CN103460346A - Coating liquid for diffusing impurity - Google Patents
Coating liquid for diffusing impurity Download PDFInfo
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- CN103460346A CN103460346A CN2012800170092A CN201280017009A CN103460346A CN 103460346 A CN103460346 A CN 103460346A CN 2012800170092 A CN2012800170092 A CN 2012800170092A CN 201280017009 A CN201280017009 A CN 201280017009A CN 103460346 A CN103460346 A CN 103460346A
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- coating fluid
- pva
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- impurity
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/228—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 liquid phase, e.g. alloy diffusion processes
Abstract
A coating liquid for diffusing an impurity, comprising (A) a polyvinyl alcohol-based resin, (B) an impurity and (C) a polyhydric alcohol having a boiling point of 100 C or higher, wherein the content of the polyhydric alcohol (C) in the coating liquid is 70% by weight or more. Therefore, the coating liquid is suitable for screen printing and enables continuous printing for a long time and printing after an idle period, and even if a semiconductor substrate after forming a coating film is fired in an upright state, a semiconductor in which a difference in resistance between an upper portion and a lower portion is small is obtained.
Description
Technical field
The present invention relates to a kind ofly coat the Impurity Diffusion coating fluid on substrate while forming impurity diffusion layer on semiconductor substrate, more specifically, relate to a kind of Impurity Diffusion coating fluid that utilizes silk screen printing to be coated with that is suitable for.
Background technology
As the method for making semiconductor for semiconductor elements such as transistor, diode, solar cells, extensively adopt following method: the liquid material that coating contains the impurity such as phosphorus, boron on the semiconductor substrates such as germanium, silicon, after forming epithelium, burn till, thereby form impurity diffusion layer in substrate.
As this liquid material is coated to the method on substrate, what extensively adopt is method of spin coating, but in recent years, has advanced the maximization of substrate in order to cut down manufacturing cost, when diameter becomes more than 4 inches, be difficult to form the epithelium of uniform film thickness according to this method of spin coating.
Therefore, as also adapting to the coating process of large-scale wafer, study silk screen print method, proposed a kind of impure diffusion coating fluid that is suitable for this print process.
For example, as utilizing silk screen printing to form the diffusion coating fluid of uniform epithelium on semiconductor substrate, proposed to contain phosphorus compound, boron compound, water soluble polymer, water as impurity, and the diffusion coating fluid of viscosity in particular range.(for example, with reference to patent documentation 1,2.）
Coating fluid to patent documentation 1 or 2 carries out silk screen printing, burn till and the semiconductor that obtains, because the content uniformity high, epithelium of impurity is high, thereby be the semiconductor that the resistance value deviation is little, very excellent, but, moisture evaporation in coating fluid, the situation of thickening, occur in the difference of the environment during according to use sometimes.
Therefore, proposed to use high boiling organic solvent that volatility is lower than water as solvent, the diffusion coating fluid that contains the organic binder bond such as the organic phosphorus compound that dissolves in organic solvent, the polyvinyl acetate that dissolves in organic solvent and thixotropic agent.(for example, with reference to patent documentation 3.）
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-53353 communique
Patent documentation 2: TOHKEMY 2007-35719 communique
Patent documentation 3:WO2009/116569 communique
Summary of the invention
the problem that invention will solve
For be formed with the semiconductor substrate of epithelium with coating fluid by Impurity Diffusion on surface, after drying, by burning till, thereby Impurity Diffusion is to forming diffusion layer in substrate, usually, this burn till be make many substrates in stove with uprightly, state side by side carries out.
Yet, the epithelium obtained for the coating fluid that utilizes patent documentation 3, exist is perhaps that in the concentration difference that impurity occurs up and down, the semi-conductive resistance value obtained is in the tendency that difference occurs up and down because the starting stage burning till flows and moves to the bottom of substrate.
That is, the object of the present invention is to provide a kind of Impurity Diffusion coating fluid, it is the coating fluid that is suitable for silk screen printing, even if the semiconductor substrate after epithelium is formed burns till with erectility, also can access the little semiconductor of upper and lower difference of resistance value.
for the scheme of dealing with problems
In view of the foregoing, the inventor conducts in-depth research, and found that, by following Impurity Diffusion, with coating fluid, can solve problem of the present invention, thereby completed the present invention, described Impurity Diffusion contains polyvinyl alcohol resin with coating fluid, and (being designated hereinafter simply as PVA is resin.) (A), impurity (B) and boiling point be the polyalcohol (C) more than 100 ℃, and the content of this polyalcohol (C) is more than 70 % by weight in coating fluid.
That is, maximum of the present invention is characterised in that: at Impurity Diffusion, with in coating fluid, as the main component of solvent, using boiling point is the polyalcohol more than 100 ℃, and to contain PVA be resin.
It should be noted that, by PVA, be that resin is known with coating fluid at patent documentation 1,2 etc. for Impurity Diffusion, but be usining in the coating fluid of water as primary solvent, to be used as the PVA of water-soluble resin be resin, even dissolved for being insoluble to common organic solvent that also unsettled to have the PVA of the possibility of separating out be resin for take the coating fluid that organic solvent is main body according to environmental change, normally be difficult to expect.
the effect of invention
Impurity Diffusion of the present invention has the advantages such as following advantage with coating fluid, industrial extremely useful: by carry out silk screen printing on semiconductor substrate, can obtain uniform epithelium; Due to the viscosity stability excellence, thereby the printing of idle periods that can realize long continuous printing, interval; Even if the semiconductor substrate after epithelium is formed burns till with erectility, also can access impurity concentration upper allowance below nominal size, be the little semiconductor of upper lower deviation of resistance value.
Embodiment
Below the explanation to structure condition of record is an example (typical example) of embodiments of the present invention, and the present invention is not limited to these contents.
Below, the present invention will be described in detail.
It is that resin (A), impurity (B) and boiling point are the polyalcohol (C) more than 100 ℃ that Impurity Diffusion of the present invention contains PVA with coating fluid, and the content of the polyalcohol in coating fluid (C) is more than 70 % by weight.
Below, describe successively.
[PVA is resin (A)]
At first, PVA the present invention used is that resin (A) describes.
PVA is that resin (A) is that the polyvinyl ester that monomer copolymerization obtains is the material that the resin saponification obtains for making vinyl acetate, and vinyl alcohol construction unit and the vinyl acetate construction unit suitable by saponification degree form.
