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WO2018108628A1 - Procédé de génération de couches minces contenant du silicium - Google Patents

Procédé de génération de couches minces contenant du silicium Download PDF

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Publication number
WO2018108628A1
WO2018108628A1 PCT/EP2017/081512 EP2017081512W WO2018108628A1 WO 2018108628 A1 WO2018108628 A1 WO 2018108628A1 EP 2017081512 W EP2017081512 W EP 2017081512W WO 2018108628 A1 WO2018108628 A1 WO 2018108628A1
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Prior art keywords
group
compound
general formula
process according
dip
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PCT/EP2017/081512
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English (en)
Inventor
Maraike Ahlf
Kerstin Schierle-Arndt
David Dominique Schweinfurth
Torben ADERMANN
Daniel Loeffler
Sabine Weiguny
Kinga Izabela LESZCZYNSKA
David Scheschkewitz
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Basf Se
Universitaet Des Saarlandes
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Publication of WO2018108628A1 publication Critical patent/WO2018108628A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide

Definitions

  • the present invention is in the field of processes for the generation of thin silicon-containing films on substrates, in particular atomic layer deposition processes.
  • Thin inorganic films serve different purposes such as barrier layers, dielectrics, conducting features, capping, or separation of fine structures.
  • Several methods for the generation of thin inorganic films are known. One of them is the deposition of film forming compounds from the gaseous state on a substrate. Therefore, volatile precursors are required which can be deposited on a substrate and then be transformed into the desired composition in the film.
  • silicon halogenides such as S12CI6, are used.
  • S12CI6 silicon halogenides
  • these compounds are difficult to handle and often leave a significant amount of residual halogens in the film, which is undesirable for some applications.
  • US 8 802 882 discloses a CVD process employing tetraaminodisilene precursors.
  • these precursors are so unstable that they can hardly be handled and do not yield films of suffi- cient quality.
  • US 8 535 760 discloses a CVD process employing hydrogen or halogen substitued tetrasi- lyldisilene precursors.
  • these precursors are also so unstable that they can hardly be handled and do not yield films of sufficient quality.
  • R 1 , R 2 , R 3 and R 4 are an alkyl group, an alkenyl group, an aryl group, a silyl group, or an amine group, and
  • R 1 and R 2 and at least one of R 3 and R 4 is a branched group containing at least five non-hydrogen atoms and
  • R 1 and R 2 and not more than one of R 3 and R 4 is an amine group.
  • the present invention further relates to the use of the compound of general formula (I), wherein R 1 , R 2 , R 3 and R 4 are an alkyl group, an alkenyl group, an aryl group, a silyl group, or an amine group, and
  • R 1 and R 2 and at least one of R 3 and R 4 is a branched group containing at least five non-hydrogen atoms and
  • R 1 and R 2 and not more than one of R 3 and R 4 is an amine group for a film deposition process.
  • R 1 , R 2 , R 3 , and R 4 are an alkyl group, an alkenyl group, an aryl group, a silyl group, or an amine group. It is possible that all R 1 , R 2 , R 3 , and R 4 are the same or different to each other. Preferably, R 1 and R 4 are the same and R 2 and R 3 are the same and R 1 and R 2 are the same or different to each other.
  • At least one of R 1 and R 2 and at least one of R 3 and R 4 is a branched group containing at least five non-hydrogen atoms.
  • a non-hydrogen atom is any atom except hydrogen, for example carbon, nitrogen, or silicon.
  • a branched group is any group in which the atom which is bound to one of the disilene silicon atoms is bound to at least two further non-hydrogen atoms.
  • the branched group contains at least five non-hydrogen atoms, preferably at least six, more preferably at least seven, in particular at least eight.
  • At least three of R 1 , R 2 , R 3 , and R 4 are a branched group, in particular all R 1 , R 2 , R 3 , and R 4 are a branched group.
  • at least one of the branched groups is an alkyl substituted aryl group as described below, more preferably at least two of the branched groups are alkyl substituted aryl groups, even more preferably at least three of R 1 , R 2 , R 3 , and R 4 are alkyl sub- stituted aryl groups, in particular all of R 1 , R 2 , R 3 , and R 4 are alkyl substituted aryl groups.
  • At least one of the branched groups is a silyl group as described below, more preferably at least two of the branched groups are silyl groups, even more preferably at least three of R 1 , R 2 , R 3 , and R 4 are silyl groups, in particular all of R 1 , R 2 , R 3 , and R 4 are silyl groups.
