CN104081517A - Material for forming passivation film for semiconductor substrate, method of manufacturing semiconductor substrate comprising passivation film for semiconductor substrate, solar cell element, and method of manufacturing solar cell element - Google Patents
Material for forming passivation film for semiconductor substrate, method of manufacturing semiconductor substrate comprising passivation film for semiconductor substrate, solar cell element, and method of manufacturing solar cell element Download PDFInfo
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Abstract
The present invention provides a material for forming a passivation film for a semiconductor substrate, which comprises a compound further comprising an acidic group. With this invention, a passivation film for a semiconductor substrate that has an excellent passivation effect can be formed by an easy method.
Description
Technical field
The present invention relates to be used to form semiconductor substrate with the material of passivating film, there is the manufacture method of manufacture method, solar cell device and the solar cell device of the semiconductor substrate of passivating film for semiconductor substrate.
Background technology
Manufacturing process to silicon solar cell unit in the past describes.
First, in order promoting to fall into luminous effect, to realize high efficiency, to prepare to be formed with the p-type silicon substrate of texture structure, then, at phosphorous oxychloride (POCl
3), at 800 ℃～900 ℃, carry out the processing of tens of minutes in the mixed-gas atmosphere of nitrogen and oxygen, be formed uniformly N-shaped diffusion layer.In this method in the past, use mist to carry out the diffusion of phosphorus, therefore not only on surface, form N-shaped diffusion layer, and in side, the back side also forms N-shaped diffusion layer.Therefore, in order to remove the N-shaped diffusion layer of side, carry out lateral erosion quarter.In addition, the N-shaped diffusion layer at the back side need to be transformed to p
+type diffusion layer.For this reason, by printing, wait and give Aluminum Paste overleaf, burn till, make N-shaped diffusion layer become p
+type diffusion layer obtains ohmic contact simultaneously.
But the conductivity of the aluminium lamination being formed by Aluminum Paste is low.Therefore,, in order to reduce film resistor, the aluminium lamination that is conventionally formed at the whole back side must have the thickness of 10 μ m～20 μ m left and right after burning till.And then, because the thermal coefficient of expansion of silicon and aluminium differs widely, therefore, burn till with cooling process in, make to produce in silicon substrate larger internal stress, thereby cause crystal boundary damage (damage), crystal defect to increase and warpage.
In order to address the above problem, there is the amount of giving that reduces Aluminum Paste and the method that makes the attenuation of backplate layer.But, if reduce the amount of giving of Aluminum Paste, from diffusion into the surface to the inner aluminium quantitative change of p-type silicon semiconductor substrate, obtain insufficient.Result: cannot realize required BSF (Back Surface Field, back surface field) effect (because of p
+the existence of type diffusion layer and making generates the effect that the collection efficiency of charge carrier improves), therefore produce the problem that the characteristic of solar cell reduces.
Based on above-mentioned situation, proposed by the part on silicon substrate surface is given Aluminum Paste and formed partly p
+the method that the point of type diffusion layer and aluminium electrode contacts (for example, with reference to No. 3107287 communique of Japan Patent).
This kind, in the situation that a side contrary with sensitive surface (below also referred to as " rear side ") has the solar cell of point-contact junction structure, need to suppress on the surface of the part except aluminium electrode the recombination velocity of minority carrier.Rear side passivating film as for this purposes, has proposed SiO
2film etc. (for example, with reference to TOHKEMY 2004-6565 communique).In this situation, by forming oxide-film, make the not associative key end-blocking of silicon atom of the back surface layer portion of silicon substrate, thereby make to cause that the surface level density of combination again reduces.
In addition, also proposed to use SiNx (silicon nitride) film of the antireflection film that is widely used as sensitive surface side as the back side, to use the method (for example, with reference to TOHKEMY 2010-537423 communique) of passivating film.
And then, also proposed to use polyimide film as the way (for example, with reference to the 71st Applied Physics association lecture meeting (Japanese original text: the Intraoperative Talk meeting of drilling is learned by 71HuiApplied Yong physical society) 15p-ZB-14) of the passivating film of rear side.
Summary of the invention
The problem that invention will solve
But, the SiO proposing in TOHKEMY 2004-6565 communique and TOHKEMY 2010-537423 communique
2film and SiNx film generally form with thermal oxidation method or CVD method etc.In thermal oxidation method, conventionally need 1000 ℃ of above high-temperature process, and need to manage the process conditions such as gas flow, gas flow distribution.In addition, in the situation that using CVD method, sometimes according to the difference of the kind of used reacting gas, can make reactant gas decompose, can expect the effect of hydrogen passivation thus, but because output (through put) is low, device safeguards the problem that manufacturing installation cost is high that exists such as frequent.
And then, while using the peristome of passivating film at the formation back side, conventionally use photo-mask process, therefore at aspects such as process number, installation costs, also have problems.
In addition, also need to have the passivating film of the passivation effect more excellent than the passivating film of the polyimides proposing in the 71st Applied Physics association lecture meeting (Japanese original text: the Intraoperative Talk meeting of drilling is learned by 71HuiApplied Yong physical society) 15p-ZB-14.
The present invention completes in view of above existing issue, and its problem is to provide and can forms and have the material of passivating film for semiconductor substrate that is used to form of passivating film for the semiconductor substrate of excellent passivation effect with easy method.In addition, its problem is also to provide and has the manufacture method of manufacture method, solar cell device and the solar cell device of the semiconductor substrate of passivating film for the semiconductor substrate of passivation effect excellence.
For solving the means of problem
As described below for solving the concrete means of above-mentioned problem.
<1> material that is used to form semiconductor substrate use passivating film, it comprises the compound with acidic groups.
<2> is according to the material of passivating film for semiconductor substrate that is used to form described in <1>, and wherein, above-mentioned acidic groups is Bronsted acid (bronsted acid) property base.
<3> is according to the material of passivating film for semiconductor substrate that is used to form described in <1> or <2>, wherein, the above-mentioned compound with acidic groups is organic acid.
<4> is according to the material of passivating film for semiconductor substrate that is used to form described in <3>, wherein, above-mentioned organic acid is at least a kind that is selected from polyacrylic acid, poly-perfluoroolefine sulfonic acid, sulfonated polystyrene derivative and sulfonation poly arylene ether sulfone.
<5> is according to the material of passivating film for semiconductor substrate that is used to form described in <1> or <2>, wherein, the above-mentioned compound with acidic groups is inorganic acid.
<6> is according to the material of passivating film for semiconductor substrate that is used to form described in <5>, and wherein, above-mentioned inorganic acid is polyphosphoric acid or heteropoly acid.
<7> is according to the material of passivating film for semiconductor substrate that is used to form described in <6>, wherein, above-mentioned heteropoly acid is at least a kind that is selected from phosphotungstic acid, silico-tungstic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid and phosphomolybdic acid.
<8> is according to the material of passivating film for semiconductor substrate that is used to form described in any one in <1>～<7>, wherein, the above-mentioned compound with acidic groups shows following acidity: the pH value of the aqueous solution that the above-mentioned containing ratio with the compound of acidic groups is 5 quality % at 25 ℃ reaches below 5.
