US20090292053A1 - Film-forming composition - Google Patents
Film-forming composition Download PDFInfo
- Publication number
- US20090292053A1 US20090292053A1 US12/307,848 US30784807A US2009292053A1 US 20090292053 A1 US20090292053 A1 US 20090292053A1 US 30784807 A US30784807 A US 30784807A US 2009292053 A1 US2009292053 A1 US 2009292053A1
- Authority
- US
- United States
- Prior art keywords
- film
- forming composition
- dopant
- dopant element
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000002019 doping agent Substances 0.000 claims abstract description 74
- 238000009792 diffusion process Methods 0.000 claims abstract description 60
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 33
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 58
- 239000011248 coating agent Substances 0.000 abstract description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 46
- 239000000377 silicon dioxide Substances 0.000 abstract description 23
- 239000004065 semiconductor Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 238000005530 etching Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
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- -1 B2O3 Chemical class 0.000 description 6
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- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
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- 239000003377 acid catalyst Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
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- 239000011701 zinc Substances 0.000 description 3
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- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
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- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 229930182830 galactose Natural products 0.000 description 2
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- 239000008103 glucose Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Inorganic materials O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
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- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- RXJWOBGGPLEFEE-UHFFFAOYSA-N triethyl(propoxy)silane Chemical compound CCCO[Si](CC)(CC)CC RXJWOBGGPLEFEE-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- PHPGKIATZDCVHL-UHFFFAOYSA-N trimethyl(propoxy)silane Chemical compound CCCO[Si](C)(C)C PHPGKIATZDCVHL-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Definitions
- the present invention relates to a film-forming composition used in diffusion of a dopant employed when a dopant semiconductor is produced.
- a dopant is doped into an intrinsic semiconductor such as silicon or germanium, whereby dopant semiconductors such as P-type semiconductors having a positive hole, or N-type semiconductors having a free electron are produced.
- dopant semiconductors do not conduct electric current in general, they can be readily changed so as to conduct electric current by applying a certain voltage since just a low amount of energy is required to excite the electron from the valence band to the conduction band.
- the dopant element which may be used in doping into a silicon substrate is a 13 group element such as boron or gallium in the case of P-type semiconductors, or a 15 group element such as phosphorus, arsenic or antimony in the case of N-type semiconductors.
- a method for diffusing a dopant a variety of diffusion methods have been developed, and known methods include a gas diffusion method, a solid diffusion method, a coating diffusion method, and the like.
- Patent Document 1 discloses a method for diffusing a dopant by the solid diffusion method, and a dopant film used in the method.
- a coating solution containing a dopant is used to coat on a semiconductor substrate, and the solvent is volatilized to form a dopant diffusion source layer, followed by a thermal diffusion treatment to allow the dopant element to be diffused into the semiconductor substrate.
- This method is advantageous in that a dopant region can be formed by a comparatively simple manipulation without using an expensive apparatus.
- a coating solution for forming a silica-based coating film contains a hydrolysate such as, for example, alkoxysilane, and thus a coating film including silicon dioxide as a principal component can be formed by coating the solution on a semiconductor substrate, and then heating (for example, see, Patent Document 2).
- Patent Document 1 Japanese Patent No. 2639591
- Patent Document 2 Japanese Patent Application Laid-open No. H9-183948 A
- the dopant film described in Patent Document 1 does not contain silicon, an object such as prevention of contamination of other contaminant by forming a silica-based coating film concomitantly with diffusion of the dopant, cannot be achieved.
- the diffusion of the dopant using a dopant film described in Patent Document 1 is carried out by a solid diffusion method, an expensive apparatus is required, leading to disadvantages in that it is not suited for large-scale production.
- boron oxide or the like is further included in the coating solution for forming a silica-based coating film described in Patent Document 2, sufficient diffusion of the dopant cannot be effected. Thus, the intended value of resistance cannot be exhibited.
- the present invention was made in view of the foregoing problems, and an object of the invention is to provide a film-forming composition for use in a coating diffusion method, capable of diffusing a dopant at a higher concentration, and further capable of concomitantly forming a silica-based coating film.
- the present inventors found that by using a film composition that contains a polymeric silicon compound, an oxide of a dopant element or a salt including the dopant element, and porogene, the dopant can be diffused into a silicon wafer at a high concentration, and can concomitantly form a silica-based coating film. Accordingly, the present invention has been completed.
