CN107093550A - The manufacture method of n-type diffusion layer formation composition, the manufacture method of n-type diffusion layer and solar cell device - Google Patents

The manufacture method of n-type diffusion layer formation composition, the manufacture method of n-type diffusion layer and solar cell device Download PDF

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Publication number
CN107093550A
CN107093550A CN201610917021.9A CN201610917021A CN107093550A CN 107093550 A CN107093550 A CN 107093550A CN 201610917021 A CN201610917021 A CN 201610917021A CN 107093550 A CN107093550 A CN 107093550A
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diffusion layer
type diffusion
layer formation
formation composition
glass powder
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Inventor
佐藤铁也
吉田诚人
野尻刚
冈庭香
町井洋
町井洋一
岩室光则
木泽桂子
织田明博
足立修郎
足立修一郎
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/2225—Diffusion sources
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251—Diffusion into or out of group IV semiconductors
    • H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
    • H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides a kind of n-type diffusion layer formation composition, and it includes：It it is more than 500 DEG C and less than 900 DEG C containing donor element and softening temperature, average grain diameter is less than 5 μm of glass powder；And decentralized medium.

Description

N-type diffusion layer formation composition, the manufacture method of n-type diffusion layer and solar energy The manufacture method of cell device
The present invention is the divisional application of the patent of invention of Application No. 201280031501.5, and parent application day is 2012 July 3, female case denomination of invention is identical with above-mentioned title.
Technical field
The present invention relates to a kind of n-type diffusion layer formation composition of solar cell device, the manufacturer of n-type diffusion layer The manufacture method of method and solar cell device, more specifically, semiconductor substrate can be used as the present invention relates to a kind of The specific region of silicon forms the technology of n-type diffusion layer.
Background technology
The manufacturing process of conventional silicon solar cell element is illustrated.
First, high efficiency is sought to promote light slumping, prepares to be formed with the p-type of texture structure in smooth surface Silicon substrate, next, in the phosphorous oxychloride (POCl as the compound containing donor element3), nitrogen, the mixed gas ring of oxygen Under border, n-type diffusion layer is identically formed with the processing of 800 DEG C~900 DEG C progress dozens of minutes.In the conventional method, Because carrying out the diffusion of phosphorus using mixed gas, so n-type diffusion layer is not only formed on surface, and at side, the back side also shape Into n-type diffusion layer.Accordingly, it would be desirable to the pullback step of the n-type diffusion layer for removing side.In addition, the n-type diffusion layer at the back side must P must be converted into+Aluminum Paste is assigned in type diffusion layer, n-type diffusion layer overleaf, is turned by the diffusion of aluminium by n-type diffusion layer Change p into+Type diffusion layer.
On the other hand, in the manufacture field of semiconductor, it is proposed that following method：It is used as the chemical combination containing donor element Thing, coating contains phosphorus pentoxide (P2O5) or ammonium dihydrogen phosphate (NH4H2PO4) etc. phosphatic solution, be consequently formed n-type diffusion Floor (referring for example to Japanese Unexamined Patent Publication 2002-75894 publications).In addition, in order to form diffusion layer, phosphorus will be contained as donor element Paste be coated on as diffusion source on silicon substrate, and it is also known come the technology for forming diffusion layer to carry out thermal diffusion (referring for example to No. 4073968 publications of Japanese Patent No.).
The content of the invention
Invent problem to be solved
But, in these methods, donor element or compound containing it are from the solution or paste as diffusion source Disperse, thus it is identical with using the gas-phase reaction method of above-mentioned mixed gas, and when forming diffusion layer, phosphorus also diffuses to side and the back of the body Face, thus also form n-type diffusion layer beyond the part being coated with.In addition, usual silicon substrate used in solar cells The upper surface of the semiconductor substrates such as plate, the difference of height with convex portion and recess is 5 μm or so of texture structure.Due to being coated on this On the face of the texture structure of sample, so n-type diffusion layer forms uneven sometimes.
So, when forming n-type diffusion layer, in the gas phase reaction using phosphorous oxychloride, not only n-type is needed to expand in script The one side (being usually smooth surface or surface) for dissipating layer forms n-type diffusion layer, and in another side (non-illuminated surface or the back side) or side Face also forms n-type diffusion layer.In addition, in solution of the coating comprising the compound containing phosphorus or paste and the side for carrying out thermal diffusion It is identical with gas-phase reaction method in method, n-type diffusion layer is also formed beyond surface.Therefore, must to make element that there is pn-junction structure It must be etched in side, n-type diffusion layer is overleaf converted into p-diffusion layer.Generally, overleaf it is coated with as the 13rd race member The paste of the aluminium of element, and burnt till, so that n-type diffusion layer is converted into p-diffusion layer.In addition, phosphorus is not in coating solution Equably spread, and form uneven n-type diffusion layer, the decrease in efficiency for causing solar cell overall.And then, formerly In the preceding known method for being coated the paste for containing the donor elements such as phosphorus as diffusion source, contain donor element Compound is vaporized gasification, and also towards the region for needing to spread with external diffusion, therefore, it is difficult to optionally formed to expand in specific region Dissipate layer.
The present invention is in view of conventional the problem of point of the above and the invention that completes, its problem are to provide a kind of n-type diffusion Layer forms the manufacture method with composition, the manufacture method of n-type diffusion layer and solar cell device, above-mentioned n-type diffusion layer Formation can be applied to the solar cell device using semiconductor substrate with composition, and not forming n-type in unwanted region expands Layer is dissipated, and uniform n-type diffusion layer can be formed in a short time in specific region.
Means for solving the problems
The technical scheme for solving above-mentioned problem is as follows.
<1>A kind of n-type diffusion layer formation composition, it includes：It it is more than 500 DEG C containing donor element and softening temperature And less than 900 DEG C, average grain diameter is less than 5 μm of glass powder；And decentralized medium.
<2>As described above<1>Described n-type diffusion layer formation composition, wherein, the d90 of above-mentioned glass powder is 20 μm Below.
<3>Such as<1>Or<2>Described n-type diffusion layer formation composition, wherein, above-mentioned donor element is selected from P (phosphorus) And it is at least one kind of in Sb (antimony).
<4>Such as<1>~<3>Any one of n-type diffusion layer formation composition, wherein, contain above-mentioned alms giver member The glass powder of element is included：Selected from by P2O3、P2O5And Sb2O3At least one kind of material containing donor element in the group constituted, with And selected from by SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2And MoO3Constituted Group at least one kind of glass ingredient material.
<5>A kind of manufacture method of n-type diffusion layer, it includes：Assign on a semiconductor substrate<1>~<4>Any one of The process of described n-type diffusion layer formation composition；And heat diffusion treatment is implemented to the semiconductor substrate after above-mentioned imparting Process.
