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WO2013026177A1 - Dopants phosphorés; procédés de réalisation de zones dopées au phosphore dans des substrats semi-conducteurs au moyen de dopants phosphorés, et procédés de fabrication de tels dopants phosphorés - Google Patents

Dopants phosphorés; procédés de réalisation de zones dopées au phosphore dans des substrats semi-conducteurs au moyen de dopants phosphorés, et procédés de fabrication de tels dopants phosphorés Download PDF

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Publication number
WO2013026177A1
WO2013026177A1 PCT/CN2011/001392 CN2011001392W WO2013026177A1 WO 2013026177 A1 WO2013026177 A1 WO 2013026177A1 CN 2011001392 W CN2011001392 W CN 2011001392W WO 2013026177 A1 WO2013026177 A1 WO 2013026177A1
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WO
WIPO (PCT)
Prior art keywords
phosphorous
dopant
acid
combinations
ammonium
Prior art date
Application number
PCT/CN2011/001392
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English (en)
Inventor
Hongmin Huang
Carol Gao
Zhe Ding
Albert Peng
Ya Qun Liu
Bright ZHANG
Original Assignee
Honeywell International Inc.
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
Application filed by Honeywell International Inc. filed Critical Honeywell International Inc.
Priority to PCT/CN2011/001392 priority Critical patent/WO2013026177A1/fr
Priority to TW101130292A priority patent/TWI608525B/zh
Publication of WO2013026177A1 publication Critical patent/WO2013026177A1/fr

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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
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/2225—Diffusion sources
    • 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
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251—Diffusion into or out of group IV semiconductors
    • H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides

Definitions

  • the present invention generally relates to dopants, methods for doping regions of semiconductor-comprising materials, and methods for forming dopants, and more particularly relates to substantially silane-free phosphorous-comprising dopants, thixotropic phosphorous-comprising dopants, methods for forming phosphorous-doped regions in semiconductor materials using such phosphorous-comprising dopants, and methods for forming such phosphorous-comprising dopants.
  • Photolithography is a well-known method for performing such doping of semiconductor materials.
  • To dope a semiconductor material photolithography requires the use of a mask that is formed and patterned on the semiconductor materials. Ion implantation is performed to implant conductivity-determining type ions into the semiconductor materials. A high- temperature anneal then is performed to cause the impurity dopants to diffuse into the semiconductor materials.
  • a silicon wafer 12 having a light-receiving front side 14 and a back side 16 is provided with a basic doping, wherein the basic doping can be of the n-type or of the p-type.
  • the silicon wafer is further doped at one side (in FIG. 1, front side 14) with a dopant of opposite charge of the basic doping, thus forming a p-n junction 18 within the silicon wafer.
  • Photons from light are absorbed by the light-receiving side 14 of the silicon wafer to the p-n junction where charge carriers, i.e., electrons and holes, are separated and conducted to a conductive contact, thus generating electricity.
  • the solar cell is usually provided with metallic contacts 20, 22 on the light-receiving front side as well as on the back side, respectively, to carry away the electric current produced by the solar cell.
  • the metal contacts on the light-receiving front side pose a challenge in regard to the degree of efficiency of the solar cell because the metal covering of the front side surface causes shading of the effective area of the solar cell.
  • FIG. 2 illustrates another common type of solar cell 30.
  • Solar cell 30 also has a silicon wafer 12 having a light-receiving front side 14 and a back side 16 and is provided with a basic doping, wherein the basic doping can be of the n-type or of the p-type.
  • the light-receiving front side 14 has a rough or textured surface that serves as a light trap, preventing absorbed light from being reflected back out of the solar cell.
  • the metal contacts 32 of the solar cell are formed on the back side 16 of the wafer.
  • the silicon wafer is doped at the backside relative to the metal contacts, thus forming p-n junctions 18 within the silicon wafer.
  • Solar cell 30 has an advantage over solar cell 10 in that all of the metal contacts of the cell are on the back side 16. In this regard, there is no shading of the effective area of the solar cell. However, for all contacts to be formed on the back side 16, the doped regions adjacent to the contacts have to be quite narrow.
  • Phosphorous is commonly used to form n-type regions in semiconductor materials. Both solar cell 10 and solar cell 30 benefit from the use of very fine, narrow phosphorous- doped regions formed within a semiconductor substrate.
  • the present-day method of doping described above that is, photolithography, presents significant drawbacks. For example, while doping of substrates in fine-lined patterns is possible with photolithography, DhotolithoeraDhv is an expensive and time consuming process.
  • Other well-known methods for performing doping of semiconductor materials such as screen printing, roller printing, spray application, and spin application, use a liquid dopant that is applied to the semiconductor materials.
  • the dopants commonly are formed by hydrolysis and polymerization in a sol-gel process using silanes.
  • Use of silanes in a sol-gel process has a number of drawbacks.
  • the molecular weight of the resulting dopant tends to continue to increase with time.
