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CN104067395A - Mask-forming composition, method for producing solar cell substrate, and method for producing solar cell element - Google Patents

Mask-forming composition, method for producing solar cell substrate, and method for producing solar cell element Download PDF

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Publication number
CN104067395A
CN104067395A CN201380005060.6A CN201380005060A CN104067395A CN 104067395 A CN104067395 A CN 104067395A CN 201380005060 A CN201380005060 A CN 201380005060A CN 104067395 A CN104067395 A CN 104067395A
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China
Prior art keywords
mask
composition
mask formation
metal
alkali
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CN201380005060.6A
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Chinese (zh)
Inventor
织田明博
吉田诚人
野尻刚
仓田靖
岩室光则
野部茂
冈田悠平
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Resonac Corp
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Hitachi Chemical Co Ltd
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Publication of CN104067395A publication Critical patent/CN104067395A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251—Diffusion into or out of group IV semiconductors
    • H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
    • 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
    • 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

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  • Photovoltaic Devices (AREA)

Abstract

本发明提供一种掩模形成用组合物，其含有硅化合物、含碱土金属或碱金属的金属化合物、和分散介质。The present invention provides a mask-forming composition containing a silicon compound, a metal compound containing an alkaline earth metal or an alkali metal, and a dispersion medium.

Description

Mask forms by composition, the manufacture method of used for solar batteries substrate and the manufacture method of solar cell device
Technical field
The present invention relates to mask forms by composition, the manufacture method of used for solar batteries substrate and the manufacture method of solar cell device.
Background technology
Manufacturing process to silicon solar cell element in the past describes.
First, in order promoting to fall into luminous effect, to realize high efficiency, to prepare to be formed with the p-type silicon substrate of texture structure, next, at phosphorous oxychloride (POCl 3), at 800 ℃～900 ℃, carry out the processing of tens of minutes in the mixed-gas atmosphere of nitrogen and oxygen, be formed uniformly N-shaped diffusion layer.Then, at electrode paste agents such as sensitive surface coating Ag, and side is coated with the electrode paste agents such as aluminium overleaf, burns till afterwards, obtains thus solar cell device.
But, due to sunlight do not incide sensitive surface side electrode under, so this part is not generated electricity.Developed a kind of back electrode type solar cell, it does not have electrode at sensitive surface for this reason, has overleaf N-shaped diffusion layer and p +type diffusion layer, and on each diffusion layer, there is n electrode and p electrode (for example, with reference to TOHKEMY 2011-507246 communique).
To forming the method for such back electrode type solar cell, describe.At the sensitive surface of N-shaped silicon substrate and whole of the back side, form mask.Herein, mask has the function that obstruction dopant spreads in silicon substrate.Then, remove silicon substrate the back side a part of mask and form peristome.And, if make p-type dopant be diffused into the back side of silicon substrate from the peristome of mask, can make only corresponding with peristome region form p +type diffusion layer.Then, the mask at the back side of silicon substrate is all removed, afterwards, again at whole of the back side of silicon substrate, formed mask.Then, will be formed with above-mentioned p +a part of mask in the region that the region of type diffusion layer is different is removed and forms peristome, makes N-shaped dopant from this peristome, be diffused into the back side of silicon substrate, forms n +type diffusion layer.Then, the mask at the back side of silicon substrate is all removed, thereby formed p overleaf +type diffusion layer and n +type diffusion layer.And then, form texture structure, antireflection film, passivating film, electrode etc., complete thus back electrode type solar cell.
As aforementioned mask, proposed to utilize the method (for example, with reference to TOHKEMY 2002-329880 communique) of the oxide-film generating at substrate surface by thermal oxidation method.On the other hand, also propose use and comprised SiO 2the mask formation method of sheltering paste of precursor (for example, with reference to TOHKEMY 2007-49079 communique).
Summary of the invention
The problem that invention will solve
But, for what record in above-mentioned TOHKEMY 2002-329880 communique, pass through thermal oxidation method for the method for substrate surface generation oxide-film, because its processing procedure (throughput) is long, the problem that therefore exists manufacturing cost to uprise.