<9> is according to the material of passivating film for semiconductor substrate that is used to form described in <8>, and wherein, above-mentioned pH value is below 2.5.
<10> is according to the material of passivating film for semiconductor substrate that is used to form described in any one in <1>～<9>, and it also contains liquid medium.
<11> is according to the material of passivating film for semiconductor substrate that is used to form described in <10>, wherein, above-mentioned liquid medium comprises at least a kind that is selected from water, methyl alcohol, ethanol, 1-propyl alcohol and 2-propyl alcohol.
<12> manufacture method with the semiconductor substrate of semiconductor substrate use passivating film, it comprises following operation: on semiconductor substrate, give the material that is used to form semiconductor substrate use passivating film described in any one in <1>～<11>, form semiconductor substrate passivating film.
<13> is according to the manufacture method of the semiconductor substrate of passivating film for semiconductor substrate that has described in <12>, it also comprises following operation: being used to form before semiconductor substrate is imparted on above-mentioned semiconductor substrate with the material of passivating film above-mentioned, on above-mentioned semiconductor substrate, give hydrofluoric acid aqueous solution.
<14> solar cell device, it has: semiconductor substrate, electrode and the semiconductor substrate passivating film with pn knot, wherein, above-mentioned semiconductor substrate is described in any one, to be used to form semiconductor substrate filming with the material of passivating film in <1>～<11> with passivating film.
The manufacture method of a <15> solar cell device, it comprises following operation: be used to form the material of passivating film for semiconductor substrate described in any one having pn knot and be provided with in giving <1>～<11> on the semiconductor substrate of electrode, form semiconductor substrate passivating film.
Invention effect
According to the present invention, can provide and can form and there is the material of passivating film for semiconductor substrate that is used to form of passivating film for the semiconductor substrate of excellent passivation effect with easy method.In addition, can also provide and there is the manufacture method of manufacture method, solar cell device and the solar cell device of the semiconductor substrate of passivating film for the semiconductor substrate of passivation effect excellence.
Accompanying drawing explanation
Fig. 1 schematically shows to have the cutaway view of an example of the manufacture method of the solar cell device of passivating film for the semiconductor substrate of present embodiment.
Fig. 2 schematically shows to have the cutaway view of an example of the manufacture method of the solar cell device of passivating film for the semiconductor substrate of present embodiment.
Fig. 3 schematically shows to have the cutaway view of the back electrode type solar cell device of passivating film for the semiconductor substrate of present embodiment.
Embodiment
In this specification, independently operation be not only in term " operation ", but also have the situation that cannot clearly be different from other operation, as long as can realize in this case the expection object of this operation, is also contained in this term.In addition the numerical value that the front and back that the number range of, using "～" to illustrate in this specification represents to contain "～" are recorded is respectively as minimum value and peaked scope.And then, about the amount of each composition in the composition of this specification, in the situation that there is the multiple material that is equivalent to each composition in composition, unless otherwise specified, all refer to the total amount of this many kinds of substance existing in composition.
< is used to form the material > of passivating film for semiconductor substrate
The semiconductor substrate that is used to form of the present invention at least comprises and has the compound of acidic groups and contain as required other compositions such as liquid medium and form with the material of passivating film.
By the semiconductor substrate that is used to form that at least comprises the compound with acidic groups is imparted on semiconductor substrate and makes and film with the material of passivating film, thereby can in required region, form with easy method the passivating film with excellent passivation effect.
Think that its reason is for example: the acidic groups with the compound of acidic groups interacts with the defect that is present in semiconductor substrate surface, can make defect end-blocking thus.For example, in the situation that acidic groups is Bronsted acidity base, the proton of Bronsted acidity base be called as dangling bonds (dangling bond) formation semiconductor substrate element for example silicon end not associative key react, can make dangling bonds end-blocking.This dangling bonds can become charge carrier (electronics, hole) again in conjunction with place, therefore, by making dangling bonds end-blocking, the life-span that can improve charge carrier.
Utilize Photoconductivity decay by microwave reflectance damped method to measure by the useful life of the minority carrier in the semiconductor substrate of passivating film being formed with semiconductor substrate, can evaluate thus the passivation effect of the semiconductor substrate use passivating film in this specification.
At this, useful life τ can utilize like that according to following formula (I) the bulk lifetime τ of semiconductor-based intralamellar part
bτ surface lifetime with semiconductor substrate surface
srepresent.In the situation that the surface level density of semiconductor substrate surface is little, τ
sbecome large, result makes useful life τ become large.In addition, even if the defects such as dangling bonds of semiconductor-based intralamellar part tail off, bulk lifetime τ
balso can become large, make useful life τ also become large.That is, can evaluate by measuring useful life τ the bulk properties of the semiconductor substrates such as interfacial characteristics between passivating film and semiconductor substrate and dangling bonds.
1/τ＝1/τ
b+1/τ
s (I)
In addition, useful life is longer, represents that the recombination velocity of minority carrier is slower.Conventionally known: in the situation that use the semiconductor substrate of useful life length as solar cell, conversion efficiency can improve.
[compound with acidic groups]
In the present invention, the compound that has an acidic groups can be any one in organic acid or inorganic acid.Organic acid can be organic high molecular compound, can be also organic low molecular compounds, but be preferably organic high molecular compound.Inorganic acid can be inorganic macromolecule compound, can be also low-molecular inorganic compound, but be preferably inorganic macromolecule compound.
Above-mentioned acidic groups be Bronsted acidity base or lewis acidity base all can, from improving the viewpoint of passivation effect, be preferably Bronsted acidity base.
Bronsted acidity base is the functional group of confession under directions protic.For example can enumerate sulfonic group, carboxyl, phosphonate group, phosphate and phenol hydroxyl.
Organic acid is preferably the organic high molecular compound with Bronsted acidity base.There is no particular restriction for high molecular main chain.As the oligomer or the polymer that form main chain, can enumerate: polyether-ketone, polythiaether, polyphosphazene, polyphenylene, polybenzimidazoles, polyether sulfone, poly arylene ether sulfone, polyphenylene oxide, Merlon, polyurethanes, polyamide, polyimides, polyureas, polysulfones, polysulfonates, polybenzoxazole, polybenzothiozole, polythiazole, polyphenylene quinoxaline, poly quinoline, polysiloxanes, poly-triazine, polydiene, polypyridine, poly-pyrimidine, Ju Evil thiazole, poly-four azepine pyrenes, Ju oxazole, polyvinylpyridine, polyvinyl imidazol, PVP, poly-(methyl) acrylate derivative, polystyrene derivative, Kynoar, polytetrafluoroethylene, polychlorotrifluoroethylene etc.
As the organic macromolecule concrete example with Bronsted acidity base, be preferably at least a kind that is selected from poly-(methyl) acrylic acid, poly-perfluoroolefine sulfonic acid, sulfonated polystyrene derivative and sulfonation polyaryl ether, more preferably poly-(methyl) acrylic acid or sulfonated polystyrene derivative.