As above-mentioned vinyl acetate, it is monomer, can enumerate: vinyl formate, vinyl acetate, propionate, valeric acid vinyl acetate, vinyl butyrate, isobutyric acid vinyl acetate, pivalic acid vinyl acetate, capric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, tertiary ethylene carbonate etc., consider preferably to use vinyl acetate from the economy aspect.
The PVA that the present invention uses is that the average degree of polymerization (measuring according to JIS K6726) of resin (A) is generally 100～4000, the PVA that particularly preferably uses average degree of polymerization 200～2000 is resin, and further preferably using the PVA of average degree of polymerization 300～1500 is resin.
When this average degree of polymerization is too small, coating fluid is low viscosity, sometimes is difficult to realize good silk screen printing, or films and become film, the quantity delivered deficiency of impurity.On the contrary, excessive silk screen printing, the easy bad tendency of printing that occurs of existence of also being not suitable for.
In addition, the PVA used as the present invention is resin (A), and usually can use the PVA that saponification degree (measuring according to JIS K6726) is 50 % by mole～100 % by mole is resin.
Wherein, because the main component of the solvent of coating fluid of the present invention is that boiling point is the polyalcohol more than 100 ℃, therefore, inhomogeneity viewpoint from coating fluid, preferably to the material of the dissolubility excellence of this solvent, as such PVA, be resin (A), preferably use PVA that saponification degree is low be resin, with the modified PVA of the compatibility excellence of polyalcohol.
For example, while using unmodified PVA to be resin (A) as PVA of the present invention, preferably saponification degree is 50 % by mole～90 % by mole, more preferably 60 % by mole～85 % by mole, is particularly preferably 70 % by mole～80 % by mole.In situation for unmodified PVA, when its saponification degree is too high, sometimes to usining polyalcohol, as the dissolubility of the solvent of main body, reduce, have to reduce content.In addition, when saponification degree is too low, make the semiconductor substrate that is formed with the coating epithelium by coating fluid while uprightly burning till, the semi-conductive resistance value sometimes obtained difference occurs up and down substrate.
In addition, as modified PVA, be resin, can use: make various monomer copolymerizations, the material that its saponification is obtained when the manufacture polyvinyl ester is resin; Import the material that various functional groups obtain in unmodified PVA by post-modification.
As for vinyl acetate be the monomer of monomer copolymerization, can enumerate: the olefines such as ethene, propylene, isobutene, α-octene, α-laurylene, α-octadecylene; 3-butene-1-ol, 4-amylene-1-ol, 5-hexen-1-ol, 3, the derivative such as the hydroxyl alpha-olefines such as 4-dihydroxy-1-butylene and acyl group compound thereof; Unsaturated acids, its salt, monoesters or the dialkyls such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid; The nitrile such as acrylonitrile, methacrylonitrile; The amide-types such as DAAM, acrylamide, Methacrylamide; Alkene sulfonic acid class or its salt such as vinyl sulfonic acid, allyl sulphonic acid, methallylsulfonic acid; The alkyl vinyl ethers; Dimethyl-allyl vinyl ketone, NVP, vinyl chloride, ethylene thiazolinyl ethyl, 2,2-dialkyl group-4-vinyl-DOX, allylin, 3,4-diacetoxy-vinyl compounds such as 1-butylene; Methylvinyl acetate, acetic acid-substituted acetic acid vinyl esters such as 1-methoxy-ethylene ester; Vinylidene chloride; Isosorbide-5-Nitrae-diacetoxy-2-butylene; Vinylene carbonate etc.
In addition; be resin as the PVA that imports functional group by rear reaction, can enumerate: by the PVA that there is acetoacetyl with reacting of ketene dimer, be resin, by the PVA that there is polyoxy alkylidene (poly alkylene oxide group) with reacting of oxirane, be resin, be that react the PVA obtained with PVA be resin etc. for aldehyde compound that resin or make has various functional groups by the PVA with hydroxyalkyl that reacts with epoxy compounds etc.
Be modification kind in resin, be the content of the Component units that derives from various monomers in copolymer or the functional group that imports by rear reaction for this modified PVA, because the different qualities according to the modification kind can be very different, therefore cannot treat different things as the same, be generally 1 % by mole～20 % by mole, particularly preferably use the scope of 2 % by mole～10 % by mole.
At these various modified PVAs, be in resin, preferably using the PVA that has a construction unit of 1,2-diol structure at side chain that has that following general formula (1) means in the present invention is resin.
It should be noted that the R in general formula (1)
1, R
2, and R
3mean independently of one another hydrogen atom or organic group, X means singly-bound or bonding chain, R
4, R
5, and R
6mean independently of one another hydrogen atom or organic group.
[Chemical formula 1]
Wherein, most preferably there is 1 of general formula (1) expression, the R in 2-diol structure unit
1～R
3and R
4～R
6the PVA that is all the construction unit that (1') means of following general formula that hydrogen atom, X are singly-bound is resin.
[Chemical formula 2]
In addition, the R in the construction unit meaned for this general formula (1)
1～R
3and R
4～R
6so long as damage not significantly the amount of the degree of resin properties, it can be also organic group, as described organic group, such as enumerating: the alkyl of the carbon numbers such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group 1～4 etc., this organic group also can have the functional groups such as halogen group, hydroxyl, ester group, carboxylic acid group, sulfonic group as required.
In addition, the aspect of the stability from the aspect of thermal stability, high temperature, under acid condition, 1 of general formula (1) expression, X in 2-diol structure unit most preferably is singly-bound, in the scope of not damaging effect of the present invention, can be also the bonding chain, as this bonding chain, except the hydrocarbon such as alkylidene, alkenylene, alkynylene, phenylene, naphthylene (these hydrocarbon also can replace by halogens such as fluorine, chlorine, bromine etc.), can also enumerate :-O-,-(CH
2o)
m-,-(OCH
2)
m-,-(CH
2o)
mcH
2-,-CO-,-COCO-,-CO(CH
2)
mcO-,-CO(C
6h
4) CO-,-S-,-CS-,-SO-,-SO
2-,-NR-,-CONR-,-NRCO-,-CSNR-,-NRCS-,-NRNR-,-HPO
4-,-Si(OR)
2-,-OSi(OR)
2-,-OSi(OR)
2o-,-Ti(OR)
2-,-OTi(OR)
2-,-OTi(OR)
2o-,-Al(OR)-,-OAl(OR)-,-OAl(OR) O-etc. (R is substituting group arbitrarily independently of one another, is preferably hydrogen atom, alkyl, and in addition, m is 1～5 integer).Wherein, during from manufacture or the aspect of the stability in while use, preferred the carbon number alkylidene below 6, particularly methylene, or-CH
2oCH
2-.