  • the increasing molecular weight of the dopant causes gelling of the dopant.
  • the dopant is unstable and must be transferred and stored at low temperatures. Further, if gelling occurs during use, it can cause clogging of screens during screen printing.
  • the sol-gel process typically requires a solvent or solvent system that can be unsafe during manufacture and environmentally unfriendly.
  • phosphorous-comprising dopants that can be used in doping processes that result in fine-featured patterns. It is also desirable to provide phosphorous-comprising dopants that do not comprise silanes. In addition, it is desirable to provide methods for forming phosphorous-comprising dopants that comprise substantially no silanes and that can be used in doping processes that are time and cost efficient. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, taken in conjunction with the accompanying drawings and this background of the invention.
  • a phosphorous- comprising dopant comprises a phosphorous source comprising a phosphorous-comprising salt, a phosphorous-comprising acid, phosphorous-comprising anions, or combinations thereof, an alkaline material, cations from an alkaline material, or combinations thereof, and a liquid medium.
  • the phosphorous-comprising dopant comprises less than 0.1 wt. % silanes, oligomers and/or polymers derived from silanes, or a combination thereof.
  • a method for forming phosphorous-doped regions in a semiconductor material comprises providing a phosphorous-comprising dopant formed using a phosphorous-comprising acid, a phosphorous-comprising salt, or combinations thereof and an alkaline material, cations from an alkaline material, or combinations thereof, in a liquid medium.
  • the phosphorous- comprising dopant comprises less than 0.1 wt. % silanes, oligomers and/or polymers derived from silanes, or a combination thereof.
  • the phosphorous-comprising dopant is deposited overlying at least a portion of the semiconductor material.
  • the liquid medium of the phosphorous-comprising dopant is caused to evaporate and phosphorous elements derived from the phosphorous-comprising dopant are diffused into the semiconductor material.
  • a method of forming a phosphorous-comprising dopant comprises providing a phosphorous source comprising a phosphorous-comprising acid or phosphorous-comprising salt, or combinations thereof, and combining the phosphorous source with an alkaline material and a liquid medium.
  • the phosphorous-comprising dopant comprises less than 0.1 wt. % silanes, oligomers and/or polymers derived from silanes, or a combination thereof.
  • a phosphorous-comprising dopant comprises a phosphorous source comprising a phosphorous-comprising salt, a phosphorous-comprising acid, phosphorous-comprising anions, or combinations thereof, an alkaline material, cations from an alkaline material, or combinations thereof, a liquid medium, and treated silica particles.
  • a phosphorous-comprising dopant comprises a phosphorous source comprising a phosphorous-comprising salt, a phosphorous- comprising acid, phosphorous-comprising anions, or combinations thereof, a hydrocarbon group-comprising alkaline material, cations from a hydrocarbon group-comprising alkaline material, or combinations thereof, and a liquid medium.
  • FIG. 1 is a schematic illustration of a conventional solar cell with a light-side contact and a back side contact
  • FIG. 2 is a schematic illustration of another conventional solar cell with back side contacts
  • FIG. 3 is a cross-sectional view of an inkjet printer mechanism distributing ink on a substrate
  • FIG. 4 is a cross-sectional view of an aerosol jet printer mechanism distributing ink on a substrate
  • FIG. 5 is a flowchart of a method for forming phosphorous-doped regions in a semiconductor material using a non-contact printing process in accordance with an exemplary embodiment of the present invention
  • FIG. 6 is a flowchart of a method for fabricating a phosphorous-comprising dopant for use in the method of FIG. 5 in accordance with an exemplary embodiment of the present invention.
  • FIG. 7 is a flowchart of a method for fabricating a phosphorous-comprising dopant for use in the method of FIG. 5 in accordance with another exemplary embodiment of the present invention.
  • Phosphorous-comprising dopants for forming phosphorous-doped regions in semiconductor materials methods for fabricating such phosphorous-comprising dopants, and methods for forming phosphorous-doped regions in semiconductor material using such phosphorous-comprising dopants are provided herein.
  • the phosphorous-doped regions are formed using a "doping process.”
  • the term "doping process” includes deposition and diffusion, where deposition includes both "non-contact printing processes” and contact printing processes.
  • non-contact printing processes include but are not limited to “inkjet printing” and "aerosol jet printing.”
  • the terms “inkjet printing,” an “inkjet nrintine orocess.” “aerosol iet orintine.” and an “aerosol iet printing process” refer to a non- contact printing process whereby a fluid is projected from a nozzle directly onto a substrate to form a desired pattern.
  • a print head 52 has several tiny nozzles 54, also called jets.
  • An aerosol jet printing mechanism 60 uses a mist generator or nebulizer 62 that atomizes a fluid 64.
  • the atomized fluid 66 is aerodynamical ly focused using a flow guidance deposition head 68, which creates an annular flow of sheath gas, indicated by arrow 72, to collimate the atomized fluid 66.