<6>A kind of manufacture method of solar cell device, it includes：Assign on a semiconductor substrate<1>~<4>In appoint The process of n-type diffusion layer formation composition described in one；Heat diffusion treatment is implemented to the semiconductor substrate after above-mentioned imparting, And the process for forming n-type diffusion layer；And the process that electrode is formed in the above-mentioned n-type diffusion layer formed.
<7><1>~<4>Any one of n-type diffusion layer formation composition manufacture n-type diffusion layer in should With.
<8><1>~<4>Any one of n-type diffusion layer formation composition manufacture include semiconductor substrate, n Application in the solar cell device of type diffusion layer and electrode.
The effect of invention
According to the present invention, it is possible to provide a kind of n-type diffusion layer formation composition, the manufacture method of n-type diffusion layer and too The manufacture method of positive energy cell device, above-mentioned n-type diffusion layer formation can be applied to the sun using semiconductor substrate with composition Energy cell device, it does not form n-type diffusion layer in unwanted region, and can in a short time be formed uniformly in specific region N-type diffusion layer.
Brief description of the drawings
Fig. 1 is the profile of one of the manufacturing process for conceptually representing the solar cell device of the present invention.
Fig. 2A is the plan from the solar cell device observed by surface.
Fig. 2 B are by the stereogram of Fig. 2A a part of enlarged representation.
Embodiment
First, the n-type diffusion layer formation to the present invention is illustrated with composition, then to being formed using n-type diffusion layer Illustrated with the n-type diffusion layer of composition and the manufacture method of solar cell device.
In addition, in this manual, " process " this term refers not only to independent process, when can not be bright with other processes When really being distinguish between, as long as reaching the expected effect of the process, then it is also contained in this term.In addition, in this specification In, "~" represents to include its front and rear described numerical value respectively as minimum value and the scope of maximum.And then, in this specification In, for the amount of each composition in composition, when there is a variety of materials equivalent to each composition in the composition, an important affair First without special instruction, then it represents that the total amount of many kinds of substance in the presence of composition.
The n-type diffusion layer formation composition of the present invention include at least containing donor element and softening temperature be 500 DEG C with Upper and less than 900 DEG C, the glass powder (hereinafter sometimes referred to simply as " glass powder ") that average grain diameter is less than 5 μm, and it is scattered Medium；And then consider the imparting adaptability (coating) of composition etc., other additives can be also contained as needed.
Here, so-called n-type diffusion layer formation composition, refers to following material：Including containing donor element and softening Temperature is more than 500 DEG C and less than 900 DEG C, and average grain diameter is less than 5 μm of glass powder, is assigned to semiconductor substrate After make the donor element thermal diffusion, thus can form n-type diffusion layer.
By using including being more than 500 DEG C and less than 900 DEG C containing donor element and softening temperature, average grain diameter is 5 μ The n-type diffusion layer formation composition of below m glass powder, so that the viscosity of glass during heat diffusion treatment will not become It is too low, in addition, making glass powder melt in a short time.Thus, n-type diffusion layer is formed at desired position, without in the back of the body Face or side form unwanted n-type diffusion layer.
Therefore, if the n-type diffusion layer formation composition of the application present invention, gas phase that need not be previously widely used is anti- Pullback step necessary to Ying Fazhong, so that process is simplified.In addition, also without the n-type diffusion layer that will be formed in the back side It is converted into p+The process of type diffusion layer.Therefore, the p at the back side+The forming method of type diffusion layer, or backplate material, shape And thickness and unrestricted, the manufacture method or material applied, the selection free degree of shape expand.In addition, by backplate The generation of the internal stress in semiconductor substrate caused by thickness is inhibited, and the warpage of semiconductor substrate is also inhibited, Details will be aftermentioned.
In addition, make glass powder melting contained in n-type diffusion layer formation composition of the invention by burning till, So as to form glassy layer in n-type diffusion layer.But, previous gas-phase reaction method or assign containing phosphatic solution or In the method for paste, glassy layer is also formed in n-type diffusion layer, therefore, the present invention generated in glassy layer can with it is previous Method is removed likewise by etching.Therefore, though compared with previous method, n-type diffusion layer formation group of the invention Compound does not produce unwanted product yet, does not increase process yet.
In addition, alms giver's composition in glass powder is not easy to be vaporized in burning till, therefore n-type diffusion layer is because being vaporized gas Produce and suppressed without being made only in surface and being also formed in the situation at the back side or side.
Be used as its reason, it is believed that alms giver's composition in glass with being securely joined with as the other elements of constitution element, Therefore it is not volatile.
So, n-type diffusion layer formation of the invention can form the n of desired concentration with composition at desired position Type diffusion layer, therefore the region of the high selectivity of the concentration of n-type donor element (dopant) can be formed.On the other hand, by making Gas-phase reaction method for the general method of n-type diffusion layer is used alone the method containing phosphatic solution to form n-type The region of the high selectivity of the concentration of donor element is in general difficulty.
The glass powder containing donor element of the present invention is described in detail.
So-called donor element, refers to that by making it spread (doping) in semiconductor substrate n-type diffusion layer can be formed Element.As donor element, the element of the 15th race can be used, for example, can enumerate P (phosphorus), Sb (antimony), Bi (bismuth) and As (arsenic) Deng.From the viewpoint of security, vitrified easiness etc., suitably P or Sb.
As the material containing donor element for donor element being directed into glass powder, can enumerate P2O3、P2O5、 Sb2O3、Bi2O3And As2O3, it is preferable to use selected from by P2O3、P2O5And Sb2O3It is at least one kind of in the group constituted.
In addition, the glass powder containing donor element can adjusting component ratio as needed, thus, it is possible to control melting temperature Degree, softening temperature, glass transition temperature, chemical durability etc..It is preferred that also including glass ingredient material as described below.
As glass ingredient material, SiO can be enumerated2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、 CdO、SnO、ZrO2、WO3、MoO3、MnO、La2O3、Nb2O5、Ta2O5、Y2O3、TiO2、ZrO2、GeO2、TeO2And Lu2O3Deng preferably Using selected from by SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2、WO3、MoO3 And it is at least one kind of in the groups that are constituted of MnO, more preferably using being selected from by SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、 BeO、ZnO、PbO、CdO、SnO、ZrO2And MoO3It is at least one kind of in the group constituted.