It as this PVA, is the manufacture method of resin, have no particular limits, preferably use: the method for the copolymer saponification of the compound that to be (i) monomer by vinyl acetate mean with following general formula (2), (ii) by vinyl acetate, be monomer with the method for the copolymer saponification of the compound of following general formula (3) expression and decarboxylation, by vinyl acetate, be (iii) the copolymer saponification of compound of monomer and following general formula (4) expression and the method for de-ketal.
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
R in above-mentioned general formula (2), (3), (4)
1, R
2, R
3, X, R
4, R
5, R
6identical during all with the situation of general formula (1).In addition, R
7and R
8be hydrogen atom or R independently of one another
9in-CO-(formula, R
9for alkyl).R
10and R
11be hydrogen atom or alkyl independently of one another.
For (i), (ii) and method (iii), for example can use the method illustrated in TOHKEMY 2006-95825.
Wherein, from the aspect of copolyreaction and industrial operation excellence, in method (i), the compound meaned as general formula (2), preferably used 3,4-, bis-acyloxy-1-butylene, particularly preferably uses 3,4-diacetoxy-1-butylene.
In the present invention, when the PVA that use has a construction unit that this general formula (1) means is resin, the PVA that can use saponification degree to be 50 % by mole～100 % by mole is resin, further preferably using the PVA that saponification degree is 60 % by mole～90 % by mole is resin, and the PVA that particularly preferably uses saponification degree to be 70 % by mole～80 % by mole is resin.
This is because, due to 1 of side chain, the 2-diol structure, even if saponification degree is higher than unmodified PVA, also improve the dissolubility of polyalcohol.
In addition, this PVA be in resin, comprise 1, the content of 2-diol structure unit is generally 1 % by mole～30 % by mole, and then, be preferably 3 % by mole～20 % by mole, be particularly preferably 5 % by mole～10 % by mole.When this content is too low, sometimes in the situation that the PVA of high saponification degree is resin, insufficient to the dissolubility of polyalcohol; On the contrary, during this too high levels, there is the tendency that drying property reduces, productivity ratio reduces.
It should be noted that, PVA is 1 in resin (A), and the containing ratio of 2-diol structure unit can be resin by fully saponified PVA
1h-NMR spectrogram (solvent: DMSO-d6, internal standard compound: tetramethylsilane) obtain, particularly, origin come from hydroxyl proton, methine protons and methene proton in 1,2-diol units, main chain methene proton, calculate and get final product with the peak area of the proton of the hydroxyl of main chain bonding etc.
In addition, the PVA used in the present invention is that resin (A) can be a kind of, it can be also two or more mixtures, now, can use: above-mentioned unmodified PVA combination each other, unmodified PVA and the PVA of the construction unit with general formula (1) expression are the combination of resin, the PVA that saponification degree, the degree of polymerization, modification degree etc. are different has a construction unit that general formula (1) means is resin combination each other, and unmodified PVA or the PVA with construction unit that general formula (1) means are that resin and other modified PVAs are the combinations such as combination of resin.
The content that Impurity Diffusion of the present invention is resin (A) with the PVA in coating fluid is generally 1 % by weight～40 % by weight, particularly preferably uses 3 % by weight～30 % by weight, especially preferably uses the scope of 5 % by weight～25 % by weight.
This PVA is the content of resin (A) when too small, has the viscosity of coating fluid, is difficult to stably form the tendency of filming; On the contrary, in the time of too much, because the viscosity of coating fluid uprises, there is coating workability step-down, easily cause the tendency that in silk screen printing, mesh stops up.
[impurity (B)]
Then, the impurity (B) used in the present invention is described.
As this impurity (B), for example can use 13 group element compounds, 15 group element compounds.In addition, these compounds may be used alone, can also be used in combination.
Above-mentioned 15 group element compounds, for usually to be used as the material of impurity in the manufacture of N type semiconductor, can be enumerated: phosphorus compound, antimonial, wherein preferably used phosphorus compound.
As this phosphorus compound, so long as in the manufacture of N type semiconductor, the material as impurity can be used usually, particularly, can enumerate: the phosphoric acid classes such as phosphoric acid, phosphorus pentoxide; The phosphoric acid salt such as melamine phosphate, ammonium phosphate; The chloride such as phosphorus chloride, phosphorus oxychloride; Phosphoric acid ester etc.
Wherein, as the material of the dissolubility excellence of the polyalcohol of boiling point more than 100 ℃ to as the main component of solvent, can enumerate: phosphoric acid, phosphorus pentoxide, phosphoric acid ester, particularly preferably used phosphoric acid ester.
The phosphoric acid ester used in the present invention refers to all or part of material replaced by organic group of 3 hydrogen that phosphoric acid has; can use known various compound; from suppressing the aspect of automatic doping (autodoping), phosphono oxygen base (methyl) acrylate (acid phosphoxy (meth) acrylate) class of wherein especially preferably using following general formula (5) to mean.
[chemical formula 6]
R in above-mentioned general formula (5)
12for hydrogen or methyl, R
13for hydrogen, methyl or-CH
2the Cl base, R
14for the alkyl of hydrogen, carbon number 1～10, phenyl or-NH
3c
2h
4the OH base, the positive integer that n is 1～10, m, l are 1 or 2, m+l=3.
The commercially available product of phosphono oxygen base (methyl) esters of acrylic acid meaned as this general formula (5), can enumerate: UNI-CHEMICAL CO., the PHOSMER series of LTD. system; NIPPON KAYAKU CO., the KAYAMER series of LTD. system; The LIGHT ESTER series of grease company of common prosperity society system; DAIHACHI CHEMICAL INDUSTRY CO., the MR of LTD. system is serial, AR is serial, PS is serial; SHIN-NAKAMURA CHEMICAL CO., the NK ESTER series of LTD system etc.
