WO2014101988A1 - Oxidmedien zum gettern von verunreinigungen aus siliziumwafern - Google Patents
Oxidmedien zum gettern von verunreinigungen aus siliziumwafern Download PDFInfo
- Publication number
- WO2014101988A1 WO2014101988A1 PCT/EP2013/003837 EP2013003837W WO2014101988A1 WO 2014101988 A1 WO2014101988 A1 WO 2014101988A1 EP 2013003837 W EP2013003837 W EP 2013003837W WO 2014101988 A1 WO2014101988 A1 WO 2014101988A1
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- WO
- WIPO (PCT)
- Prior art keywords
- acid
- silicon
- getter
- oxide
- media
- Prior art date
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012803 melt mixture Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004801 process automation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
-
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- 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
-
- 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
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- 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
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- 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
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- H—ELECTRICITY
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- 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
- H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
-
- 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
- H01L21/322—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections
- H01L21/3221—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections of silicon bodies, e.g. for gettering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
- H01L31/0288—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table characterised by the doping material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a novel process for the preparation of printable, low to high viscosity oxide media, and their use in solar cell manufacturing, as well as the improved lifetime products produced using these novel media.
- a silicon wafer (monocrystalline, multicrystalline or quasi-monocrystalline, p- or n-type base doping) is freed of adherent saw damage by means of an etching process and "simultaneously", usually in the same etching bath, texturized in this case, the creation of a preferred Surface (texture) as a result of the etching step or simply to understand the targeted, but not particularly oriented roughening of the wafer surface
- the aforementioned etching solutions for treating the silicon wafers typically consist of dilute potassium hydroxide solution to which isopropyl alcohol has been added as solvent. It may instead be added other alcohols having a higher vapor pressure or higher boiling point than isopropyl alcohol, provided that the desired ⁇ tzgebnis can be achieved, As the desired etching result is typically obtained a morphology of randomly arranged, or rather etched from the original surface,
- CONFIRMATION COPY Pyramids is characterized by square base.
- the density, the height and thus the base area of the pyramids can be influenced by a suitable choice of the above-mentioned constituents of the etching solution, the etching temperature and the residence time of the wafers in the etching basin.
- Temperature range of 70 - ⁇ 90 ° C performed, with ⁇ tzabträge of up to 10 pm per wafer side can be achieved.
- the etching solution may consist of potassium hydroxide solution with an average concentration (10-15%).
- this etching technique is hardly used in industrial practice. More often becomes one
- Etching solution consisting of nitric acid, hydrofluoric acid and water used.
- This etching solution can be modified by various additives such as sulfuric acid, phosphoric acid, acetic acid, N-methylpyrrolidone and also surfactants, which u. a.
- Wetting properties of the etching solution and their etch rate can be specifically influenced.
- These acid etch mixtures produce a morphology of interstitially arranged etch pits on the surface.
- the etching is typically carried out at temperatures in the range between 4 ° C to ⁇ 10 ° C and the ⁇ tzabtrag here is usually 4 pm to 6 pm.
- the wafers are placed in a tube furnace in a quartz glass tube of a controlled atmosphere consisting of dried nitrogen, dried oxygen and phosphoryl chloride.
- the wafers are introduced at temperatures between 600 and 700 ° C in the quartz glass tube.
- the gas mixture is transported through the quartz glass tube.
- the phosphoryl chloride decomposes into a vapor consisting of phosphorus oxide (eg P2O5) and chlorine gas.
- the vapor of phosphorus oxide is deposited among other things on the wafer surfaces (occupancy).
- the silicon surface is oxidized at these temperatures to form a thin oxide layer. In this layer, the deposited phosphorus oxide is embedded, whereby a mixed oxide of silicon dioxide and phosphorus oxide formed on the wafer surface.
- This mixed oxide is called phosphosilicate glass (PSG).
- PSG phosphosilicate glass
- the mixed oxide serves the silicon wafer as a diffusion source, wherein in the course of the diffusion, the phosphorus oxide diffuses in the direction of the interface between PSG glass and silicon wafer and is reduced there by reaction with the silicon on the wafer surface (silicothermally) to phosphorus.
- the resulting phosphor has a solubility which is orders of magnitude greater in silicon than in the glass matrix from which it is formed, and thus dissolves preferentially in silicon due to the very high segregation coefficient.
- the phosphorus in silicon diffuses along the concentration gradient into the volume of silicon. In this diffusion process, concentration gradients of the order of 105 between typical
- a PSG layer is formed, which typically has a layer thickness of 40 to 60 nm. in the
- the composition of the gas mixture is adjusted so that the further supply of phosphoryl chloride is suppressed.
- the surface of the silicon is further oxidized by the oxygen contained in the gas mixture, whereby a phosphorus depleted silicon dioxide layer is also generated between the actual doping source, the phosphorus oxide highly enriched PSG glass and the silicon wafer
- the tube furnace is automatically cooled and the wafers can be removed from the process tube at temperatures between 600 ° C to 700 ° C.