As the concrete example of the glass powder containing donor element, can enumerate including the above-mentioned material containing donor element with it is upper The system of both glass ingredient materials is stated, can be enumerated：P2O5-SiO2System is (with the material containing donor element-glass ingredient material Order record, it is as follows), P2O5-K2O systems, P2O5-Na2O systems, P2O5-Li2O systems, P2O5- BaO systems, P2O5- SrO systems, P2O5- CaO systems, P2O5- MgO systems, P2O5- BeO systems, P2O5- ZnO systems, P2O5- CdO systems, P2O5- PbO systems, P2O5- SnO systems, P2O5-GeO2 System, P2O5-TeO2System etc. includes P2O5As the system of the material containing donor element, P is included instead of above-mentioned2O5System P2O5 And include Sb2O3It is used as the glass powder of the system of the material containing donor element.
In addition, or such as P2O5-Sb2O3System, P2O5-As2O3As system etc., comprising twoing or more the thing containing donor element The glass powder of matter.
Exemplified with the compound glass for including two kinds of compositions in above-mentioned, but it is alternatively P2O5-SiO2- CaO etc. is wrapped as needed Glass powder containing materials more than three kinds of compositions.
Preferably the containing ratio of glass ingredient material in glass powder considers melting temperature, softening temperature, glass Change transition temperature, chemical durability and suitably set, it is however generally that, preferably more than 0.1 mass % and below 95 mass %, more Preferably more than 0.5 mass % and below 90 mass %.
Specifically, SiO is contained in glass powder2When SiO2Containing ratio be preferably more than 10 mass % and 90 matter Measure below % scope.
From DIFFUSION TREATMENT when diffusivity, from the viewpoint of dropping liquid, the softening temperature of glass powder is necessary for more than 500 DEG C And less than 900 DEG C.Additionally, it is preferred that for more than 600 DEG C and less than 800 DEG C, more preferably more than 700 DEG C and less than 800 DEG C.Soft Change temperature to be less than in the case of 500 DEG C, the viscosity of glass becomes too low during DIFFUSION TREATMENT, and produce dropping liquid, therefore sometimes in spy N-type diffusion layer is also formed beyond fixed part.In addition, in the case where softening temperature is higher than 900 DEG C, glass powder is endless sometimes Full-fusing, thus uniform n-type diffusion layer can not be formed.
If the softening temperature of glass powder is in more than 500 DEG C and less than 900 DEG C of scope, it will not also produce as described above Raw dropping liquid, therefore after DIFFUSION TREATMENT, by n-type diffusion layer can be formed as desired shape towards specific region.For example with a μm Wide linear pattern is assigned during n-type diffusion layer formation composition, and it is b ＜ 1.5a μm that can keep the line width b after DIFFUSION TREATMENT Scope linear pattern.
The softening temperature of glass powder can be used the hot thermogravimetric amount of DTG-60H type differentials of Shimadzu Seisakusho Ltd.'s (strain) manufacture same When determine device, and obtained by hot (DTA) curve of differential etc..
As the shape of glass powder, substantially spherical, flat, bulk, tabular and flakey etc. can be enumerated, from n is made From the viewpoint of coating (imparting adaptability) for substrate or uniform diffusivity during type diffusion layer formation composition, reason What is thought is substantially spherical, flat or tabular.
The average grain diameter of glass powder is needed for less than 5 μm.Additionally, it is preferred that for 0.1 μm~5 μm, more preferably 0.5 μm~ 4μm。
By the way that the average grain diameter of glass powder is set into less than 5 μm, so as to be in above-mentioned model even in use softening temperature In the case of enclosing interior glass powder, it can also melt in a short time, so as to be readily available smooth glassy layer.Therefore, pass through The average grain diameter of glass powder is set to less than 5 μm, so as to form uniform n-type diffusion layer.
The whether uniform situation of n-type diffusion layer, the n-type diffusion layer that can be for example obtained by being coated on semiconductor substrate Deviation (the standard deviation of film resistor in face：Form σ) confirms.When the deviation (σ) of sheet resistance is shown for example Less than 10, preferably less than 5, when more preferably less than 2, it can be evaluated to form uniform n-type diffusion layer.
In the present invention, as film resistor, using the Loresta-EP MCP-T360 using Mitsubishi Chemical's (strain) manufacture Type low-resistivity meter, and the value determined by four probe method at 25 DEG C.
In addition, σ, be by the face being coated with by said determination method obtained 25 at sheet resistance The quadratic sum divided by data number of deviation, are calculated further according to by the thus square root of the value of gained.
In addition, usual semiconductor substrate upper surface used in solar cells, the height with convex portion and recess Difference is 5 μm or so of texture structure.Therefore, by the way that the average grain diameter of glass powder is set into less than 5 μm, so as to be lifted for recessed The tracing ability on portion surface, therefore it is uneven also to reduce diffusion.
Here, in this manual, as long as in advance without special instruction, then the average grain diameter of glass represents the average grain of volume Footpath, can be determined by laser light scattering diffraction approach particle size distribution device (manufacture of Beckman Coulter companies) etc..
The d90 of glass powder used in the present invention is preferably less than 20 μm.In addition, d90 is more preferably less than 15 μm, More preferably less than 10 μm.So-called d90, refers to when describing the volume distributed median accumulation curve of particle diameter, from particle diameter most herein Small particle plays particle diameter when accumulating successively and reaching overall 90%.Volume distributed median accumulation curve can be same with above-mentioned average grain diameter It is measured sample, laser light scattering diffraction approach particle size distribution device (manufacture of Beckman Coulter companies) etc. can be passed through To determine.
If the d90 of above-mentioned glass powder is less than 20 μm, in the presence of following tendency：Formed by above-mentioned n-type diffusion layer Assigned to semiconductor substrate upper surface, can suppressed as the generation of the big stomata caused by oversize grain with composition, and can Make being more evenly distributed of donor element.
, it is necessary to which the softening temperature of glass powder is 500 DEG C~900 DEG C for the glass powder in the present invention, average grain Footpath is less than 5 μm.Additionally, it is preferred that the softening temperature for being glass is 600 DEG C~800 DEG C, average grain diameter is 0.1 μm~5 μm, more excellent The softening temperature for electing glass as is 700 DEG C~800 DEG C, and average grain diameter is 0.5 μm~4 μm.
In addition, for above-mentioned glass powder, it is preferred that the softening temperature of glass powder is 500 DEG C~900 DEG C, Average grain diameter is less than 5 μm, and d90 is less than 20 μm, it is further preferred that the softening temperature of glass is 600 DEG C~800 DEG C, it is average Particle diameter is 0.1 μm~5 μm, and d90 is less than 15 μm, it is further preferred that, the softening temperature of glass is 700 DEG C~800 DEG C, is put down Equal particle diameter is 0.5 μm~4 μm, and d90 is less than 10 μm.
