CN103348449A - Composition for forming n-type diffusion layer, process for producing n-type diffusion layer, and process for producing solar cell - Google Patents

Composition for forming n-type diffusion layer, process for producing n-type diffusion layer, and process for producing solar cell Download PDF

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CN103348449A
CN103348449A CN2012800083179A CN201280008317A CN103348449A CN 103348449 A CN103348449 A CN 103348449A CN 2012800083179 A CN2012800083179 A CN 2012800083179A CN 201280008317 A CN201280008317 A CN 201280008317A CN 103348449 A CN103348449 A CN 103348449A
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diffusion layer
type diffusion
composition
forms
glass
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町井洋一
吉田诚人
野尻刚
冈庭香
岩室光则
足立修一郎
佐藤铁也
木泽桂子
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
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    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
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    • H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
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Abstract

A composition for forming an n-type diffusion layer, comprising: a dispersion medium; and a glass powder comprising at least one component selected from ZrO2, Al2O3, TiO2, ZnO, MgO, CaO, SrO and BaO and P2O5.

Description

N type diffusion layer forms with composition, the manufacture method of n type diffusion layer and the manufacture method of solar battery cell
Technical field
The present invention relates to a kind of n type diffusion layer formation composition, the manufacture method of n type diffusion layer and the manufacture method of solar battery cell, more specifically, the present invention relates to a kind of can be in the technology that forms n type diffusion layer as the specific part of the silicon substrate of semiconductor substrate.
Background technology
Manufacturing process to existing silicon solar cell unit describes.
At first, in order to promote that falling into luminous effect seeks high efficiency, prepares to be formed with the p-type silicon substrate of texture structure, then at phosphorous oxychloride (POCl 3), under the mixed-gas environment of nitrogen and oxygen with 800 ℃～900 ℃ processing of carrying out dozens of minutes, and similarly form n type diffusion layer.In this existing method, carry out the diffusion of phosphorus because using mist, so not only form n type diffusion layer on the surface, and in the side, the back side also forms n type diffusion layer.Therefore, need carve operation with the lateral erosion of the n type diffusion layer that removes the side.In addition, the n type diffusion layer at the back side must convert p to +The type diffusion layer.Therefore, give the Aluminum Paste that contains as the aluminium of the 13rd family's element on the n type diffusion layer overleaf after, heat-treat, convert p by the diffusion of aluminium to from n type diffusion layer +The type diffusion layer obtains ohmic contact simultaneously.
On the other hand, in semi-conductive manufacturing field, proposed to contain phosphorus pentoxide (P by coating 2O 5) or ammonium dihydrogen phosphate (NH 4H 2PO 4) wait phosphatic solution to form the method (for example, with reference to TOHKEMY 2002-75894 communique) of n type diffusion layer.But because using solution in the method, so identical with the gas-phase reaction method that uses above-mentioned mist, the diffusion of phosphorus also arrives side and the back side, not only forms n type diffusion layer on the surface, and in the side, the back side also forms n type diffusion layer.
As mentioned above, when forming n type diffusion layer, in the gas-phase reaction of using phosphorous oxychloride, not only originally needing the one side of n type diffusion layer (to be generally sensitive surface, the surface) forms n type diffusion layer, and also form n type diffusion layer at another side (non-sensitive surface, the back side) or side.In addition, contain phosphatic solution and carry out in the method for thermal diffusion in coating, identical with gas-phase reaction method, also form n type diffusion layer at the face except the surface.Therefore, in order to have the pn junction structure, must carry out etching as element in the side, convert n type diffusion layer to the p-type diffusion layer overleaf.Usually, be coated with the paste as the aluminium of the 13rd family's element overleaf, and burn till, thereby convert n type diffusion layer to the p-type diffusion layer.
Summary of the invention
The present invention researches and develops and finishes in view of above existing problem points, its problem is, provide a kind of in the manufacturing process of the solar battery cell that uses crystalline silicon substrate, can not form unwanted n type diffusion layer and form with composition, n type diffusion layer at the n type diffusion layer that specific part forms n type diffusion layer and to form manufacture method, the manufacture method of n type diffusion layer and the manufacture method of solar battery cell with composition.
The method that solves above-mentioned problem is as described below.
＜1 〉. a kind of n type diffusion layer forms uses composition, and it contains decentralized medium and comprise and is selected from ZrO 2, Al 2O 3, TiO 2, at least a and P among ZnO, MgO, CaO, SrO and the BaO 2O 5Glass powder.
＜2 〉. according to＜1〉described n type diffusion layer forms and uses composition, described glass powder to contain the P of 30 quality %～90 quality % 2O 5
＜3 〉. according to＜1〉or＜2〉described n type diffusion layer form that to use composition, the equal particle diameter of the body of described glass powder be below the 100 μ m.
＜4 〉. a kind of manufacture method of n type diffusion layer has aforementioned＜1 of coating～＜3 in each described n type diffusion layer form operation with composition and the operation of implementing heat diffusion treatment.
＜5 〉. a kind of manufacture method of solar battery cell has in aforementioned＜1 of semiconductor substrate coating～＜3 in each described n type diffusion layer form operation with composition, and implement the operation that heat diffusion treatment forms n type diffusion layer.