- Composition of the gas atmosphere used for doping the formation of a so-called boron skin can be detected on the wafers.
- This boron skin is dependent on various influencing factors: decisive for the doping atmosphere, the temperature, the doping time, the
- Pretreatment were subjected (for example, their structuring with diffusion-inhibiting and / or -unterbindenden layers and
- Dopant sources eg boric oxide and boron nitride
- Doping sources for example, dilute solutions of phosphoric or boric acid, as well as sol-gel-based systems or solutions of polymeric Borazilitatien can be used.
- additional thickening polymers characterized, and contain dopants in a suitable form.
- dopants in a suitable form.
- evaporation of Solvents from the aforementioned doping media are usually followed by a high-temperature treatment during which undesirable and interfering additives which cause the formulation are either "burned" and / or pyrolyzed., The removal of solvents and the burn-out may or may not , take place simultaneously.
- the coated substrates usually pass through a continuous furnace at temperatures between 800 ° C and 1000 ° C, to shorten the cycle time, the temperatures in comparison to
- Gas phase diffusion in the tube furnace can be slightly increased.
- the prevailing in the continuous furnace gas atmosphere can according to the
- Nitrogen dry air, a mixture of dry oxygen and dry nitrogen and / or, depending on the design of the furnace to be passed, zones of one and the other of the above
- Driving the dopant can in principle be decoupled from each other.
- the wafers present after the doping are coated on both sides with more or less glass on both sides of the surface. More or less in this case refers to modifications that can be applied in the context of the doping process: double-sided diffusion vs. quasi one-sided diffusion mediated by back-to-back arrangement of two wafers in a parking space of the process boats used.
- the latter variant allows a predominantly one-sided doping, but does not completely prevent the diffusion on the back.
- the wafers are on the one hand transhipped in batches in wet process boats and with their help in a solution of dilute hydrofluoric acid, typically 2% to 5%, immersed and left in this until either the surface is completely removed from the glasses, or Process cycle has expired, which represents a sum parameter of the necessary ⁇ tzdauer and the automatic process automation.
- the complete removal of the glasses can be determined, for example, by the complete dewetting of the silicon wafer surface by the dilute aqueous hydrofluoric acid solution.
- the complete removal of a PSG glass is achieved under these process conditions, for example with 2% hydrofluoric acid solution within 210 seconds at room temperature.
- the etching of corresponding BSG glasses is slower and requires longer process times and possibly also higher concentrations of the hydrofluoric acid used. After etching, the wafers are rinsed with water.
- the etching of the glasses on the wafer surfaces can also be carried out in a horizontally operating method in which the wafers are introduced in a constant flow into an etching system in which the wafers pass through the corresponding process tanks horizontally (inline system).
- the wafers are conveyed on rollers and rollers either through the process tanks and the etching solutions contained therein or the etching media are transported onto the wafer surfaces by means of roller application.
- the typical residence time of the wafers in the case of etching the PSG glass is about 90 seconds, and the hydrofluoric acid used is somewhat more concentrated than in the batch process
- the concentration of hydrofluoric acid is typically 5%.
- the tank temperature compared to the
- edge isolation is a process-technical necessity that results from the system-inherent characteristics of the double-sided diffusion intended unilateral back-to-back diffusion.
- edge isolation is a process-technical necessity that results from the system-inherent characteristics of the double-sided diffusion intended unilateral back-to-back diffusion.
- parasitic pn junction On the (later) back side of the solar cell there is a large-area parasitic pn junction which, although due to process technology, is partly, but not completely, removed in the course of the later processing.
- the Front and back of the solar cell via a parasitic and
- the wafers are unilaterally via an etching solution
- etching solution consisting of nitric acid and hydrofluoric acid.
- the etching solution may contain as minor constituents, for example, sulfuric acid or phosphoric acid.
- the etching solution is imparted via rollers to the
- the etching removal typically achieved with these methods amounts to approximately 1 ⁇ m silicon (including the glass layer present on the surface to be treated).
- the glass layer remaining on the opposite side of the wafer serves as a mask before
- Plasma etching processes are performed. This plasma etching is then usually carried out before the glass etching. For this purpose, several wafers are stacked on each other and the outer edges become the plasma
- the plasma is filled with fluorinated gases, for example
- Tetrafluoromethane fed.
- the glass etching is then generally carried out.
- Solar cells with an anti-reflection coating which usually consists of amorphous and hydrogen-rich silicon nitride.
- Antireflection coatings are conceivable. Possible coatings may include titanium dioxide, magnesium fluoride, tin dioxide and / or
- the layer generates an electric field due to the numerous incorporated positive charges that charge carriers in the silicon can keep away from the surface and the recombination of these charge carriers at the
- this layer depending on its optical parameters, such as refractive index and layer thickness, this layer generates a reflection-reducing property which contributes to the fact that more light can be coupled into the later solar cell. Both effects can increase the conversion efficiency of the solar cell.