In addition, for above-mentioned glass powder, it is further preferred that the softening temperature of glass is 600 DEG C~800 DEG C, putting down Equal particle diameter is 0.1 μm~5 μm, and d90 is less than 15 μm, and the glass powder containing above-mentioned donor element includes being selected from by P2O3、 P2O5And Sb2O3At least one kind of material containing donor element in the group constituted, and selected from by SiO2、K2O、Na2O、Li2O、 BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2And MoO3At least one kind of glass ingredient thing in the group constituted Matter, it is further preferred that, the softening temperature of glass is 700 DEG C~800 DEG C, and average grain diameter is 0.5 μm~4 μm, and d90 is 10 μm Hereinafter, and containing above-mentioned donor element glass powder include be selected from by P2O3、P2O5And Sb2O3At least 1 in the group constituted The material containing donor element is planted, and selected from by SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、 CdO、SnO、ZrO2And MoO3At least one kind of glass ingredient material in the group constituted.
Glass powder containing donor element is made by following order.
First, raw material is weighed, for example, weighs the above-mentioned material containing donor element and glass ingredient material, is then filled with Into crucible.As the material of crucible, it can enumerate：Platinum, platinum-rhodium, iridium, aluminum oxide, quartz, carbon etc..The material of crucible can be examined Consider melting temperature, environment, suitably selected with the reactivity of melt substance etc..
Then, using electric furnace and with glass constitute adaptable temperature to the above-mentioned material containing donor element and glass into Material is divided to be heated and liquation is made.Now, it is generally desirable to be stirred with making liquation become uniform mode.
Next, make obtained liquation flow out to oxidation zirconia substrate or carbon base plate etc. it is upper and by liquation vitrifying.
Finally, crush glass and form powdered.Crushing can be using side known to jet mill, ball mill, ball mill etc. Method.
N-type diffusion layer formation is contemplated that imparting is suitable with the containing ratio of the glass powder containing donor element in composition Diffusivity of answering property (coating) donor element etc. is determined.In general, the glass dust in n-type diffusion layer formation composition The containing ratio at end is preferably more than 0.1 mass % and below 95 mass %, more preferably more than 1 mass % and 90 mass % with Under, more preferably more than 1.5 mass % and below 85 mass %, particularly preferably more than 2 mass % and 80 mass % with Under.
Hereinafter, decentralized medium is illustrated.
So-called decentralized medium, refers to the medium for making above-mentioned glass powder scattered in the composition.Specifically, using selected from It is at least one kind of as decentralized medium in the group being made up of binding agent and solvent.
As binding agent, for example, it can enumerate：Polyvinyl alcohol, polyacrylamide resin, polyvinyl lactam resin, polyethylene pyrrole Pyrrolidone, polyethylene oxide resin, polysulfonate acid, acrylamide alkyl sulfonic acid, cellulose ether resins, cellulose derivative, carboxylic first Base cellulose, hydroxyethyl cellulose, ethyl cellulose, gelatin, starch and starch derivatives, sodium alginate and sodium alginate derive Thing, xanthans and xanthan derivatives, guar gum and guar derivative, scleroglucan and scleroglucan derivative, bassora gum And bassora gum derivative, dextrin and dextrin derivative, (methyl) acrylic resin, (methyl) acrylate (such as (first Base) acid alkyl ester resin, (methyl) dimethylaminoethyl acrylate resin etc.), butadiene resin, styrene resin and Their copolymer.In addition, can suitably select silicone resin in addition.These binding agents can be used alone a kind or by 2 kinds with On be applied in combination.
There is no particular restriction for the molecular weight of binding agent, it is generally desirable to according to the desired viscosity as composition come appropriate Adjustment.
As solvent, for example, it can enumerate：Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-isobutyl-ketone, methyl- Normal-butyl ketone, methyl-isobutyl ketone, methyl-n-amyl ketone, methyl-n-hexyl ketone, metacetone, dipropyl ketone, diisobutyl The ketone solvents such as ketone, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4- pentanediones, acetonyl acetone；Diethyl ether, Methyl ethyl ether, methyl-positive propyl ether, diisopropyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxanes, dimethyl dioxane, second Glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol two Ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl n-propyl ether, diethylene glycol methyl-n-butyl ether, diethylene glycol two positive third Ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl n-hexyl ether, TRIGLYME, triethylene glycol diethyl ether, triethylene glycol Methyl ethyl ether, triethylene glycol methyl n-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol methyl n-hexyl ether, tetraethylene glycol two Methyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol methyl ethyl ether, tetraethylene glycol methyl n-butyl ether, diethylene glycol di-n-butyl ether, four Ethylene Glycol Methyl n-hexyl ether, tetraethylene glycol di-n-butyl ether, Propylene Glycol Dimethyl Ether, propane diols diethyl ether, propane diols di-n-propyl ether, third Dibutyl ether, dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethylether, the positive fourth of dipropylene glycol methyl Ether, DPG di-n-propyl ether, DPG di-n-butyl ether, dipropylene glycol methyl n-hexyl ether, tripropylene glycol dimethyl ether, 3 the third two Diethylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl N-hexyl ether, four Propylene Glycol Dimethyl Ethers, four propane diols diethyl ether, four propylene glycol methyl ethyl ethers, four propylene glycol methyl n-butyl ethers, two The ether solvents such as propane diols di-n-butyl ether, four propylene glycol methyl n-hexyl ethers, four propane diols 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- methoxybutyls, methyl amyl acetate, acetic acid 2- ethyls butyl ester, acetic acid 2- ethylhexyls, acetic acid 2- (2- butoxy second Epoxide) ethyl ester, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, nonyl acetate, methyl acetoacetate, acetoacetate second Ester, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, DPG list Ether acetate, ethylene acetate, methoxy triethylene acetic acid esters, ethyl propionate, n-butyl propionate, propionic acid isoamyl Ester, diethy-aceto oxalate, dibutyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, N_amyl lactate, ethylene glycol list first Ether propionic ester, ethylene glycol monoethyl ether propionic ester, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, propane diols list first The ester solvents such as ether acetic acid ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, gamma-butyrolacton, gamma-valerolactone；Second Nitrile, 1-METHYLPYRROLIDONE, N- ethyl pyrrolidones, N- propyl pyrroles alkanone, N- butyl pyrrolidines ketone, N- hexyl pyrrolidines The aprotic poles such as ketone, N- cyclohexyl pyrrolidones, DMF, DMA, dimethyl sulfoxide (DMSO) Property solvent；Methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, 2- first Base butanol, sec-amyl alcohol, tert-pentyl alcohol, 3- methoxybutanols, n-hexyl alcohol, 2- methyl anyl alcohols, secondary hexyl alcohol, 2- ethyl butanols, secondary enanthol, N-octyl alcohol, 2-Ethylhexyl Alcohol, sec-octyl alcohol, n-nonyl alcohol, Decanol, secondary undecyl alcohol, Exxal 12, secondary tetradecyl alchohol, secondary heptadecanol, Phenol, cyclohexanol, methyl cyclohexanol, benzylalcohol, ethylene glycol, 1,2-PD, 1,3-BDO, diethylene glycol, DPG, three The alcoholic solvents such as ethylene glycol, tripropylene glycol；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethyleneglycol monophenylether, diethylene glycol list first Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol list n-hexyl ether, Triethylene glycol ethyl ether, tetraethylene glycol list The glycol monoethers such as n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, DPE, Tripropylene glycol monomethyl Ether are molten Agent；α-terpinenes, α-terpineol, oreodaphene alkene, alloocimene, limonene, dipentene, australene, nopinene, terpinol, perfume (or spice) The terpene solvent such as celery ketone, ocimenum, phellandrene；Water.These solvents, which can be used alone, or two or more to be applied in combination by a kind.N is made During type diffusion layer formation composition, from the viewpoint of the imparting adaptability to substrate, preferably α-terpineol, diethylene glycol list N-butyl ether, diethylene glycol mono-n-butyl ether acetic acid esters, as preferred solvent, can enumerate α-terpineol, diethylene glycol Dan Zhengding Ether.