The concrete example as it, can enumerate: R
12for methyl, R
13for hydrogen, R
14for hydrogen, n are 1, m is 1, l is 2 compound (for example UNI-CHEMICAL CO., LTD. system " PHOSMER-MH "); R
12for methyl, R
13for hydrogen, R
14for-NH
3c
2h
4the compound (for example, UNI-CHEMICAL CO., LTD. system " PHOSMER-MH ") that OH, n are 1, m is 1, l is 2; R
12for methyl, R
13for hydrogen, R
14for hydrogen, n are 4～5, m is 1, l is 2 compound (for example, UNI-CHEMICAL CO., LTD. system " PHOSMER-PE ") etc.
Wherein, from the present invention the PVA that uses be the viewpoint of the compatibility of resin, preferably use R in general formula (5)
12for the phosphono oxygen ylmethyl esters of acrylic acid of methyl, R
13for hydrogen and n are the material below 5, in particular for 1, R
14for the material of hydrogen, and the material that m is 1, l is 2.
Impurity Diffusion of the present invention is generally 0.1 % by weight～30 % by weight with the content of 15 group element compounds in coating fluid, particularly preferably uses 0.1 % by weight～10 % by weight, especially preferably uses the scope of 0.1 % by weight～5 % by weight.
In addition, with respect to PVA, be resin (A) 100 weight portions, the content of 15 group element compounds is generally 1 weight portion～300 weight portions, particularly preferably uses 2 weight portions～200 weight portions, especially preferably uses the scope of 3 weight portions～50 weight portions.
When the content of this 15 group element compound is few, the content of 15 family's elements (phosphorus etc.) in diffusion layer is few, sometimes can't obtain sufficient resistance value.In addition, when the content of 15 group element compounds is too much, PVA is that the dissolubility of resin (A) is insufficient sometimes.
It should be noted that, this 15 group element compound can be used single compound, also can be used in combination two or more compounds.
In addition, above-mentioned 13 group element compounds, for usually to be used as the material of impurity in the manufacture of P type semiconductor, can be enumerated: boron compound, aluminium compound, but wherein preferably use boron compound.
As the concrete example of this boron compound, can enumerate: the boric acid classes such as boric acid, diboron trioxide; The borate families such as ammonium borate; The halide such as boron trifluoride, boron chloride, Boron tribromide, triiodide boron; The borate esters such as trimethylborate, triethyl borate, triisopropyl borate ester; Boron nitride etc.
Wherein, from the aspect of easiness of operation, preferably use boric acid, borate family, borate ester, boron nitride.
The borate ester used in the present invention refers to all or part of material replaced by organic group of 3 hydrogen that boric acid has, can use known various compound, from the aspect of Impurity Diffusion, wherein especially preferably use trimethylborate, triethyl borate.
Impurity Diffusion of the present invention is generally 0.1 % by weight～30 % by weight with the content of 13 group element compounds in coating fluid, particularly preferably uses 0.1 % by weight～10 % by weight, especially preferably uses the scope of 0.1 % by weight～5 % by weight.
In addition, with respect to PVA, be resin (A) 100 weight portions, the content of 13 group element compounds is generally 1 weight portion～300 weight portions, particularly preferably uses 3 weight portions～200 weight portions, especially preferably uses the scope of 5 weight portions～50 weight portions.
When the content of this 13 group element compound is few, the content of 13 family's elements (boron etc.) in diffusion layer can lack, and sometimes can't obtain sufficient resistance value.In addition, when the content of 13 group element compounds is too much, PVA is that the dissolubility of resin (A) is insufficient sometimes.
[polyalcohol (C)]
Impurity Diffusion of the present invention is characterised in that with coating fluid, and using boiling point as the main component of solvent is the polyalcohol (C) more than 100 ℃.
By this polyalcohols (C) is used as to main component, can obtain the viscosity stability of the excellence of coating fluid.
This polyalcohol (C) is that boiling point is the polyalcohol more than 100 ℃, further preferably uses the polyalcohol that boiling point is 150 ℃～400 ℃, particularly 175 ℃～300 ℃.
In addition, as this polyalcohol, aliphatic alcohol, aromatic alcohols all can be used, but are the deliquescent aspect of resin (A) from PVA, preferred aliphat alcohol.
As this polyalcohol (C), particularly can enumerate: the di-alcohols such as ethylene glycol (197 ℃), diethylene glycol (244 ℃), triethylene glycol (287 ℃), TEG (314 ℃), propylene glycol (188 ℃); The polyalcohols that the ternarys such as glycerine (290 ℃), trimethylolpropane (292 ℃), D-sorbite (296 ℃), mannitol (290～295 ℃), pentaerythrite (276 ℃), polyglycereol are above etc.It should be noted that, the value in () is boiling point.
These alcohol can be used separately, for adjusting viscosity, regulate dissolubility that PVA is the dissolubility of resin, phosphorus compound, various additives, dispersiveness, to the wetability of base material etc., preferred embodiment for two or more alcohol is used in combination.Wherein, preferably make the combination of spent glycol and glycerine, ethylene glycol now is different according to the characteristic of expectation from the compounding beguine of glycerine, but usually, the value of ethylene glycol/glycerol is 20/80～100/0, and then can from 30/70～90/10, particularly 50/50～80/20 scope, select.
In addition, the solvent beyond use polyalcohol capable of being combined, as this solvent, can enumerate: the lower alcohol series solvents such as water, 3-hydroxy-2,2,4-trimethylpentyl isobutylate (TPM), methyl alcohol, ethanol, isopropyl alcohol; The carbitol series solvents such as methyl carbitol, ethyl carbitol, butyl carbitol; The cellosolve series solvents such as ethyl cellosolve, isopentyl cellosolve, hexyl cellosolve; And aliphatic hydrocarbon series solvent, higher fatty acids series solvent, aromatic hydrocarbon series solvent etc.
The compounding amount of the solvent beyond this polyalcohol, be generally below 20 % by weight with respect to the total amount of solvent, below 10 % by weight.
The content of polyalcohol in coating fluid for Impurity Diffusion of the present invention (C) is more than 70 % by weight, further preferably uses the scope of 70 % by weight～90 % by weight, particularly 75 % by weight～90 % by weight.