  • R 1 and R 2 and not more than one of R 3 and R 4 is an amine group. It has been observed that if more than one amine group is attached a silicon atom of the disilene group, the compound of general formula (I) is not stable enough for the process of the present invention.
  • R 1 and R 4 are the same or a different amine group and R 2 and R 3 are an alkyl group, an alkenyl group, an aryl group, or a silyl group.
  • An alkyl group can be linear or branched.
  • Examples for a linear alkyl group are methyl, ethyl, n- propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl.
  • Examples for a branched alkyl group are iso-propyl, iso-butyl, sec-butyl, tert-butyl, 2-methyl-pentyl, 2-ethyl-hexyl, cyclo- propyl, cyclohexyl, indanyl, norbornyl.
  • the alkyl group is a Ci to Cs alkyl group, more preferably a Ci to C6 alkyl group, in particular a Ci to C 4 alkyl group, such as methyl, ethyl, iso- propyl or tert-butyl.
  • Alkyl groups can be substituted, for example by halogens such as F, CI, Br, I, in particular F; by hydroxyl groups; by ether groups; or by amines such as dialkylamines.
  • An alkenyl group contains at least one carbon-carbon double bond.
  • the double bond can include the carbon atom with which the alkenyl group is bound to the rest of the molecule, or it can be placed further away from the place where the alkenyl group is bound to the rest of the molecule, preferably it is placed further away from the place where the alkenyl group is bound to the rest of the molecule.
  • Alkenyl groups can be linear or branched.
  • linear alkenyl groups in which the double bond includes the carbon atom with which the alkenyl group is bound to the rest of the molecule include 1-ethenyl, 1 -propenyl, 1-n-butenyl, 1 -n-pentenyl, 1 -n- hexenyl, 1 -n-heptenyl, 1 -n-octenyl.
  • linear alkenyl groups in which the double bond is placed further away from the place where alkenyl group is bound to the rest of the molecule include 1-n-propen-3-yl, 2-buten-1-yl, 1-buten-3-yl, 1-buten-4-yl, 1 -hexen-6-yl.
  • Examples for branched alkenyl groups in which the double bond includes the carbon atom with which alkenyl group is bound to the rest of the molecule include 1 -propen-2-yl, 1-n-buten-2-yl, 2-buten-2-yl, cyclopenten-1-yl, cyclohexen-1-yl.
  • Examples for branched alkenyl groups in which the double bond is placed further away from the place where alkenyl group is bound to the rest of the molecule include 2-methyl-1 -buten-4-yl, cyclopenten-3-yl, cyclohexene-3-yl.
  • alkenyl group with more than one double bonds examples include 1 ,3-butadien-1 -yl, 1 ,3-butadien-2-yl, cyclopen- tadien-5-yl.
  • the alkenyl group is a Ci to Cs alkenyl group, more preferably a Ci to C6 alkenyl group, in particular a Ci to C 4 alkenyl group.
  • Aryl groups include aromatic hydrocarbons such as phenyl, cyclopentadienyl, naphthalyl, an- thrancenyl, phenanthrenyl groups and heteroaromatic groups such as pyrryl, furanyl, thienyl, pyridinyl, quinoyl, benzofuryl, benzothiophenyl, thienothienyl.
  • aromatic hydrocarbons such as phenyl, cyclopentadienyl, naphthalyl, an- thrancenyl, phenanthrenyl groups and heteroaromatic groups such as pyrryl, furanyl, thienyl, pyridinyl, quinoyl, benzofuryl, benzothiophenyl, thienothienyl.
  • Several of these groups or combinations of these groups are also possible like biphenyl, thienophenyl or furanylthienyl.
  • Aryl groups can be substituted for example by halogens like fluoride, chloride, bromide, iodide; by pseudohalogens like cyanide, cyanate, thiocyanate; by alcohols; alkyl groups; alkoxy groups; amine groups like dimethylamine or bis(trimethylsilyl)amine; or aryl groups.
  • the aryl group is preferably a Cs to C20 aryl group, more preferably a C6 to C16 aryl group.
  • Alkyl and alkoxy substituted aromatic hydrocarbons are preferred, in particular 2,4, 6-trimethylphenyl, 2-iso- propylphenyl, 2,6-diisopropylphenyl, and 2,4,6-triisopropylphenyl, pentamethylcyclopentadienyl, 2,6-dimethoxyphenyl and 2,4,6-trimethoxyphenyl.