- the present invention provides the following.
- a first aspect of the present invention provides a film-forming composition for constituting a diffusion film provided for diffusing a dopant element into a silicon wafer, the film-forming composition including: (A) a polymeric silicon compound; (B) an oxide of the dopant element, or a salt including the dopant element; and (C) porogene.
- the film-forming composition of the present invention is a film-forming composition for constituting a diffusion film provided for diffusing a dopant element into a silicon wafer, the film-forming composition including: (A) a polymeric silicon compound; (B) an oxide of the dopant element, or a salt including the dopant element; and (C) porogene.
- the film-forming composition of the present invention may also contain as a component (E) in place of the component (C), a reducing agent that reduces the component (B).
- the film-forming composition of the present invention can be used in a coating diffusion method, is capable of diffusing a dopant element at a higher concentration into a silicon wafer, and further capable of forming a silica-based coating film, which can serve as a protective film, concomitantly with the diffusion of the dopant. Consequently, more efficient diffusion of the dopant element is enabled while suppressing contamination of a contaminant during diffusing a dopant.
- the film-forming composition according to this embodiment is a film-forming composition containing: (A) a polymeric silicon compound; (B) an oxide of a dopant element, or a salt including the dopant element; (C) porogene; and (D) a solvent capable of dissolving the polymeric silicon compound.
- the polymeric silicon compound included in the film-forming composition according to this embodiment is not particularly limited, and may be for example, one or more selected from the group consisting of a siloxane polymer compound having a Si—O bond in a main chain, a silicon carbide polymer compound having a Si—C bond in a main chain, a polysilane polymer compound having a Si—Si bond in a main chain, and a silazane polymer compound having a Si—N bond in a main chain. Moreover, any mixture of these compounds can be used. Also, a siloxane polymer compound is particularly preferably used among these.
- the siloxane polymer compound as the polymeric silicon compound in the film-forming composition according to this embodiment be a hydrolysis condensation polymerization product prepared using at least one kind of alkoxysilanes represented by the following formula (F) as a starting material.
- R 1 represents a hydrogen atom or a monovalent organic group
- R 2 represents a monovalent organic group
- n is an integer of 1 to 3.
- an alkyl group, an aryl group, an allyl group, and a glycidyl group may be exemplified.
- an alkyl group and an aryl group preferred are an alkyl group and an aryl group.
- the alkyl group having 1 to 5 carbon atoms such as e.g., a methyl group, an ethyl group, a propyl group and a butyl group.
- the alkyl group may be linear or branched, and may include substitution of a hydrogen atom with a fluorine atom.
- the aryl group preferred are those having 6 to 20 carbon atoms, such as e.g., a phenyl group and a naphthyl group.
- monoalkyltrialkoxysilane such as monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltripropoxysilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltripropoxysilane, monopropyltrimethoxysilane and monopropyltriethoxysilane, and monophenyltrialkoxysilane such as monophenyltrioxysilane and monophenyltriethoxysilane;
- dialkyldialkoxysilane such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane and dipropyldiethoxysilane, and diphenyldialkoxysilane such as diphenyldimethoxysilane and diphenyldiethoxysilane; and
- trialkylalkoxysilane such as trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, tripropylmethoxysilane and tripropylethoxysilane, and triphenylalkoxysilane such as triphenylmethoxysilane and triphenylethoxysilane, and the like.
- monomethyltrialkoxysilane such as monomethyltrimethoxysilane, monomethyltriethoxysilane and monomethyltripropoxysilane may preferably be used.
- the mass-average molecular weight of the siloxane polymer compound may be preferably no less than 200 and no greater than 50,000, and more preferably no less than 1,000 and no greater than 3,000. By adjusting the mass-average molecular weight to fall within the range described above, the coating properties and film-forming ability can be improved.
- the siloxane polymer compound is preferably included in an amount of 1 to 60% by mass, and preferably 10 to 30% by mass based on the mass of the entire film-forming composition.
- Condensation of the alkoxysilane represented by the formula (F) is carried out by hydrolyzing alkoxysilane in an organic solvent to which an acid catalyst is added, and allowing the resulting hydrolysate to be condensed and polymerized.