There is no particular restriction for organic acid molecular weight, can suitably select according to object.Organic acid molecular weight is preferably 100～5 in weight average molecular weight, and 000,000, more preferably 1000～1,000,000, more preferably 3,000～300,000.If organic acid weight average molecular weight is more than 100, processability improves, and can obtain more uniform surface passivation effect.If organic acid weight average molecular weight is 5,000, below 000, when being scattered in decentralized medium, easily forms uniform solution, and easily process.
In addition, weight average molecular weight can adopt gel permeation chromatography (GPC) and utilize conventional method to measure (utilization has adopted the calibration curve of polystyrene standard to convert).
Inorganic acid is preferably polyphosphoric acid or heteropoly acid.As the example of heteropoly acid, can enumerate H
2xY
12o
40nH
2(X is P, As, Ge, Si etc. to compound shown in O; Y is Mo, W, V etc.; N is 1～100 integer).As heteropoly acid, particularly, can exemplify phosphotungstic acid, silico-tungstic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid, phosphomolybdic acid etc.
As the compound with lewis acidity base, can exemplify alkyl boron compound, alkyl aluminum compound, ionic liquid etc.
As alkyl boron compound, can enumerate for example three (pentafluorophenyl group) borine, four (pentafluorophenyl group) boric acid triphenyl methyl esters, dimethylaniline four (pentafluorophenyl group) borate.
As alkyl aluminum compound, can enumerate for example trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three hexyl aluminium.
Ionic liquid refers to that fusing point is below 100 ℃ and at 100 ℃ of salt that are below aqueous outward appearance.There is no particular restriction for the composition of ionic liquid, as long as comprise cation and anion.As cation, can enumerate ammonium, pyridine, pyrrolidines, pyrroles, oxazole, oxazoline, imidazoles, Phosphonium and sulfonium.As anion, can enumerate N (SO
2f)
2 - ,n (SO
2cF
3)
2 -, N (SO
2c
2f
5) 2
-, BF
4 -, PF
6 -, CF
3sO
3 -and CF
3cO
2 -.Preferably these cations and anion are combined to the ionic liquid forming.Above-mentioned ionic liquid can be used separately, also can two or more mixing use.
In these anion, be especially applicable to being used as the N (SO of hydrophobic anion
2f)
2 -, N (SO
2cF
3)
2 -, N (SO
2c
2f
5)
2 -, CF
3sO
3 -or CF
3cO
2 -.By using hydrophobic anion, thereby make to utilize treatability, the especially treatability in air atmosphere of the ionic liquid that this hydrophobic anion forms to become easy.In addition, made to adopt the semiconductor substrate that is used to form of this ionic liquid also to become easy by the treatability of the material of passivating film.
More than the ionic conductance of ionic liquid is preferably 0.01mS/cm, more preferably more than 0.1mS/cm.If the ionic conductance of ionic liquid is more than 0.01mS/cm, can fully obtain the passivation effect based on ionic liquid.The ionic conductance of ionic liquid can be used conductivity meter to measure at 25 ℃.
The acid degree of the above-mentioned compound with acidic groups is larger, more preferred.Acidity degree can be by being dissolved in the compound with acidic groups the aqueous solution and the pH value of this aqueous solution being measured indirectly and measured.Particularly, the containing ratio that there is the compound of acidic groups be the aqueous solution of the 5 quality % pH value at 25 ℃ be preferably below 5, more preferably below 3, more preferably below 2.5.By forming at passivating film with using the compound with acidic groups of acid degree below demonstration in material, can obtain sufficient passivation effect, described acid degree is: containing ratio is that the aqueous solution of the 5 quality % pH value at 25 ℃ reaches below 5.That is, can improve the life-span of charge carrier.
In the above-mentioned water-fast situation of compound with acidic groups, can be by being that the dispersion liquid of the 5 quality % pH value at 25 ℃ is measured and indirectly measured acid degree to the containing ratio of making particulate and being scattered in the compound that contains acidic groups in water.Particulate specifically refers to have 10nm～particle of the particle diameter of about 200nm.In addition, even if comprise the pH value under the state of methyl alcohol beyond dewatering, ethanol, propyl alcohol etc. in the aqueous solution or dispersion liquid, also no problem.
The assay method of pH value can be any one in indicator method, metal electrode method, glass electrode method, preferably uses glass electrode method.By utilizing glass electrode method to measure, can obtain the value that error is little, reappearance is high.
For showing following acid degree, be that containing ratio is for the aqueous solution of 5 quality % or concrete example that the pH value of dispersion liquid at 25 ℃ reaches the compound with acidic groups below 5, as organic acid, can enumerate polyacrylic acid, poly-perfluoroolefine sulfonic acid, sulfonated polystyrene derivative, sulfonation poly arylene ether sulfone, sulfonated polyimide, sulfonation polyurethanes, sulfonated polyether sulfone, sulfonation poly-(ether ether sulfone), sulfonated polyether acid imide, sulfonated polyether acid amides.As inorganic acid, can enumerate polyphosphoric acid, phosphotungstic acid, silico-tungstic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid and phosphomolybdic acid, sulfate radical active oxidation zirconium, tin oxide, manganese oxide.
Be used to form semiconductor substrate with in material 100 mass parts of passivating film, the content with the compound of acidic groups is preferably 0.1 mass parts～100 mass parts, more preferably 1 mass parts～90 mass parts, 5 mass parts～80 mass parts more preferably.
Especially when being used to form the content of semiconductor substrate with polyphosphoric acid, polyacrylic acid, sulfonated polystyrene, phosphotungstic acid or Nafion (registered trade mark) in material 100 mass parts of passivating film and being 5 mass parts～100 mass parts, passivation effect significantly improves, when being used to form the content of semiconductor substrate with sulfonated polystyrene or Nafion (registered trade mark) in material 100 mass parts of passivating film and being 5 mass parts～100 mass parts, passivation effect more significantly improves.
The semiconductor substrate that is used to form of the present invention preferably also contains liquid medium with the material of passivating film.The compound with acidic groups can be dissolved in liquid medium, also can disperse with solid state or emulsion state.
As liquid medium, can from following solvent, select suitable solvent, but be not limited to these solvents, described solvent is: water; Chloroform, carrene, 1, the halogenated aliphatic hydrocarbon solvents such as 2-dichloroethanes, trichloroethanes, tetrachloroethanes, trichloroethylene, tetrachloro-ethylene; The halogenated aromatic such as dichloro-benzenes, trichloro-benzenes hydrocarbon solvent; The nitro compound such as nitromethane, nitrobenzene; The alkyl benzene solvents such as trimethylbenzene, tributyl benzene, durol, pentamethylbenzene; The heterocyclic compounds such as sulfolane; The sturated aliphatic hydrocarbon solvent of straight chain, side chain or the ring-types such as octane, decane, cyclohexane; The non-proton property polar solvents such as DMA, DMF, dimethyl sulfoxide (DMSO), METHYLPYRROLIDONE, HMPA (hexamethylphosphoramide); The alcoholic solvents such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol; And the phenol solvent such as phenol, cresols.