In addition, for the use of recording in TOHKEMY 2007-49079 communique, contain SiO 2the method of sheltering paste of precursor, it physically prevents the diffusion of donor element or recipient element, and reason SiO 2the mask forming is difficult to form fine and close film and easily forms pin hole (pinhole), is therefore difficult to prevent fully that dopant from spreading to substrate.
For this reason, the present invention is the invention completing in view of above problem in the past, and its problem is to provide and can prevents fully that donor element or recipient element from forming with composition, having used this mask to form the manufacture method of used for solar batteries substrate and the manufacture method of solar cell device of use composition to the mask of semiconductor substrate diffusion.
For solving the means of problem
As described below for solving the concrete means of above-mentioned problem.
<1> mask formation composition, it contains silicon compound, alkaline including earth metal or alkali-metal metallic compound and decentralized medium.
The mask formation composition of <2> as described in above-mentioned <1>, wherein, the gross mass ratio of the described alkaline including earth metal in nonvolatile component or alkali-metal metallic compound is more than 5 quality % and lower than 100 quality %.
The mask formation composition of <3> as described in above-mentioned <1> or <2>, wherein, described alkaline including earth metal or alkali-metal metallic compound comprise more than a kind that is selected from magnesium, calcium, sodium, potassium, lithium, rubidium, caesium, beryllium, strontium, barium and radium as metallic element.
The mask formation composition of <4> as described in any one in above-mentioned <1>～<3>, wherein, described alkaline including earth metal or alkali-metal metallic compound comprise be selected from magnesium oxide, calcium oxide, magnesium carbonate, calcium carbonate, magnesium sulfate, calcium sulfate, calcium nitrate, magnesium hydroxide and calcium hydroxide more than a kind.
The mask formation composition of <5> as described in any one in above-mentioned <1>～<4>, wherein, described alkaline including earth metal or alkali-metal metallic compound are to be the particle of solid at normal temperatures, and the volume average particle size of described particle is below 30 μ m.
The mask formation composition of <6> as described in any one in above-mentioned <1>～<5>, wherein, described silicon compound comprises silicone resin.
The mask formation composition of <7> as described in any one in above-mentioned <1>～<6>, wherein, described silicon compound is the silicone resin that alkoxy silane hydrolytic condensation is obtained.
The mask formation composition of <8> as described in any one in above-mentioned <1>～<7>, wherein, described silicon compound is by the silicone resin that is selected from a kind of above compound hydrolysis condensation in tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four butoxy silanes and obtains.
The mask formation composition of <9> as described in any one in above-mentioned <1>～<8>, wherein, described decentralized medium comprise be selected from water, alcohol series solvent, ethylene glycol mono-ether series solvent and terpenic series solvent more than a kind.
The mask formation composition of <10> as described in any one in above-mentioned <1>～<9>, it also comprises organic bond.
The mask formation composition of <11> as described in above-mentioned <10>, wherein, described organic bond comprise be selected from acrylic resin and celluosic resin more than a kind.
The mask formation composition of <12> as described in any one in above-mentioned <1>～<11>, it also contains thixotropic agent.
The manufacture method of a <13> used for solar batteries substrate, it comprises following operation:
Mask described in any one in above-mentioned <1>～<12> is formed with composition and is imparted on semiconductor substrate and the operation of formation mask according to pattern form; And
To the part doping donor element that does not form mask on described semiconductor substrate or recipient element, at described semiconductor-based intralamellar part, divide the operation that forms diffusion layer.
The manufacture method of the used for solar batteries substrate of <14> as described in above-mentioned <13>, wherein, giving described mask formation is print process or ink-jet method by the method for composition.
The manufacture method of a <15> solar cell device, it is included in the operation that forms electrode on the diffusion layer that utilizes the used for solar batteries substrate that the manufacture method described in above-mentioned <13> or <14> obtains.
Invention effect
According to the present invention, can provide and can prevent fully that donor element or recipient element from forming with composition, having used this mask to form the manufacture method of used for solar batteries substrate and the manufacture method of solar cell device of use composition to the mask of semiconductor substrate diffusion.
Accompanying drawing explanation
Fig. 1 is the cutaway view of an example that schematically shows the manufacturing process of used for solar batteries substrate of the present invention and solar cell device.
Embodiment
First, mask of the present invention is formed and described with composition, then, to using mask to form, by the manufacture method of used for solar batteries substrate and the manufacture method of solar cell device of composition, describe.