  • a silyl group is a silicon atom with typically three substituents.
  • a silyl group has the formula S1E3, wherein E is hydrogen, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aryloxy group, or a silyl group. It is possible that all three E are the same or that two E are the same and the remaining E is different or that all three E are different to each other. It is also possible that two E together form a ring including the Si atom. Alkyl and aryl groups are as described above.
  • silyl groups examples include S1H3, methylsilyl, trimethylsilyl, triethylsilyl, tri-n-propylsilyl, tri-iso-propylsilyl, tricyclohexylsilyl, dimethyl-tert-butylsilyl, dimethylcyclohexylsi- lyl, methyl-di-iso-propylsilyl, triphenylsilyl, phenylsilyl, dimethylphenylsilyl, pentamethyldisilyl.
  • An amine group is a nitrogen atom with two substituents which is preferably hydrogen, an alkyl group, an aryl group or a silyl group as defined above, more preferably a silyl group, in particular a trialkylsilyl group. It is possible that the two substituents are the same or different to each other.
  • Preferred amine groups bis(trimethylsilyl)amine, tert-butyl-trimethylsilylamine and di(tert- butyl)amine.
  • the molecular weight of the compound of general formula (I) is up to
  • Me stands for methyl, iPr for iso-propyl, tBu for tert-butyl, TMS for trimethylsilyl, Cp * for pen- tamethylcyclopentadienyl, Tip for 2,4,6-triisopropylphenyl, Dip for 2,6-diisopropylphenyl, Mes for 2,4,6-trimethylphenyl, Tmp for 2,2,6,6-tetramethylpiperidinyl, Dmop for 2,6-dimethoxyphenyl, Tmop for 2,4,6-trimethoxyphenyl.
  • R 1 , R 2 , R 3 , and R 4 form a ring together.
  • R 1 and R 3 are a silyl group which forms a ring.
  • the compound of general formula (I) hence becomes a compound of general formula (la).
  • R 11 and R 12 are an alkyl group, an alkenyl group, an aryl group, a silyl group, or an amine group as defined above for R 1 , R 2 , R 3 , and R 4 .
  • the compound of general formula (I) used in the process according to the present invention is preferably used at high purity to achieve best results.
  • High purity means that the substance employed contains at least 90 wt.-% compound of general formula (I), preferably at least 95 wt.-% compound of general formula (I), more preferably at least 98 wt.-% compound of general formula (I), in particular at least 99 wt.-% compound of general formula (I).
  • the purity can be determined by elemental analysis according to DIN 51721 (Prufung fester Brennstoffe - Beêt des Gehaltes an Kohlenstoff und Wasserstoff -maschine nach Radmacher-Hoverath, August 2001 ).
  • the compound of general formula (I) can be deposited from the gaseous or aerosol state. It can be brought into the gaseous or aerosol state by heating it to elevated temperatures. In any case a temperature below the decomposition temperature of the compound of general formula (I) has to be chosen. Preferably, the heating temperature ranges from slightly above room temperature to 400 °C, more preferably from 30 °C to 300 °C, even more preferably from 40 °C to 250 °C, in particular from 50 °C to 200 °C.
  • Another way of bringing the compound of general formula (I) into the gaseous or aerosol state is direct liquid injection (DLI) as described for example in US 2009 / 0 226 612 A1 .
  • the compound of general formula (I) is typically dissolved in a solvent and sprayed in a carrier gas or vacuum. Depending on the vapor pressure of the compound of general formula (I), the temperature and the pressure the compound of general formula (I) is either brought into the gaseous state or into the aerosol state.
  • Various solvents can be used provided that the compound of general formula (I) shows sufficient solubility in that solvent such as at least 1 g/l, preferably at least 10 g/l, more preferably at least 100 g/l.
  • the aerosol comprising the compound of general formula (I) should contain very fine liquid droplets or solid particles.
  • the liquid droplets or solid particles have a weight average diameter of not more than 500 nm, more preferably not more than 100 nm.
  • the weight average diameter of liquid droplets or solid particles can be determined by dynamic light scattering as described in ISO 22412:2008.
  • the metal-containing compound can be brought into the gaseous state by direct liquid evaporation (DLE) as described for example by J. Yang et al. (Journal of Materials Chemistry C, volume 3 (2015) page 12098-12106).