In these solvents, preferably at least contain at least a kind that is selected from alcoholic solvent, more preferably contain at least a kind that is selected from methyl alcohol, ethanol, 1-propyl alcohol and 2-propyl alcohol.By containing at least one alcoholic solvent, can improve semiconductor substrate, the wetability of silicon substrate especially.
Above-mentionedly be used to form semiconductor substrate there is no particular restriction with the content of the liquid medium in the material of passivating film.For example, in being used to form total amount 100 mass parts of semiconductor substrate with the material of passivating film, be preferably 1 mass parts～99 mass parts, 40 mass parts～95 mass parts more preferably.
The above-mentioned semiconductor substrate that is used to form can further contain silane coupler with the material of passivating film.By containing silane coupler, can improve semiconductor substrate, the wetability of silicon substrate especially.
As silane coupler, there is no particular restriction, can from normally used silane coupler, suitably select.
The above-mentioned semiconductor substrate that is used to form can contain surfactant with the material of passivating film.Surfactant can be any one in cation system, anion system, nonionic system.By containing surfactant, sometimes can further give fixed charge to passivating film.
The above-mentioned semiconductor substrate that is used to form can further contain inorganic filler with the material of passivating film.By containing inorganic filler, existence can improve mechanical strength, moisture retention, reflectivity, the stable on heating tendency of passivating film for semiconductor substrate.
As inorganic filler, can enumerate Al
2o
3(aluminium oxide), SiO
2(silica), ZrO
2(zirconia), TiO
2(titanium oxide), SiC (carborundum), MgO (magnesium oxide), AlN (aluminium nitride), BN (boron nitride), their composite oxides etc.Wherein, particularly preferably use and be selected from Al
2o
3, SiO
2, ZrO
2and TiO
2in metal oxide.These metal oxides are because having a plurality of hydroxyls on its surface easily and water interacts, so moisture retention is high.Therefore,, by adding these metal oxides as inorganic filler, can improve the moisture retention of passivating film for semiconductor substrate.
Inorganic filler is as long as become required composition at formation semiconductor substrate with the moment of passivating film.That is, can by containing inorganic filler precursor, the semiconductor substrate that is used to form with the compound of acidic groups and liquid medium is imparted on semiconductor substrate and in carrying out dry operation and makes inorganic filler precursor be changed to inorganic filler with the material of passivating film.
For example, also can will contain as SiO
2the semiconductor substrate that is used to form of silane alkoxide (silane alkoxide) of precursor with the material of passivating film, be imparted on semiconductor substrate, and after drying process in be hydrolyzed into SiO
2.Now, can add catalyst.
There is no particular restriction for the weight average aggregate particle size of inorganic filler.Wherein, weight average aggregate particle size (50%D) is preferably 10nm～30 μ m, more preferably 0.1～10 μ m.
If the weight average aggregate particle size of inorganic filler is more than 10nm, can be used to form semiconductor substrate with disperseing more equably in the material of passivating film.If the weight average aggregate particle size of inorganic filler is below 30 μ m, there is the tendency that can fully obtain the semiconductor substrate mechanical strength of passivating film, moisture retention, reflectivity, stable on heating raising effect.The weight average aggregate particle size of inorganic filler can utilize laser light scattering diffraction approach particle size distribution device etc. to measure.
To the content of inorganic filler, there is no particular restriction, and preferably containing with respect to being used to form 100 mass parts of the compound with acidic groups contained in the material of semiconductor substrate with passivating film is the inorganic filler of 0.01 mass parts～100 mass parts.If the content of inorganic filler is more than 0.01 mass parts with respect to being used to form 100 mass parts of the compound with acidic groups contained in the material of semiconductor substrate with passivating film, can fully obtain adding the effect of inorganic filler.If the content of inorganic filler is below 100 mass parts with respect to compound 100 mass parts with acidic groups, the flexibility that can suppress passivating film reduces, and can suppress the generation of pin hole (pin hole) etc.
Especially for silicon solar cell, when using the above-mentioned material that is used to form semiconductor substrate use passivating film to use passivating film at the opposition side formation back side with sensitive surface, can improve reflectivity by containing inorganic filler.Now, as inorganic filler, preferably use SiO
2.
Semiconductor substrate of the present invention is used with the encapsulant that passivating film can be used as semiconductor substrate (preferably solar cell device).The substitute that for example also can be used as the polyvinyl acetate of the encapsulant that is mainly used as solar cell device is used.
< has the manufacture method > of the semiconductor substrate of passivating film for semiconductor substrate
Of the present invention have semiconductor substrate and comprise following operation by the manufacture method of the semiconductor substrate of passivating film: on semiconductor substrate, give contain have acidic groups compound be used to form the material of passivating film for semiconductor substrate, form semiconductor substrate passivating film.Said method can comprise other operations such as drying process as required.
Manufacture method according to above-mentioned semiconductor substrate with passivating film, can form the semiconductor substrate passivating film with excellent passivation effect.Forming semiconductor substrate can be any one in p-type or N-shaped with the semiconductor substrate of passivating film.
In the situation that semiconductor substrate is formed at passivating film on the p-type layer of semiconductor substrate, the p-type layer on semiconductor substrate can be both the p-type layer that derives from p-type semiconductor substrate, can be also with p-type diffusion layer or p
+the form of type diffusion layer is formed at the p-type layer on semiconductor substrate.
In the situation that semiconductor substrate is formed at passivating film on the N-shaped layer of semiconductor substrate, the N-shaped layer on semiconductor substrate can be both the N-shaped layer that derives from N-shaped semiconductor substrate, can be also with N-shaped diffusion layer or n
+the form of type diffusion layer is formed on the N-shaped layer on semiconductor substrate.
In the present invention, preferably further there is following operation: being used to form before semiconductor substrate is imparted on semiconductor substrate with the material of passivating film of compound with acidic groups, the operation of giving hydrofluoric acid aqueous solution on semiconductor substrate will contained.In addition, more preferably further there is following operation: before giving hydrofluoric acid aqueous solution, on semiconductor substrate, give the operation of aqueous alkali.
; preferably, with hydrofluoric acid aqueous solution, the surface of semiconductor substrate being washed before being imparted on semiconductor substrate being used to form the material of semiconductor substrate with passivating film, more preferably after the surface with aqueous alkali washing semi-conductor substrate, with hydrofluoric acid aqueous solution, wash.
By utilizing hydrofluoric acid aqueous solution to wash semiconductor substrate surface, can remove the oxides such as Si oxide that exist at semiconductor substrate surface, and can further improve passivation effect.
The dangling bonds that in addition, can make to be present in semiconductor substrate surface becomes Si-H key etc.By it being given to the above-mentioned material that is used to form semiconductor substrate use passivating film, thereby may make the stabilisations such as formed Si-H key.
As hydrofluoric acid aqueous solution, can enumerate and contain the aqueous solution that is selected from least a kind of material in hydrogen fluoride and ammonium fluoride.As the concentration of the hydrofluoric acid of hydrofluoric acid aqueous solution, there is no particular restriction, can use the aqueous solution of 0.1 quality %～40 quality %, is preferably 0.5 quality %～10 quality %.If the concentration of the hydrofluoric acid of hydrofluoric acid aqueous solution is more than 0.1 quality %, there is the tendency that can obtain sufficient clean result.If the concentration of the hydrofluoric acid of hydrofluoric acid aqueous solution is below 40 quality %, can suppress the reduction of the operability of washing process.