It should be noted that, in this specification, independently operation be not only in term " operation ", but also have the situation that cannot clearly be different from other operation, as long as can realize in this case the predictive role of this operation, is also contained in this term.In addition, "～" in this specification represents that the numerical value that comprises its front and back record is respectively as minimum value and peaked scope.And then, about the amount of each composition in the composition of this specification, in the situation that there is the multiple material that is equivalent to each composition in composition, unless otherwise specified, all refer to the total amount of this many kinds of substance existing in composition.
In addition, sometimes donor element or recipient element are called to dopant.
< mask forms uses composition >
Mask of the present invention forms with composition and contains silicon compound, alkaline including earth metal or alkali-metal metallic compound (also claiming below " specific compound ") and decentralized medium.Mask of the present invention forms with donor element or recipient element that composition hinders as dopant and spreads to semiconductor substrate.Therefore, the mask of the application of the invention forms the region formation mask of not wanting to spread donor element or recipient element at semiconductor substrate with composition, can prevent fully donor element in described region and the diffusion of recipient element.Therefore, can in semiconductor substrate, optionally form doped region.Its reason can be considered as follows.
If mask is formed with containing specific compound in composition and be coated with this mask on semiconductor substrate, form with giving doped compound after composition, between specific compound and doped compound, react.Because the reactivity of this reaction is higher with reacting of semiconductor substrate than doped compound, therefore think that this reaction can hinder donor element or recipient element spreads to semiconductor substrate.
It should be noted that, in general, as the doped compound that contains donor element or recipient element, can use phosphorous oxide, boron oxide, phosphorous oxychloride etc., these compounds are acid compound (or reacting with water and aobvious acid compound).Therefore, particularly preferably making specific compound is alkali compounds.Therefore between the specific compound of alkali compounds and doped compound, acid-base reaction occurs, and the reactivity of this acid-base reaction is high, more effectively hinders donor element or recipient element spreads to semiconductor substrate.
In addition, even for example, because alkaline including earth metal or alkali-metal metallic compound are also stable under high temperature (more than 500 ℃), therefore, when making donor element or recipient element thermal diffusion to semiconductor substrate, can give full play to effect of the present invention.
In addition, alkaline including earth metal or alkali-metal metallic compound can not work as the recombination center of charge carrier when fusing into semiconductor substrate in semiconductor substrate, therefore can suppress to make the conversion efficiency of used for solar batteries substrate to reduce such unfavorable condition.
(alkaline including earth metal or alkali-metal metallic compound)
Mask of the present invention forms and contains alkaline including earth metal or alkali-metal metallic compound with composition.The mask formation composition that contains alkaline including earth metal or alkali-metal metallic compound by use, can hinder donor element or recipient element spreads to semiconductor substrate.
Alkaline including earth metal or alkali-metal metallic compound are lower at normal temperature (approximately 20 ℃) can be that liquid can be also solid.Want at high temperature also can keep sufficient mask performance, need at high temperature also can keep stable chemical property, from then on plant viewpoint and set out, preferably making metallic compound for example, at the high temperature (more than 500 ℃) that thermal diffusion occurs lower is solid.Here, for example, as alkaline including earth metal or alkali-metal metallic compound, can list and contain alkaline-earth metal or alkali-metal metal oxide and alkaline including earth metal or alkali-metal slaine.
As alkaline including earth metal or alkali-metal metallic compound, be not particularly limited, be preferably and can under the more than 700 ℃ high temperature that makes donor element or recipient element thermal diffusion, become the material of alkali compounds.From showing stronger alkaline viewpoint, preferably make metallic compound contain and be selected from more than a kind in magnesium, calcium, sodium, potassium, lithium, rubidium, caesium, beryllium, strontium, barium and radium as metallic element, more preferably contain more than a kind that is selected from magnesium, calcium, barium, potassium, sodium as metallic element, further preferably contain more than a kind that is selected from magnesium, calcium and potassium as metallic element, from the viewpoint of the easiness of hypotoxicity, acquisition, further preferably contain a kind of being selected from magnesium and calcium above as metallic element.
And, viewpoint from chemical stability, be preferably from contain more than a kind metal oxide, metal carbonate, metal nitrate, metal sulfate and the metal hydroxides being selected from these metallic elements, select more than a kind, be more preferably selected from metal oxide, metal carbonate and metal hydroxides more than a kind.