N-type diffusion layer formation with the containing ratio of the decentralized medium in composition be consider coating, donor concentration and determine Fixed.
In view of assign adaptability, n-type diffusion layer formation be more preferably with the viscosity of composition more than 10mPas and Below 1000000mPas.
The manufacture method of the n-type diffusion layer of the present invention includes：Above-mentioned n-type diffusion layer formation is assigned on a semiconductor substrate to use The process of composition and the process for implementing heat diffusion treatment to the semiconductor substrate after above-mentioned imparting.In addition, the present invention is too The manufacture method of positive energy cell device includes：The process for assigning above-mentioned n-type diffusion layer formation composition on a semiconductor substrate； Heat diffusion treatment is implemented to the semiconductor substrate after above-mentioned imparting, so as to form the process of n-type diffusion layer；And formed The process that electrode is formed in above-mentioned n-type diffusion layer.
One side reference picture 1, while the manufacture method of the n-type diffusion layer and solar cell device to the present invention is said It is bright.Fig. 1 is the constructed profile of one of the manufacturing process for conceptually representing the solar cell device of the present invention.In addition, In Fig. 1,10 represent p-type semiconductor substrate, and 12 represent n-type diffusion layer, and 14 represent p+Type diffusion layer, 16 represent antireflection film, 18 Surface electrode is represented, 20 represent backplate (electrode layer).In figures in the following, identical is marked to identical inscape Symbol, and omit the description.In addition, illustrated below for the example using silicon substrate as p-type semiconductor substrate, but this hair In bright, semiconductor substrate is not limited to silicon substrate.
In Fig. 1 (1), the silicon substrate as p-type semiconductor substrate 10 is assigned alkaline solution to remove damaged layer, and pass through Etch and obtain texture structure.
Specifically, using 20 mass % caustic soda remove from ingot casting cut into slices when produced silicon face damaged layer.Connect Get off, be etched using the mixed liquor of 1 mass % caustic soda and 10 mass % isopropanols, and form texture structure (Tu Zhong provinces The slightly record of texture structure).For solar cell device, by forming texture structure in smooth surface (surface) side, from And light slumping is promoted, high efficiency can be sought.
In Fig. 1 (2), above-mentioned n-type diffusion layer formation is assigned with composition to the surface of p-type semiconductor substrate 10 and become On the face of smooth surface, n-type diffusion layer formation composition layer 11 is formed.In the present invention, adding method is simultaneously unrestricted, for example, can lift Go out print process, spin-coating method, hairbrush coating, spray-on process, doctor blade method, roll coater method, ink-jet method etc..
There is no particular restriction for the imparting amount of above-mentioned n-type diffusion layer formation composition.For example, as glass powder amount, can It is set to 0.01g/m2~100g/m2, preferably 0.1g/m2~10g/m2。
In addition, according to the composition of n-type diffusion layer formation composition, sometimes for for making institute in composition after imparting The drying process of the solvent volatilization contained.At this moment, when using heating plate at a temperature of 80 DEG C~300 DEG C or so, 1 point is dried Clock~10 minute, are dried 10 minutes~30 minutes or so when using drying machine etc..The drying condition depends on n-type diffusion layer shape Constituted into the solvent of composition, above-mentioned condition is not particularly limited in the present invention.
In addition, in the manufacture method using the present invention, the p at the back side+The manufacture of type diffusion layer (high concentration electric field layer) 14 Method is not limited to the method that p-diffusion layer is converted to by n-type diffusion layer based on aluminium, can also use previously known any side Method, the selection free degree of manufacture method expands.Thus, for example the composition 13 of the element containing the 13rd races such as B (boron) can be assigned, So as to form p+Type diffusion layer 14.
As the composition 13 of the above-mentioned element containing the 13rd races such as B (boron), for example, it can enumerate to use and contain acceptor elements Glass powder replace the glass powder containing donor element, and with n-type diffusion layer formation composition identical mode The p-diffusion layer formation composition of composition.As long as the element of the race of acceptor elements the 13rd, for example, can enumerate B (boron), Al (aluminium) and Ga (gallium) etc..In addition, the glass powder containing acceptor elements is preferably comprised selected from by B2O3、Al2O3And Ga2O3Constituted Group in it is at least one kind of.
And then, p-diffusion layer formation is assigned with composition to the method at the back side of silicon substrate and spread n-type with already described The method that layer formation is assigned with composition to silicon substrate is identical.
In the heat diffusion treatment identical mode with n-type diffusion layer formation composition described later, to being imparted to the back side P-diffusion layer formation carry out heat diffusion treatment with composition, thus can overleaf form p+Type diffusion layer 14.Furthermore it is preferred that p The formation of type diffusion layer is carried out simultaneously with the heat diffusion treatment of composition with n-type diffusion layer formation with the heat diffusion treatment of composition.
Next, the temperature more than fusing point of glass powder in the composition, such as at 600 DEG C~1200 DEG C, to shape Heat diffusion treatment is carried out into having above-mentioned n-type diffusion layer formation with the p-type semiconductor substrate 10 of composition layer 11.Pass through the thermal diffusion Processing, shown in such as Fig. 1 (3), donor element spreads into semiconductor substrate, so as to form n-type diffusion layer 12.Heat diffusion treatment can Using known continuous oven, batch furnace etc..In addition, furnace inner environment during heat diffusion treatment also can suitably be adjusted to air, oxygen Gas, nitrogen etc..