  • DLE direct liquid evaporation
  • the metal-containing compound or the reducing agent is mixed with a solvent, for example a hydrocarbon such as tetradecane, and heated below the boiling point of the solvent.
  • a solvent for example a hydrocarbon such as tetradecane
  • the pressure is 10 bar to 10 "7 mbar, more preferably 1 bar to 10 -3 mbar, in particular 10 to 0.1 mbar, such as 1 mbar.
  • the compound of general formula (I) is deposited or brought in contact with the solid substrate from solution.
  • Deposition from solution is advantageous for compounds which are not stable enough for evaporation.
  • the solution needs to have a high purity to avoid undesirable contaminations on the surface.
  • Deposition from solution usually requires a solvent which does not react with the compound of general formula (I).
  • solvents examples include ethers like diethyl ether, methyl-tert-butylether, tetrahydrofurane, 1 ,4-dioxane; ketones like acetone, methylethylketone, cyclopentanone; esters like ethyl acetate; lactones like 4-butyrolac- tone; organic carbonates like diethylcarbonate, ethylene carbonate, vinylenecarbonate; aromatic hydrocarbons like benzene, toluene, xylene, mesitylene, ethylbenzene, styrene; aliphatic hydrocarbons like n-pentane, n-hexane, n-octane, cyclohexane, iso-undecane, decaline, hexa- decane.
  • ethers like diethyl ether, methyl-tert-butylether, tetrahydrofuran
  • Ethers are preferred, in particular diethylether, methyl-tert-butyl-ether, tetrahydrofurane, and 1 ,4-dioxane.
  • concentration of the compound of general formula (I) depend among others on the reactivity and the desired reaction time. Typically, the concentration is 0.1 mmol/l to 10 mol/l, preferably 1 mmol/l to 1 mol/l, in particular 10 to 100 mmol/l.
  • the reaction temperature for solution deposition is typically lower than for deposition from the gaseous or aerosol phase, typically 20 to 150 °C, preferably 50 to 120 °C, in particular 60 to 100 °C.
  • the deposition takes place if the substrate comes in contact with the compound of general formula (I).
  • the deposition process can be conducted in two different ways: either the substrate is heated above or below the decomposition temperature of the compound of general formula (I). If the substrate is heated above the decomposition temperature of the compound of general formula (I), the compound of general formula (I) continuously decomposes on the surface of the solid substrate as long as more compound of general formula (I) in the gaseous or aerosol state reaches the surface of the solid substrate. This process is typically called chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • an inorganic layer of homogeneous composition e.g. the metal oxide or nitride, is formed on the solid substrate as the organic material is desorbed from the metal M.
  • the solid substrate is heated to a temperature in the range of 300 to 1000 °C, preferably in the range of 350 to 600 °C.
  • the substrate is below the decomposition temperature of the metal-containing compound.
  • the solid substrate is at a temperature equal to or slightly above the temperature of the place where the metal-containing compound is brought into the gaseous state, often at room temperature or only slightly above.
  • the temperature of the substrate is 5 °C to 40 °C higher than the place where the metal-containing compound is brought into the gaseous state, for example 20 °C.
  • the temperature of the substrate is from room temperature to 600 °C, more preferably from 100 to 450 °C, such as 150 to 350 °C, for example 220 °C or 280 °C.
  • the deposition of compound of general formula (I) onto the solid substrate is either a physisorp- tion or a chemisorption process.
  • the compound of general formula (I) is chemisorbed on the solid substrate.
  • One can determine if the compound of general formula (I) chemisorbs to the solid substrate by exposing a quartz microbalance with a quartz crystal having the surface of the substrate in question to the compound of general formula (I) in the gaseous or aerosol state. The mass increase is recorded by the eigenfrequency of the quartz crystal. Upon evacuation of the chamber in which the quartz crystal is placed the mass should not decrease to the initial mass, but about a monolayer of the residual compound of general formula (I) remains if chemisorption has taken place.
  • the X-ray photoelectron spectroscopy (XPS) signal (ISO 13424 EN - Surface chemical analysis - X-ray photoelectron spectroscopy - Reporting of results of thin-film analysis; October 2013) of M changes due to the bond formation to the substrate.
  • XPS X-ray photoelectron spectroscopy
  • the temperature of the substrate in the process according to the present invention is kept below the decomposition temperature of the compound of general formula (I), typically a monolayer is deposited on the solid substrate. Once a molecule of general formula (I) is deposited on the solid substrate further deposition on top of it usually becomes less likely.