- the alkoxysilane added to the reaction system it may be used alone or in combination of two or more.
- the hydrolysis and condensation polymerization of the alkoxysilane can be carried out by, for example, adding an aqueous solution containing an acid catalyst dropwise to an organic solvent containing one or more of the alkoxysilane represented by the formula (F), and allowing to react.
- the degree of hydrolysis of alkoxysilane can be adjusted by the quantity of water added, in general, the number of moles of water added is 1.0 to 10.0 times the number of moles of alkoxysilane represented by the above formula (F).
- the quantity of water added in moles is no less than 1.0 times the number of moles of alkoxysilane, it is possible to sufficiently increase the degree of hydrolysis, thereby facilitating the coating film formation.
- the quantity of water added in moles is no greater than 10.0 times the number of moles of alkoxysilane, it is possible to prevent gelation by suppressing production of the polymer having branches through condensation polymerization, whereby stability of the film-forming composition can be improved.
- the acid catalyst added in carrying out the hydrolysis reaction and the condensation polymerization reaction of the alkoxysilane represented by the formula (F) is not particularly limited, but any of conventionally used organic acid and inorganic acid can be used.
- the organic acid include carboxylic acids such as acetic acid, propionic acid and butyric acid
- examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the like.
- the acid catalyst may be directly added to an organic solvent in which alkoxysilane was dissolved, or may be added in the form of an acidic aqueous solution after dissolving in water to be used in hydrolysis of alkoxysilane.
- silica-based coating film serves as a protective film, whereby contamination of a contaminant other than the dopant element to which the diffusion is intended can be prevented.
- Examples of the dopant element added to the film-forming composition according to this embodiment include 13 group elements such as boron, gallium etc., 15 group elements such as phosphorus, arsenic, antimony etc., and other elements such as zinc and copper, and the like. Also, the dopant element can be added in the form of the oxide, halide, the inorganic salt such as nitrate, sulfate etc., or the salt of organic acid such as acetic acid to the film-forming composition.
- phosphorus compounds such as P 2 O 5 , NH 4 .H 2 PO 4 , (RO) 3 P, (RO) 2 P(OH), (RO) 3 PO, (RO) 2 P 2 O 3 (OH) 3 , and (RO)P(OH) 2
- boron compounds such as B 2 O 3 , (RO) 3 B, RB(OH) 2 , and R 2 B(OH)
- antimony compounds such as H 3 SbO 4 , (RO) 3 Sb, SbX 3 , SbOX, and Sb 4 O 5 X
- arsenic compounds such as H 3 AsO 3 , H 2 AsO 4 , (RO) 3 As, (RO) 5 As, (RO) 2 As(OH), R 3 AsO, and RAs ⁇ AsR
- zinc compounds such as Zn(OR) 2 , ZnX 2 , and Zn(NO 2 ) 2
- gallium compounds such as (RO) 3 Ga, RGa(OH), RGa(OH) 2
- boron oxide, phosphorus oxide and the like can be preferably used.
- the film-forming composition contains an oxide of a dopant element or a salt including the dopant element
- the dopant can be diffused into a silicon wafer by coating the film composition on a silicon wafer, and subjecting to a thermal diffusion treatment.
- the mass ratio of the siloxane polymer compound (A) to the oxide of a dopant element or a salt including the dopant element (B) falls within the range of 1:0.01 to 1:1.
- the dopant can be diffused at a high concentration, and also, formation of a uniform coating film is facilitated.
- porogene means a material which is decomposed during baking of the coating film formed from the film-forming composition, and forms pores on the silica-based coating film finally formed.
- the porogene for example, polyalkylene glycol or an end-alkylated product thereof; a monosaccharide such as glucose, fructose or galactose, or a derivative thereof; a disaccharide such as sucrose, maltose or lactose, or a derivative thereof; or a polysaccharide, or a derivative thereof can be included.
- polyalkylene glycol is preferred, and polypropylene glycol is more preferred.
- the porogene has a mass-average molecular weight of preferably no less than 300 and no greater than 10,000, and more preferably no less than 500 and no greater than 5,000.
- the mass-average molecular weight being no less than 300 leads to inhibition of decomposition and volatilization when the film-forming composition is coated and dried, and thus porogene can act satisfactorily during the thermal diffusion treatment.