The heat diffusion treatment time can be according to the containing ratio of donor element contained in n-type diffusion layer formation composition Appropriate selection.For example, can be set to 1 minute~60 minutes, more preferably 2 minutes~30 minutes.
The glassy layers (not shown) such as phosphoric acid glass are formed on the surface of the n-type diffusion layer 12 formed.Therefore, etching is passed through To remove the phosphoric acid glass.Etching can be using the method being impregnated in the acid such as hydrofluoric acid, the method being impregnated in the alkali such as caustic soda Etc. any known method.During using the engraving method being impregnated in the acid such as hydrofluoric acid, there is no particular restriction for dip time, leads to It can often be set to 0.5 minute~30 minutes, preferably be set to 1 minute~10 minutes.
In the forming method of the n-type diffusion layer of the invention shown in Fig. 1 (2) and Fig. 1 (3), in desired position shape Into n-type diffusion layer 12, without overleaf or sideways forming unwanted n-type diffusion layer.
Therefore, in the conventional widely used method by gas-phase reaction method to form n-type diffusion layer, for removing shape Pullback step into the unwanted n-type diffusion layer in side is necessary, and still, manufacturing method according to the invention is not required to Pullback step is wanted, so that process is simplified.Thus, can be in a short time desired by the manufacture method of the present invention Position form the uniform n-type diffusion layer of desired shape.
In addition, in conventional manufacture method, it is necessary to which the unwanted n-type diffusion layer that will be formed in the back side is converted into p-type Diffusion layer, as the conversion method, using following method：It is coated with n-type diffusion layer overleaf as the 13rd race's element The paste of aluminium, and burnt till, aluminium is diffused to n-type diffusion layer, so that n-type diffusion layer is converted into p-diffusion layer.In the party In method, in order to which n-type diffusion layer fully is converted into p-diffusion layer, and then p is formed+The high concentration electric field layer of type diffusion layer, and Need the aluminum amount more than to a certain degree, it is therefore necessary to formed very thick by aluminium lamination.But, the thermal coefficient of expansion of aluminium is with being used as substrate Silicon thermal expansion coefficient difference it is very big, therefore during burning till and cooling down, larger inside can be produced in silicon substrate The reason for stress, warpage as silicon substrate.
The internal stress can cause damage to the crystal boundary of crystallization, there is power loss and become this big technical problem.In addition, sticking up The conveyance of the bent solar cell device in module process or with the connection procedure for the copper cash for being referred to as lug line (TAB) In, it is easy to make solar cell device damaged.In recent years, due to the raising of slicing technology, thus silicon substrate thickness by Gradually it is thinned, so as to there is the tendency that solar cell device is more prone to rupture.
But, manufacturing method according to the invention does not form unwanted n-type diffusion layer overleaf, therefore without carrying out From n-type diffusion layer to the conversion of p-diffusion layer, from without making aluminium lamination thickening.As a result, the inside that can suppress in silicon substrate should The generation of power or warpage.As a result, the increase of power loss or the breakage of solar cell device can be suppressed.
In addition, when the manufacture method using the present invention, the p at the back side+The manufacture of type diffusion layer (high concentration electric field layer) 14 Method is not limited to the method that p-diffusion layer is converted to by n-type diffusion layer based on aluminium, can also use any method, manufacture The selection free degree of method expands.
For example, it is preferable to the glass powder containing donor element will be replaced using the glass powder containing acceptor elements, and Assigned with the p-diffusion layer formation constituted with n-type diffusion layer formation with composition identical mode with composition to silicon substrate The back side (with the face for the face opposite side for imparting n-type diffusion layer formation composition), and carry out burning till processing, thus overleaf Form p+Type diffusion layer (high concentration electric field layer) 14.
In addition, as described later, the material overleaf used in electrode 20 is not limited to the aluminium of the 13rd race, can apply such as Ag (silver) or Cu (copper) etc., the thickness of backplate 20 also can more be thinly formed than conventional thickness.
In Fig. 1 (4), antireflection film 16 is formed in n-type diffusion layer 12.The known technology of the application of antireflection film 16 carrys out shape Into.For example, when antireflection film 16 is silicon nitride film, by by SiH4With NH3Mixed gas as raw material plasma chemical gas (CVD) method is mutually deposited to be formed.Now, hydrogen spreads in crystallization, is not involved in the track of silicon atom bonding, i.e. dangling bonds can be with Hydrogen bonding, so that defect passivation (hydrogen passivation).
More specifically, NH is compared in above-mentioned mixed gas flow3/SiH4For 0.05~1.0, the pressure of reative cell is 13.3Pa (0.1Torr)~266.6Pa (2Torr), temperature during film forming is 300 DEG C~550 DEG C, the electric discharge for plasma Frequency is formation under conditions of more than 100kHz.
In Fig. 1 (5), on the antireflection film 16 of surface (smooth surface), coating surface electricity is printed by silk screen print method Pole is with metal paste and dries it, forms surface electrode metal paste oxidant layer 17.Surface electrode is with metal paste by (1) metal Particle and (2) glass particle include (3) resinoid bond, (4) other additives as needed as required composition.
Next, the p at the above-mentioned back side+Also backplate metal paste oxidant layer 19 is formed on type diffusion layer 14.As above institute State, in the present invention, backplate is not particularly limited with material, the forming method of metal paste oxidant layer 19.For example, bag can be assigned Backplate paste containing metals such as aluminium, silver or copper, and it is dried and is formed backplate metal paste oxidant layer 19.This When, it is also provided with silver electrode for the connection between the solar cell device in module process, in a part that can be overleaf and is formed Use silver paste agent.
In Fig. 1 (6), electrode is burnt till with metal paste oxidant layer 17 solar cell device is made.If 600 DEG C~ Several seconds~a few minutes are burnt till in the range of 900 DEG C, then in face side, as the antireflection film 16 of dielectric film because of electrode metal paste Contained glass particle in agent and melt, and then the surface of p-type semiconductor substrate 10 is also locally melted, the clipped wire in paste Sub (such as silver particles) form contact site with p-type semiconductor substrate 10 and solidified.Thus, the surface electrode 18 and p-type formed Semiconductor substrate 10 is switched on.It this will be referred to as burn through (fire through).In addition, overleaf side, similarly to back side electricity Pole is burnt till with the backplate of metal paste oxidant layer 19 with metal paste, so as to form backplate 20.