When the content of this polyalcohol (C) is very few, exist the viscosity of coating fluid to become too high, the coating workability reduces, easily causes the tendency that in silk screen printing, mesh stops up.On the contrary, in the time of too much, exist the viscosity of coating fluid become too low and be difficult to stably form film, dryly need tendency for a long time, and then the content of the impurity in diffusion layer becomes very few sometimes.
[surfactant (D)]
Impurity Diffusion of the present invention is with in coating fluid, for improving wetability to semiconductor surface, suppress coating fluid foaming, prevent from resulting from the purposes such as the printing of bubble is bad, preferably compounding surfactant (D).
As the surfactant used in coating fluid of the present invention, can enumerate known nonionic surface active agent, cationic surface active agent, anionic surfactant, any all can use, but from bringing few aspect such as semi-conductive metal ingredient into, preferred nonionic surface active agent.
As this nonionic surface active agent, can use known material, particularly can enumerate: the hydrocarbon system surfactants such as the block copolymer of epoxy ethane-epoxy propane, acetylenic glycols derivative; Silicon-type surfactant, fluorine are surfactant; The mixture of organic modified polyorganosiloxane and particular polymer etc.
Wherein, in coating fluid of the present invention, from suppressing the aspect of foaming and defoaming excellence, preferably use the hydrocarbon system surfactant, particularly the acetylenic glycols derivative.
As this acetylenic glycols derivative, the material that preferably uses following formula (6) to mean.
[chemical formula 7]
R in above-mentioned general formula (6)
15, R
18the alkyl that means independently of one another carbon number 1～20, be particularly preferably the alkyl of carbon number 1～5, especially preferably uses the alkyl of carbon number 3～5.In addition, R
16, R
17the alkyl that means independently of one another carbon number 1～3, particularly preferably used methyl.It should be noted that R
15and R
18, and R
16and R
17can be the same or different separately, the group of same structure but preferred use is respectively done for oneself.
In addition, s, the t integer of carbon number 0～30 of respectively doing for oneself, and then preferably use the material that s+t is 1～10, and particularly preferably use the material that s+t is 1～5, especially preferably use the material that s+t is 1～3.
As this acetylenic glycols derivative, particularly, can enumerate: 2, 5, 8, 11-tetramethyl-6-dodecyne-5, the ethylene oxide adduct of 8-glycol, 5, 8-dimethyl-6-dodecyne-5, the ethylene oxide adduct of 8-glycol, 2, 4, 7, 9-tetramethyl-5-decine-4, the ethylene oxide adduct of 7-glycol, 4, 7-dimethyl-5-decine-4, the ethylene oxide adduct of 7-glycol, 2, 3, 6, 7-tetramethyl-4-octyne-3, the ethylene oxide adduct of 6-glycol, 3, 6-dimethyl-4-octyne-3, the ethylene oxide adduct of 6-glycol, 2, 5-dimethyl-3-hexin-2, the ethylene oxide adduct of 5-glycol etc.
Wherein, preferably using is 2,4,7,9-tetramethyl-5-decine-4, the acetylenic glycols derivative that the addition amount (m+n) of the ethylene oxide adduct of 7-glycol and oxirane is 1～2.
As the commercially available product of the surfactant of this acetylenic glycols derivative, can enumerate: the SURFINOL series of day letter chemical industrial company system etc.
Compounding amount for Impurity Diffusion of the present invention with the surfactant (D) of compounding in coating fluid is 0.1 % by weight～10 % by weight usually in coating fluid, particularly preferably uses 0.3 % by weight～8 % by weight, especially preferably uses the scope of 0.5 % by weight～5 % by weight.When the compounding amount of this surfactant (D) is very few, sometimes suppress bubble/defoaming effect insufficient; On the contrary, in the time of too much, sometimes from fluid separation applications, can't obtain homogeneous solution.
[inorganic particles (E)]
At Impurity Diffusion of the present invention, use in coating fluid, for the purpose of improving the silk screen printing characteristic, can the various inorganic particles of compounding (E).
As this inorganic particles (E), be suitably for cataloid, amorphous silica, aerosil etc. silica-based, wherein preferably use cataloid.
For the compounding amount of this inorganic particles (E), in coating fluid, be 0.5 % by weight～20 % by weight usually, particularly preferably use the scope of 1 % by weight～10 % by weight.
[Impurity Diffusion coating fluid]
It is that resin (A), impurity (B) and boiling point are the polyalcohol (C) more than 100 ℃ that Impurity Diffusion of the present invention contains above-mentioned PVA with coating fluid, the content of this polyalcohol (C) is 70 % by weight in coating fluid, as required, also contain surfactant (D) and inorganic particles (E) and other additive.
With coating fluid, the viscosity under 20 ℃ is generally 300mPas～100 to this Impurity Diffusion, and 000mPas, particularly preferably used 500mPas～10, and 000mPas is especially preferably used 700mPas～6, the scope of 000mPas.In addition, this viscosity is to use Brookfield viscometer to measure.
When the concentration of this coating fluid and viscosity are too small, sometimes be difficult to stably form and film, or the content of the impurity in diffusion layer is insufficient; On the contrary, when concentration and viscosity are excessive, exist the coating workability to reduce, easily cause the tendency that in silk screen printing, mesh stops up.
Impurity Diffusion of the present invention is not particularly limited by the preparation method of coating fluid, for example can enumerates: be that resin (A) is dissolved into the method in polyalcohol (C) successively or simultaneously with impurity (B) by above-mentioned PVA; Preparing respectively PVA is polyalcohol (C) solution of resin (A) and impurity (B), and the method that they are mixed etc., when this dissolving, preparation, are preferably carried out in heating, stirring.
In addition, for surfactant (D), inorganic particles (E), other additive, can adopt following any method: compounding after the preparation of above-mentioned coating fluid, or compounding in the process of above-mentioned preparation.
The excellent storage stability of coating fluid for thus obtained Impurity Diffusion of the present invention, thereby can prepare in a large number rear keeping or packing is transferred, in addition, also can be used to midway and the preservation of part that will be residual.
[semiconductor]
Then, the semiconductor that uses Impurity Diffusion of the present invention to obtain with coating fluid is described.
This semiconductor is coating Impurity Diffusion of the present invention coating fluid on the semiconductor substrates such as silicon, germanium, and through super-dry, each operation of burning till, spreading, in semiconductor substrate, the diffusion layer of formation impurity is manufactured.