According to the present invention, can provide a kind of in the manufacturing process of the solar battery cell that uses crystalline silicon substrate, can not form unwanted n type diffusion layer and form at the n type diffusion layer that specific part is forming n type diffusion layer and to use composition.In addition, can provide a kind of this n type diffusion layer of using to form with the manufacture method of the n type diffusion layer of composition and the manufacture method of solar battery cell.
Description of drawings
Fig. 1 is the profile of an example that schematically shows the manufacturing process of solar battery cell of the present invention.
Fig. 2 A is the vertical view from the viewed solar battery cell in surface.
Fig. 2 B is the stereogram that the part of Fig. 2 A is amplified expression.
Embodiment
At first, n type diffusion layer formation of the present invention is described with composition, describe with the n type diffusion layer of composition and the manufacture method of solar battery cell using n type diffusion layer to form afterwards.
Need to prove that in this manual, " operation " this term not only refers to independently operation, in the time can't being distinguished clearly with other operations, as long as reach the effect of the expection of this operation, then be also contained in this term.
In addition, in this manual, use the number range of "～" expression to represent to comprise that the numerical value of putting down in writing before and after it is respectively as minimum value and peaked scope.
And then, with regard to the amount of each composition in the composition, in composition, exist under the situation of a plurality of materials that are equivalent to each composition, do not specify as long as have in advance, then represent the total amount of existing these a plurality of materials in the composition.
[n type diffusion layer forms and uses composition]
N type diffusion layer of the present invention forms and contains glass powder and decentralized medium with composition, and then considers coating etc., also can contain other additives as required.In addition, above-mentioned glass powder contains the P as phosphorus composition 2O 5Be used as containing the material of donor element, and comprise and be selected from ZrO 2, Al 2O 3, TiO 2, at least a glass ingredient material that is used as among ZnO, MgO, CaO and the BaO.
Herein, so-called n type diffusion layer forms and use composition, refer to contain donor element and can be by making this donor element thermal diffusion after being coated on the silicon substrate, thereby the material of formation n type diffusion layer uses among the present invention P (phosphorus) as donor element.And the n type diffusion layer of the application of the invention forms use composition, only at desired position formation n type diffusion layer, and not overleaf or the side form unwanted n type diffusion layer.
Therefore, use composition if application n type diffusion layer of the present invention forms, then do not need necessary lateral erosion operation at quarter in the existing gas-phase reaction method that extensively adopts, thereby operation is simplified.In addition, do not need to convert n type diffusion layer to p overleaf yet +The operation of type diffusion layer.Therefore, the p at the back side +The formation method of type diffusion layer, perhaps the material of backplate, shape and thickness are also unrestricted, and the selection degree of freedom of applicable manufacture method or material, shape obtains enlarging.In addition, be inhibited by the generation of the internal stress in the caused silicon substrate of the thickness of backplate, the warpage of silicon substrate also is inhibited, and details is with aftermentioned.
In addition, by burning till n type diffusion layer of the present invention is formed with the glass powder fusion that contains in the composition, form glassy layer at n type diffusion layer.But, contain in the method for phosphatic solution at existing gas-phase reaction method or coating, also form glassy layer at n type diffusion layer, so the glassy layer that generates among the present invention can similarly remove with existing method by etching.
Therefore, even compare with existing method, n type diffusion layer of the present invention forms can not produce unwanted product with composition yet, can not increase operation yet.
In addition, glass powder is with to contain phosphatic solution different, even in sintering process, the volatilization of donor element also is inhibited, therefore n type diffusion layer not only is formed on the surface because of the generation of the volatilization gas that contains donor element, and the situation that also is formed up to the back side or side is prevented.It is as follows that its reason can be thought: because the element of alms giver's composition in glass powder is combined, perhaps be fed in the glass, therefore be difficult to volatilization.
And then, form with in the composition at n type diffusion layer of the present invention, as mentioned above, use P 2O 5As the material that contains donor element, and use is selected from ZrO 2, Al 2O 3, TiO 2, at least a as the glass ingredient material among ZnO, MgO, CaO, SrO and the BaO.Thus, compare with the above-mentioned situation of glass ingredient material of not using, the regioselectivity when n type diffusion layer forms promotes.
Particularly, can think: because phosphorous oxide is big for the solubility of water, therefore if n type diffusion layer forms with the glass powder moisture absorption that contains in the composition, then phosphorous oxide and water react and generate phosphoric acid.And, form n type diffusion layer if use the n type diffusion layer that contains phosphoric acid to form with composition, then have following situation: phosphoric acid evaporates because of heating, the phosphoric acid that evaporates is attached to uncoated n type diffusion layer such as the back side of substrate and forms position with composition, and forms unwanted n type diffusion layer.
Can think: be selected from ZrO by use 2, Al 2O 3, TiO 2, at least a as the glass ingredient material among ZnO, MgO, CaO, SrO and the BaO, the resistance to water that n type diffusion layer forms with composition can promote, so forming and can be inhibited by the caused unwanted n type diffusion layer of the moisture absorption of glass powder.
That is, be above-mentioned formation because the n type diffusion layer of the invention described above forms with composition, form n type diffusion layer even therefore for example under hot and humid environment, preserve the back, because of the resistance to water height, also can optionally carry out the formation of n type diffusion layer according to specific part.