As the method for utilizing aqueous alkali to wash, can exemplify conventionally known RCA washing etc.For example, semiconductor substrate be impregnated in the mixed solution of ammoniacal liquor-aquae hydrogenii dioxidi, and at 60 ℃～80 ℃, it is processed, can remove thus organic substance and the particle on semiconductor substrate and wash.
Washing time is all preferably 10 seconds in any one of neutralizing treatment, hydrofluoric acid wash～and 10 minutes, more preferably 30 seconds～5 minutes.
The above-mentioned semiconductor substrate that is used to form is not particularly limited by the method that the material of passivating film is imparted on semiconductor substrate, can uses known method.As adding method, particularly, can enumerate infusion process, print process, spin-coating method, spread coating, spraying process, scraper plate method, rolling method, ink-jet method etc.
Being used to form semiconductor substrate can suitably select according to object by the amount of giving of the material of passivating film.The mode that for example, can reach 10nm～50 μ m according to the thickness that makes formed semiconductor substrate with passivating film regulates the amount of giving.
In the situation that semiconductor substrate contains liquid medium with passivation film formation material, semiconductor substrate is imparted on semiconductor substrate with passivation film formation material, make it dry and form and film, can on semiconductor substrate, form semiconductor substrate passivating film thus.
As long as drying condition can form semiconductor substrate with the filming of passivation film formation material, there is no particular restriction.For example can at 50 ℃～300 ℃, be dried.
There is no particular restriction with the average film thickness of passivating film to utilize semiconductor substrate that above-mentioned semiconductor substrate manufactures by the manufacture method of passivating film, can suitably select according to object.For example be preferably 10nm～50 μ m, more preferably 100nm～30 μ m, more preferably 500nm～20 μ m.
If semiconductor substrate is more than 10nm with the average film thickness of passivating film, there is the tendency that easily covers equably the whole desired zone of semiconductor substrate surface.In addition, there is the higher tendency of the thicker surface passivation effect of thickness.
Above-mentioned semiconductor substrate is defined as the mean value to 5 results that record with the average film thickness of passivating film.Particularly, can for example, by using contact pin type difference in height-surface-profile measuring instrument (XP-1 that Ambios company manufactures) and measuring according to conventional method.
In the present invention, in the situation that can be crosslinked by the contained compound with acidic groups in being used to form the passivating film that the material of semiconductor substrate with passivating film is imparted on semiconductor substrate and form, also can carry out crosslinking Treatment.By carrying out crosslinking Treatment, can further improve the thermal endurance of passivating film for semiconductor substrate.There is no particular restriction for the method for crosslinking Treatment, can from normally used cross-linking method, suitably select.
Above to the liquid semiconductor substrate that is used to form is imparted to semiconductor substrate surface with the material of passivating film and manufactures semiconductor substrate and be illustrated by the method for passivating film, also can make semiconductor substrate be configured to membranaceous and be attached on semiconductor substrate and manufacture semiconductor substrate passivating film with passivation film formation material.
Particularly, semiconductor substrate can have following operation by the manufacture method of passivating film: on semiconductor substrate, attach to contain and have the compound of acidic groups and be configured to the membranaceous material of passivating film for semiconductor substrate that is used to form.
And then, preferably: in attaching, be configured to the membranaceous semiconductor substrate that is used to form with before the material of passivating film, utilize hydrofluoric acid aqueous solution to wash the surface of semiconductor substrate.
As attaching, be configured to the membranaceous method of the material of passivating film for semiconductor substrate that is used to form, particularly, can illustration pressurization pressing, heating pressing, transfer printing etc.
The membranaceous semiconductor substrate that is used to form for example can be used to form semiconductor substrate with the material of passivating film and obtains with the material of passivating film by the sheet material impregnation that makes to consist of fiber.By making fibre plate impregnation be used to form the material of passivating film for semiconductor substrate, can improve film strength.As fiber, can illustration: the polyamide-based fiber such as nylon; The polyester fibers such as dacron (Dacron), terylene (Terylene) and Supreme Being's Telon (Tetron); The vinylal fibres such as vinylon (Vinylon); The polyvinyl chloride fibers such as Luo Weilun (Rhovylon) and day U.S. dragon (Teviron); The vinylidene fibres such as saran (Saran) and Wu Yulun (Kurehalon); The acrylic fibers such as Orlon (Orlon), Acrilan (Acrilan), Ke Lisi synthetic fibre (Creslan), vonnel (Vonnel) and Cashmilan (Cashmilon); The polyolefin series fiber such as polyethylene and polypropylene; The carbon fluorine series fibers such as special teflon (Teflon) (registered trade mark); And the polyurethane series fiber such as spandex (Spandex).
< solar cell device >
Solar cell device of the present invention has: semiconductor substrate, electrode and the semiconductor substrate passivating film with pn knot, wherein, described semiconductor substrate with passivating film be contain have acidic groups compound be used to form semiconductor substrate filming with the material of passivating film.
Above-mentioned solar cell device for example can utilize the manufacture method of solar cell device described later to manufacture.The semiconductor substrate that is used to form that use contains the compound with acidic groups forms semiconductor substrate passivating film with the material of passivating film, can improve thus the useful life of semiconductor substrate.Can the be improved solar cell of conversion efficiency of its result.
The manufacture method > of < solar cell device
The manufacture method of solar cell device of the present invention comprises following operation: give the semiconductor substrate that contains the compound with acidic groups passivating film having pn knot and be provided with on the semiconductor substrate of electrode, manufacture thus semiconductor substrate passivating film.Below, with reference to accompanying drawing, the execution mode of the manufacture method of solar cell device of the present invention is described.
Fig. 1 is that schematically showing of exemplifying with cutaway view form has the process chart of an example of the manufacture method of the solar cell device of passivating film for the semiconductor substrate of present embodiment.But, this process chart to using method of the present invention without any restriction.
As shown in Fig. 1 (a), at the near surface formation n+ of p-type semiconductor substrate 1 type diffusion layer 2, and on surface, form antireflection film 3.As antireflection film 3, known have silicon nitride film, an oxidation titanium film etc.At antireflection film 3 and n
+between type diffusion layer 2, can there is the surface protection film (not shown) of silica etc.In addition, can use passivating film of the present invention as surface protection film.
Then, as shown in Fig. 1 (b), the material that aluminium electrode paste agent etc. forms backplate 5 is given in a part of region overleaf, afterwards it is heat-treated and forms backplate 5, and make aluminium diffusion and form p
+type diffusion layer 4.
Then, as shown in Fig. 1 (c), in sensitive surface side (antireflection film 3 sides), give electrode formation paste, afterwards it heat-treated and form surface electrode 7.The material that contains the glass powder with logical (fire through) property of burning by use, as electrode formation paste, can connect antireflection film 3 as shown in Fig. 1 (c), forms and n
+the surface electrode 7 of type diffusion layer 2 contact and obtain ohmic contact.