- the antireflection reduction is most pronounced in the wavelength range of the light of 600 nm.
- the directional and non-directional reflection shows a value of about 1% to 3% of the originally incident light (perpendicular incidence to the surface normal of the silicon wafer).
- the above-mentioned silicon nitride films are currently deposited on the surface generally by direct PECVD method.
- a gas atmosphere of argon is ignited a plasma, in which silane and ammonia are introduced.
- the silane and the ammonia are converted in the plasma by ionic and radical reactions to silicon nitride and thereby deposited on the wafer surface.
- the properties of the layers can z. B. adjusted and controlled by the individual gas flows of the reactants.
- the deposition of the above-mentioned silicon nitride layers can also be carried out using hydrogen as the carrier gas and / or the reactants alone. Typical deposition temperatures are in the range between 300 ° C to 400 ° C.
- Alternative deposition methods may be, for example, LPCVD and / or sputtering. 5. Generation of front side electrode grid After depositing the antireflection coating is on with
- Silicon nitride coated wafer surface defines the front electrode.
- the electrode has been established using the screen printing method using metallic
- the sum of the residual constituents results from the necessary for the formulation of the paste theological aids, such as solvents, binders and thickeners.
- the silver paste contains a special Glasfrit mixture, mostly oxides and mixed oxides based on
- the glass frit fulfills essentially two functions: on the one hand it serves as a bonding agent between the wafer surface and the mass of the silver particles to be sintered, on the other hand it is responsible for the penetration of the silicon nitride covering layer in order to enable the direct ohmic contact to the underlying silicon.
- the penetration of the silicon nitride takes place via an etching process with subsequent diffusion of silver present dissolved in the glass frit matrix into the silicon surface, whereby the ohmic contact formation is achieved.
- the silver paste is deposited by screen printing on the wafer surface and then dried at temperatures of about 200 ° C to 300 ° C for a few minutes. For the sake of completeness, it should be mentioned that double-printing processes also find industrial application, which make it possible to print on an electrode grid generated during the first printing step, a congruent second.
- Silver metallization increases, which can positively influence the conductivity in the electrode grid.
- the solvents contained in the paste are expelled from the paste.
- the printed wafer passes through a continuous furnace.
- Such an oven generally has several heating zones, which can be independently controlled and tempered.
- the wafers are heated to temperatures up to about 950 ° C.
- the single wafer is, however, usually this peak temperature only for exposed for a few seconds.
- the wafer has temperatures of 600 ° C to 800 ° C. In these
- Temperatures are contained in the silver paste contained organic impurities such as binder, and the etching of the silver paste.
- Silicon nitride layer is initiated. During the short time interval of the prevailing peak temperatures, contact formation occurs.
- the front electrode grid consists of thin fingers
- the rear bus buses are also usually by means of
- the back electrode is defined following the pressure of the bus buses.
- the electrode material is made of aluminum, therefore, to define the electrode, an aluminum-containing paste by screen printing on the remaining free area of the wafer back with a
- Edge distance ⁇ 1 mm is printed.
- the paste is composed of up to 80% aluminum. The remaining components are those already mentioned under point 5 (such as solvents, binders, etc.).
- the aluminum paste is bonded to the wafer during co-firing by causing the aluminum particles to start to melt during heating and remove silicon from the wafer in the wafer
- the melt mixture acts as a dopant source and gives aluminum to the silicon (solubility limit: 0.016 atomic percent), whereby the silicon is p + doped as a result of this drive-in.
- a eutectic mixture of aluminum and silicon which solidifies at 577 ° C. and has a composition with a mole fraction of 0.12 Si, is deposited on the wafer surface, inter alia.
- back surface field This potential wall is generally referred to as the back surface field or "back surface field”.
- edge isolation of the wafer has not already been carried out as described under point 3, this is typically carried out after co-firing with the aid of laser beam methods.
- a laser beam is directed to the front of the solar cell and the front p-n junction is severed by means of the energy coupled in by this beam.
- This trench with a depth of up to 15 pm as a result of
- this laser trench is 30 pm to 60 pm wide and about 200 pm away from the edge of the solar cell.
- solar cell architectures with both n-type and p-type base material include:
- structured diffusion barriers may be deposited on the silicon wafers prior to depositing the glasses to define the regions to be doped.