Below, sometimes with ZrO 2, Al 2O 3, TiO 2, ZnO, MgO, CaO, SrO and BaO be generically and collectively referred to as " the glass ingredient material that promotes resistance to water ".
＜glass powder 〉
Glass powder of the present invention is elaborated.
As mentioned above, glass powder of the present invention contains the P as phosphorus composition 2O 5Be used as containing the material of donor element, and contain at least a glass ingredient material that is used as of the glass ingredient material of above-mentioned lifting resistance to water.
P as the material that contains donor element 2O 5In the P (phosphorus) that contains be can be by being entrained in a kind of of the element (donor element) that forms n type diffusion layer in the silicon substrate, and with regard to the viewpoint of fail safe, vitrified easiness etc., be preferred element among donor element.
As the glass ingredient material, use glass ingredient material at least a of above-mentioned lifting resistance to water.Also can use the glass ingredient material of the lifting resistance to water more than 2 kinds.
In addition, except the glass ingredient material that promotes resistance to water, also can and with the glass ingredient material beyond the glass ingredient material that promotes resistance to water (below, be sometimes referred to as " other glass ingredient materials ").With the glass ingredient material and other glass ingredient materials that promote resistance to water, can control resistance to water, melt temperature, softening point, glass transition temperature, chemical durability etc. by also.
As other glass ingredient materials, for example can enumerate: SiO 2, K 2O, Na 2O, Li 2O, BeO, PbO, CdO, SnO, MoO 3, La 2O 3, Nb 2O 5, Ta 2O 5, Y 2O 3, GeO 2, TeO 2And Lu 2O 3Deng.
Among above-mentioned other glass ingredient materials, with regard to the viewpoint of resistance to water, more preferably SiO 2, Y 2O 3, Nb 2O 5And La 2O 3
On the other hand, among above-mentioned other glass ingredient materials, for the Na that might cause that resistance to water descends 2O, K 2O and Li 2O with regard to the viewpoint of resistance to water, is preferably below the 5 quality % of glass powder integral body, does not more preferably contain Na 2O, K 2O and Li 2O.
In the above-mentioned glass powder, P 2O 5The ratio that contains be preferably 30 quality %～90 quality %, 35 quality %～85 quality % more preferably.
As the concrete example of glass powder, for example can enumerate: P 2O 5-ZrO 2Be glass, P 2O 5-Al 2O 3Be glass, P 2O 5-TiO 2Be glass, P 2O 5-ZnO is glass, P 2O 5-MgO is glass, P 2O 5-CaO is glass, P 2O 5-BaO glass, P 2O 3-SrO is glass.
In above-mentioned illustration comprise the compound glass of 2 kinds of compositions, but also can be P as required 2O 5-Al 2O 3-ZnO, P 2O 5-CaO-SiO 2Deng the above compound glass of 3 kinds of compositions.
Glass ingredient material in the glass powder (namely, promote glass ingredient material and other glass ingredient materials of resistance to water) to contain ratio comparatively ideal be to consider resistance to water, melt temperature, softening point, glass transition temperature, chemical durability and suitable the setting, usually be preferably more than the 0.1 quality % and below the 95 quality %, more preferably more than the 0.5 quality % and below the 90 quality %.
In addition, with regard to the viewpoint of resistance to water, the ratio that contains of the glass ingredient material of the lifting resistance to water in the glass powder is preferably more than the 1 quality % and below the 50 quality %, more preferably more than the 5 quality % and below the 40 quality %, more preferably more than the 5 quality % and below 30 quality.
And then with regard to the viewpoint of resistance to water, the content that promotes the glass ingredient material of resistance to water is preferably more than 0.05 times and below 2 times of content of the material that contains donor element, more preferably more than 0.1 times and below 1 times.
Particularly, for example at P 2O 5-CaO is under the situation of glass, and the ratio that contains of CaO is preferably more than the 1 quality % and below the 50 quality %, more preferably more than the 5 quality % and below the 30 quality %.
With regard to the viewpoint of the diffusivity during with regard to DIFFUSION TREATMENT, dropping liquid stream, the softening point of glass powder is preferably 200 ℃～1000 ℃, more preferably 300 ℃～900 ℃.
The equal particle diameter of the body of glass powder is comparatively ideal to be below the 100 μ m.During the glass powder of the particle diameter below use has 100 μ m, be easy to obtain level and smooth filming.And then the particle diameter of glass powder is more preferably below the 50 μ m.More preferably below the 10 μ m.The lower limit of the equal particle diameter of body of glass powder is not particularly limited, but if consider the dispersiveness of coating or the manufacturing cost of glass powder, then is preferably more than the 0.01 μ m, more preferably more than the 0.1 μ m, and then more preferably more than the 0.5 μ m.
Here, the frequency distribution of above-mentioned glass powder is for example to use particle size distribution device (Beckman coulter company manufacturing, model: LS13320) as determinator, measure and obtain making glass powder be dispersed in the dispersion liquid that forms in the solvent (for example water).
Shape as glass powder, can enumerate roughly spherical, flat, bulk, tabular, and flakey etc., when forming with composition with regard to making n type diffusion layer for regard to the coating or even diffusible viewpoint of substrate, comparatively ideal is spherical, flat or tabular roughly.
Glass powder is to make by following program.