Reference picture 2 is illustrated to the shape of surface electrode 18.In addition, in fig. 2,30 represent bus electrode, and 32 represent Finger electrode.Surface electrode 18 includes bus electrode 30 and the finger electrode 32 intersected with the bus electrode 30.Fig. 2A be from Surface observation to surface electrode 18 is made to the finger electrode 32 that intersects comprising bus electrode 30 and with the bus electrode 30 Composition solar cell device plan, Fig. 2 B are by the stereogram of Fig. 2A a part of enlarged representation.
Such surface electrode 18 can for example, by above-mentioned metal paste silk-screen printing or electrode material plating, Being formed using methods such as the evaporations of electrode material of electron beam heating in high vacuum.It is well known that including bus electrode 30 The electrode of light surface side is typically used as with the surface electrode 18 of finger electrode 32, the bus electrode and finger-like of light surface side can be applied The known forming method of electrode.
In above-mentioned, to forming n-type diffusion layer on surface, p is overleaf formed+Type diffusion layer, and then set on each layer The solar cell device for being equipped with surface electrode and backplate is illustrated, but if being expanded using the n-type of the present invention Layer formation composition is dissipated, then can also make the solar cell device of rear-face contact type.
The solar cell device of rear-face contact type is that electrode is provided entirely in into the back side and increases the area of smooth surface Solar cell device.That is, overleaf in the solar cell device of contact-type, it is necessary to overleaf form n-type diffusion position and p+Type spread both positions and to form pn-junction structure.The n-type diffusion layer formation composition of the present invention can be at specific position N-type diffusion position is formed, therefore, the manufacture of the solar cell device of rear-face contact type can be suitably applied to.
In the present invention, making for above-mentioned n-type diffusion layer formation composition when manufacturing n-type diffusion layer is also included respectively With and above-mentioned n-type during solar cell device of the manufacture containing above-mentioned semiconductor substrate and n-type diffusion layer and electrode spread The use of layer formation composition.As described above, by using the n-type diffusion layer formation composition of the present invention, so as to not Unwanted n-type diffusion layer is formed, and uniform n-type can be obtained with desired shape in specific region in a short time and expanded Layer is dissipated, in addition, unwanted n-type diffusion layer can not be formed and the solar cell device with such n-type diffusion layer is obtained.
Embodiment
Hereinafter, embodiments of the invention are further illustrated, but the present invention is not limited by these embodiments.This Outside, as long as no special instructions, chemicals has all used reagent.If in addition, in advance without explanation, then " % " expression " matter Measure % ".And then, as long as flow divided by the area of section of electric furnace in advance without explanation, the then gas that " cm/s " expression is flowed into stove " linear velocity " of gained.
[embodiment 1]
It is 15 μm to be 4 μm and d90 to shape of particle for substantially spherical, average grain diameter using automatic mortar kneading device P2O5-SiO2(softening temperature is 700 DEG C, P to-CaO systems glass2O5：50%, SiO2：43%, CaO：7%) powder 3g, ethyl cellulose Plain 2.1g, and terpineol 24.9g mix and paste, are prepared for n-type diffusion layer formation composition.
In addition, the TM-1000 types sweep type electricity that glass particle shape is manufactured using Hitachi High-Technologies (strain) Sub- microscope is observed and judged.The average grain diameter and d90 of glass use the LS 13 that Beckman Coulter (strain) are manufactured 320 type laser light scattering diffraction approach particle size distribution devices (determine wavelength：632nm) calculate.The softening temperature of glass uses island The hot thermogravimetric amount of DTG-60H type differentials that Tianjin makes institute's (strain) manufacture determines device simultaneously, and by hot (DTA) curve of differential come Obtain.
Then, prepared paste is coated on to the surface of p-type silicon substrate using silk-screen printing, and in 150 DEG C of heating Dried 5 minutes on plate.Next, being kept for 1.5 minutes in 450 DEG C of baking oven is set to, depart from ethyl cellulose.Connect down Come, in big air-flow (0.9cm/s) environment, keep 10 minutes, thus carry out at thermal diffusion in 950 DEG C of electric furnace is set to Reason, thereafter to removing glassy layer and impregnating substrate 5 minutes in hydrofluoric acid, then carries out flowing water cleaning.Then, done It is dry.
Be coated with n-type diffusion layer formation composition side surface film resistor be 60 Ω/, P (phosphorus) diffusion and Form n-type diffusion layer.In addition, the deviation of the sheet resistance in coated face is σ=0.8, forms uniform n-type and expand Dissipate layer.On the other hand, the film resistor at the back side can not determine for 1000000 Ω/more than, not form n-type diffusion layer.
In addition, film resistor is the Loresta-EP MCP-T360 type low-resistivity meters manufactured using Mitsubishi Chemical's (strain), And be measured by four probe method at 25 DEG C.
In addition, σ represents standard deviation, it passes through the quadratic sum of the deviation of the sheet resistance at 25 in coated face Divided by the square root of the value obtained by data number is calculated.
[embodiment 2]
The average grain diameter of glass powder is set to 2 μm and d90 is set to 6.5 μm, in addition, with same as Example 1 Mode form n-type diffusion layer.
Be coated with n-type diffusion layer formation composition side surface film resistor be 33 Ω/, P (phosphorus) diffusion and Form n-type diffusion layer.In addition, the deviation of the sheet resistance in coated face is σ=0.5, forms uniform n-type and expand Dissipate layer.On the other hand, the film resistor at the back side can not determine for 1000000 Ω/more than, not form n-type diffusion layer.
[embodiment 3]
The average grain diameter of glass powder is set to 0.7 μm and d90 is set to 3.4 μm, in addition, with the phase of embodiment 1 Same mode forms n-type diffusion layer.
Be coated with n-type diffusion layer formation composition side surface film resistor be 25 Ω/, P (phosphorus) diffusion and Form n-type diffusion layer.In addition, the deviation of the sheet resistance in coated face is σ=0.3, forms uniform n-type and expand Dissipate layer.On the other hand, the film resistor at the back side can not determine for 1000000 Ω/more than, not form n-type diffusion layer.
[embodiment 4]
Be to shape of particle using automatic mortar kneading device substantially spherical, average grain diameter be 2 μm and d90 be 6.5 μm, P with the softening temperature higher than embodiment 12O5-SiO2(softening temperature is 800 DEG C, P to-CaO systems glass2O5：44%, SiO2： 49%, CaO：7%) powder 3g, ethyl cellulose 2.1g, and terpineol 24.9g have carried out mixing and paste, so as to be prepared for N-type diffusion layer formation composition.Next, prepared paste is coated on to the surface of p-type silicon substrate using silk-screen printing, And dried 5 minutes in 150 DEG C of heating plate.Next, in big air-flow (0.9cm/s) environment, being set to 950 DEG C of electricity Keep carry out heat diffusion treatment in stove within 10 minutes, then impregnate substrate 5 minutes in hydrofluoric acid to remove glassy layer, Then flowing water cleaning is carried out.Then, it is dried.