  • non-contact printing processes are particularly attractive processes for fabricating doped regions in semiconductor materials for a variety of reasons.
  • a dopant that is used to form the doped regions touches or contacts the surface of the substrate upon which the dopant is applied.
  • non-contact processes are suitable for a variety of substrates, including rigid and flexible substrates.
  • non-contact processes are additive processes, meaning that the dopant is applied to the substrate in the desired pattern.
  • steps for removing material after the printing process, such as is required in photolithography are eliminated.
  • non-contact processes are additive processes, they are suitable for substrates having smooth, rough, or textured surfaces.
  • Non-contact processes also permit the formation of very fine features on semiconductor materials.
  • features such as, for example, lines, dots, rectangles, circles, or other geometric shapes, having at least one dimension of less than about 200 microns ( ⁇ ) can be formed.
  • features having at least one dimension of less than about 100 ⁇ can be formed.
  • features having at least one dimension of less than about 20 ⁇ can be formed.
  • non-contact processes involve digital computer printers that can be programmed with a selected pattern to be formed on a substrate or that can be provided the pattern from a host computer, no new masks or screens need to be produced when a change in the pattern is desired. All of the above reasons make non-contact printing processes cost-efficient processes for fabricating doped regions in semiconductor materials, allowing for increased throughput compared to photolithography.
  • non-contact printing processes may be used for forming doped regions in a semiconductor material in accordance with certain exemplary embodiments of the methods contemplated herein, the invention is not so limited and, in other exemplary embodiments, the phosphorous-comprising dopants can be deposited using other application processes such as screen printing, spray application, spin application, and roller application.
  • Screen printing involves the use of a patterned screen or stencil that is disposed over a semiconductor material. Liquid dopant is placed on top of the screen and is forced through the screen to deposit on the semiconductor material in a pattern that corresponds to the pattern of the screen.
  • Spin application involves spinning the semiconductor material at a high spin speed such as, for example, up to 1200 revolutions per minute or even higher, while spraying the liquid dopant onto the spinning semiconductor material at a desired fluid pressure.
  • Spinning causes the liquid dopant to spread outward substantially evenly across the semiconductor material.
  • the liquid dopant also can be sprayed onto an unmoving semiconductor material at a desired fluid pressure at a position substantially at the center of the semiconductor material.
  • the fluid pressure causes the dopant to spread radially and substantially evenly across the wafer.
  • Roller printing involves a roller upon which is engraved a pattern. The liquid dopant is applied to the engraved pattern of the roller, which is pressed against a semiconductor material and rolled across the semiconductor material, thereby transferring the liquid dopant to the semiconductor material according to the pattern on the roller.
  • a method 100 for forming a phosphorous-doped region in a semiconductor material includes the step of providing a semiconductor material (step 102).
  • semiconductor material will be used to encompass semiconductor materials conventionally used in the semiconductor industry from which to make electrical devices.
  • Semiconductor materials include monocrystalline silicon materials, such as the relatively pure or lightly impurity- doped monocrystalline silicon materials typically used in the semiconductor industry, as well as polycrystalline silicon materials, and silicon admixed with other elements such as germanium, carbon, and the like.
  • semiconductor material encompasses other materials such as relatively pure and impurity-doped germanium, gallium arsenide, zinc oxide, glass, and the like.
  • the method 100 can be used to fabricate a variety semiconductor devices including, but not limited to. microelectronics, solar cells, displays, RFID components, microelectromechanical systems (MEMS) devices, optical devices such as microlenses, medical devices, and the like.
  • MEMS microelectromechanical systems
  • the semiconductor material is subjected to a pre- dopant treatment (step 1 12).
  • a pre-dopant treatment is any treatment that facilitates adhesion and performance of a formed pattern of a subsequently-applied dopant, described in more detail below, to the semiconductor material or that facilitates diffusion of the phosphorous elements of the subsequently-applied dopant into the semiconductor material.
  • pre-dopant treatments include cleaning of the semiconductor material to remove particles, native oxides, organic or inorganic contamination, or the like from the semiconductor material, or treating the semiconductor material so that it becomes more hydrophilic or hydrophobic.
  • Examples of pre-dopant treatment includes applying to the semiconductor material acids, such as hydrofluoric acid (HF), hydrochloric acid (HC1), sulfuric acid (H 2 S0 4 ), and/or nitric acid (HN0 3 ), bases, such as ammonium hydroxide (NH 4 OH), sodium hydroxide (NaOH), potassium hydroxide (KOH), and tetramethylammonium hydroxide (TMAH), oxidizers, such as hydrogen peroxide (H 2 0 2 ), solvents, such as water, acetone, isopropyl alcohol (IP A), ethanol, and/or tetrahydrofuran (THF), heating the semiconductor material to a temperature no higher than 800°C, or a combination thereof.