Use the method for coating fluid as coating Impurity Diffusion on semiconductor substrate, can use known method, particularly, can enumerate: silk screen print method, woodburytype, toppan printing, offset printing method, method of spin coating, comma rubbing method, die head rubbing method, die lip rubbing method etc.Wherein, by coating fluid of the present invention can be obtained to maximum effect for silk screen print method, even if also can obtain uniform coated film to the large-scale wafer more than 4 inches.
The coating weight of the coating fluid on semiconductor substrate is different from the impurity content of expectation according to the content of the impurity compound in the kind of substrate, semi-conductive purposes, coating fluid, at common 1g/m
2～100g/m
2, 1g/m particularly
2～50g/m
2scope in implement.
In ensuing drying process, wait volatile ingredient except anhydrating from coated film, as its condition, carry out suitably setting and get final product, usually under the temperature conditions of 20 ℃～300 ℃, particularly 100 ℃～200 ℃, use the drying time of 1 minute～60 minutes, particularly 5 minutes～30 minutes.Drying means is not particularly limited, can uses the known methods such as heated-air drying, infrared dehydration, vacuumize.
It should be noted that, also can implement continuously painting process and drying process as required.
In ensuing firing process (degreasing process), use electric furnace etc. is removed the most of organic principle in coated film.Condition for this operation, need to suitably regulate according to the composition of coating fluid, the thickness of coated film, but usually, under the temperature conditions of 300 ℃～1000 ℃, particularly 400 ℃～800 ℃, within the time of 1 minute～120 minutes, particularly 5 minutes～60 minutes, implement.
And then in diffusing procedure, Impurity Diffusion, in semiconductor substrate, forms diffusion layer, with firing process, similarly uses electric furnace etc., under the temperature conditions of 800 ℃～1400 ℃, with monolithic or overlapping several pieces state, carry out.
It should be noted that, while implementing firing process with diffusing procedure in an operation or spread in firing process and while obtaining the resistance value of expecting, also can omit diffusing procedure.
For this semi-conductive sheet resistance, content that can be by impurity, diffusion temperature, diffusion time etc. are controlled, and usually, can obtain in the scope of 0.03 Ω/～10000 Ω/, be suitable for the semiconductor of the sheet resistance of target purposes.
Embodiment
Below, the present invention will be described to enumerate embodiment, but for the present invention, only otherwise exceeding its purport just is not subject to the restriction of the record of embodiment.
It should be noted that, as long as no special explanation, " part ", " % " in example refer to weight basis.
Production Example 1
[PVA is the manufacture of resin (A1)]
Drop into 1500 parts of vinyl acetates, 648 parts of methyl alcohol, 0.33 % by mole of azodiisobutyronitrile (with respect to the vinyl acetate added) in the reaction vessel that possesses reflux condenser, dropping funel, mixer, flow down intensification at nitrogen while stirring, at 60 ℃, start polymerization.Aggregate rate at vinyl acetate reaches for 90% the moment, adds meta-dinitro-benzent and finishes polymerization, then, by the method that is blown into methanol vapor, unreacted vinyl acetate monomer is removed to system, makes the methanol solution of copolymer.
Then, further dilute above-mentioned methanol solution with methyl alcohol, after being adjusted to concentration 30%, be added in kneader, on one side solution temperature is remained on to 35 ℃, on one side thus 2% methanol solution that adds NaOH makes Na with respect to 1 mole of the vinyl acetate construction unit in copolymer measure the ratio that reaches 3.4 mMs carries out saponification.When carrying out saponification, saponified separating out, carry out isolated by filtration becoming the granular moment, with methyl alcohol, fully cleans, and dry in air drier, the PVA that makes target is resin (A1).
For gained PVA, be the saponification degree of resin (A1), the quantity of alkali consumption required by the hydrolysis to residual vinyl acetate analyzed, and result is 78.0 % by mole.In addition, for average degree of polymerization, according to JIS K6726, analyzed, result is 1400.(table 1)
Production Example 2
[PVA is the manufacture of resin (A2)]
Add 700 parts of 1000 parts of vinyl acetates, methyl alcohol, 3 in the reaction vessel that possesses reflux condenser, dropping funel, mixer, 4-diacetoxy-88 parts of 1-butylene, drop into 1.5 % by mole of azodiisobutyronitriles (with respect to the vinyl acetate added), flow down intensification (approximately 60 ℃) at nitrogen while stirring, start polymerization.When polymerization starts, according to the HANNA method, drip the mixed liquor of 3,4-diacetoxy-31 parts of 1-butylene and 122.3 parts of methyl alcohol, appended respectively 0.5 % by mole of azodiisobutyronitrile (with respect to the vinyl acetate added) at the 2nd hour with the moment of the 4th hour midway.Reach for 93.9% the moment at the 9th hour from polymerization starts, aggregate rate vinyl acetate, add meta-dinitro-benzent and finish polymerization, then, by the method that is blown into methanol vapor, unreacted vinyl acetate monomer is removed to system, made the methanol solution of copolymer.
Then, further dilute above-mentioned methanol solution with methyl alcohol, after being adjusted to concentration 30%, be added in kneader, solution temperature is remained on to 35 ℃ on one side, 2% methanol solution that adds on one side NaOH makes with respect to the vinyl acetate construction unit and 3 in copolymer, thereby the Na amount of 1 mole of the summation of 4-diacetoxy-1-butylene construction unit reaches the ratio of 3.4 mMs, carries out saponification.When carrying out saponification, saponified separating out, carry out isolated by filtration becoming the granular moment, with methyl alcohol, fully cleans, and dry in air drier, the PVA that makes target is resin (A2).
For gained PVA, be the saponification degree of resin (A2), the quantity of alkali consumption required by the hydrolysis to residual vinyl acetate and 3,4-diacetoxy-1-butylene analyzed, and result is 79.7 % by mole.In addition, for average degree of polymerization, according to JIS K6726, analyzed, result is 450.In addition, for general formula (1), mean 1, the content of 2-diol structure unit, by by
1h-NMR(300mHz proton N MR, d6-DMSO solution, internal standard compound: tetramethylsilane, 50 ℃) integrated value measured calculates, and result is 6 % by mole.(table 1)
Embodiment 1
The making of coating fluid for the diffusion of<phosphorus >
Adding saponification degree in 85 parts of ethylene glycol (C) is that the unmodified PVA that 78.0 % by mole, average degree of polymerization are 1400 is 10 parts of resins (A1), and limit adds the thermal agitation limit and dissolves.Compounding therein is as 3 parts of the phosphorus pentoxides (B2) of impurity (B), compounding as surfactant (D), R in general formula (6)
15, R
18for 2-methyl-propyl, R
16, R
17for 2,4,7 of methyl, s+t ≈ 1.3,9-tetramethyl-5-decine-4, (D1) 2 parts of the ethylene oxide adducts of 7-glycol (NISSIN CHEMICAL INDUSTRY CO., " SURFINOL420 " of LTD. system), make phosphorus diffusion coating fluid.