Be coated with n-type diffusion layer formation composition side surface film resistor be 42 Ω/, P (phosphorus) diffusion and Form n-type diffusion layer.In addition, the deviation of the sheet resistance in coated face is σ=0.5, forms uniform n-type and expand Dissipate layer.On the other hand, the film resistor at the back side can not determine for 1000000 Ω/more than, not form n-type diffusion layer.
[comparative example 1]
The average grain diameter of glass powder is set to 8 μm and d90 is set to 50 μm, in addition, with same as Example 1 Mode form n-type diffusion layer.
Be coated with n-type diffusion layer formation composition side surface film resistor be 120 Ω/, P (phosphorus) diffusion and Form n-type diffusion layer.But, deviation (σ=10.7) can be seen in the sheet resistance in face, it is uneven.
[comparative example 2]
The average grain diameter of glass powder is set to 30 μm and d90 is set to 110 μm, in addition, with the phase of embodiment 1 Same mode forms n-type diffusion layer.
Be coated with n-type diffusion layer formation composition side surface film resistor be 300 Ω/, P (phosphorus) diffusion and Form n-type diffusion layer.But, deviation (σ=24.9) can be seen in the sheet resistance in face, it is uneven.
[comparative example 3]
It is 6.5 μm to be 2 μm and d90 to shape of particle for substantially spherical, average grain diameter using automatic mortar kneading device P2O5(softening temperature is 300 DEG C, P to-SnO systems glass2O5：30%, SnO：70%) powder 3g, ethyl cellulose 2.1g, and terpin Alcohol 24.9g has carried out mixing and paste, so as to be prepared for n-type diffusion layer formation composition.
Then, prepared paste is coated on p-type silicon substrate surface using silk-screen printing it is 120 μm wide thin-line-shaped, And dried 5 minutes in 150 DEG C of heating plate.Next, in nitrogen stream (0.9cm/s) environment, being set to 950 DEG C of electricity Keep carry out heat diffusion treatment in stove within 10 minutes, then impregnate substrate 5 minutes in hydrofluoric acid to remove glassy layer, Then flowing water cleaning is carried out.Then, it is dried.
The film resistor that n-type diffusion layer formation is coated into thin-line-shaped part with composition is 120 Ω/, and P (phosphorus) expands Dissipate and form n-type diffusion layer.In addition, the width for the thin-line-shaped pattern being coated with becomes 400 μm, the glass melted is generated Drop falls, therefore can not realize the selectivity diffusion to specific part.
[comparative example 4]
Using automatic mortar kneading device to ammonium dihydrogen phosphate (NH4H2PO4) powder 20g, ethyl cellulose 3g and acetic acid 2- (2- Butoxyethoxies) ethyl ester 7g has carried out mixing and paste, is prepared for n-type diffusion layer formation composition.
Next, prepared paste to be coated on to the surface of p-type silicon substrate using silk-screen printing, and 150 DEG C plus Dried 5 minutes on hot plate.Next, keeping carry out heat diffusion treatment in 1000 DEG C of electric furnace is set within 10 minutes, then Substrate is impregnated 5 minutes in hydrofluoric acid in order to remove glassy layer, flowing water cleaning, drying is then carried out.
Be coated with n-type diffusion layer formation composition side surface film resistor be 14 Ω/, P (phosphorus) diffusion and Form n-type diffusion layer.But, the film resistor at the back side is 50 Ω/, is overleaf also formed with n-type diffusion layer.
[comparative example 5]
Using automatic mortar kneading device to ammonium dihydrogen phosphate (NH4H2PO4) powder 1g, pure water 7g, polyvinyl alcohol 0.7g, And isopropanol 1.5g is mixed, and prepares solution, so as to be prepared for n-type diffusion layer composition.
Next, using spin coater (2000rpm, 30 seconds) by prepared solution coating in the surface of p-type silicon substrate, and Dried 5 minutes in 150 DEG C of heating plate.Next, keeping 10 minutes to carry out thermal expansion in 1000 DEG C of electric furnace is set to Processing is dissipated, then impregnates substrate 5 minutes in hydrofluoric acid to remove glassy layer, flowing water cleaning, drying is then carried out.
Be coated with n-type diffusion layer formation composition side surface film resistor be 10 Ω/, P (phosphorus) diffusion and Form n-type diffusion layer.But, the film resistor at the back side is 100 Ω/, is overleaf also formed with n-type diffusion layer.
By referring to and by whole disclosed in Japanese patent application filed in 5 days July in 2011 2011-149249 Content is introduced into this specification.
Described all documents, patent application and technical specification are with recording specifically and respectively in this specification By referring to and introduce each document, patent application and technical specification situation be identical degree, by referring to and be introduced into Into this specification.

Claims (6)

1. a kind of n-type diffusion layer formation composition, it includes：Containing donor element, softening temperature is more than 500 DEG C and 900 Below DEG C, and average grain diameter is less than 5 μm of glass powder；And decentralized medium.
2. n-type diffusion layer formation composition according to claim 1, wherein, the d90 of the glass powder for 20 μm with Under.
3. n-type diffusion layer formation composition according to claim 1 or 2, wherein, the donor element is selected from phosphorus P And it is at least one kind of in antimony Sb.
4. according to n-type diffusion layer formation composition according to any one of claims 1 to 3, wherein, contain alms giver member The glass powder of element includes：Selected from by P2O3、P2O5And Sb2O3At least one kind of material containing donor element in the group constituted, with And selected from by SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2And MoO3Constituted Group at least one kind of glass ingredient material.
5. a kind of manufacture method of n-type diffusion layer, it includes：Entitle requires any one of 1~4 institute on a semiconductor substrate The process for the n-type diffusion layer formation composition stated；And heat diffusion treatment is implemented to the semiconductor substrate after the imparting Process.
6. a kind of manufacture method of solar cell device, it includes：Appoint on a semiconductor substrate in entitle requirement 1~4 The process of n-type diffusion layer formation composition described in one；Heat diffusion treatment is implemented to the semiconductor substrate after the imparting, So as to the process for forming n-type diffusion layer；And the process that electrode is formed in the n-type diffusion layer formed.
CN201610917021.9A 2011-07-05 2012-07-03 The manufacture method of n-type diffusion layer formation composition, the manufacture method of n-type diffusion layer and solar cell device Pending CN107093550A (en)

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