At first, raw materials weighing (for example above-mentioned material and the glass ingredient material that contains donor element) is filled in the crucible then.The material of crucible can be enumerated platinum, platinum-rhodium, iridium, aluminium oxide, quartz, carbon etc., can consider the reactivity etc. of melt temperature, environment and melt substance and suitably selects.
Next, heat and make liquation to form corresponding temperature with glass by electric furnace.At this moment, comparatively ideal is that uniform mode stirs so that liquation becomes.
Then, the uniform liquation that becomes is flowed out on zirconia substrate or the carbon base plate etc. and with the liquation vitrifying.
At last, pulverize glass and form Powdered.Pulverizing can be used known method such as jet mill, ball mill, ball mill.
The ratio that contains that n type diffusion layer forms with the glass powder in the composition is that the diffusivity etc. of consideration coating, donor element decides.Usually, the ratio that contains that n type diffusion layer forms with the glass powder in the composition is preferably more than the 0.1 quality % and below the 95 quality %, more preferably more than the 1 quality % and below the 90 quality %, and then more preferably more than the 5 quality % and below the 80 quality %.
＜decentralized medium 〉
Next, decentralized medium is described.
So-called decentralized medium refers to the medium that above-mentioned glass powder is disperseed.Particularly, adopt binding agent or solvent etc. as decentralized medium.
As binding agent, for example can suitably select: (methyl) dimethylaminoethyl acrylate polymer, polyvinyl alcohol, polyacrylamide, the polyvinyl amide-type, polyvinylpyrrolidone, poly-(methyl) acrylic compounds, the poly(ethylene oxide) class, poly-sulfonic acid, acrylamide alkyl sulfonic acid, cellulose ethers, cellulose derivative, carboxymethyl cellulose, hydroxyethylcellulose, ethyl cellulose, gelatin, starch and starch derivatives, the sodium alginate class, xanthans, guar gum and guar derivative, scleroglucan and scleroglucan derivative, bassora gum and bassora gum derivative, dextrin and dextrin derivative, acrylic resin, acrylate, butadiene resin, styrene resin and these copolymer, and silicon dioxide etc.These can use a kind or will be used in combination more than 2 kinds separately.
There is no particular restriction for the molecular weight of binding agent, and comparatively ideal is according to as the desired viscosity of composition and suitable the adjustment.
As solvent, for example can enumerate: acetone, methyl ethyl ketone, methyl n-pro-pyl ketone, methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl n hexyl ketone, metacetone, dipropyl ketone, DIBK, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2, ketone series solvents such as 4-pentanedione, acetonyl acetone; Anaesthetie Ether, methyl ethyl ether, the methyl n-propyl ether, Di Iso Propyl Ether, oxolane, methyltetrahydrofuran diox, dimethyl dioxane, ethylene glycol dimethyl ether, the ethylene glycol bisthioglycolate ethylether, the ethylene glycol bisthioglycolate n-propyl ether, the ethylene glycol bisthioglycolate butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diethylene glycol (DEG) methyl ethyl ether, diethylene glycol (DEG) methyl n-propyl ether, diethylene glycol (DEG) methyl n-butyl ether, diethylene glycol (DEG) di ether, the diethylene glycol (DEG) di-n-butyl ether, the diethylene glycol (DEG) diola, the triethylene glycol dimethyl ether, the triethylene glycol Anaesthetie Ether, the triethylene glycol methyl ethyl ether, triethylene glycol methyl n-butyl ether, the triethylene glycol di-n-butyl ether, the triethylene glycol diola, the TEG dimethyl ether, the TEG Anaesthetie Ether, the TEG methyl ethyl ether, TEG methyl n-butyl ether, the diethylene glycol (DEG) di-n-butyl ether, TEG methyl-n-hexyl ether, the TEG di-n-butyl ether, the propylene glycol dimethyl ether, the propylene glycol Anaesthetie Ether, propylene glycol di ether, the propylene glycol dibutyl ethers, the DPG dimethyl ether, the DPG Anaesthetie Ether, the DPG methyl ethyl ether, DPG methyl n-butyl ether, DPG di ether, the DPG di-n-butyl ether, the DPG diola, the tripropylene glycol dimethyl ether, the tripropylene glycol Anaesthetie Ether, the tripropylene glycol methyl ethyl ether, tripropylene glycol methyl-n-butyl ether, the tripropylene glycol di-n-butyl ether, the tripropylene glycol diola, four propylene glycol dimethyl ethers, four propylene glycol Anaesthetie Ethers, four propylene glycol methyl ethyl ethers, four propylene glycol methyl-n-butyl ether, the DPG di-n-butyl ether, four propylene glycol methyl-n-hexyl ether, ether series solvents such as four propylene glycol di-n-butyl ethers; Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, acetic acid 3-methoxyl group butyl ester, methyl amyl acetate, acetic acid 2-ethyl butyl ester, acetic acid 2-Octyl Nitrite, acetic acid 2-(2-butoxy ethyoxyl) ethyl ester, benzyl acetate, cyclohexyl acetate, the methyl acetate cyclohexyl, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, diethylene glycol (DEG) methyl ether acetic acid esters, diethylene glycol monoethyl ether acetate, the dipropylene glycol methyl ether acetic acid esters, DPG ethylether acetic acid esters, ethylene acetate, methoxyl group triethylene glycol acetic acid esters, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, the ethanedioic acid di-n-butyl, methyl lactate, ethyl lactate, n-butyl lactate, the lactic acid n-pentyl ester, Ethylene Glycol Methyl ether propionic ester, the glycol ethyl ether propionic ester, Ethylene Glycol