- a disadvantage of this method is that in each case only one polarity (n or p) of the
- Doping can be achieved. Somewhat simpler than the structuring of the doping sources or of any diffusion barriers is the direct one
- Wafer surfaces deposited dopant sources This method makes it possible to save costly structuring steps. However, it can not compensate for the disadvantage of a possible simultaneous simultaneous doping of two polarities on the same surface at the same time (co-diffusion), since this method is also based on a predeposition of a dopant source, which is activated only subsequently for the emission of the dopant. Disadvantage of this (post-) doping from such sources is the inevitable laser damage to the substrate: the laser beam must by absorbing the radiation into heat
- UMG upgraded metallurgical grade
- this silicon contains much higher impurity concentrations, especially 3d transition metals, e.g. Ti, Fe, Cu. These metals are extremely detrimental in the electrically active part of solar cells because they form charge carrier recombination centers in the bandgap of silicon.
- gettering is a process of removing or moving contaminants where they are less harmful to the solar cell. In general, this step is done by so-called HCI gettering. It is a process based on the reaction of
- the voltage of the cell can be increased in various ways.
- Various solutions have been described in the literature on this subject. These include u. a. following approaches: the concept of the selective emitter, that of the local back field, that of the
- both the current efficiency and the voltage of the solar cells must be increased.
- both solar cell parameters are mutually dependent quantities.
- the current efficiency, the short-circuit current Isc can no longer be increased significantly or disproportionately without further means, since this is dependent on the light intensity coupled or absorbed onto the solar cell, provided that no concentration of the incident light intensity is undertaken.
- the short-circuit current density can not simply be increased arbitrarily - the solar spectrum (AM1.5 according to IEC 60904-3 Ed.2) provides an integrated light intensity of 804.6 W / m 2 in the wavelength range between 280 nm and 100 nm), which corresponds to 43.5 mA / cm 2 - so that one possible optimization parameter is the
- the concept of the selective emitter optimizes the proportion of the emitter at the dark current saturation density
- the concept of the local back surface field addresses the inflowing portion of the base.
- the dark current saturation density does not depend solely on the effects due to modifications to the wafer surface as part of the technological implementation of the two concepts mentioned but not exclusively on their benefits
- Charge carrier lifetime depends on many factors and can therefore easily be manipulated. Without specifying these factors in detail, it is often referred to as "material quality.”
- material quality One long-known and frequently discussed cause that adversely affects the material quality of silicon is the introduction of contaminants into the volume of the crystal
- Contaminants are typically elements of transition metals, such as iron, copper and nickel, which can significantly reduce charge carrier lifetimes (> three orders of magnitude, corresponding to milliseconds to microseconds and less).
- transition metals such as iron, copper and nickel
- gold is targeted for the production of certain integrated circuits
- Contamination can be prevented or eliminated (cured) can be.
- the present invention provides a process for producing a grip and abrasion-resistant layer with a Getter bin on silicon wafers
- the oxide medium is printed on silicon wafer in a highly viscous form and, in addition to the getter effect after its thermal densification and glazing, produces an effect as a diffusion barrier against phosphorus and boron diffusion.
- gettering media prepared using boron-containing compounds selected from the group consisting of boron oxide, boric acid, and borane acid can be used in the process according to the invention
- phosphorus-containing compounds selected from the group phosphorus (V) oxide, phosphoric acid, polyphosphoric acid, phosphoric acid esters and phosphoric acid esters with alpha- and / or beta-standing
- the layers glazed on the surfaces may be exposed to the substrate by temperature treatment at a temperature in the range between 750 ° C and 1100 ° C, preferably between 850 ° C and 1100 ° C, silicon-doping atoms, such as boron and / or phosphorus , whereby the conductivity of the substrate is influenced.
- treated substrates differ by at least two powers of ten from doping intended doped regions.
- the getter medium can be printed on hydrophilic and / or hydrophobic silicon wafer surfaces.
- getter media according to the invention their drying, compaction and glazing and optionally doping by suitable
- Acid mixture can be etched and therefore hydrophobic
- Silicon wafer surfaces are obtained. Suitable for this
- Etching mixtures contain as etchant hydrofluoric acid in a concentration of 0.001 to 10 wt .-%. But you can also 0.001 to 10 wt .-%
- These alkoxysilanes and Alkoxyalkylsilane be through
- Malonic acid, pyruvic acid, malic acid, 2-oxoglutaric reacted in the desired getter media, in particular printable gettering media are obtained based on hybrid sols and or gels, if alcoholates / esters, acetates, hydroxides or oxides of aluminum,
- Germanium, zinc, tin, titanium, zirconium, or lead, or mixtures thereof are used in the condensation reaction.
- the getter medium is dissolved to a high-viscosity, approximately glassy mass and the resulting product, either by addition of a suitable solvent or
- the "capping agent" selected from the group consisting of acetoxytrialkylsilanes, alkoxytrialkylsilanes, halotrialkylsilanes and derivatives thereof, individually or in admixture, in which context the gettering medium is formulated without the addition of thickener as a highly viscous oxidizing medium.
