systems and devices
USD990534S1 (en) 2020-09-11 2023-06-27 Asm Ip Holding B.V. Weighted lift pin
KR20220036866A (en) 2020-09-16 2022-03-23 에이에스엠 아이피 홀딩 비.브이. Silicon oxide deposition method
USD1012873S1 (en) 2020-09-24 2024-01-30 Asm Ip Holding B.V. Electrode for semiconductor processing apparatus
TW202218049A (en) 2020-09-25 2022-05-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Semiconductor processing method
US12009224B2 (en) 2020-09-29 2024-06-11 Asm Ip Holding B.V. Apparatus and method for etching metal nitrides
KR20220045900A (en) 2020-10-06 2022-04-13 에이에스엠 아이피 홀딩 비.브이. Deposition method and an apparatus for depositing a silicon-containing material
CN114293174A (en) 2020-10-07 2022-04-08 Asm Ip私人控股有限公司 Gas supply unit and substrate processing apparatus including the same
TW202229613A (en) 2020-10-14 2022-08-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of depositing material on stepped structure
KR20220050048A (en) 2020-10-15 2022-04-22 에이에스엠 아이피 홀딩 비.브이. Method of manufacturing semiconductor device, and substrate treatment apparatus using ether-cat
TW202217037A (en) 2020-10-22 2022-05-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of depositing vanadium metal, structure, device and a deposition assembly
TW202223136A (en) 2020-10-28 2022-06-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method for forming layer on substrate, and semiconductor processing system
TW202229620A (en) 2020-11-12 2022-08-01 特文特大學 Deposition system, method for controlling reaction condition, method for depositing
TW202229795A (en) 2020-11-23 2022-08-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 A substrate processing apparatus with an injector
TW202235649A (en) 2020-11-24 2022-09-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Methods for filling a gap and related systems and devices
KR20220076343A (en) 2020-11-30 2022-06-08 에이에스엠 아이피 홀딩 비.브이. an injector configured for arrangement within a reaction chamber of a substrate processing apparatus
US12255053B2 (en) 2020-12-10 2025-03-18 Asm Ip Holding B.V. Methods and systems for depositing a layer
TW202233884A (en) 2020-12-14 2022-09-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming structures for threshold voltage control
US11946137B2 (en) 2020-12-16 2024-04-02 Asm Ip Holding B.V. Runout and wobble measurement fixtures
TW202232639A (en) 2020-12-18 2022-08-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Wafer processing apparatus with a rotatable table
TW202231903A (en) 2020-12-22 2022-08-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Transition metal deposition method, transition metal layer, and deposition assembly for depositing transition metal on substrate
TW202242184A (en) 2020-12-22 2022-11-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Precursor capsule, precursor vessel, vapor deposition assembly, and method of loading solid precursor into precursor vessel
TW202226899A (en) 2020-12-22 2022-07-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Plasma treatment device having matching box
USD981973S1 (en) 2021-05-11 2023-03-28 Asm Ip Holding B.V. Reactor wall for substrate processing apparatus
USD980813S1 (en) 2021-05-11 2023-03-14 Asm Ip Holding B.V. Gas flow control plate for substrate processing apparatus
USD1023959S1 (en) 2021-05-11 2024-04-23 Asm Ip Holding B.V. Electrode for substrate processing apparatus
USD980814S1 (en) 2021-05-11 2023-03-14 Asm Ip Holding B.V. Gas distributor for substrate processing apparatus
USD990441S1 (en) 2021-09-07 2023-06-27 Asm Ip Holding B.V. Gas flow control plate
USD1060598S1 (en) 2021-12-03 2025-02-04 Asm Ip Holding B.V. Split showerhead cover
EP4435516A1 (en) * 2023-03-16 2024-09-25 Shin-Etsu Chemical Co., Ltd. Method for forming resist underlayer film and patterning process

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6051321A (en) * 1997-10-24 2000-04-18 Quester Technology, Inc. Low dielectric constant materials and method
US6177199B1 (en) * 1999-01-07 2001-01-23 Alliedsignal Inc. Dielectric films from organohydridosiloxane resins with low organic content
US6410149B1 (en) * 1998-08-27 2002-06-25 Alliedsignal Inc. Silane-based nanoporous silica thin films and precursors for making same
US6472076B1 (en) * 1999-10-18 2002-10-29 Honeywell International Inc. Deposition of organosilsesquioxane films