  • the deposition of the compound of general formula (I) on the solid substrate preferably represents a self- limiting process step.
  • the typical layer thickness of a self-limiting deposition processes step is from 0.005 to 1 nm, preferably from 0.01 to 0.5 nm, more preferably from 0.02 to 0.4 nm, in particular from 0.05 to 0.2 nm.
  • the layer thickness is typically measured by ellipsometry as described in PAS 1022 DE (Referenz compiler GmbH vonmetryen und dielektrischen Ma- terialeigenticianen architect der Schichtdicke diinner Schichten and Ellipsometrie; February 2004).
  • the deposited compound of general formula (I) by removal of organic parts after which further compound of gen- eral formula (I) is deposited.
  • This sequence is preferably performed at least twice, more preferably at least 10 times, in particular at least 50 times. Normally, the sequence is performed not more than 1000 times.
  • Removing all organic parts in the context of the present invention means that not more than 10 wt.-% of the carbon present in the deposited compound of general formula (I) remains in the deposited layer on the solid substrate, more preferably not more than 5 wt.-%, in particular not more than 1 wt.-%.
  • the decomposition can be effected in various ways.
  • the temperature of the solid substrate can be increased above the decomposition temperature.
  • the deposited compound of general formula (I) to a plasma like an oxygen plasma, hydrogen plasma, ammonia plasma, or nitrogen plasma; to oxidants like oxygen, oxygen radicals, ozone, nitrous oxide (N2O), nitric oxide (NO), nitrogendioxde (NO2) or hydrogenperoxide; to ammonia or ammonia derivatives for example tert-butylamine, iso-propyl- amine, dimethylamine, methylethylamine, or diethylamine; to hydrazine or hydrazine derivatives like ⁇ , ⁇ -dimethylhydrazine; to solvents like water, alkanes, or tetrachlorocarbon; or to boron compound like borane.
  • a plasma like an oxygen plasma, hydrogen plasma, ammonia plasma, or nitrogen plasma
  • oxidants like oxygen, oxygen radicals, ozone, nitrous oxide (N2O), nitric oxide (NO), nitrogendioxde (NO2) or hydrogenper
  • a deposition process comprising a self-limiting process step and a subsequent self-limiting reaction is often referred to as atomic layer deposition (ALD).
  • ALD atomic layer deposition
  • the process according to the present invention is preferably an ALD process.
  • the ALD process is described in detail by George (Chemical Reviews 1 10 (2010), 1 1 1 -131 ).
  • a compound of general formula (I) is deposited on a solid substrate.
  • the solid substrate can be any solid material. These include for example metals, semimetals, oxides, nitrides, and polymers. It is also possible that the substrate is a mixture of different materials. Examples for metals are tantalum, tungsten, cobalt, nickel, platinum, ruthenium, palladium, manganese, aluminum, steel, zinc, and copper. Examples for semimetals are silicon, germanium, and gallium arsenide. Examples for oxides are silicon dioxide, titanium dioxide, zirconium oxide, and zinc oxide.
  • nitrides silicon nitride, aluminum nitride, titanium nitride, tantalum nitride and gallium nitride.
  • polymers are pol- yethylene terephthalate (PET), polyethylene naphthalene-dicarboxylic acid (PEN), and polyam- ides.
  • the solid substrate can have any shape. These include sheet plates, films, fibers, particles of various sizes, and substrates with trenches or other indentations.
  • the solid substrate can be of any size. If the solid substrate has a particle shape, the size of particles can range from below 100 nm to several centimeters, preferably from 1 ⁇ to 1 mm. In order to avoid particles or fibers to stick to each other while the compound of general formula (I) is deposited onto them, it is preferably to keep them in motion. This can, for example, be achieved by stirring, by rotating drums, or by fluidized bed techniques.
  • a particular advantage of the process according to the present invention is that the compound of general formula (I) is very versatile, so the process parameters can be varied in a broad range. Therefore, the process according to the present invention includes both a CVD process as well as an ALD process.
  • films of various thicknesses are generated.
  • the sequence of depositing the compound of general formula (I) onto a solid substrate and decomposing the deposited compound of general formula (I) is performed at least twice.
  • This sequence can be re- peated many times, for example 10 to 500, such as 50 or 100 times. Usually, this sequence is not repeated more often than 1000 times.
  • the thickness of the film is proportional to the number of sequences performed. However, in practice some deviations from proportionality are observed for the first 30 to 50 sequences. It is assumed that irregularities of the surface structure of the solid substrate cause this non-proportionality.