Methyl ether acetic acid ester, ethylene glycol monoethyl ether acetate, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, gamma-butyrolacton, ester series solvents such as gamma-valerolactone; Acetonitrile, N-methyl pyrrolidone, N-ethyl pyrrolidone, N-propyl pyrrole alkane ketone, N-butyl pyrrolidine ketone, N-hexyl pyrrolidones, N-cyclohexyl pyrrolidones, N, dinethylformamide, N, non-proton property polar solvents such as N-dimethylacetylamide, dimethyl sulfoxide (DMSO); Methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, the 2-methyl butanol, sec-amyl alcohol, tert-pentyl alcohol, the 3-methoxybutanol, n-hexyl alcohol, the 2-methyl anyl alcohol, secondary hexyl alcohol, the 2-ethyl butanol, secondary enanthol, n-octyl alcohol, 2-Ethylhexyl Alcohol, secondary octanol, n-nonyl alcohol, Decanol, secondary undecyl alcohol, trimethyl nonyl alcohol, secondary myristyl alcohol, secondary heptadecyl alcohol, phenol, cyclohexanol, methyl cyclohexanol, benzyl alcohol, ethylene glycol, 1, the 2-propylene glycol, 1,3-butanediol, diethylene glycol (DEG), DPG, triethylene glycol, pure series solvent such as tripropylene glycol; Glycol monoether series solvents such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl phenyl ether, diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary n-butyl ether, diglycol monotertiary n-hexyl ether, ethyoxyl triethylene glycol, TEG list n-butyl ether, propylene glycol monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, tripropylene glycol monomethyl ether; Terpene series solvents such as α-terpinenes, α-terpineol, myrcene, alloocimene, citrene, dipentene, australene, nopinene, terpinol, carvol, ocimenum, phellandrene; Water.These may be used alone or in combination of two or more kinds.
N type diffusion layer forms with the ratio that contains of the decentralized medium in the composition considers that coating, donor concentration (P (phosphorus) concentration) decide.
Consider coating, the viscosity that n type diffusion layer forms with composition is preferably more than the 10mPaS and below the 1000000mPaS, more preferably more than the 50mPas and below the 500000mPaS.
[manufacture method of n type diffusion layer and solar battery cell]
Below, with reference to Fig. 1 on one side the manufacture method of of the present invention n type diffusion layer and solar battery cell described on one side.Fig. 1 is the constructed profile of an example that schematically shows the manufacturing process of solar battery cell of the present invention.In following accompanying drawing, to identical inscape mark prosign.
Among Fig. 1 (1), remove damaged layer to giving alkaline solution as the silicon metal of p-type semiconductor substrate 10, and obtain texture structure by etching.
Specifically, utilize 20 quality % caustic soda to remove the damaged layer of the silicon face that when ingot is cut into slices, produces.Then utilize the mixed liquor of 1 quality % caustic soda and 10 quality % isopropyl alcohols to carry out etching, thereby form texture structure (record of omit texture structure among the figure).Solar battery cell can promote to fall into luminous effect by form texture structure in sensitive surface (surface) side, seeks high efficiency.
Among Fig. 1 (2), the formation of said n type diffusion layer is namely become on the face of sensitive surface with the surface that composition is coated on p-type semiconductor substrate 10, form n type diffusion layer and form with composition layer 11.Among the present invention, coating process is also unrestricted, print process, spin-coating method, hairbrush coating, spray-on process is for example arranged, scrape the skill in using a kitchen knife in cookery, roll coater method, ink-jet method etc.
Said n type diffusion layer forms the coating weight of using composition, and there is no particular restriction, for example can be made as 10g/m 2～250g/m 2, be preferably 20g/m 2～150g/m 2
In addition, form the composition of using composition according to n type diffusion layer, need sometimes to make the drying process of the solvent evaporates that contains in the composition for after coating.In this case, under the temperature about 80 ℃～300 ℃, drying is 1～10 minute when using heating plate, and drying is about 10～30 minutes when using drying machine etc.This drying condition forms with n type diffusion layer uses the solvent composition of composition relevant, is not particularly limited in the present invention in above-mentioned condition.
In addition, when using manufacture method of the present invention, the p at the back side +The manufacture method of type diffusion layer (high concentration electric field layer) 14 is not limited to convert formed n type diffusion layer the method for p-type diffusion layer to by aluminium, also can adopt existing known any method, thereby can enlarge the selection degree of freedom of manufacture method.Therefore, the composition 13 that for example can give the element that contains B (boron) grade in an imperial examination 13 families forms high concentration electric field layer 14.
Then, under 600 ℃～1200 ℃, carry out heat diffusion treatment to being formed with the semiconductor substrate 10 that said n type diffusion layer forms with composition layer 11.By this heat diffusion treatment, shown in Fig. 1 (3), donor element spreads in semiconductor substrate, forms n type diffusion layer 12.But the continuous oven of heat diffusion treatment application of known, batch furnace etc.In addition, also can suit to be adjusted to air, oxygen, the nitrogen etc. of the furnace inner environment during heat diffusion treatment.