  • acids such as hydrofluoric acid (HF), hydrochloric acid (HC1), sulfuric acid (H 2 S0 4 ), and/or nitric acid (HN0 3 )
  • bases such as ammonium hydroxide (NH 4 OH
  • the method 100 further includes the step of providing a phosphorous-comprising dopant (step 104), which step may be performed before, during or after the step of providing the semiconductor material.
  • a phosphorous-comprising dopant step 104
  • the dopant is formulated so that it can be printed to form fine or small features, such as lines, dots, circles, squares, or other geometric shapes.
  • the dopant is formulated so that features having at least one dimension of less than about 200 ⁇ can be printed.
  • the dopant is formulated so that features having at least one dimension less than about 100 ⁇ ⁇ can be printed.
  • the dopant is formulated so that features having a dimension of less than about 20 ⁇ can be printed.
  • the dopant results in minimal, if any, clogging of the inkjet printer nozzles. Clogging of the nozzles results in down-time of the printer, thus reducing throughput.
  • the ink is formulated so that, after it is deposited on the substrate and hiffh-temnerature annealine ( discussed in more detail below) is performed, the resulting doped region has a sheet resistance in the range of no less than about 1 ohms/square ( ⁇ /sq.) ⁇
  • the dopants contemplated herein are formulated with substantially no silanes, that is, the dopants have less than 0.1 weight percent (wt.%) silanes, oligomers and/or polymers derived from silanes, or a combination thereof.
  • the dopants contemplated herein have no silanes, oligomers and/or polymers derived from silanes, or a combination thereof.
  • the use of silanes, such as in a sol-gel process, for forming liquid dopants demonstrates a number of drawbacks. For example, at room temperature the molecular weight of the dopant formed from silanes tends to continue to increase with time.
  • the increasing molecular weight of the dopant causes gelling of the dopant.
  • the dopant is unstable and must be transferred and stored at low temperatures.
  • the dopants contemplated herein are not formed using silanes, they have stable molecular weights. Accordingly, they can be transferred and stored at room temperature. Further, because the molecular weights are stable, gelling does not occur during use, and the dopants will not cause clogging of the nozzles of inkjet printers or the screens of screen printers during printing.
  • the sol-gel process typically requires a solvent or solvent system that can be costly, unsafe during manufacture, and environmentally unfriendly.
  • the dopants contemplated herein can utilize an aqueous system.
  • the line widths of the dopants formed using silanes are more difficult to control than the line widths of the dopants contemplated herein, particularly when printing smaller feature sizes.
  • the silane-formed dopants are also more costly and complex to manufacture, due in part to the hydrolysis and polymerization steps, compared to the dopants contemplated herein.
  • a method 150 for fabricating a phosphorous-comprising dopant includes the step of providing a phosphorous source (step 152).
  • Phosphorous-comprising dopants used in the method of FIG. 5 may be manufactured using a variety of inorganic or organic non-metal-comprising phosphorous sources.
  • the phosphorous source is an inorganic, non-metal, phosphorous-comprising acid, phosphorous-comprising salt, or a combination thereof.
  • inorganic and organic phosphorous-comprising acids include, but are not limited to, phosphoric acid (H 3 P0 4 ), phosphorous acid (H 3 P0 3 ), hypophosphorous acid
  • inorganic and organic phosphorous-comprising salts include, but are not limited to, ammonium phosphate ((NH 4 ) 3 P0 4 ), ammonium dihydrogen phosphate (NH H 2 P0 4 ,), diammonium hydrogen phosphate ((NH ) 2 HP0 4 ), ammonium phosphite ((NH 4 ) 3 P0 3 ), diammonium hydrogen phosphite ((NH 4 ) 2 HP0 3 ), ammonium dihydrogen phosphite (NH 4 H 2 P0 3 ), ammonium hypophosphite ((NH 4 ) 3 P0 2 ), diammonium hydrogen hypophosphite ((NH 4 ) 2 HP0 2 ), ammonium dihydrogen hypophosphite (NH 4 H 2 P0 2 ), ammonium pyrophosphate ((NH 4 ) 4 P 2 0 4 ), triammonium hydrogen pyrophosphate ((NH 4 ) 3 HP 2
  • a phosphorous-comprising salt can be formed, such as in a liquid medium and/or an alkaline material described in more detail below, to form a phosphorous-comprising source.
  • the phosphorous concentration of a resulting doped region in a semiconductor material depends, at least in part, on the concentration of the phosphorous in the phosphorous-comprising dopant.
  • the phosphorous source is present in the phosphorous-comprising dopant so that the dopant has a pH in the range of from about 0 to about 10.
  • the pH of the phosphorous-comprising dopant can be controlled so as to minimize the corrosive effects of the dopant on the nozzle and/or any other part of a printer.
  • the phosphorous-comprising dopant has a pH of about from 1 to 7.
  • the phosphorous weight percent of the phosphorous source comprises no greater than about 60% by weight of the phosphorous-comprising dopant.
  • the method further includes combining the phosphorous source with an alkaline material, a liquid medium, or both an alkaline material and a liquid medium (step 154).