Finally, as shown in Fig. 1 (d), utilize silk screen printing etc. to give in the region except backplate 5 at the back side of p-type semiconductor substrate 1 to contain have acidic groups compound be used to form the material of passivating film for semiconductor substrate, and it is dried and forms passivating film 6.By the region except backplate 5, form passivating back film 6, thereby can manufacture the solar cell device of generating efficiency excellence.
In utilization, comprise in the solar cell device that the manufacture method of manufacturing process shown in Fig. 1 manufactures, can form with the form of point-contact junction structure the backplate being formed by aluminium etc.Therefore, can reduce warpage by the caused substrate of difference of the thermal coefficient of expansion of semiconductor and aluminium etc.Afterwards, can further utilize evaporation etc. at whole electrode that forms aluminium etc., in addition, also can be whole formation without the electrode at high temperature burning till.
In addition, the method that part overleaf forms passivating film has only been shown in (d) of Fig. 1, but the side (edge) of p-type semiconductor substrate 1 that also can be the rear side except p-type semiconductor substrate 1 is also given and is used to form semiconductor substrate and with the material of passivating film, in side, also forms passivating film (not shown).Thus, can manufacture the solar cell device that generating efficiency is more excellent.In addition, can also not form passivation layer at the back side of semiconductor substrate and only in side, give the material of passivating film for semiconductor substrate that is used to form of the present invention, thereby form passivation layer.The semiconductor substrate that is used to form of the present invention is with the material of passivating film during the position more than the crystal defect the side for as semiconductor substrate, and its effect is large especially.
Fig. 2 is that schematically showing of exemplifying with cutaway view form has another routine process chart of the manufacture method of the solar cell device of passivating film for the semiconductor substrate of present embodiment.Particularly, Fig. 2 comprises the process chart of following operation with cutaway view formal specification: according to required pattern, give aluminium electrode paste agent or can utilize heat diffusion treatment to form p
+the p-type diffusion layer formation composition of type diffusion layer, and it is heat-treated and forms p
+type diffusion layer, afterwards, removes aluminium electrode paste agent or p
+type diffusion layer forms the heat treatment thing with composition.
At this, as p-type diffusion layer formation composition, can enumerate the mixture containing containing recipient element material and glass ingredient.
As shown in Fig. 2 (a), at the near surface formation n of p-type semiconductor substrate 1
+type diffusion layer 2, and on surface, form antireflection film 3.As antireflection film 3, known have silicon nitride film, an oxidation titanium film etc.
Then,, as shown in Fig. 2 (b), in a part of region at the back side of p-type semiconductor substrate 1, give p
+type diffusion layer formation composition, and it is heat-treated and forms p at the back side of p-type semiconductor substrate 1
+type diffusion layer 4.At p
+on type diffusion layer 4, form p
+type diffusion layer forms the heat treatment thing 8 with composition.Replace the formation of p-type diffusion layer to use composition with aluminium electrode paste agent in the situation that, at p
+on type diffusion layer 4, form the heat treatment thing 8 of aluminium electrode paste agent.
Then,, as shown in Fig. 2 (c), utilize etching etc. to remove and be formed at p
+p-type diffusion layer on type diffusion layer 4 forms the heat treatment thing 8 with composition or aluminium electrode paste agent.
Then, as shown in Fig. 2 (d), electrode formation paste is optionally given respectively in a part of region at sensitive surface (surface) and the back side, and it is heat-treated and forms surface electrode 7 at sensitive surface (surface), and forms overleaf backplate 5.The material that contains the glass powder with the burning general character by use, as the electrode formation paste of coating sensitive surface side, can connect antireflection film 3 as shown in Fig. 2 (d), forms and n
+the surface electrode 7 of type diffusion layer 2 contact and obtain ohmic contact.
In the region that forms backplate, formed p
+type diffusion layer 4.Therefore, the electrode that forms backplate 5 forms and is not limited to aluminium electrode paste agent with paste, also can use silver electrode paste etc. can form the paste for use in electrode agent of more low-resistance electrode.Thus, also can further improve generating efficiency.
Finally, as shown in Fig. 2 (e), in the region except backplate 5 at the back side of p-type semiconductor substrate 1, give contain have acidic groups compound be used to form the material of passivating film for semiconductor substrate, and it is dried and forms passivating film 6.By the region except backplate 5, form passivating back film 6, can manufacture the solar cell device of generating efficiency excellence.Afterwards, can further utilize evaporation etc. at whole electrode that forms aluminium etc., in addition, also can be whole formation without the electrode at high temperature burning till.
In addition, the method that part overleaf forms passivating film has only been shown in (e) of Fig. 2, but the side (edge) of p-type semiconductor substrate 1 that also can be beyond the rear side of p-type semiconductor substrate 1 is also given and is used to form semiconductor substrate and with the material of passivating film, in side, also forms passivating film (not shown).Thus, can manufacture the solar cell device that generating efficiency is more excellent.In addition, can also not form passivating film 6 overleaf and only in side, give the material of passivating film for semiconductor substrate that is used to form of the present invention, thereby form passivating film.Of the present invention be used to form semiconductor substrate with the material of passivating film especially when the position more than the crystal defect for as side, its effect is large especially.
To using, at sensitive surface, be formed with n in the above-described embodiment
+the situation of the p-type semiconductor substrate of type diffusion layer is illustrated, but at sensitive surface, is formed with p in use
+in the situation of the N-shaped semiconductor substrate of type diffusion layer, also can similarly manufacture solar cell device.It should be noted that, now, side forms n overleaf
+type diffusion layer.
And then, be used to form semiconductor substrate and only also can be used to form as shown in Figure 3 with the material of passivating film the sensitive surface side of back electrode type solar cell device or the passivating film 6 of rear side that side overleaf disposes electrode.
As shown in the schematic sectional view of Fig. 3, at the near surface of the sensitive surface side of p-type semiconductor substrate 1, form n
+type diffusion layer 2, forms passivating film 6 and antireflection film 3 on its surface.As antireflection film 3, known have silicon nitride film, an oxidation titanium film etc.In addition, passivating film 6 forms with the material of passivating film by giving the semiconductor substrate that is used to form of the present invention.
Rear side at p-type semiconductor substrate 1 forms p
+type diffusion layer 4 and n
+type diffusion layer 2, and backplate 5 is set respectively thereon.Do not forming the region division passivating film 6 of backplate 5.
P
+type diffusion layer 4 can form with composition or aluminium electrode paste agent and it is heat-treated to form by give p-type diffusion layer at desired zone as described above.In addition n,
+type diffusion layer 2 can be by for example giving and can utilize heat diffusion treatment to form n at desired zone
+the N-shaped diffusion layer of type diffusion layer forms and heat-treats to form with composition and to it.As N-shaped diffusion layer formation composition, can enumerate the mixture containing containing donor element material and glass ingredient.
Be separately positioned on p
+type diffusion layer 4 and n
+backplate 5 on type diffusion layer 2 can be by forming and form with paste with normally used electrodes such as silver electrode pastes.