The heat diffusion treatment time can form the suitably selection with the containing ratio of the donor element that contains in the composition etc. according to n type diffusion layer.For example, can be made as 1～60 minute more preferably 2～30 minutes.
Owing to be formed with glassy layers such as phosphoric acid glass (not shown) on the surface of formed n type diffusion layer 12, so remove this phosphoric acid glass by etching.Etching can be used method in the acid such as being immersed in hydrofluoric acid, is immersed in the known method such as method in the alkali such as caustic soda.
Form in the formation method of the n type diffusion layer of the present invention that forms n type diffusion layer 12 with composition 11 at the use n type of the present invention diffusion layer shown in Fig. 1 (2) and Fig. 1 (3), only form n type diffusion layer 12 at desired position, not overleaf or the side form unwanted n type diffusion layer.
Therefore, though need lateral erosion to carve operation, manufacturing method according to the invention in order to remove the unwanted n type diffusion layer that is formed at the side existing passing through of extensively adopting in the method that gas-phase reaction method forms n type diffusion layer, then do not need lateral erosion to carve operation, thereby operation is oversimplified.
In addition, in existing manufacture method, the unwanted n type diffusion layer that must will be formed on the back side converts the p-type diffusion layer to, as its conversion method, adopt following method: coating is as the paste of the aluminium of the 13rd family's element on the n type diffusion layer overleaf, and burn till, make aluminium diffuse to n type diffusion layer and convert n type diffusion layer to the p-type diffusion layer.In the method, in order to convert n type diffusion layer to the p-type diffusion layer fully, and then form p +The high concentration electric field layer of layer, and need above to a certain degree aluminium amount, therefore must form aluminium lamination thicker.But the thermal coefficient of expansion of aluminium differs greatly with the thermal coefficient of expansion of the silicon that is used as substrate, therefore in the process of burning till and cooling off, produces bigger internal stress in silicon substrate, and becomes the reason of the warpage of silicon substrate.
Exist this internal stress that the crystal boundary of crystallization is caused damage, power loss becomes big technical problem.In addition, the transportation of the solar battery cell of warpage in the modularization operation or with the connection procedure of the lead that is called as lug (Tab) line in, make the unit breakage easily.In recent years, because the raising of slicing technology, so the slimming gradually of the thickness of crystalline silicon substrate, thereby the tendency that exists the unit to be more prone to break.
But manufacturing method according to the invention does not form unwanted n type diffusion layer overleaf, therefore need not to carry out by the conversion of n type diffusion layer to the p-type diffusion layer, and needn't make the aluminium lamination thickening.Its result can suppress generation or the warpage of the internal stress in the silicon substrate.As a result of, can suppress the increase of power loss, or the breakage of unit.
In addition, when using manufacture method of the present invention, the p at the back side +The manufacture method of type diffusion layer (high concentration electric field layer) 14 is not limited to convert formed n type diffusion layer the method for p-type diffusion layer to by aluminium, also can adopt existing known any method, can enlarge the selection degree of freedom of manufacture method.
In addition, as described later, the material that is used for the surface electrode 20 at the back side is not limited to the aluminium of the 13rd family, for example can use Ag (silver) or Cu (copper) etc., the also more unfertile land formation of comparable existing thickness of the thickness of the surface electrode 20 at the back side.
Among Fig. 1 (4), form anti-reflective film 16 at n type diffusion layer 12.Anti-reflective film 16 is that the technology of application of known forms.For example, when anti-reflective film 16 is silicon nitride film, by with SiH 4With NH 3Mist form as PCVD (CVD) method of raw material.At this moment, hydrogen spreads in crystallization, and the track that does not participate in the key Cheng Jian of silicon atom is dangling bonds and hydrogen bonding, makes defective passivation (hydrogen passivation).
More specifically, compare NH at above-mentioned mixed gas flow 3/ SiH 4Be 0.05～1.0, the pressure of reative cell is that (13.3Pa～266.6Pa), the temperature during film forming is 300 ℃～550 ℃ to 0.1～2Torr, and the frequency that is used for isoionic discharge is to form under the above condition of 100kHz.
Among Fig. 1 (5), by silk screen print method surface electrode is coated on the anti-reflective film 16 on surface (sensitive surface) with the printing of metal paste, and made its drying, thereby form surface electrode 18.Surface electrode uses the metal paste with (1) metallic and the essential composition of (2) glass particle conduct, and comprises (3) resinoid bond, (4) other additives etc. as required.
Next, on the high concentration electric field layer 14 at the above-mentioned back side, also form backplate 20.As mentioned above, the material of backplate 20 or formation method are not particularly limited among the present invention.For example, can be coated with the backplate paste of metals such as comprising aluminium, silver or copper, and make its drying and formation backplate 20.At this moment, for the connection between the unit in the module operation, the silver-colored paste of silver electrode formation can be set also in a zone.
Among Fig. 1 (6), electrode is burnt till, make solar battery cell.If in 600 ℃～900 ℃ scope, burn till several seconds～a few minutes, can fusion take place in face side owing to the glass particle that electrode contains in the metal paste as the anti-reflective film 16 of dielectric film then, and then the also fusion of a part on silicon 10 surfaces, the metallic in the paste (for example silver particles) forms contact site with silicon substrate 10 and solidifies.Thus, formed surface electrode 18 is switched on silicon substrate 10.It is logical that this is called burning.