Particularly preferably use: the composite oxides of the metal oxides such as sodium oxide molybdena, potassium oxide, lithia, calcium oxide, magnesium oxide, rubidium oxide, cesium oxide, beryllium oxide, strontium oxide strontia, barium monoxide, radium oxide and these metal oxides; The metal hydroxidess such as NaOH, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, strontium hydroxide, barium hydroxide, hydroxide radium; The metal carbonates such as sodium carbonate, potash, lithium carbonate, calcium carbonate, magnesium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, strontium carbonate, brium carbonate, radium carbonate; The metal nitrates such as sodium nitrate, potassium nitrate, lithium nitrate, calcium nitrate, magnesium nitrate, rubidium nitrate, cesium nitrate, beryllium nitrate, strontium nitrate, barium nitrate, nitric acid radium; The metal sulfates such as sodium sulphate, potassium sulfate, lithium sulfate, calcium sulfate, magnesium sulfate, rubidium sulfate, cesium sulfate, beryllium sulfate, strontium sulfate, barium sulfate, radium sulfate etc.
More preferably use in composite oxides, metal hydroxides and the metal carbonate be selected from above-mentioned metal oxide, these metal oxides more than a kind.
Wherein, viewpoint from the easiness of hypotoxicity and acquisition, preferably use and be selected from sodium carbonate, sodium oxide molybdena, potash, potassium oxide, calcium carbonate, calcium hydroxide, calcium oxide, magnesium carbonate, magnesium hydroxide, magnesium sulfate, calcium sulfate, calcium nitrate, in calcium nitrate and magnesium oxide more than a kind, more preferably use and be selected from magnesium oxide, calcium oxide, magnesium carbonate, calcium carbonate, magnesium sulfate, calcium sulfate, calcium nitrate, in magnesium hydroxide and calcium hydroxide more than a kind, further preferably use and be selected from calcium carbonate, calcium oxide, magnesium carbonate, in calcium sulfate and magnesium oxide more than a kind, further preferably use calcium carbonate.
At alkaline including earth metal or alkali-metal metallic compound at normal temperatures for solid and be shape of particle in the situation that, the particle diameter of this particle is preferably below 30 μ m, 0.01 μ m～30 μ m more preferably, more preferably 0.02 μ m～10 μ m, is further preferably 0.03 μ m～5 μ m.
If particle diameter is below 30 μ m, can make donor element or recipient element spread equably (doping) to the region of the requirement of semiconductor substrate.In addition, if particle diameter is more than 0.01 μ m, easily at mask, form with disperseing equably alkaline including earth metal or alkali-metal metallic compound in composition.In addition, alkaline including earth metal or alkali-metal metallic compound also can be dissolved in decentralized medium.
It should be noted that, particle diameter represents volume average particle size, can measure by laser light scattering diffraction approach particle size distribution device etc.Volume average particle size can be irradiated to the scattered light intensity of the laser on particle and the relation of angle and be calculated based on Mie scattering theory by detection.Decentralized medium during mensuration is not particularly limited, and preferably the decentralized medium as the particle of determination object is not dissolved in use.
As obtaining particle diameter, be the method for the particle of the specific compound below 30 μ m, be not particularly limited, for example, can obtain by carrying out pulverization process.As breaking method, can adopt dry type comminuting method and case of wet attrition method.As dry type comminuting method, can use injector-type mill, vibrating mill, ball mill etc.As case of wet attrition method, can use ball mill, ball mill etc.
If the impurity being produced by reducing mechanism when pulverization process is blended into mask and forms with in composition, may cause the life-span of the charge carrier in semiconductor substrate to be reduced, therefore, the material of crushing container, bead, ball etc. is preferably selected the material little on the impact of semiconductor substrate.Material as the suitable container using when pulverizing etc., can list aluminium oxide, partially stabilized zirconia etc.In addition, as obtaining particle diameter, be the method for the particle of the specific compound below 30 μ m, except breaking method, can also use vapour phase oxidation process, Hydrolyze method etc.