In addition, using aluminium electrode paste agent to form p
+in the situation of type diffusion layer 4, can not remove the heat treatment thing of aluminium electrode paste agent and directly it be used as electrode.
The passivating film 6 that is arranged at the back side can be used to form semiconductor substrate and is dried to form with the material of passivating film and to it by giving in the region that backplate 5 is not set.In addition, passivating film 6 not only can be formed on the back side of semiconductor substrate 1, but also can be formed on side (not shown).
In having the back electrode type solar cell device of structure shown in Fig. 3, owing to not having electrode in sensitive surface side, so light-receiving area is large, and generating efficiency is excellent.And then, by the region not forming backplate, form passivating film, can further improve generating efficiency.
Embodiment
Below, utilize embodiment to be described more specifically the present invention, but the present invention is not subject to the restriction of these embodiment.It should be noted that, in case of no particular description, raw material is all used reagent.In addition, in case of no particular description, " % " is quality criteria.
< embodiment 1>
(preparation of solution for pH pH-value determination pH)
Polyphosphoric acid (with the pure pharmaceutical worker of light industry system) is dissolved in to water, makes the 5 quality % polyphosphoric acid aqueous solution.Use the pH value of pH meter (hole field makes made D-21) to this aqueous solution at 25 ℃ to measure, result is 1.4.
(passivating film forms the preparation with material)
Polyphosphoric acid is dissolved in to ethanol, is prepared into 10% polyphosphoric acid ethanolic solution, obtain passivating film formation material.
(formation of passivating film)
Using surface is that (SUMCO company system, 25mm are square, thickness: 625 μ m) as semiconductor substrate for the monocrystalline type p-type silicon substrate of mirror shape.Use RCA cleaning solution (Northeast chemical company system, trade name Frontier Cleaner-A01) at 70 ℃, silicon substrate washing, after 5 minutes, at room temperature to be flooded them 5 minutes in 2.5 quality % hydrofluoric acid aqueous solutions.Then, after water washs, with ethanol, wash, then carry out air-dry.
Afterwards, at passivating film, form with flooding in material after silicon substrate, carry out air-dryly, on the hot plate of 90 ℃, be dried after 10 minutes, at room temperature place coolingly, formed passivating film.
(mensuration of useful life)
Determinator in useful life (Japanese Shi Meilebo company system, trade name WT-2000PVN), and utilize Photoconductivity decay by microwave reflectance damped method at 25 ℃, the life-span of utilizing above-mentioned operation to form the silicon substrate of passivating film to be measured, result useful life is 140 μ s.
< embodiment 2>
Replace 10% polyphosphoric acid ethanolic solution in embodiment 1 and directly use polyphosphoric acid, in addition, prepare similarly to Example 1 passivating film formation material, and formed passivating film.The useful life of measuring similarly to Example 1 and obtaining is 135 μ s.
< embodiment 3>
Replace 10% polyphosphoric acid ethanolic solution in embodiment 1 and use 10% ethanolic solution of polyacrylic acid (He Guangchun medicine industrial group system, weight average molecular weight 25,000), in addition, formed similarly to Example 1 passivating film.
The pH value of the 5% polyacrylic acid aqueous solution of measuring similarly to Example 1 and obtaining is 2.1.The useful life of measuring similarly to Example 1 and obtaining is 70 μ s.
< embodiment 4>
Replace 10% polyphosphoric acid ethanolic solution in embodiment 1 and use 10% ethanolic solution of polyacrylic acid (He Guangchun medicine industrial group system, weight average molecular weight 5,000), in addition, formed similarly to Example 1 passivating film.
The pH value of the 5% polyacrylic acid aqueous solution of measuring similarly to Example 1 and obtaining is 2.2.The useful life of measuring similarly to Example 1 and obtaining is 70 μ s.
< embodiment 5>
(passivating film forms the preparation with material)
Make the 20% sulfonated polystyrene aqueous solution (with Optical Chemical Company's system) evaporate solid after, residue is dissolved in to ethanol, make 5% sulfonated polystyrene ethanolic solution.With this 5% sulfonated polystyrene ethanolic solution, replace the 10% polyphosphoric acid ethanolic solution using in embodiment 1, formed passivating film.
The 20% sulfonated polystyrene aqueous solution is diluted, make the 5% sulfonated polystyrene aqueous solution, measure similarly to Example 1 and the pH value that obtains is 1.2.The useful life of measuring similarly to Example 1 and obtaining is 190 μ s.
< embodiment 6>
Replace 10% polyphosphoric acid ethanolic solution in embodiment 1 and use phosphotungstic acid (H
3[PW
12o
40] nH
2o, He Guangchun medicine industrial group system) 10% ethanolic solution, in addition, formed similarly to Example 1 passivating film.
The pH value of 5% phosphotungstic acid aqueous solution of measuring similarly to Example 1 and obtaining is 1.6.The useful life of measuring similarly to Example 1 and obtaining is 150 μ s.
< embodiment 7>
Replace 10% polyphosphoric acid ethanolic solution in embodiment 1 and use 5% dispersion liquid (1-propyl alcohol/2-propyl alcohol=45/55 (mass ratio), the water: 15～20%, Aldrich company system) of Nafion (registered trade mark) resin, in addition, formed similarly to Example 1 passivating film.
Under the state of water, 1-propyl alcohol, 2-propyl alcohol mixed dispersion liquid (5%), measure similarly to Example 1 and the pH value that obtains is 2.2.The useful life of measuring similarly to Example 1 and obtaining is 230 μ s.
< comparative example 1>
Do not carry out the coating of 10% polyphosphoric acid ethanolic solution in embodiment 1, in addition, measured similarly to Example 1 the useful life of silicon substrate.Useful life is 25 μ s.
< comparative example 2>
Replace 10% polyphosphoric acid ethanolic solution in embodiment 1 and use 5% polyvinyl alcohol (He Guangchun medicine industrial group system, the degree of polymerization 1000, the partly-hydrolysed type) aqueous solution, in addition, formed similarly to Example 1 passivating film.
The pH value of 5% polyvinyl alcohol water solution of measuring similarly to Example 1 and obtaining is 5.7.The useful life of measuring similarly to Example 1 and obtaining is 25 μ s.
< comparative example 3>
Replace 10% polyphosphoric acid ethanolic solution in embodiment 1 and use polyimides/METHYLPYRROLIDONE solution (unexposed concentration, molecular weight etc.) (Hitachi Chemical DuPont MicroSystems company system, trade name PIX-1400), in addition, formed similarly to Example 1 passivating film.
Make the sedimentation once again in aqueous solvent of above-mentioned polyimide solution, water repeated washing 3 times, obtains polyimides aqueous dispersion (5%).Use this polyimides aqueous dispersion, measure similarly to Example 1 and the pH value that obtains is 7.2.The useful life of measuring similarly to Example 1 and obtaining is 25 μ s.
[table 1]
As known from the above, by give the semiconductor substrate that contains the compound with acidic groups at semiconductor substrate surface, with passivation film formation material, on semiconductor substrate, form passivating film, thereby the useful life that increases substantially the minority carrier in semiconductor substrate and in surface, obtains excellent passivation effect.