- the mass-average molecular weight being no greater than 10,000 leads to ease in decomposition during the thermal diffusion treatment, whereby porogene can act satisfactorily.
- the content of porogene in the film-forming composition is preferably 2% by mass to 20% by mass, and more preferably 3% by mass to 10% by mass based on the mass of the entire film-forming composition.
- a porous silica-based coating film can be formed from the film-forming composition coated on the silicon wafer.
- a porous silica-based coating film By providing a porous silica-based coating film, migration rate of the dopant element in the silica-based coating film is improved, and thus diffusion of the dopant element into the silicon wafer is believed to be accelerated.
- the silica-based coating film formed as described above can be porous, the following time period for etching can be reduced.
- the effect of preventing the dopant element, which is derived from the outside of the film formed from the film-forming composition, from diffusing into the silicon wafer can be improved.
- the porogene serves as a reducing agent for reducing the dopant element.
- the film-forming composition according to this embodiment constitutes a diffusion film for diffusing a dopant element into a silicon wafer, the film-forming composition including: (A) a polymeric silicon compound; (B) an oxide of the dopant element, or a salt containing the dopant element; and (E) a reducing agent that reduces the component (B).
- porogene that serves as a reducing agent include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and end-alkylated products thereof; monosaccharides such as glucose, fructose and galactose, and derivatives thereof; disaccharides such as sucrose, maltose and lactose, and derivatives thereof; and polysaccharides, and derivatives thereof, and the like.
- polyalkylene glycol is preferred, and polypropylene glycol is more preferred.
- the reducing agent does not leave its oxide in the silica-based coating film after the thermal diffusion treatment.
- the quantity of porogene can be determined appropriately depending on the quantity of the oxide of the dopant element added to the film-forming composition, and the content of the polymeric silicon compound.
- the content of the reducing agent in the film-forming composition is preferably 2% by mass to 20% by mass, and more preferably 3% by mass to 10% by mass based on the mass of the entire film-forming composition.
- the oxide of the dopant element or a salt containing the dopant element is reduced to give the dopant element, whereby diffusion to the silicon wafer can be facilitated.
- a dopant semiconductor having a desired resistance value can be readily obtained.
- the film-forming composition according to this embodiment contains a solvent.
- any organic solvent which has been conventionally used can be employed as the solvent.
- the solvent include monovalent alcohols such as methanol, ethanol, propanol, butanol, 3-methoxy-3-methyl-1-butanol, and 3-methoxy-1-butanol; alkylcarboxylic acid esters such as methyl-3-methoxypropionate, and ethyl-3-ethoxypropionate; polyhydric alcohols such as ethylene glycol, diethylene glycol, and propylene glycol; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate
- the quantity of the solvent is not particularly limited, but it is preferably used to give a solid content of 1 to 100% by mass, and in light of improved coating properties, it is more preferably used to give a solid content of 3 to 20% by mass.
- a surfactant can be included in the film-forming composition according to this embodiment as needed. It is possible to improve coating properties on the silicon wafer, smoothness and spreading properties by adding the surfactant. These may be used alone, or in combination.
- the film-forming composition according to this embodiment is coated on a silicon wafer to form a film, and thereafter subjected to a thermal diffusion treatment, thereby executing formation of a silica-based coating film, and dopant diffusion.
- a thermal diffusion treatment thereby executing formation of a silica-based coating film, and dopant diffusion.
- dopant diffusion is allowed only on a certain region, formation of a protective film, patterning and the like are carried out prior to coating of the film-forming composition.
- the coating of the film-forming composition can be carried out with an appropriate method which is usually carried out by persons skilled in the art.
- Specific examples of the method for coating include a spraying method, a roll coating method, a spin-coating method, and the like.
- the coating quantity of the film-forming composition can be predetermined appropriately depending on the solid content.
- the film-forming composition coated on the silicon wafer be subjected to a heating treatment. Accordingly, a coating film can be formed on the silicon wafer.
- a thermal diffusion treatment is carried out for diffusing into the silicon wafer the dopant element from the coating film formed on the silicon wafer, and further forming a silica-based coating film.
- the thermal diffusion treatment is carried out at, for example, from 600° C. to 1200° C.