  • liquid mediums suitable for use in formulating the phosphorous-comprising dopant include alcohol solvents, such as methanol, ethanol, propanol, 2-propanol, isopropanol (IPA), butanol, pentanol, and ethylene glycol, 1,2,6-hexanetriol, ⁇ -phenylethyl alcohol, polyethylene glycols; phenolic solvents, such as phenol and cresol; ethers and derivatives thereof, such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetrahydrofuran (THF), dioxane, trioxane, , diethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate (PGMEA); ketones solvents and derivatives thereof, such as
  • Alkaline materials may be used in the phosphorous-comprising dopant to at least partially neutralize the phosphorous source so that the resulting dopant has a pH in the range of from about 0 to about 10.
  • the alkaline material (or the cations therefrom) is present in the resulting dopant so that the dopant has a pH in the range of from about 1 to about 7.
  • the alkaline material comprises no greater than about 50% by weight of the phosphorous-comprising dopant.
  • Alkaline materials suitable for use in forming the phosphorous-comprising dopant include any non-metal alkaline materials that are soluble in the liquid medium, if present.
  • alkaline materials suitable for use in the phosphorous-comprising dopant include, but are not limited to, ammonium alkaline materials such as ammonium hydroxide (NH 4 )OH, and hydrocarbon group-comprising alkaline materials such as, for example, (NR 7 R 8 R 9 R 10 )OH, ( R 7 R 8 R 9 H)OH, (NR 7 R 8 H 2 )OH, (NR 7 H 3 )OH, where R 7 , R 8 , R 9 , and R 10 are each independently alkyls, aryls, or the like, or any combination thereof.
  • ammonium alkaline materials such as ammonium hydroxide (NH 4 )OH
  • hydrocarbon group-comprising alkaline materials such as, for example, (NR 7 R 8 R 9 R 10 )OH, ( R 7 R 8 R 9 H)OH, (NR 7 R 8 H 2 )OH, (NR 7 H 3 )OH, where R 7 , R 8 , R 9 , and R 10
  • the phosphorous source and the liquid medium and/or the alkaline material are mixed using any suitable mixing or stirring process that forms a mixture.
  • a reflux condenser, a low speed sonicator or a high shear mixing apparatus such as a homogenizer, a microfluidizer, a cowls blade high shear mixer, an automated media mill, or a ball mill, may be used for several seconds to an hour or more to form the phosphorous- comprising dopant.
  • a reflux condenser, a low speed sonicator or a high shear mixing apparatus such as a homogenizer, a microfluidizer, a cowls blade high shear mixer, an automated media mill, or a ball mill, may be used for several seconds to an hour or more to form the phosphorous- comprising dopant.
  • the phosphorous source, the liquid medium and the alkaline material can be in the form of separate components added together, it will be appreciated that two or more of the components can be combined together first, followed
  • the alkaline material may be provided in the form of an aqueous alkaline material composition, in which the water portion of the composition comprises at least a portion of the liquid medium of the resulting dopant.
  • the phosphorous source may be provided in the form of an aqueous phosphorous source composition, in which the water portion of the composition comprises at least a portion of the liquid medium of the resulting dopant.
  • a functional additive is added to the ohosohorous source before, during, and/or after combination with the liquid medium and/or the alkaline material (step 156). For example, it may be desirable to minimize the amount of the resulting phosphorous-comprising dopant that spreads beyond the penned area, that is, the area upon which the dopant is deposited, into unpenned areas of the semiconductor material before the predetermined annealing temperature of the annealing process is reached.
  • a viscosity modifier is added.
  • viscosity-modifiers include celluloses, glycerol, polyethylene glycol, polypropylene glycol, ethylene glycol/propylene glycol copolymer, organo-modified siloxanes, ethylene glycol/siloxane copolymers, polyelectrolyte, oleic acid and the like, and combinations thereof.
  • Suitable additives that may be used to form the phosphorous-comprising dopant include dispersants, surfactants, polymerization inhibitors, wetting agents, antifoaming agents, detergents and other surface-tension modifiers, flame retardants, pigments, plasticizers, thickeners, rheology modifiers, and mixtures thereof.
  • FIG. 7 illustrates a method 200 for fabricating a phosphorous-comprising dopant, such as that used in the method of FIG. 5, in accordance with another exemplary embodiment of the invention.
  • method 200 includes the step of providing a phosphorous source (step 202). Any of the phosphorous sources described above with respect to step 152 of method 150 can be used.
  • the phosphorous source is combined with an alkaline material (step 204). Any of the alkaline materials described above with reference to step 154 of method 150 can be used and any of the methods discussed above for combining the components may be used.
  • a liquid medium such as any of the liquid mediums set forth above, also can be added to the phosphorous source.
  • Method 200 further includes combining silica particles with a liquid medium (step 206).