- the highly viscous getter medium in the claimed process by spin or dip coating, drop casting, curtain or slot dye coating, screen or flexoprinting, gravure, inkjet or aerosol jet printing, offset printing, Micro Contact Printing, electrohydrodynamic
- a getter medium in the form of a printable oxide medium of the present invention contains, characterized by the use of alcoholates / esters, acetates , Hydroxides or oxides of aluminum, germanium, zinc, tin, titanium, zirconium or lead during manufacture.
- This getter medium is advantageously storage-stable for a period of at least three months and can be used to produce diffusion barriers in processing processes of silicon wafers for photovoltaic,
- microelectronic, micromechanical and micro-optical applications are used or for the production of diffusion barriers in
- Microelectronic, micromechanical and micro-optical applications or also for the production of PERC, PERL, PERT, IBC solar cells and others, wherein the solar cells further architectural features, such as MWT, EWT, selective emitter, selective front surface field, selective back surface field and bifaciality.
- it can be used for the production of thin, dense glass layers, which act as a sodium and potassium diffusion barrier in the LCD technique due to a thermal treatment or for producing thin, dense glass layers on the cover glass of a display consisting of doped SiO 2 , which the diffusion of ions from the coverslip into the liquid crystalline phase into it.
- Minority carrier can be extended.
- silicon are sufficiently low, take place.
- the gettering is preferably carried out in a variable plateau time downstream of the diffusion in the course of the diffusion process.
- printable, low to high viscosity oxide media as getter media which can be prepared in anhydrous sol-gel based synthesis, by symmetrically condensing from two to four times and or
- the alkoxysilanes and alkoxyalkylsilanes used may contain individual or various saturated, unsaturated, branched, unbranched aliphatic, alicyclic and aromatic radicals, which in turn may be attached to any position of the alkoxide radical by heteroatoms selected from the group O, N, S, Cl and Br can be functionalized.
- boron-containing media preference is given to compounds selected from the group boron oxide, boric acid and boric acid esters
- oxide media having good properties are obtained when the
- phosphorus-containing compounds are selected from the group consisting of:
- Phosphorus (V) oxide Phosphorus (V) oxide, phosphoric acid, polyphosphoric acid, phosphoric acid esters and phosphonic acid esters with alpha- and beta-standing
- the condensation reaction can, as stated above, be carried out in the presence of strong carboxylic acids.
- the acidity of the carboxylic acids is higher when at the alpha-C atom, a substituent with a
- carboxylic acids are acids from the group of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, mono-, di- and trichloroacetic acid, glyoxylic acid, tartaric acid, maleic acid, malonic acid, Pyruvic acid, malic acid, 2-oxoglutaric particularly suitable for use in the method according to the invention.
- the printable oxide media in the form of doping media based on hybrid sols and or gels, using alcoholates or esters, acetates, hydroxides or oxides of aluminum, germanium, zinc, tin, titanium, zirconium or lead, and mixtures thereof.
- hybrid sols can be prepared by adding suitable sequestering agents, complex and
- the oxide medium can be up to a highly viscous, approximately glassy mass be resolved, and the product obtained, either by the addition of a suitable solvent or
- Solvent mixture brought back into solution or transformed by means of intensive shear mixing devices in a sol state and recover by partial or complete structural recovery (gelation) to a homogeneous gel.
- Capping means a significant increase in storage stability.
- the added "capping means" need not necessarily in the
- End groups such as silanol groups, chemically abreacted and thus further uncontrolled and undesirable
- the oxide media produced according to the invention can be produced by spin coating or dip coating, drop casting, curtain or slot dye coating, screen printing or flexoprinting, gravure, ink jet or aerosol jet printing, offset printing or microcontact printing , Electrohydrodynamic Dispensing, Roller or Spray Coating, Ultrasonic Spray Coating, Pipe Jetting, Laser Transfer Printing, Päd Printing or Rotary Screen Printing.
- Correspondingly prepared oxide media are particularly well suited for the production of PERC, PERL, PERT, IBC oil cells and others, whereby the solar cells have further architectural features such as MWT, EWT, selective emitter, selective front surface field, selective back surface field and bifaciality or for the production of thin, dense glass layers, which act as a sodium and potassium diffusion barrier in the LCD technique as a result of a thermal treatment, in particular for the production of thin, dense glass layers on the cover glass of a display, consisting of doped SiO 2 , which the diffusion prevent ions from the cover glass into the liquid crystalline phase.
- the present invention accordingly relates to the new, according to the invention
- Oxidmedien which have been prepared according to the method described above and which binary or ternary systems from the group SiO 2 -P2O 5, SiO 2 -B 2 O 3 and SiO 2 -P 2 O 5 -B 2 O 3 and S1O2-Al2O3-B2O3 and / or higher-grade mixtures characterized by the use of alcoholates or esters, acetates,
- Masking agents, complex and chelating in a sub stoichiometric to a stoichiometric ratio on the one hand sterically stabilize and on the other hand specifically influence and control their condensation and Geiticiansrate, but also in terms of theological properties.