In addition, the particle of specific compound also can for example, for particle (silicon oxide particle) that the compound by except alkaline including earth metal or alkali-metal metallic compound is formed be as carrier and the surface-coated of this carrier or disperse to support the material of alkaline including earth metal or alkali-metal metallic compound.This form can make the effective surface area of alkaline including earth metal or alkali-metal metallic compound increase, and may make to hinder donor element or recipient element and improve to the characteristic of semiconductor substrate diffusion.
As above-mentioned carrier, preferably demonstrate 10m 2the material of BET specific area more than/g, can illustration SiO 2, the inorganic material such as active carbon, carbon fiber, zinc oxide particle.
The shape of above-mentioned particle is not particularly limited, and can be spherical, flat roughly, flakey, bulk, ellipsoid shape, arbitrary shape in tabular and bar-shaped.The shape of above-mentioned particle can be confirmed by electron microscope etc.
Mask forms by the diffusivity of containing ratio consideration coating, donor element or the recipient element of the alkaline including earth metal in composition or alkali-metal metallic compound etc. and decides.Conventionally, mask forms with the ratio that contains of the alkaline including earth metal in composition or alkali-metal metallic compound and forms with more than being preferably 0.1 quality % in composition 100 quality % and below 95 quality % at mask, more preferably more than 0.1 quality % and below 80 quality %, more preferably more than 0.1 quality % and below 50 quality %, more than being particularly preferably 2 quality % and below 50 quality %, more than most preferably being 5 quality % and below 20 quality %.
If the containing ratio of alkaline including earth metal or alkali-metal metallic compound is more than 0.1 quality %, donor element can be hindered fully or recipient element spreads in semiconductor substrate.If the containing ratio of alkaline including earth metal or alkali-metal metallic compound is below 95 quality %, make mask form and become well by the dispersiveness of the alkaline including earth metal in composition or alkali-metal metallic compound, the coating of substrate is improved.
In addition, mask forms gross mass ratio with the alkaline including earth metal in whole nonvolatile component of composition and alkali-metal metallic compound, and to be preferably 5 quality % above and lower than 100 quality %, and more preferably 20 quality % are above and below 99 quality %.By the gross mass ratio of this metallic compound is set in above-mentioned scope, thereby have, can access the tendency that sufficient mask is controlled effect.
Herein, nonvolatile component refers to nonvolatile composition when heat-treating above for 600 ℃.It should be noted that, nonvolatile component can utilize thermogravimetric analysis meter TG to obtain, and total containing ratio of the alkaline including earth metal in nonvolatile component and alkali-metal metallic compound can utilize ICP emission spectrographic analysis/mass spectrometry (ICP-MS method), atomic absorption method to obtain.
(silicon compound)
Mask of the present invention forms and contains silicon compound with composition.It as inorganic bond performance function, easily at high temperature makes alkaline including earth metal or alkali-metal metallic compound bonded to one another by containing silicon compound, and easily makes alkaline including earth metal or alkali-metal metallic compound and semiconductor substrate bonding.
As silicon compound, from forming by the dispersed viewpoint composition at mask, preferably comprise silicone resin.Silicone resin more preferably comprises the hydrolytic condensate of alkoxy silane.Aspect easily control reactivity, chemical stability, alkoxy silane is excellent.
Yi Bian referring to, hydrolytic condensation alkoxysilane compound containing trialkylsilyl group in molecular structure is hydrolyzed and (the H that dewaters herein, 2o), Yi Bian make its condensation, carry out polymerization.Such silicone resin is preferably with R 3siO-(R 2siO) n-OSiR 3(in formula, R 2and R 3for alkoxyl, and can be identical or different.N is 1～10,000 integer.) compound that represents.
As the alkoxyl that forms alkoxysilane compound containing trialkylsilyl group in molecular structure, be preferably the alkoxyl of straight chain shape or a chain, the alkoxyl of the straight chain shape of carbon number 1～24 or chain more preferably, the alkoxyl of the straight chain shape of further preferred carbon number 1～10 or a chain, is particularly preferably the straight chain shape of carbon number 1～4 or the alkoxyl of a chain.
As above-mentioned alkoxyl, specifically, can enumerate methoxyl group, ethyoxyl, propoxyl group, butoxy, isopropoxy, isobutoxy, amoxy, own oxygen base, octyloxy, 2-ethyl hexyl oxy, tertiary octyloxy, last of the ten Heavenly stems oxygen base, dodecyloxy, tetradecyloxyaniline, 2-hexyl oxygen in last of the ten Heavenly stems base, hexadecane oxygen base, octadecane oxygen base, cyclohexyl methoxyl group, octyl group cyclohexyloxy etc.