<to coating, the printing evaluation of semiconductor substrate >
Use the phosphorus diffusion coating fluid of above-mentioned making, carry out silk screen printing according to following printing condition on P type semiconductor substrate (polysilicon, 156mm is square, 200 μ m are thick), after utilizing scraper (scraper) to supply with under the state of coating fluid to place the stipulated time (30,60 minutes), again printed.
The state of visualization gained printing surface, estimate printing according to following appreciation condition.Show the result in table 3.
(printing condition)
Printing machine: NEWLONG SEIMITU KOGYO CO., LTD system " LS-34GX "
Scraper plate (Squeegee): NEWLONG SEIMITU KOGYO CO., LTD NM SQUEEGEE(processed hardness: 60)
Blade angle: 80 degree
Scraper: NEWLONG SEIMITU KOGYO CO., LTD NM SQUEEGEE(processed hardness: 60)
Scraper angle: 86 degree
Squeegee pressure: 0.2MPa
Half tone: TOKYO PROCESS SERVICE CO., LTD. system
The version size: 450mm is square
Mesh (mesh) kind: V330
Emulsion kind: TN-1
Emulsion thickness: 10 μ m
Pattern: L/S=80～220 μ m, every 20 μ m/L * 3
Solid pattern (solid pattern) 2 places that 30mm is square
Printing environment: 23 ℃, 60%RH
(appreciation condition)
Zero: all pattern is printed out.
△: the part at the whole patterns that are printed out confirms fuzzy.
*: in pattern, a part confirms obvious breach.
<make semiconductor, measure sheet resistance
In hot air circular drying machine, under 150 ℃, will be with the phosphorus of above-mentioned making diffusion coating fluid, with above-mentioned same printing condition under, the semiconductor substrate drying that square solid pattern silk screen printing obtains with 150mm 2 minutes.Thereafter, semiconductor substrate is dropped into to temperature with upright state: 850 ℃, gaseous species: in the tube furnace (tube furnace) of nitrogen+oxygen (4%), gas flow: 50L/ minute, keep taking out after 15 minutes, clean while shaking in 46% aqueous hydrogen fluoride solution.Like this, obtain the semiconductor that there is phosphorus-diffused layer in semiconductor substrate.
Use resistance measurer (MITSUBISHI CHEMICAL ANALYTECH CO., LTD. system " LORESTA ", used the PSP probe) measure the sheet resistance value of the top (while when burnt till, making semiconductor be erectility, apart from the part of the top 30mm of diffusion layer) of the semi-conductive diffusion layer of gained and bottom (while when burnt till, making semiconductor be erectility, apart from the part of the below 30mm of diffusion layer).Show the result in table 3.
Embodiment 2
In embodiment 1, as impurity (B), use phosphate (R in general formula (5)
12for methyl, R
13for hydrogen, R
14for hydrogen, n are 1, m is 1, l is 2 phosphono oxygen ylmethyl acrylate (UNI-CHEMICAL CO.; LTD. make " PHOSMER-M ")) (B1) 7 parts; make the mixture of spent glycol and glycerine as polyalcohol (C); use and take compound (the DOW CORNING TORAY CO. that aminoalkoxy silane is main component as surfactant (D); LTD. make " SH-21 ") (D2), the compounding amount of each composition of setting as shown in table 2.In addition, make similarly to Example 1 the phosphorus diffusion and use coating fluid, similarly estimated.Evaluation result is shown in to table 3.
Embodiment 3
In embodiment 1, make the mixture of spent glycol and glycerine as polyalcohol (C), and then be dispersed in 10 parts of cataloid solution (FUJIMI CORPORATION system " PLANERLITE4101 ") in water 80wt%, the compounding amount of each composition of setting as shown in table 2 as the cataloid of inorganic particles (E) compounding 20wt%.In addition, make similarly to Example 1 the phosphorus diffusion and use coating fluid, similarly estimated.Evaluation result is shown in to table 3.
Embodiment 4
In embodiment 2, the PVA that is gained in resin (A) use Production Example 2 as PVA is resin (A2), makes the mixture of spent glycol and glycerine as polyalcohol (C), not compounding surfactant (D), the compounding amount of each composition of setting as shown in table 2.In addition, make similarly to Example 1 the phosphorus diffusion and use coating fluid, similarly estimated.Evaluation result is shown in to table 3.
Embodiment 5
In embodiment 4, use water-based emulsion (the KYOEISHA CHEMICAL CO. of the mixture that contains organic modified polyorganosiloxane and particular polymer as surfactant (D), LTD. make " AKUALEN SB-630 " (D3), the compounding amount of each composition of setting as shown in table 2.In addition, make similarly to Example 4 the phosphorus diffusion and use coating fluid, similarly estimated.Evaluation result is shown in to table 3.
Embodiment 6
In embodiment 1, use boric acid (B3) 2 parts as impurity (B), making ethylene glycol (C1) is 86 parts.In addition, make similarly to Example 1 the Impurity Diffusion coating fluid.
Use the coating fluid of gained, as semiconductor substrate, use the N type semiconductor substrate, in addition, similarly to Example 1 semiconductor substrate is carried out silk screen printing, carries out the printing evaluation.In addition, use above-mentioned coating fluid, according to following standard, make semiconductor, carry out sheet resistance mensuration.Show the result in table 3.