Shape to surface electrode 18 describes.Surface electrode 18 comprises bus-bar electrode 30, reaches the finger electrode 32 that intersects with this bus-bar electrode 30.Fig. 2 A is the vertical view by the surface observation solar battery cell, in the described solar battery cell, surface electrode 18 is that Fig. 2 B is the stereogram that the part amplification of Fig. 2 (A) is represented by bus-bar electrode 30 and the structure that constitutes with finger electrode 32 that this bus-bar electrode 30 intersects.
This surface electrode 18 can be by for example above-mentioned metal paste silk screen printing or the plating of electrode material, the methods such as evaporation of the electrode material that utilizes the electron beam heating in the high vacuum form.As everyone knows, the surface electrode 18 that comprises bus-bar electrode 30 and finger electrode 32 is typically used as the electrode of sensitive surface side, can use the known formation method of bus-bar electrode and the finger electrode of sensitive surface side.
In above-mentioned, to form n type diffusion layer on the surface, form p overleaf +The type diffusion layer, and then the solar battery cell that each layer is provided with surface electrode and backplate is illustrated, but use composition if use n type diffusion layer of the present invention to form, then also can make the solar battery cell of carrying on the back contact-type.
The solar battery cell of back of the body contact-type is electrode all to be arranged on the back side and the solar battery cell that increases the area of sensitive surface.That is, in the solar battery cell of back of the body contact-type, must form n type diffusion position and p overleaf +Both form the pn junction structure type diffusion position.N type diffusion layer of the present invention forms with composition can only form n type diffusion position at specific position, therefore can be applied to carry on the back the manufacturing of the solar battery cell of contact-type aptly.In addition, n type diffusion layer of the present invention forms with composition and also can be applicable to for example only form high concentration n type diffusion layer (n under electrode ++Layer) selective emitter.
Need to prove, by reference the full content that discloses among the Japanese Patent Application 2011-032430 is quoted to this specification.
All documents of putting down in writing in this specification, patent application, and technical specification be with put down in writing particularly and individually by with reference to quoting each document, patent application, and identical degree during technical specification, by with reference to being incorporated in this specification.
Embodiment
Below, be described more specifically embodiments of the invention, but the present invention is not limited by these embodiment.In addition, as long as there be not special the record in advance, then chemicals has all used reagent.In addition, as long as do not have explanation, then " % " expression " quality % " in advance.
Embodiment 1
With P 2O 5-CaO is glass (P 2O 5: 80%, CaO:20%) powder (the equal particle diameter of body is 3 μ m) is loaded in the container that has broken a seal, 50 ℃ of temperature, places 24 hours under the environment of humidity 70%.
Next, this glass powder 10g, ethyl cellulose 5g and acetic acid 2-(2-butoxy ethyoxyl) ethyl ester 85g are mixed and pasteization, preparation n type diffusion layer forms uses composition.
By silk screen printing the formation of n type diffusion layer is become 15g/m with composition with coating weight 2～20g/m 2Mode be coated on p-type silicon substrate surface, and on 150 ℃ heating plate dry 5 minutes.Then, utilize the electric furnace of setting 1000 ℃ for to carry out 10 minutes heat diffusion treatment, subsequently, in order to remove glassy layer substrate was flooded in hydrofluoric acid 5 minutes, carry out flowing water then and clean.Carry out drying subsequently.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 15 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.(above can't the mensuration of 1000000 Ω/) do not form n type diffusion layer to the film resistor at the back side in order to measure the upper limit.
Need to prove that the value of the film resistor on above-mentioned surface is equally spaced to carry out 5 point * 5 mensuration in the zone of 156cm * 156cm, and represent its average value (also identical in following embodiment and the comparative example).
Embodiment 2
As glass powder, use P 2O 5-ZnO is glass (P 2O 5: 70%, ZnO:30%) powder (the equal particle diameter of body is 3 μ m) in addition, forms n type diffusion layer in similarly to Example 1 mode.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 20 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.
(above can't the mensuration of 1000000 Ω/) do not form n type diffusion layer to the film resistor at the back side in order to measure the upper limit.
Embodiment 3
As glass powder, use P 2O 5-SiO 2-CaO is glass (P 2O 5: 50%, SiO 2: 40%, CaO:10%) powder (the equal particle diameter of body is 1 μ m) in addition, forms n type diffusion layer in similarly to Example 1 mode.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 17 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.
(above can't the mensuration of 1000000 Ω/) do not form n type diffusion layer to the film resistor at the back side in order to measure the upper limit.
Embodiment 4
As glass powder, use P 2O 5-Al 2O 3-ZnO is glass (P 2O 5: 65%, Al 2O 3: 5%, ZnO:30%) powder (the equal particle diameter of body is 5 μ m) in addition, forms n type diffusion layer in similarly to Example 1 mode.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 17 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.
(above can't the mensuration of 1000000 Ω/) do not form n type diffusion layer to the film resistor at the back side in order to measure the upper limit.
Embodiment 5
As glass powder, use P 2O 5-ZnO-TiO 2Be glass (P 2O 5: 60%, ZnO:35%, TiO 2: powder (the equal particle diameter of body is 3 μ m) 5%) in addition, forms n type diffusion layer in similarly to Example 1 mode.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 21 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.