- the silica-based coating film formed in the thermal diffusion treatment can serve as a protective film for preventing diffusion of other contaminant into the silicon wafer during the thermal diffusion treatment. Thus, accuracy of the resistance value of the formed dopant semiconductor can be kept at a high level.
- the silica-based coating film after the thermal diffusion treatment is removed by etching.
- etching hydrofluoric acid, a mixture of hydrofluoric acid and nitric acid, an aqueous solution of sodium hydroxide or potassium hydroxide, or the like may be used.
- the protective film formed on the under layer of the silica-based coating film for the pattern formation can be concomitantly removed.
- a film-forming composition was prepared by adding boron oxide to give a concentration of 1.5 g/100 ml, and polypropylene glycol having a mass-average molecular weight of 2,000 to give a concentration of 5%, based on the total quantity.
- the film-forming composition was spin-coated on a silicon wafer “6 inch CZ-N ⁇ 100>” (manufactured by Mitsubishi Materials Corporation). Heating treatment at 80° C., 150° C., and 200° C. each for 60 sec was carried out to form a film.
- the silicon wafer on which the film was formed was subjected to a thermal diffusion treatment by baking under a nitrogen environment in a baking furnace at 1,000° C. for 15 min, 30 min, and 45 min.
- the silicon wafer after the thermal diffusion treatment was immersed in 5% hydrofluoric acid at room temperature for 10 min to remove the film from the silicon wafer by etching.
- a film-forming composition was prepared in a similar manner to Example 1 except that 10% polypropylene glycol having a mass-average molecular weight of 2,000 was added, and then coating film formation, the thermal diffusion treatment and etching were carried out.
- a film-forming composition was prepared in a similar manner to Example 1 except that 3% polypropylene glycol having a mass-average molecular weight of 2,000 was added, and then coating film formation, the thermal diffusion treatment and etching were carried out.
- a film-forming composition was prepared in a similar manner to Example 1 except that 6% polypropylene glycol having a mass-average molecular weight of 2,000 was added, and then coating film formation, the thermal diffusion treatment and etching were carried out. The thermal diffusion treatment was carried out for a time period of 30 min.
- a film-forming composition was prepared in a similar manner to Example 1 except that 7% polypropylene glycol having a mass-average molecular weight of 2,000 was added, and then coating film formation, the thermal diffusion treatment and etching were carried out. The thermal diffusion treatment was carried out for a time period of 30 min.
- a film-forming composition was prepared in a similar manner to Example 1 except that 5% polypropylene glycol having a mass-average molecular weight of 400 was added, and then coating film formation, the thermal diffusion treatment and etching were carried out. The thermal diffusion treatment was carried out for a time period of 15 min.
- a film-forming composition was prepared by adding P 2 O 5 to give a concentration of 1.5 g/100 ml, and polypropylene glycol having a mass-average molecular weight of 4,000 to give a concentration of 6%, based on the total quantity.
- This film-forming composition was used in the coating film formation in a similar manner to Example 1, and subjected to the thermal diffusion treatment at 900° C. The thermal diffusion treatment was carried out for a time period of 30 min.
- a film-forming composition was prepared in a similar manner to Example 1 except that polypropylene glycol having a mass-average molecular weight of 2,000 was not added, and then coating film formation, the thermal diffusion treatment and etching were carried out.
- a film-forming composition was prepared in a similar manner to Example 7 except that polypropylene glycol having a mass-average molecular weight of 4,000 was not added, and then coating film formation, the thermal diffusion treatment and etching were carried out.
- the resistance value was determined. Variation of the resistance value depending on the difference in the content of polypropylene glycol, and the time period of the thermal diffusion treatment is shown in Table 1 below.
- Example 2 From Example 1, Example 2, and Comparative Example 1, it was found that a lower resistance value was exhibited by the silicon wafer of Example 1 as compared with that of Comparative Example 1. More specifically, it was proven that boron oxide was reduced by adding polypropylene glycol, whereby efficient diffusion into the silicon wafer was permitted. In contrast, Example 2 demonstrated a lower degree of reduction in the resistance value as compared with the case of Example 1.
- Example 3 From Example 1, Example 3, and Comparative Example 1, it was found that a lower resistance value was exhibited by the silicon wafer of Example 3 as compared with that of Comparative Example 1, and that further lower resistance value was exhibited in Example 1.