  • One sequence of the process according to the present invention can take from milliseconds to several minutes, preferably from 0.1 second to 1 minute, in particular from 1 to 10 seconds.
  • the process according to the present invention yields a silicon-containing film.
  • the film can be only one monolayer of deposited compound of formula (I), several consecutively deposited and decomposed layers of the compound of general formula (I), or several different layers wherein at least one layer in the film was generated by using the compound of general formula (I).
  • the film can contain defects like holes. These defects, however, generally constitute less than half of the surface area covered by the film.
  • the film is preferably an inorganic film. In order to generate an inorganic film, all organic parts have to be removed from the film as described above.
  • the film can contain silicon oxide, silicon nitride, silicon boride, silicon carbide, or mixtures such as silicon carbide nitride, preferable the film contains silicon oxide and silicon nitride.
  • the film can have a thickness of 0.1 nm to 1 ⁇ or above depending on the film formation process as described above.
  • the film has a thickness of 0.5 to 50 nm.
  • the film preferably has a very uniform film thickness which means that the film thickness at different places on the substrate varies very little, usually less than 10 %, preferably less than 5 %.
  • the film is preferably a conformal film on the surface of the substrate. Suitable methods to determine the film thickness and uniformity are XPS or ellipsometry.
  • the film obtained by the process according to the present invention can be used in an electronic element or in the fabrication of an electronic element.
  • Electronic elements can have structural features of various sizes, for example from 10 nm to 100 ⁇ , such as 100 nm or 1 ⁇ .
  • the process for forming the films for the electronic elements is particularly well suited for very fine struc- tures. Therefore, electronic elements with sizes below 1 ⁇ are preferred.
  • Examples for electronic elements are field-effect transistors (FET), solar cells, light emitting diodes, sensors, or capacitors.
  • FET field-effect transistors
  • the film according to the present invention serves to increase the reflective index of the layer which reflects light.
  • An example for a sensor is an oxygen sensor, in which the film can serve as oxygen conductor, for example if a metal oxide film is prepared.
  • the film can act as dielectric layer or as diffusion barrier.
  • the process according to the present invention yields silicon-containing films with decreased etch-rates, i.e. films which are more stable in etch pro- Des in comparison to silicon-containing films.
  • This effect is particularly pronounced if etching is performed with hydrogen fluoride (HF) or ammonium fluoride (NH 4 F).
  • HF hydrogen fluoride
  • NH 4 F ammonium fluoride
  • Figure 1 shows the thermogravimetric analysis of compound 1-1 .
  • Figure 2 shows the thermogravimetric analysis of compound I-7.
  • Figure 5 shows the thermogravimetric analysis of compound la-5
  • Dip2SiCl2, 1 ,2,2-tris(2,6-diisopropylphenyl)disilenyllithium were prepared based on the procedures given by Abersfelder in PhD Thesis, Imperial College London 2012, page 278-279.
  • a precooled solution of DipSiC (0.430 g, 1 .46 mmol) in thf (-10 mL) was added to a precooled (— 100 °C) and stirred solution of Dip-disilenide (1 .06 g, 1 .46 mmol) in thf (-12 mL) placed in a 10OmL-Schlenk flask.
  • thermogravimetric analysis curve of la-2 is depicted in Figure 4.
  • Si Si ' .
  • thermogravimetric analysis curve of la-5 is depicted in Figure 5.

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Abstract

La présente invention concerne le domaine des procédés de génération de couches minces inorganiques sur des substrats. En particulier, la présente invention concerne un procédé de production d'une couche mince contenant du silicium inorganique consistant à déposer un composé de formule générale (I) sur un substrat solide. Dans la formule (I), R1, R2, R3 et R4 représentent un groupe alkyle, un groupe alcényle, un groupe aryle, un groupe silyle ou un groupe amine, et au moins l'un de R1 et R2 et au moins l'un de R3 et R4 est un groupe ramifié contenant au moins cinq atomes autres que l'hydrogène et pas plus d'un de R1 et R2 et pas plus de l'un de R3 et R4 est un groupe amine.
PCT/EP2017/081512 2016-12-13 2017-12-05 Procédé de génération de couches minces contenant du silicium WO2018108628A1 (fr)

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US11505562B2 (en) 2017-12-20 2022-11-22 Basf Se Process for the generation of metal-containing films

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