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615272A (en) 1968-11-04 1971-10-26 Dow Corning Condensed soluble hydrogensilsesquioxane resin
JPS59178749A (en) 1983-03-30 1984-10-11 Fujitsu Ltd wiring structure
JPS6086017A (en) 1983-10-17 1985-05-15 Fujitsu Ltd Production method of polyhydrogen silsesquioxane
US4636440A (en) 1985-10-28 1987-01-13 Manville Corporation Novel process for coating substrates with glass-like films and coated substrates
JPS63107122A (en) 1986-10-24 1988-05-12 Fujitsu Ltd Method for flattening uneven substrate
US4756977A (en) 1986-12-03 1988-07-12 Dow Corning Corporation Multilayer ceramics from hydrogen silsesquioxane
US4822697A (en) 1986-12-03 1989-04-18 Dow Corning Corporation Platinum and rhodium catalysis of low temperature formation multilayer ceramics
US4749631B1 (en) 1986-12-04 1993-03-23 Multilayer ceramics from silicate esters
US4808653A (en) 1986-12-04 1989-02-28 Dow Corning Corporation Coating composition containing hydrogen silsesquioxane resin and other metal oxide precursors
US5008320A (en) 1986-12-04 1991-04-16 Dow Corning Corporation Platinum or rhodium catalyzed multilayer ceramic coatings from hydrogen silsesquioxane resin and metal oxides
US4847162A (en) 1987-12-28 1989-07-11 Dow Corning Corporation Multilayer ceramics coatings from the ceramification of hydrogen silsequioxane resin in the presence of ammonia
US4842888A (en) 1988-04-07 1989-06-27 Dow Corning Corporation Ceramic coatings from the pyrolysis in ammonia of mixtures of silicate esters and other metal oxide precursors
US4905117A (en) 1988-09-02 1990-02-27 Westinghouse Electric Corp. Circuit and method for DC content protection of parallel VSCF power systems
DE3834088A1 (en) 1988-10-07 1990-04-12 Basf Ag METHOD FOR PRODUCING HOMOPOLYMERISATES OF ETHEN AND COPOLYMERISATES OF ETHEN WITH HIGHER (ALPHA) MONOOLEFINES BY MEANS OF A ZIEGLER CATALYST SYSTEM
US4885186A (en) * 1988-12-29 1989-12-05 Bell Communications Research, Inc. Method for preparation of silicate glasses of controlled index of refraction
US4999397A (en) 1989-07-28 1991-03-12 Dow Corning Corporation Metastable silane hydrolyzates and process for their preparation
US5010159A (en) 1989-09-01 1991-04-23 Dow Corning Corporation Process for the synthesis of soluble, condensed hydridosilicon resins containing low levels of silanol
CA2027031A1 (en) * 1989-10-18 1991-04-19 Loren A. Haluska Hermetic substrate coatings in an inert gas atmosphere
US5116637A (en) 1990-06-04 1992-05-26 Dow Corning Corporation Amine catalysts for the low temperature conversion of silica precursors to silica
US5262201A (en) 1990-06-04 1993-11-16 Dow Corning Corporation Low temperature process for converting silica precursor coatings to ceramic silica coatings by exposure to ammonium hydroxide or an environment to which water vapor and ammonia vapor have been added
US5063267A (en) 1990-11-28 1991-11-05 Dow Corning Corporation Hydrogen silsesquioxane resin fractions and their use as coating materials
US5145723A (en) * 1991-06-05 1992-09-08 Dow Corning Corporation Process for coating a substrate with silica
JP2795002B2 (en) 1991-09-19 1998-09-10 日本電気株式会社 Method for producing HgCdTe thin film
JP3153367B2 (en) 1992-11-24 2001-04-09 ダウ・コ−ニング・コ−ポレ−ション Molecular weight fractionation method for polyhydrogensilsesquioxane
JP2790163B2 (en) * 1993-07-29 1998-08-27 富士通株式会社 Method for forming silicon oxide film, method for manufacturing semiconductor device, and method for manufacturing flat display device
US5441765A (en) 1993-09-22 1995-08-15 Dow Corning Corporation Method of forming Si-O containing coatings
US5547703A (en) 1994-04-11 1996-08-20 Dow Corning Corporation Method of forming si-o containing coatings
US5456952A (en) * 1994-05-17 1995-10-10 Lsi Logic Corporation Process of curing hydrogen silsesquioxane coating to form silicon oxide layer
US5567658A (en) * 1994-09-01 1996-10-22 Taiwan Semiconductor Manufacturing Company, Ltd. Method for minimizing peeling at the surface of spin-on glasses
US5618878A (en) 1995-04-07 1997-04-08 Dow Corning Corporation Hydrogen silsesquioxane resin coating composition
JPH0950993A (en) * 1995-08-08 1997-02-18 Fujitsu Ltd Insulating film forming method and semiconductor device
US5961851A (en) 1996-04-02 1999-10-05 Fusion Systems Corporation Microwave plasma discharge device
US6287990B1 (en) * 1998-02-11 2001-09-11 Applied Materials, Inc. CVD plasma assisted low dielectric constant films
US6054206A (en) 1998-06-22 2000-04-25 Novellus Systems, Inc. Chemical vapor deposition of low density silicon dioxide films
US6303192B1 (en) * 1998-07-22 2001-10-16 Philips Semiconductor Inc. Process to improve adhesion of PECVD cap layers in integrated circuits
US6231989B1 (en) * 1998-11-20 2001-05-15 Dow Corning Corporation Method of forming coatings
US6143360A (en) * 1999-12-13 2000-11-07 Dow Corning Corporation Method for making nanoporous silicone resins from alkylydridosiloxane resins