As above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure, from the easiness obtaining, the viewpoint of chemical stability, preferably comprise be selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four butoxy silanes more than a kind.
From the dispersed viewpoint composition for mask forms, the weight average molecular weight of silicone resin (Mw) is preferably 150～100,000, and more preferably 1000～50,000.It should be noted that, weight average molecular weight be utilize gel permeation chromatography (GPC) method to measure and use the calibration curve of polystyrene standard to convert and value.
Silicone resin can utilize known method to obtain.For example can pass through water (H 2o) and above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure in aftermentioned decentralized medium, stir and obtain.In addition, for Reaction time shorten, can add catalyst.As catalyst, can enumerate hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid, hydrofluoric acid etc., wherein, preferably use nitric acid.
Use in the present invention in the situation of silicone resin as silicon compound, can be by pre-synthesis silicone resin and alkaline including earth metal or alkali-metal metallic compound, decentralized medium and organic bond be mixed together to prepare mask formation composition, in addition, can also be by by water and above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure, be mixed together to prepare mask formation composition with alkaline including earth metal or alkali-metal metallic compound and decentralized medium.
In addition, as silicon compound, can contain Si oxide (SiO 2, SiO etc.).Shape as Si oxide, is not particularly limited, for example, in emboliform situation, can illustration roughly spherical, flat, bulk, tabular, flakey etc.At Si oxide, be in emboliform situation, its volume average particle size is preferably below 20 μ m, more preferably below 5 μ m.In the situation that use has the Si oxide of the volume average particle size below 20 μ m, this Si oxide is easily dispersed in mask and forms with in composition, and productivity ratio is improved.It should be noted that, the lower limit of volume average particle size is not particularly limited, but more than being preferably 0.01 μ m.
At mask of the present invention, form with in composition, the containing ratio of silicon compound preferably surpasses 0 quality % and is below 99.9 quality %, more preferably more than 0.5 quality % and below 90 quality %, more preferably more than 10 quality % and below 80 quality %.By making the containing ratio of silicon compound, be below 99.9 quality %, can bring into play fully by containing the mask that alkaline including earth metal or alkali-metal metallic compound bring and form the effect of sheltering with composition.
In addition, the quality ratio of the total content of alkaline including earth metal and alkali-metal metallic compound and the total content of silicon compound (alkaline including earth metal and alkali-metal metallic compound)/(silicon compound) is preferably 99.9/0.1～0.1/99.9, and more preferably 99/1～20/80.
(decentralized medium)
Mask of the present invention forms and contains decentralized medium with composition.Decentralized medium refers to: the medium for above-mentioned alkaline including earth metal or alkali-metal metallic compound are dispersed or dissolved in composition.In addition, as decentralized medium, can enumerate solvent, water and organic bond.
As above-mentioned solvent, for example can enumerate: acetone, methylethylketone, 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, the ketone series solvents such as 4-pentanedione, acetonyl acetone, Anaesthetie Ether, methyl ethyl ether, methyl n-propyl ether, Di Iso Propyl Ether, oxolane, methyltetrahydrofuran, diox, dimethyl dioxane, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate n-propyl ether, ethylene glycol bisthioglycolate butyl ether, diethylene glycol single-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl n-propyl ether, diethylene glycol methyl n-butyl ether, diethylene glycol diη-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol diola, triethylene glycol dimethyl ether, triethylene glycol Anaesthetie Ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl n-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol diola, TEG dimethyl ether, TEG Anaesthetie Ether, TEG methyl ethyl ether, TEG methyl n-butyl ether, diethylene glycol di-n-butyl ether, TEG diola, TEG di-n-butyl ether, propylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, propylene glycol diη-propyl ether, propylene glycol dibutyl ethers, DPG dimethyl ether, DPG Anaesthetie Ether, DPG methyl ethyl ether, DPG methyl n-butyl ether, DPG diη-propyl ether, DPG di-n-butyl ether, DPG diola, tripropylene glycol dimethyl