The mensuration of<semi-conductive making, sheet resistance >
In hot air circular drying machine, under 150 ℃, will use the Impurity Diffusion coating fluid of gained, with above-mentioned same printing condition under, the semiconductor substrate drying that square solid pattern silk screen printing obtains with 150mm 2 minutes.Semiconductor substrate with upright state dropped into to temperature: 950 ℃, gaseous species: in the tube furnace of nitrogen, gas flow: 50L/ minute, after keeping 15 minutes, stop nitrogen, with identical flow, pass into oxygen 15 minutes thereafter.Then, take out substrate, clean while shaking in 46% aqueous hydrogen fluoride solution, obtain the semiconductor that there is diffused layer of boron in semiconductor substrate, measure similarly to Example 1 the sheet resistance value of top and the bottom of its diffusion layer.Show the result in table 3.
Embodiment 7
In embodiment 2, use triethyl borate (B4) 7 parts as impurity (B), in addition, make similarly to Example 2 the Impurity Diffusion coating fluid, estimated similarly to Example 6.Evaluation result is shown in to table 3.
Comparative example 1
In embodiment 1, make spent glycol and water as solvent simultaneously, the compounding amount of each composition of setting as shown in table 2, in addition, make similarly to Example 1 the phosphorus diffusion and use coating fluid, similarly estimated.Evaluation result is shown in to table 3.
Comparative example 2
In embodiment 1, replacing PVA is resin (A) and use the polyvinyl acetate of average degree of polymerization 450, use phosphate (B1) as impurity (B), use isobutyric acid-3-hydroxyl-2 as solvent, 2,4-trimethyl pentyl ester (TPM), not compounding surfactant (D), as inorganic particles (E) compounding cataloid (FUJIMI CORPORATION system " PLANERLITE4101 "), the compounding amount of each composition of setting as shown in table 2.In addition, make similarly to Example 1 the phosphorus diffusion and use coating fluid, similarly estimated.Evaluation result is shown in to table 3.
[table 1]
[table 2]
[table 3]
Phosphorus diffusion of the present invention in silk screen printing, even after having placed certain hour, also can obtain excellent printing with coating fluid.In addition, the semiconductor obtained by coating fluid of the present invention, the difference of upper and lower sheet resistance value is little.
On the other hand, for using, using water as the coating fluid of the comparative example 1 of the solvent of main body, the printing of placing after 30 minutes is poor; For use the coating fluid of the comparative example 2 of polyvinyl acetate as binding agent, the difference of the semi-conductive upper and lower surface resistance value of gained is large.
It should be noted that, show in the above-described embodiments the concrete mode in the present invention, but above-described embodiment is not construed as limiting interpretation nothing but simple illustration.Apparent various distortion is all in protection scope of the present invention to those skilled in the art.
utilizability on industry
The coating fluid printing of idle periods that can realize long continuous printing and interval for Impurity Diffusion of the present invention, even the semiconductor substrate after epithelium is formed burns till with erectility, also can obtain the little semiconductor of upper lower deviation of resistance value, therefore, industrial extremely useful.
Claims (6)
1. an Impurity Diffusion coating fluid, is characterized in that, it contains: polyvinyl alcohol resin (A), impurity (B) and boiling point are the polyalcohol (C) more than 100 ℃, and the content of this polyalcohol (C) is more than 70 % by weight in coating fluid.
2. Impurity Diffusion coating fluid according to claim 1, wherein, the saponification degree of polyvinyl alcohol resin (A) is 50 % by mole～90 % by mole.
3. Impurity Diffusion coating fluid according to claim 1 and 2, wherein, the polyvinyl alcohol resin that polyvinyl alcohol resin (A) is the construction unit that contains 5 % by mole～10 % by mole following general formulas (1) and mean,
[Chemical formula 1]
In formula (1), R
1, R
2and R
3mean independently of one another hydrogen atom or organic group, X means singly-bound or bonding chain, R
4, R
5and R
6mean independently of one another hydrogen atom or organic group.
4. according to the described Impurity Diffusion coating fluid of claim 1～3 any one, wherein, impurity (B) is at least one of 13 group element compounds and 15 group element compounds.
5. according to the described Impurity Diffusion coating fluid of claim 1～4 any one, it contains surfactant (D).
6. according to the described Impurity Diffusion coating fluid of claim 1～5 any one, it contains inorganic particles (E).
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| JP2011-113352 | 2011-05-20 | ||
| PCT/JP2012/062745 WO2012161107A1 (en) | 2011-05-20 | 2012-05-18 | Coating liquid for diffusing impurity |
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| JP6139155B2 (en) * | 2012-05-07 | 2017-05-31 | 東京応化工業株式会社 | Diffusion agent composition and method for forming impurity diffusion layer |
| JP6099437B2 (en) * | 2013-03-07 | 2017-03-22 | 東京応化工業株式会社 | Diffusion agent composition and method for forming impurity diffusion layer |
| CN114342101A (en) * | 2019-09-26 | 2022-04-12 | 东丽株式会社 | Impurity diffusion composition, method for manufacturing semiconductor element using same, and method for manufacturing solar cell |
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| JP4541243B2 (en) * | 2005-07-22 | 2010-09-08 | 日本合成化学工業株式会社 | Boron diffusion coating solution |
| ATE518925T1 (en) * | 2007-03-22 | 2011-08-15 | Nippon Synthetic Chem Ind | AQUEOUS COMPOSITION FOR A RECORDING MEDIUM AND INKJET RECORDING MEDIUM THEREFROM |
| JP2010161317A (en) * | 2009-01-09 | 2010-07-22 | Tokyo Ohka Kogyo Co Ltd | Diffusing agent composition, method for forming impurity diffusion layer, and solar cell |
| EP2648211A4 (en) * | 2010-11-29 | 2014-07-30 | Nippon Synthetic Chem Ind | Coating liquid for impurity diffusion |
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2012
- 2012-05-18 JP JP2012114383A patent/JP2013008953A/en active Pending
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| JPH09181009A (en) * | 1995-12-26 | 1997-07-11 | Tokyo Ohka Kogyo Co Ltd | Coating liquid for boron diffusion |
| JP2002284818A (en) * | 2000-12-15 | 2002-10-03 | Nippon Synthetic Chem Ind Co Ltd:The | Novel vinyl alcohol resin and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105764873A (en) * | 2013-12-20 | 2016-07-13 | 日本合成化学工业株式会社 | Liquid spray agent for agricultural use |
| CN105764873B (en) * | 2013-12-20 | 2023-08-15 | 三菱化学株式会社 | Agricultural liquid spreading agent |
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| KR20140011354A (en) | 2014-01-28 |
| WO2012161107A1 (en) | 2012-11-29 |
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