(above can't the mensuration of 1000000 Ω/) do not form n type diffusion layer to the film resistor at the back side in order to measure the upper limit.
Embodiment 6
As glass powder, use P 2O 5-ZnO-ZrO 2Be glass (P 2O 5: 63%, ZnO:35%, ZrO 2: powder (the equal particle diameter of body is 2 μ m) 2%) in addition, forms n type diffusion layer in similarly to Example 1 mode.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 21 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.
(above can't the mensuration of 1000000 Ω/) do not form n type diffusion layer to the film resistor at the back side in order to measure the upper limit.
Embodiment 7
As glass powder, use P 2O 5-ZnO-MgO is glass (P 2O 5: 60%, ZnO:30%, MgO:10%) powder (the equal particle diameter of body is 4 μ m) in addition, forms n type diffusion layer in similarly to Example 1 mode.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 25 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.
(above can't the mensuration of 1000000 Ω/) do not form n type diffusion layer to the film resistor at the back side in order to measure the upper limit.
Embodiment 8
As glass powder, use P 2O 5-BaO-CaO is glass (P 2O 5: 60%, BaO:20%, CaO:20%) powder (the equal particle diameter of body is 3 μ m) in addition, forms n type diffusion layer in similarly to Example 1 mode.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 17 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.
(above can't the mensuration of 1000000 Ω/) do not form n type diffusion layer to the film resistor at the back side in order to measure the upper limit.
Embodiment 9
As glass powder, use P 2O 5-SiO 2-SrO is glass (P 2O 5: 45%, SiO 2: 35%, SrO:20%) powder (the equal particle diameter of body is 1 μ m) in addition, forms n type diffusion layer in similarly to Example 1 mode.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 21 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.
(above can't the mensuration of 1000000 Ω/) do not form n type diffusion layer to the film resistor at the back side in order to measure the upper limit.
Comparative example 1
With ammonium dihydrogen phosphate (NH 4H 2PO 4) powder 20g mixes and pasteization preparation n type diffusion layer composition with ethyl cellulose 3g, acetic acid 2-(2-butoxy ethyoxyl) ethyl ester 7g.
Next, by silk screen printing prepared paste is coated on p-type silicon substrate surface, and on 150 ℃ heating plate dry 5 minutes.Then, utilize the electric furnace of setting 1000 ℃ for to carry out 10 minutes heat diffusion treatment, subsequently, in order to remove glassy layer substrate was flooded in hydrofluoric acid 5 minutes, carry out flowing water then and clean drying.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 14 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.But the film resistor at the back side is 50 Ω/, also is formed with n type diffusion layer overleaf.
Comparative example 2
With ammonium dihydrogen phosphate (NH 4H 2PO 4) powder 1g and pure water 7g, polyvinyl alcohol 0.7g, isopropyl alcohol 1.5g mixes to prepare solution, prepares n type diffusion layer composition then.
Next, utilize rotation coating machine (2000rpm, 30 seconds) that prepared solution is coated p-type silicon substrate surface, and on 150 ℃ heating plate dry 5 minutes.Then, utilize the electric furnace of setting 1000 ℃ for to carry out 10 minutes heat diffusion treatment, subsequently, in order to remove glassy layer substrate was flooded in hydrofluoric acid 5 minutes, carry out flowing water then and clean drying.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 10 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.But the film resistor at the back side is 100 Ω/, also is formed with n type diffusion layer overleaf.
Comparative example 3
As glass powder, use P 2O 5-SiO 2Be glass (P 2O 5: 40%, SiO 2: powder (the equal particle diameter of body is 1 μ m) 60%) in addition, forms n type diffusion layer in similarly to Example 1 mode.
Being coated with the film resistor that n type diffusion layer forms with the surface of composition one side is 27 Ω/, P (phosphorus) diffusion and formation n type diffusion layer.
The film resistor at the back side is 750 Ω/, also is formed with n type diffusion layer overleaf.
According to above result as can be known, use composition if use the n type diffusion layer for preparing among the embodiment to form, then can not form n type diffusion layer overleaf and only form n type diffusion layer on the surface, compare with comparative example, the regioselectivity of formation n type diffusion layer is higher.

Claims (5)

1. a n type diffusion layer forms and uses composition, and it contains
Decentralized medium, and
Comprise and be selected from ZrO 2, A1 2O 3, TiO 2, at least a kind and P among ZnO, MgO, CaO, SrO and the BaO 2O 5Glass powder.
2. n type diffusion layer according to claim 1 forms and uses composition, described glass powder to contain the P of 30 quality %～90 quality % 2O 5
3. to form and use composition, the volume average particle size of described glass powder be below the 100 μ m for n type diffusion layer according to claim 1 and 2.
4. the manufacture method of a n type diffusion layer has
Each described n type diffusion layer in the coating claim 1～3 forms the operation with composition, and
Implement the operation of heat diffusion treatment.
5. the manufacture method of a solar battery cell has
Each described n type diffusion layer in semiconductor substrate coating claim 1～3 forms the operation with composition, and
Implement the operation that heat diffusion treatment forms n type diffusion layer.
CN2012800083179A 2011-02-17 2012-02-10 Composition for forming n-type diffusion layer, process for producing n-type diffusion layer, and process for producing solar cell Pending CN103348449A (en)

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