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6051321A (en) * 1997-10-24 2000-04-18 Quester Technology, Inc. Low dielectric constant materials and method
US6410149B1 (en) * 1998-08-27 2002-06-25 Alliedsignal Inc. Silane-based nanoporous silica thin films and precursors for making same
US6177199B1 (en) * 1999-01-07 2001-01-23 Alliedsignal Inc. Dielectric films from organohydridosiloxane resins with low organic content
US6472076B1 (en) * 1999-10-18 2002-10-29 Honeywell International Inc. Deposition of organosilsesquioxane films

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100375248C (en) * 2003-12-31 2008-03-12 台湾积体电路制造股份有限公司 Heterogeneous low dielectric constant material and method for forming the same
US20070269610A1 (en) * 2004-12-28 2007-11-22 Haruyo Fukui Coated Cutting Tool and Manufacturing Method Thereof
TWI747084B (en) * 2018-11-30 2021-11-21 日商國際電氣股份有限公司 Semiconductor device manufacturing method, substrate processing method, substrate processing apparatus and program

Also Published As

Publication number Publication date
DE60111926D1 (en) 2005-08-18
EP1265813B1 (en) 2005-07-13
DE60111926T2 (en) 2006-04-20
US6759133B2 (en) 2004-07-06
AU2001245905A1 (en) 2001-10-03
US20030203217A1 (en) 2003-10-30
US6576300B1 (en) 2003-06-10
JP2003528021A (en) 2003-09-24
ATE299475T1 (en) 2005-07-15
EP1265813A2 (en) 2002-12-18
WO2001070628A2 (en) 2001-09-27
TW524773B (en) 2003-03-21
WO2001070628A3 (en) 2002-04-18

Similar Documents

Publication Publication Date Title
US6558755B2 (en) Plasma curing process for porous silica thin film
US6576300B1 (en) High modulus, low dielectric constant coatings
US6913796B2 (en) Plasma curing process for porous low-k materials
US20030054115A1 (en) Ultraviolet curing process for porous low-K materials
US6231989B1 (en) Method of forming coatings
US20040058090A1 (en) Low temperature UV pretreating of porous low-k materials
US6756085B2 (en) Ultraviolet curing processes for advanced low-k materials
US20030157267A1 (en) Fluorine-free plasma curing process for porous low-k materials
US5547703A (en) Method of forming si-o containing coatings
KR100300801B1 (en) How to form an SI-O-containing film
US5116637A (en) Amine catalysts for the low temperature conversion of silica precursors to silica
EP2584593A2 (en) Formation method for silicon oxynitride film, and substrate having silicon oxynitride film manufactured using same
US5906859A (en) Method for producing low dielectric coatings from hydrogen silsequioxane resin
US5707681A (en) Method of producing coatings on electronic substrates
US6210749B1 (en) Thermally stable dielectric coatings
EP0917184A2 (en) Electronic coatings having low dielectric constant
EP0849240B1 (en) Method of producing low dielectric ceramic-like materials

Legal Events

Date Code Title Description
AS Assignment

Owner name: DOW CORNING CORPORATION, MICHIGAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:AXCELIS TECHNOLOGIES, INC.;REEL/FRAME:014211/0457

Effective date: 20030527

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载