- the oxide media By means of the oxide media thus obtained, it is possible to produce on silicon wafers, a grip and abrasion resistant layer.
- This may be done in a process wherein the surface-printed oxide medium prepared by a process within the scope of the invention is particularly preferred in a temperature range between 50 ° C and 750 ° C, preferably between 50 ° C and 500 ° C between 50 ° C and 400 ° C, by means of one or more, to be carried out sequentially Temperöne (heat treatment by means of a step function) and / or an annealing ramp, dried and compacted for glazing, whereby a grip and abrasion resistant layer is formed with a thickness of up to 500 nm.
- Oxide media according to the invention as well as after the possible doping of silicon wafers with the aid of the aforementioned, can be obtained with an acid mixture containing hydrofluoric acid and optionally
- Phosphoric acid, residue-free etching to obtain hydrophobic silicon surfaces are etched, wherein the etchant used as etchant hydrofluoric acid in a concentration of 0.001 to 10 wt .-% or 0.001 to 10 wt .-% hydrofluoric acid and 0.001 to 10 wt .-% phosphoric acid in the mixture ,
- the dried and compacted doping glasses can the
- the etching mixtures may be compositions such as buffered hydrofluoric acid mixtures (BHF), buffered oxide etch mixtures, etch mixtures consist of hydrofluoric and nitric acid, such as so-called p-etching, R-etching, S-etching, or etching mixtures, flow and
- BHF buffered hydrofluoric acid mixtures
- etch mixtures consist of hydrofluoric and nitric acid, such as so-called p-etching, R-etching, S-etching, or etching mixtures, flow and
- the desired and advantageous getter effect of the layer produced is obtained after treatment at elevated temperature in the range between 500 ° C. and 800 ° C., more preferably between 600 ° C. and 750 ° C., with and without diffusion (getter diffusion),
- Oxide media may also be formulated by suitable additives as printable dopant media. This also means that these novel oxide media can be synthesized based on the sol-gel process and, if necessary, further formulated.
- the synthesis of the sol and / or gel can be achieved by adding
- Condensation initiators e.g. of a carboxylic acid anhydride and / or a strong carboxylic acid, to be controlled specifically in the absence of water.
- the viscosity can be controlled via the stoichiometry of the addition, for example of the acid anhydride.
- the degree of crosslinking of the silica particles can be adjusted, whereby a highly swollen network can arise.
- the resulting ink is
- Suitable printing methods can be the following:
- the properties of the getter materials according to the invention can be adjusted in a more targeted manner by adding further additives, so that they are optimally suitable for special printing processes and for application to certain surfaces, with which they can interact intensively. In this way you can target properties, such as
- Requirements for the getter materials produced can also be added to other additives. These can be:
- particulate additives eg aluminum hydroxides and
- ⁇ Particulate additives eg aluminum hydroxides and
- each pressure-coating method has its own requirements for the ink to be printed and / or paste resulting from the ink.
- parameters to be set individually for the respective printing method are those such as the surface tension, the viscosity and the total vapor pressure of the ink or of the paste resulting therefrom.
- the printable media in addition to their use as
- Getter materials as scratch protection and corrosion protection layers eg. As in the manufacture of components in the metal industry, preferably in the electronics industry, and in particular in manufacturing
- MEMS photovoltaic components
- inks and pastes in the following, by way of example, but not exhaustive, fields: fabrication of thin film solar cells from thin film solar modules, production of organic solar cells, production of printed circuits, and
- TFT thin-film transistors
- LCD liquid crystals
- OLED organic light emitting diodes
- Silicon surfaces formed which forms a smooth surface even after drying and compaction. On very rough surfaces, such as the textured silicon wafer surfaces, this is more demanding, and an adapted application method must be used.
- the binders usually added to formulate pastes are generally very difficult to even not chemically clean up, or to free their cargo of metallic trace elements.
- auxiliaries are a constant source of contamination, are favored by the unwanted contamination in the form of metallic species.
- N chteile result from prolonged storage of the media in the context of the application. Longer storage leads for example to their bonding or their rapid partial (drying) on the drying
- Recombination rate at the wafer surface is dramatically increased.
- inventive printable, viscous oxide media which can be prepared by a sol-gel process.
- these oxide media can be produced as printable getter materials.
- Thickener (thickener) included.
- One-side polished p-type wafer (divided into evenly sized pieces) with a lifetime (measured by wet-chemical methanol quinhydrone passivation and quasi-static photoconductivity measurement) of
- the silicon surface provided with oxide and thus with silanol groups on the surface, acts highly adsorptive on iron cations.
- adsorbed iron may be due to a subsequent High temperature treatment penetrate the thin oxide layer and penetrate into the volume of silicon.