ether, tripropylene glycol Anaesthetie Ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl n-butyl ether, tripropylene glycol di-n-butyl ether, 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, four propylene glycol di-n-butyl ethers, four propylene glycol diolas, the 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, methylcyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, acetic acid diethylene glycol methyl ether-ether, acetic acid TC ester, acetic acid dipropylene glycol methyl ether ester, acetic acid DPG ethyl ether-ether, diacetate glycol ester, acetic acid methoxyl group triglycol ester, ethyl propionate, n-butyl propionate, isoamyl propionate, diethy-aceto oxalate, dibutyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, lactic acid n-pentyl ester, Ethylene Glycol Methyl ether propionic ester, 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, the ester series solvents such as gamma-valerolactone, acetonitrile, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, N-propyl pyrrole alkane ketone, N-butyl pyrrolidine ketone, N-hexyl pyrrolidones, N-cyclohexyl pyrrolidones, N, the non-proton property polar solvents such as dinethylformamide, DMA, 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, 2-methyl butanol, sec-amyl alcohol, tert-pentyl alcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl anyl alcohol, secondary hexyl alcohol, 2-ethyl butanol, secondary enanthol, n-octyl alcohol, 2-Ethylhexyl Alcohol, secondary octanol, n-nonyl alcohol, Decanol, secondary tip-nip, Exxal 12, secondary tetradecanol, secondary heptadecanol, phenol, cyclohexanol, methyl cyclohexanol, benzylalcohol, ethylene glycol, 1, 2-propylene glycol, 1, 3-butanediol, diethylene glycol, DPG, triethylene glycol, the alcohol series solvents such as tripropylene glycol, the glycol monoether series solvents such as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether (cellosolve), ethylene glycol list phenyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol list n-butyl ether, diethylene glycol list n-hexyl ether, ethyoxyl triethylene glycol, TEG list n-butyl ether, propylene glycol monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, tripropylene glycol monomethyl ether, the terpenic series solvents such as α-terpinenes, α-terpineol, laurene, alloocimene, citrene, dipentene (dipentene), australene, nopinene, terpinol (terpineol), carvol (carvone), ocimenum, phellandrene (phellandrene).These solvents can be used separately a kind or be used in combination two or more.
Wherein, from the viewpoint to the coating of semiconductor substrate, as decentralized medium, preferred water, alcohol series solvent, glycol monoether series solvent or terpenic series solvent, more preferably water, alcohol, cellosolve, α-terpineol, diethylene glycol list n-butyl ether or acetic acid diethylene glycol list normal-butyl ether-ether, further preferred water, alcohol, α-terpineol or cellosolve.
Mask forms with the containing ratio of the decentralized medium in composition considers that coating and concentration of dopant decide, for example at mask, form with more than being preferably 5 quality % in composition and below 99 quality %, more preferably more than 20 quality % and below 95 quality %, more preferably more than 40 quality % and below 90 quality %.
Mask of the present invention forms can contain organic bond with composition.As organic bond, can suitably select: polyvinyl alcohol; Polyacrylamide resin; Polyvinyl lactam resin; PVP resin; Polyethylene oxide resin; Poly-sulfonate resin; Acrylamide alkyl sulfonic acid resin; The cellulose derivatives such as cellulose ether, carboxymethyl cellulose, hydroxyethylcellulose, ethyl cellulose; Gelatin, gelatine derivative; Starch, starch derivatives; Sodium alginate class; Xanthans (xanthan); Guar gum, guar derivative; Scleroglucan, scleroglucan derivative; Bassora gum, bassora gum derivative; Dextrin, dextrin derivative; (methyl) acrylic resin; (methyl) acrylates such as (methyl) acid alkyl ester resin, (methyl) dimethylaminoethyl acrylate resin; Butadiene resin; Styrene resin; And the copolymer of these materials.
Wherein, the viewpoint from decomposability and the liquid sagging while preventing silk screen printing, preferably comprises acrylic resin or cellulose derivative.These materials can be used separately a kind or be used in combination two or more.
The molecular weight of organic bond is not particularly limited, and it is desirable to according to suitably adjusting as the required viscosity of composition.It should be noted that, containing ratio while containing organic bond forms with more than being preferably 0.5 quality % in composition and below 30 quality % at mask, more preferably more than 3 quality % and below 25 quality %, more preferably more than 3 quality % and below 20 quality %.