  • the silica particles may include any silica particles that have an average particle size of no greater than 100 ⁇ , preferably no greater than 1 ⁇ , and that modify the viscosity, surface tension, and/or wettability of the dopant.
  • the term "particle size" includes a diameter, a length, a width or any other suitable dimension used to characterize a size of a silira narticle in non-aeereeate form as measured using transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • silica particles suitable for use include sol-gel particles, such as those available from FOSO CHEMICAL of Japan, and, preferably, fumed silica particles, such as those from the Aerosil® series, available from Evonik Degussa Gmbh of Frankfurt, Germany, the CAB-O-SIL ® series from Cabot Corporation of Billerica, Massachusetts; and the HDK ® series available from Wacker Chemie AG of Germany; and other oxide particles.
  • the liquid medium may comprise any of the liquid mediums set forth above for step 154 of method 150 and may be combined with the silica particles using any of the methods for combining set forth above.
  • the phosphorous-comprising dopant may be formed from non-treated silica particles, treated silica particles, or a combination thereof.
  • the resulting phosphorous-comprising dopant exhibits a thixotropic property minimizes "out-diffusion" of the dopant.
  • non-treated silica particle means a silica particle with a surface that has not been modified with organic and/or inorganic functional groups.
  • a “treated silica particle” is a silica particle with a surface that has been at least partially modified by organic and/or inorganic functional groups.
  • non-treated silica particles include, but are not limited to, Aerosil® 380, Aerosil® 200, and Aerosil® 150, available from Evonik Degussa Gmbh, CAB-O-SIL ® M-5/M-5P, HP 60, and EH-5, available from Cabot Corporation; WACKER HDK - N20, and HDK ® V15/V15P, available from Wacker Chemie AG; and Quartron PL-06L, available from FOSO CHEMICAL.
  • Aerosil® 380, Aerosil® 200, and Aerosil® 150 available from Evonik Degussa Gmbh, CAB-O-SIL ® M-5/M-5P, HP 60, and EH-5, available from Cabot Corporation
  • WACKER HDK - N20, and HDK ® V15/V15P available from Wacker Chemie AG
  • Quartron PL-06L available from FOSO CHEMICAL.
  • treated particles include, but are not limited to, Aerosil® R816, Aerosil® R812, Aerosil® R972, and Aerosil® R974, available from Evonik Degussa Gmbh, CAB-O-SIL® TS 610, and CAB-O-SIL® H-300, available from Cabot Corporation, and HDK-H15 and HDK-H20, available from Wacker Chemie AG, and Quartron PL-2L-PGME, available from FUSO CHEMICAL.
  • a thixotropic property of the dopant can be realized through the formation of a silica particle grid by polarity matching of the solvent system with the selection of silica particles.
  • Such combination can involve one type or multiple types of silica particles with similar and/or different polarities.
  • silica particle grid When applying a shearing force, such silica particle grid is broken into smaller pieces, leading to a drop in viscosity. When the shearing force is removed, the silica particle grid is reestablished and the viscosity increases.
  • the phosphorous source/alkaline material combination and the particles/liquid medium combination can be mixed, using any of the methods described above, to form the phosphorous-comprising donant ( sten 208V
  • the phosphorous-comprising dopant has a pH in the range of from about 0 to about 10. In a preferred embodiment, the phosphorous-comprising dopant has a pH of from about 1 to 7.
  • the phosphorous weight percent from the phosphorous source comprises no greater than about 60% by weight of the phosphorous-comprising dopant
  • the alkaline material comprises greater than zero and no greater than about 50% by weight of the phosphorous-comprising dopant
  • the liquid medium comprises about greater than zero and no greater than about 60% by volume of the phosphorous-comprising dopant
  • the silica particles comprise no greater than about 0.1% to about 40% by weight of the phosphorous- comprising dopant.
  • method 200 illustrates that the phosphorous source and the alkaline material are combined to form a first combination and the silica particles and the liquid medium are combined to form a second combination with the first and second combinations then mixed to form the dopant
  • the phosphorous source, the alkaline material, the silica particles and the liquid medium can be combined in any suitable sequence that satisfactorily forms the phosphorous-comprising dopant.
  • a functional additive is added to the phosphorous source before, during, or after combination with the alkaline material, the silica particles and/or the liquid medium (step 210).
  • the phosphorous source may or may not disassociate to form inorganic, non-metal phosphorous- comprising anions such as, for example, H 2 P0 4 " , HP0 4 " , P0 4 " , H 2 P0 3 “ , HP0 3 " , P0 3 H 2 P0 2 “ , HP0 2 2” , P0 2 3” , H 3 P 2 0 4 ⁇ H 2 P 2 0 4 2” , HP 2 0 4 3' , P 2 0 4 4" , R n R 12 P0 2 ⁇ HRP0 3 " , and Pv U P0 3 2” , where R 11 and R 12 are alkyls, aryls, or combinations thereof.