- Iron is known to segregate at oxidic interfaces and can easily form iron silicides on the surface of silicon. These silicides provide both
- silicides possibly present on the surface, even if they can act as a sink, have an effect on the life to be observed, since superficial contaminants due to the increase in the
- iron belongs to the medium-fast diffusing contaminants and has a very large capture cross-section in p-type silicon
- Photoconductivity measurements based on the decay function after irradiation can be determined.
- the wafer is then placed in a muffle furnace at 900 ° C for five
- the service life of the treated wafer is measured with the help of wet chemical methanol quinhydrone passivation and quasi-static photoconductivity measurement) and at a
- Injection density of 5 * 10 14 cm 3 read.
- the service life is 3 ps and is therefore lower than the starting position by a factor of ⁇ 170.
- the wafer pieces are coated by spin coating at 2000 rpm for 30 seconds on both sides with getter medium according to Examples 2 and 3 (two series of experiments, not crossed). Between the two-sided coatings, in each case the sides coated first with the doping medium are fixed by brief drying at 200 ° C. on a hot plate for two minutes. The wafer pieces are then tempered on a hot plate provided with a glass ceramic at 600 ° C for each increasing duration. After Annealing, the lifetimes of the glasses coated with the glasses are determined by means of quasi-static photoconductivity measurement. The lifetime is read at an injection density of 5 * 10 14 cm "3. Some wafers by means of dilute hydrofluoric acid to the control (5%) etched wet-chemically passivated by means of the methanol quinhydrone procedure and again subjected to a lifetime determination.
- Fig. 1 shows lifetime measurements of the contaminated
- Clearly recognizable is the increase in the service life as a function of the duration of the heat treatment.
- Fig. 2 shows lifetime measurements of the contaminated
- the media according to the invention evidently have a gettering effect, ie contaminants will be drawn out of the volume of silicon into the glass layer of getter media. As a result, the effective life of the silicon pieces increases significantly.
- the gettering effect of the media according to the invention in this case is not linked to the effect of getter diffusion, as frequently described.
- the getter effect is from temperature, because it affects the diffusion coefficient of iron in silicon in exponential dependence.
- Tetraethylorthosilicate added dropwise. With stirring and constant heating to 100 ° C, the resulting ethyl acetate is distilled off. To adjust the viscosity, another 1-10 g of acetic anhydride can be added.
- a protic solvent for example, branched and unbranched, aliphatic, cyclic, saturated and unsaturated and aromatic mono-, di-, tri- and polyols (alcohols), and glycols, their monoethers, monoacetates and the like, propylene glycols, their monoethers and monoacetates, as well as binary, tertiary, quaternary and higher mixtures of such solvents in any volume and / or mass mixture ratios, said protic solvents can be arbitrarily combined with polar and non-polar aprotic solvents;
- a protic solvent for example, branched and unbranched, aliphatic, cyclic, saturated and unsaturated and aromatic mono-, di-, tri- and polyols (alcohols), and glycols, their monoethers, monoacetates and the like, propylene glycols, their monoethers and monoacetates, as well as binary, tertiary, quaternary and higher mixtures of
- Solvent is not explicitly limited to substances that are added to
- Example 3 In a 250 ml round bottom flask, 3.6 g were placed in a desiccator
- Mono-, di-, tri- and polyols as well as glycols, their monoethers, monoacetates and the like, propylene glycols, their monoethers and
- Solvents can be combined; the term solvent is explicitly not limited to substances that are in a liquid state at room temperature). The resulting mixture was refluxed until a completely clear solution was formed.