For the disclosure of No. 2012-011401, Japanese patent application, using it all as with reference to being incorporated in this specification.Whole documents, patent application and the technical standard in this specification, recorded, with the situation of specifically and respectively having recorded each document, patent application and technical standard with degree as with reference to quoting in this specification.
Claims (15)
1. be used to form a material for passivating film for semiconductor substrate, it comprises the compound with acidic groups.
2. be according to claim 1ly used to form the material of passivating film for semiconductor substrate, wherein, described acidic groups is Bronsted acidity base.
3. be according to claim 1 and 2ly used to form the material of passivating film for semiconductor substrate, wherein, described in there is acidic groups compound be organic acid.
4. be according to claim 3ly used to form the material of passivating film for semiconductor substrate, wherein, described organic acid is at least a kind that is selected from polyacrylic acid, poly-perfluoroolefine sulfonic acid, sulfonated polystyrene derivative and sulfonation poly arylene ether sulfone.
5. be according to claim 1 and 2ly used to form the material of passivating film for semiconductor substrate, wherein, described in there is acidic groups compound be inorganic acid.
6. be according to claim 5ly used to form the material of passivating film for semiconductor substrate, wherein, described inorganic acid is polyphosphoric acid or heteropoly acid.
7. be according to claim 6ly used to form the material of passivating film for semiconductor substrate, wherein, described heteropoly acid is at least a kind that is selected from phosphotungstic acid, silico-tungstic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid and phosphomolybdic acid.
8. according to the material of passivating film for semiconductor substrate that is used to form described in any one in claim 1～7, the compound wherein, with acidic groups shows following acidity: described in there is the compound of acidic groups containing ratio be that the aqueous solution of the 5 quality % pH value at 25 ℃ reaches below 5.
9. be according to claim 8ly used to form the material of passivating film for semiconductor substrate, wherein, described pH value is below 2.5.
10. according to the material of passivating film for semiconductor substrate that is used to form described in any one in claim 1～9, it also contains liquid medium.
11. materials that are used to form semiconductor substrate use passivating film according to claim 10, wherein, described liquid medium comprises at least a kind that is selected from water, methyl alcohol, ethanol, 1-propyl alcohol and 2-propyl alcohol.
12. 1 kinds have the manufacture method of the semiconductor substrate of passivating film for semiconductor substrate, it comprises following operation: on semiconductor substrate, entitle requires the material that is used to form semiconductor substrate use passivating film described in any one in 1～11, forms semiconductor substrate passivating film.
13. manufacture methods with the semiconductor substrate of semiconductor substrate use passivating film according to claim 12, it also comprises following operation: being used to form before semiconductor substrate is imparted on described semiconductor substrate with the material of passivating film described, on described semiconductor substrate, give hydrofluoric acid aqueous solution.
14. 1 kinds of solar cell devices, it has: semiconductor substrate, electrode and the semiconductor substrate passivating film with pn knot, wherein, described semiconductor substrate is described in any one, to be used to form semiconductor substrate filming with the material of passivating film in claim 1～11 with passivating film.
The manufacture method of 15. 1 kinds of solar cell devices, it comprises following operation: be used to form the material of passivating film for semiconductor substrate described in any one in requiring 1～11 having pn knot and be provided with entitle on the semiconductor substrate of electrode, form semiconductor substrate passivating film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012-011401 | 2012-01-23 | ||
| JP2012011401 | 2012-01-23 | ||
| PCT/JP2012/082099 WO2013111463A1 (en) | 2012-01-23 | 2012-12-11 | Material for forming passivation film for semiconductor substrate, method of manufacturing semiconductor substrate comprising passivation film for semiconductor substrate, solar cell element, and method of manufacturing solar cell element |
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| Publication Number | Publication Date |
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| CN104081517A true CN104081517A (en) | 2014-10-01 |
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| CN201280067367.4A Pending CN104081517A (en) | 2012-01-23 | 2012-12-11 | Material for forming passivation film for semiconductor substrate, method of manufacturing semiconductor substrate comprising passivation film for semiconductor substrate, solar cell element, and method of manufacturing solar cell element |
Country Status (4)
| Country | Link |
|---|---|
| JP (2) | JP5971260B2 (en) |
| CN (1) | CN104081517A (en) |
| TW (1) | TW201334198A (en) |
| WO (1) | WO2013111463A1 (en) |
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| JP6295673B2 (en) * | 2014-01-17 | 2018-03-20 | 日立化成株式会社 | Semiconductor substrate with passivation layer, coating type material for forming passivation layer, and solar cell element |
| JP5937258B1 (en) * | 2015-06-23 | 2016-06-22 | 株式会社神鋼環境ソリューション | Radioactive material removal method |
| EP4343870A1 (en) * | 2021-05-19 | 2024-03-27 | Panasonic Intellectual Property Management Co., Ltd. | Semiconductor material, and photoelectric conversion element |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55136403A (en) * | 1979-04-09 | 1980-10-24 | Tokyo Denshi Kagaku Kk | Material for electronic part and method of producing same |
| JP2003086582A (en) * | 2001-09-12 | 2003-03-20 | Sanken Electric Co Ltd | Method for forming protective film of semiconductor element |
| JP2004006565A (en) * | 2002-04-16 | 2004-01-08 | Sharp Corp | Solar cell and its manufacturing method |
| JP2010285518A (en) * | 2009-06-10 | 2010-12-24 | Kaneka Corp | Photocurable composition, and insulating thin film and thin film transistor obtained using the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5491197B2 (en) * | 2007-12-10 | 2014-05-14 | 株式会社カネカ | Curable composition having alkali developability, insulating thin film and thin film transistor using the same |
| CN102640268B (en) * | 2010-03-04 | 2016-03-23 | 日本瑞翁株式会社 | The manufacture method of semiconductor element substrate |
-
2012
- 2012-12-11 WO PCT/JP2012/082099 patent/WO2013111463A1/en active Application Filing
- 2012-12-11 JP JP2013555147A patent/JP5971260B2/en not_active Expired - Fee Related
- 2012-12-11 CN CN201280067367.4A patent/CN104081517A/en active Pending
- 2012-12-28 TW TW101150797A patent/TW201334198A/en unknown
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55136403A (en) * | 1979-04-09 | 1980-10-24 | Tokyo Denshi Kagaku Kk | Material for electronic part and method of producing same |
| JP2003086582A (en) * | 2001-09-12 | 2003-03-20 | Sanken Electric Co Ltd | Method for forming protective film of semiconductor element |
| JP2004006565A (en) * | 2002-04-16 | 2004-01-08 | Sharp Corp | Solar cell and its manufacturing method |
| JP2010285518A (en) * | 2009-06-10 | 2010-12-24 | Kaneka Corp | Photocurable composition, and insulating thin film and thin film transistor obtained using the same |
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| Publication number | Publication date |
|---|---|
| JP5971260B2 (en) | 2016-08-17 |
| JPWO2013111463A1 (en) | 2015-05-11 |
| WO2013111463A1 (en) | 2013-08-01 |
| JP2015228527A (en) | 2015-12-17 |
| TW201334198A (en) | 2013-08-16 |
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