- Example 1 it was revealed from Example 1, and Example 4 to Example 6 that polypropylene glycol having a mass-average molecular weight of 2,000 lead to a lower value of resistance as the content thereof increased.
- polypropylene glycol having a mass-average molecular weight of 2,000 when compared at a content of 5% with respect to polypropylene glycol having a mass-average molecular weight of 2,000 and polypropylene glycol having a mass-average molecular weight of 400, it was revealed that a lower resistance value was exhibited when polypropylene glycol having a mass-average molecular weight of 2,000 was used (i.e., in use, a polypropylene glycol having a higher molecular weight is preferred).
- Example 7 Furthermore, it was proven from Example 7 and Comparative Example 2 that a resistance value equivalent to that when polypropylene glycol was not added was exhibited, in the case in which polypropylene glycol was added even though the dopant was added in an amount of one twentieth.
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US20100162920A1 (en) * | 2008-12-29 | 2010-07-01 | Honeywell International Inc. | Boron-comprising inks for forming boron-doped regions in semiconductor substrates using non-contact printing processes and methods for fabricating such boron-comprising inks |
US20110017291A1 (en) * | 2008-04-09 | 2011-01-27 | Tokyo Ohka Kogyo Co., Ltd. | Diffusing agent composition for ink-jet, and method for production of electrode or solar battery using the composition |
WO2013062788A1 (en) * | 2011-10-24 | 2013-05-02 | Honeywell International Inc. | Dopant ink compositions for forming doped regions in semiconductor substrates, and methods for fabricating dopant ink compositions |
US8629294B2 (en) | 2011-08-25 | 2014-01-14 | Honeywell International Inc. | Borate esters, boron-comprising dopants, and methods of fabricating boron-comprising dopants |
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WO2012005253A1 (ja) * | 2010-07-07 | 2012-01-12 | 日立化成工業株式会社 | 不純物拡散層形成組成物、不純物拡散層の製造方法、及び太陽電池素子の製造方法 |
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JP5666254B2 (ja) | 2010-11-11 | 2015-02-12 | 東京応化工業株式会社 | 拡散剤組成物および不純物拡散層の形成方法 |
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JP5991846B2 (ja) * | 2012-04-24 | 2016-09-14 | 東京応化工業株式会社 | 膜形成用組成物、拡散剤組成物、膜形成用組成物の製造方法、及び拡散剤組成物の製造方法 |
WO2014014542A2 (en) | 2012-04-27 | 2014-01-23 | Burning Bush Group | High performance silicon based coating compositions |
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CN104812543B (zh) | 2012-07-03 | 2017-06-13 | 伯宁布什集团有限公司 | 硅基高性能涂料组合物 |
US9006355B1 (en) | 2013-10-04 | 2015-04-14 | Burning Bush Group, Llc | High performance silicon-based compositions |
KR102426200B1 (ko) * | 2018-01-23 | 2022-07-27 | 동우 화인켐 주식회사 | 절연막 형성용 조성물 및 이로부터 형성된 절연막 |
CN112466746B (zh) * | 2020-04-29 | 2022-04-15 | 山东芯源微电子有限公司 | 一种膜状扩散源成型机 |
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- 2007-07-02 ES ES07768026T patent/ES2401462T3/es active Active
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US20110017291A1 (en) * | 2008-04-09 | 2011-01-27 | Tokyo Ohka Kogyo Co., Ltd. | Diffusing agent composition for ink-jet, and method for production of electrode or solar battery using the composition |
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Also Published As
Publication number | Publication date |
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TW200811928A (en) | 2008-03-01 |
KR100993156B1 (ko) | 2010-11-09 |
EP2043136B1 (en) | 2012-12-19 |
TWI462158B (zh) | 2014-11-21 |
EP2043136A4 (en) | 2010-08-11 |
JP2008021951A (ja) | 2008-01-31 |
CN101479833B (zh) | 2012-06-06 |
EP2043136A1 (en) | 2009-04-01 |
US8563409B2 (en) | 2013-10-22 |
JP5026008B2 (ja) | 2012-09-12 |
KR20090026310A (ko) | 2009-03-12 |
CN101479833A (zh) | 2009-07-08 |
ES2401462T3 (es) | 2013-04-19 |
US20110263110A1 (en) | 2011-10-27 |
WO2008007576A1 (en) | 2008-01-17 |
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