- the ink-form oxide medium may be synthesized using a mixture of tetraethyl orthosilicate and aluminum trisobutylate. The partial substitution of tetraethyl orthosilicate by aluminum trisobutylate may require the substoichiometric addition of complexing ligands, such as those of acetylacetone, salicylic acid, 2,3-dihydroxy- and 3,4-dihydroxybenzoic acid, or mixtures thereof.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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US14/655,366 US20150357508A1 (en) | 2012-12-28 | 2013-12-18 | Oxide media for gettering impurities from silicon wafers |
JP2015550007A JP2016506629A (ja) | 2012-12-28 | 2013-12-18 | シリコンウェハから不純物をゲッタリングするための酸化物媒体 |
CN201380067927.0A CN104884684A (zh) | 2012-12-28 | 2013-12-18 | 用于从硅晶片吸除杂质的氧化物介质 |
SG11201505028XA SG11201505028XA (en) | 2012-12-28 | 2013-12-18 | Oxide media for gettering impurities from silicon wafers |
KR1020157020273A KR20150103129A (ko) | 2012-12-28 | 2013-12-18 | 실리콘 웨이퍼들로부터 불순물들을 게터링하기 위한 산화물 매체 |
EP13821068.7A EP2938762A1 (de) | 2012-12-28 | 2013-12-18 | Oxidmedien zum gettern von verunreinigungen aus siliziumwafern |
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KR (1) | KR20150103129A (de) |
CN (1) | CN104884684A (de) |
SG (2) | SG10201705329RA (de) |
TW (1) | TW201443108A (de) |
WO (1) | WO2014101988A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016107661A1 (de) * | 2014-12-30 | 2016-07-07 | Merck Patent Gmbh | Laserdotierung von halbleiter |
WO2016150548A3 (de) * | 2015-03-23 | 2016-11-24 | Merck Patent Gmbh | Druckbare pastöse diffusions- und legierungsbarriere zur herstellung von hocheffizienten kristallinen siliziumsolarzellen |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP6737066B2 (ja) * | 2016-08-22 | 2020-08-05 | 株式会社Sumco | エピタキシャルシリコンウェーハの製造方法、エピタキシャルシリコンウェーハ、及び固体撮像素子の製造方法 |
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WO2000054341A1 (de) * | 1999-03-11 | 2000-09-14 | Merck Patent Gmbh | Dotierpasten zur erzeugung von p, p+ und n, n+ bereichen in halbleitern |
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US20100081264A1 (en) * | 2008-09-30 | 2010-04-01 | Honeywell International Inc. | Methods for simultaneously forming n-type and p-type doped regions using non-contact printing processes |
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US20090239363A1 (en) * | 2008-03-24 | 2009-09-24 | Honeywell International, Inc. | Methods for forming doped regions in semiconductor substrates using non-contact printing processes and dopant-comprising inks for forming such doped regions using non-contact printing processes |
JP2011211036A (ja) * | 2010-03-30 | 2011-10-20 | Shin-Etsu Chemical Co Ltd | 基板処理方法、基板の製造方法及び太陽電池の製造方法 |
US9580610B2 (en) * | 2011-03-08 | 2017-02-28 | Merck Patent Gmbh | Aluminium oxide pastes and process for the use thereof |
US10134942B2 (en) * | 2012-12-28 | 2018-11-20 | Merck Patent Gmbh | Doping media for the local doping of silicon wafers |
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2013
- 2013-12-18 KR KR1020157020273A patent/KR20150103129A/ko not_active Application Discontinuation
- 2013-12-18 US US14/655,366 patent/US20150357508A1/en not_active Abandoned
- 2013-12-18 CN CN201380067927.0A patent/CN104884684A/zh active Pending
- 2013-12-18 SG SG10201705329RA patent/SG10201705329RA/en unknown
- 2013-12-18 SG SG11201505028XA patent/SG11201505028XA/en unknown
- 2013-12-18 EP EP13821068.7A patent/EP2938762A1/de not_active Withdrawn
- 2013-12-18 JP JP2015550007A patent/JP2016506629A/ja active Pending
- 2013-12-18 WO PCT/EP2013/003837 patent/WO2014101988A1/de active Application Filing
- 2013-12-27 TW TW102148894A patent/TW201443108A/zh unknown
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US3837873A (en) * | 1972-05-31 | 1974-09-24 | Texas Instruments Inc | Compositions for use in forming a doped oxide film |
US4277525A (en) * | 1978-09-01 | 1981-07-07 | Tokyo Ohka Kogyo Kabushiki Kaisha | Liquid compositions for forming silica coating films |
WO2000054341A1 (de) * | 1999-03-11 | 2000-09-14 | Merck Patent Gmbh | Dotierpasten zur erzeugung von p, p+ und n, n+ bereichen in halbleitern |
WO2002023639A1 (en) * | 2000-09-13 | 2002-03-21 | Siemens Und Shell Solar Gmbh | Photovoltaic component and module |
US20050022697A1 (en) * | 2003-07-31 | 2005-02-03 | Ramazan Benrashid | High performance sol-gel spin-on glass materials |
US20100081264A1 (en) * | 2008-09-30 | 2010-04-01 | Honeywell International Inc. | Methods for simultaneously forming n-type and p-type doped regions using non-contact printing processes |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016107661A1 (de) * | 2014-12-30 | 2016-07-07 | Merck Patent Gmbh | Laserdotierung von halbleiter |
WO2016150548A3 (de) * | 2015-03-23 | 2016-11-24 | Merck Patent Gmbh | Druckbare pastöse diffusions- und legierungsbarriere zur herstellung von hocheffizienten kristallinen siliziumsolarzellen |
Also Published As
Publication number | Publication date |
---|---|
KR20150103129A (ko) | 2015-09-09 |
TW201443108A (zh) | 2014-11-16 |
JP2016506629A (ja) | 2016-03-03 |
US20150357508A1 (en) | 2015-12-10 |
CN104884684A (zh) | 2015-09-02 |
EP2938762A1 (de) | 2015-11-04 |
SG11201505028XA (en) | 2015-07-30 |
SG10201705329RA (en) | 2017-07-28 |
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