  • the amount of liquid medium and/or alkaline material used may determine, at least in part, the extent of dissociation of the phosphorous source. Further, the interaction of the liquid medium and the alkaline material may determine, at least in part, the extent to which the alkaline material disassociates to form cations and hydroxide anions. Accordingly, upon formation, the phosphorous-comprising dopant may comprise a phosphorous-comprising salt, a phosphorous comprising acid, phosphorous-comprising anions, or combinations thereof, an alkaline material and/or cations from an alkaline material, and/or a liquid medium and, optionally, a functional additive.
  • the method 100 continues with the application of the phosphorous-comprising dopant overlying the semiconductor material (step 106).
  • the term "overlying” encompasses the terms “on” and "over”.
  • the dnnant can he annlied directlv onto the semiconductor material or may be deposited over the semiconductor material such that one or more other materials are interposed between the dopant and the semiconductor material. Examples of materials that may be interposed between the dopant and the semiconductor material are those materials that do not obstruct diffusion of the phosphorous elements of the phosphorous-comprising dopant into the semiconductor material during annealing.
  • Such materials include phosphosilicate glass, borosilicate glass, silicon nitride, or silicon oxide that forms on a silicon material. Typically such materials are removed before dopants are deposited on the silicon material; however, in various embodiments, it may be preferable to omit the removal process, thereby permitting the materials to remain on the semiconductor material.
  • the phosphorous-comprising dopant is applied overlying at least a portion of the semiconductor material using a non-contact process printer.
  • the phosphorous-comprising dopant is applied overlying the semiconductor material in a pattern that is stored in or otherwise supplied to the printer.
  • An example of an inkjet printer suitable for use includes, but is not limited to, Dimatix Inkjet Printer Model DMP 2831 available from Fujifilm Dimatix, Inc. of Santa Clara, California.
  • An example of an aerosol jet printer suitable for use includes, but is not limited to, the M3D Aerosol Jet Deposition System available from Optomec, Inc. of Albuquerque, New Mexico.
  • the phosphorous-comprising dopant is applied overlying at least a portion of the semiconductor material by screen printing, spraying, spinning, or rolling the dopant, as described above.
  • the dopant is applied to the substrate at a temperature in the range of about 15°C to about 350°C in a humidity of about 20 to about 80%.
  • the liquid medium in the dopant and any water that formed from the reaction of hydrogen cations (from a phosphorous-comprising acid) and hydroxide anions (from an alkaline material) is caused to evaporated (step 108).
  • the liquid medium and/or water may be permitted to evaporate at room temperature (about 16°C to about 28°C) or may be heated to the boiling point of the liquid medium for a sufficient time to permit the liquid medium to evaporate.
  • the liquid medium and/or water is evaporated at a temperature no greater than 800°C.
  • phosphorous elements, in an ionic state, as part of a compound, or as a combination of both, of the dopant are caused to diffuse into the semiconductor material Csteo 1 10).
  • the semiconductor material is subjected to a high-temperature thermal treatment or "anneal" to cause the phosphorous elements of the phosphorous-comprising dopant to diffuse into the semiconductor material, thus forming phosphorous -doped regions within the material (step 1 10).
  • the anneal can be performed using any suitable heat-generating method, such as, for example, electrical heating, infrared heating, laser heating, microwave heating, and the like.
  • the time duration and the temperature of the anneal is determined by such factors as the initial phosphorous concentration of the phosphorous-comprising dopant, the thickness of the dopant deposit, the desired concentration of the resulting phosphorous-doped region, and the depth to which the phosphorous is to diffuse.
  • the substrate is placed inside an oven wherein the temperature is ramped up to a temperature in the range of about 800 °C to about 1200 °C and the semiconductor material is baked at this temperature for about 2 to about 180 minutes.
  • Annealing also may be carried out in an in-line furnace to increase throughput.
  • the annealing atmosphere may contain 0 to 100% oxygen in an oxygen/nitrogen or oxygen/argon mixture.
  • the semiconductor material is subjected to an anneal temperature of about 1050°C for about from 5 to about 10 minutes in an oxygen ambient. In another embodiment, the semiconductor material is subjected to an anneal temperature of about 950°C for about 10 to about 180 minutes in an oxygen ambient. In yet another embodiment, the semiconductor material is subjected to an anneal temperature of about 850°C for about 10 to about 300 minutes in an oxygen ambient.
  • the semiconductor material then is subjected to a post-diffusion treatment (step 1 14).
  • the post-diffusion treatment removes any residues, such as, for example, phosphosilicate glass, phosphorous oxide, silicon oxide or contamination, that form during annealing of the semiconductor material. If such residue is not removed after annealing, it may have deleterious affects on the performance of a subsequently-formed device. For example, such residue may dramatically increase the contact resistance between doped semiconductor material and a metal contact formed thereon.
  • Examples of post-diffusion treatment include subjecting the semiconductor material to acids, such as hydrofluoric acid (HF), hydrochloric acid (HC1), sulfuric acid (H 2 S0 4 ), and/or nitric acid (HN0 3 ), bases, such as ammonium hydroxide ( H 4 OH), sodium hydroxide (NaOH), potassium hydroxide (KOH), tetramethylammonium hydroxide (TMAH), oxidizers, such as hydrogen peroxide (H 2 0 2 ), solvents, such as water, acetone, isopropyl alcohol (IPA), ethanol, and/or tetrahydrofuran (THF), heating the semiconductor material to a temperature no higher than 800°C, or a combination thereof.
  • acids such as hydrofluoric acid (HF), hydrochloric acid (HC1), sulfuric acid (H 2 S0 4 ), and/or nitric acid (HN0 3 )
  • bases such as ammonium hydroxide ( H 4 OH), sodium
  • ethylene glycol was added to a 25 ⁇ mL glass vessel.
  • Approximately 1 gram (g) of Aerosil® 380 fumed silica was added to the ethylene glycol and the mixture was mixed for about 15 minutes using a Heat Systems - Ultrasonics Inc. ultrasonic processor Model W-375 to form a uniform dispersion.
  • Approximately 100 mL deionized water was added to a 500 mL glass vessel.
  • Approximately 150 g 50% TMAH aqueous solution and 70 mL 85% phosphoric acid aqueous solution were added to the water and the resulting solution was stirred for thirty minutes using an electromagnetic stirrer.
  • the pH of the dopant was 7.
  • the phosphorous-comprising dopant was deposited on a bare P-type silicon wafer using a 1 pL nozzle of a Dimatix Inkjet Printer Model DMP 2831 with 12 ⁇ drop spacing.
  • EXAMPLE 3 [0052] In a 1 L glass vessel, 16.6 parts by volume 85% phosphoric acid aqueous solution was combined with 25.0 parts by volume ethylene glycol and 58.3 parts 25% TMAH aqueous solution. The solution was stirred at room temperature for thirty minutes using an electromagnetic stirrer. The solution then was filtered using a 0.45 ⁇ PVDF filter to obtain a phosphorous-comprising dopant. The pH of the dopant was 2.5. The phosphorous- comprising dopant was deposited on a bare P-type silicon wafer using a 1 pL nozzle of a Dimatix Inkjet Printer Model DMP 2831 with 15 ⁇ drop spacing.
  • the silicon wafer was baked at 200°C for about 10 minutes and then was subjected to a furnace at 980°C for about 3 hours. After deglazing with diluted hydrofluoric acid (DHF), a sheet resistance as low as 3.5 ohm/sq on the doped silicon wafer was achieved.
  • DHF diluted hydrofluoric acid
  • Aerosil 380 fumed silica and 74.8 g of CAB-O-SIL TS-610 fumed silica were slowly added so that the two fumed silicas were fully dispersed in the solution.
  • the mixture was mechanically stirred at 800 rpm for 8 hours.
  • the phosphorous-comprising dopant was deposited on a bare P-type silicon wafer using screen printing.
  • the wafer was baked at 300°C for about 1 minute. A dopant line width as thin as 50 ⁇ on the silicon wafer was achieved.
  • the phosphorous-comprising dopant was deposited on a bare P- type silicon wafer using screen printing.
  • the wafer was baked at 300°C for about 1 minute.
  • a dopant line width as thin as 50 ⁇ on the silicon wafer was achieved.
  • substantially silane-free phosphorous-comprising dopants for forming phosphorous-doped regions in semiconductor materials, methods for fabricating such phosphorous-comprising dopants, and methods for forming phosphorous-doped regions in semiconductor material using such phosphorous-comprising dopants have been provided. While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way.

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Abstract

La présente invention concerne, d'une part des dopants phosphorés sensiblement exempts de silanes, d'autre part des procédés de réalisation de régions dopées au phosphore dans un matériau semi-conducteur au moyen de dopants phosphorés sensiblement exempts de silanes, et enfin un procédé de fabrication de dopants phosphorés sensiblement exempts de silanes. Un tel dopant phosphoré comprend une source de phosphore comprenant un sel de phosphore, un acide de phosphore, des anions de phosphore, ou certaines de leurs combinaisons, une substance alcaline, des cations provenant d'une substance alcaline ou certaines de leurs combinaisons, et un milieu liquide. Ce dopant phosphoré comprend moins de 0,1% en poids de silanes, d'oligomères, et/ou de polymères dérivés de silanes, ou d'une de leurs combinaisons.
PCT/CN2011/001392 2011-08-22 2011-08-22 Dopants phosphorés; procédés de réalisation de zones dopées au phosphore dans des substrats semi-conducteurs au moyen de dopants phosphorés, et procédés de fabrication de tels dopants phosphorés WO2013026177A1 (fr)

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TW101130292A TWI608525B (zh) 2011-08-22 2012-08-21 含磷摻雜劑，使用該等含磷摻雜劑在半導體基板中形成磷摻雜區域之方法，及形成該等含磷摻雜劑之方法

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