As above-mentioned decentralized medium, can use the decentralized medium that is dissolved with above-mentioned organic bond.
(other composition)
Mask forms can also contain as required the various additives such as thickener, wetting agent, surfactant, inorganic powder, thixotropic agent as other composition on the basis of silicon compound, alkaline including earth metal or alkali-metal metallic compound, decentralized medium with composition.
As above-mentioned surfactant, can enumerate nonionic is that surfactant, cation are that surfactant, anion are surfactant etc.Wherein, from the few aspect of the impurity levels such as heavy metal of bringing into semiconductor equipment, preferably nonionic is that surfactant or cation are surfactant.And then, as nonionic, be surfactant, can enumerate silicon is that surfactant, fluorine are surfactant and hydrocarbon system surfactant, from the aspect of promptly being burnt till when the heating such as diffusion, preferred hydrocarbon system surfactant.
As hydrocarbon system surfactant, block copolymer that can illustration epoxy ethane-epoxy propane, acetylenic glycol compound etc., from the inequality of the resistance value of further reduction semiconductor equipment, more preferably acetylenic glycol compound.
As inorganic powder, can enumerate the powder of silica, silicon nitride, silica, carborundum etc.
Mask forms can also comprise with composition the thixotropic agent that contains solid constituent.Thus, can easily control thixotropy, and can form the silk screen printing with the viscosity that is suitable for silk screen printing and with mask, form with composition and have the mask formation composition for ink-jet of the viscosity that is suitable for ink jet printing.And then by controlling thixotropy, in the time of can suppressing to print, mask forms and oozes out or sagging from printed patterns with composition.Above-mentioned organic bond can have the effect of thixotropic agent concurrently, as such material, can list ethyl cellulose.
For mask of the present invention, form with for composition, the viewpoint that never can pollute semiconductor substrate, suppresses the combination again of the charge carrier in semiconductor substrate is set out, the containing ratio of iron, tungsten, gold, nickel, chromium, manganese etc. forms with being preferably in composition below 10 quality % at mask, more preferably below 5 quality %, more preferably below 1 quality %.
Mask forms and is not particularly limited by the viscosity of composition.Particularly, at 25 ℃, be preferably 1mPas～400Pas, more preferably 10mPas～100Pas.If it is more than 1mPas by the viscosity of composition that mask forms, in the time of on being applied to semiconductor substrate, be difficult for occurring liquid sagging, in addition, if mask forms, by the viscosity of composition, be below 400Pas, can form meticulous coated pattern.
It should be noted that, mask forms and can utilize Brookfield viscometer, E type viscosimeter, determination of viscoelasticity device etc. to obtain with rotation mode, Stress Control mode or strain control mode by the viscosity of composition.
Mask of the present invention forms can be by using blender (blender), mixer, mortar or rotor (rotor) to be obtained by mixing the composition of alkaline including earth metal or alkali-metal metallic compound, decentralized medium, silicon compound and interpolation as required with composition.In addition, when mixing, can heat as required.Heating-up temperature now for example can be made as 30 ℃～100 ℃.
The manufacture method > of < used for solar batteries substrate and solar cell device
The manufacture method of used for solar batteries substrate of the present invention comprises following operation: aforementioned mask is formed with composition and is imparted on semiconductor substrate and the operation of formation mask according to pattern form; And at above-mentioned semiconductor-based intralamellar part, divide the operation that forms diffusion layer to the part doping donor element that does not form aforementioned mask on above-mentioned semiconductor substrate or recipient element.
In addition, the manufacture method of solar cell device of the present invention is included in the operation that forms electrode on the diffusion layer that utilizes the used for solar batteries substrate that above-mentioned manufacture method obtains.
Herein, with reference to Fig. 1, to having used mask of the present invention to form, with the used for solar batteries substrate of composition and the manufacture method of solar cell device, describe.Fig. 1 is the cutaway view of an example that schematically shows the manufacturing process of used for solar batteries substrate of the present invention and solar cell device.
It should be noted that, used for solar batteries substrate and solar cell device to back electrode type in Fig. 1 describe, but mask of the present invention formation also can be applicable in the used for solar batteries substrate and solar cell device of arbitrary form with composition.
As other form except back electrode type, can illustration selective emitter type and two-sided illuminated.In the used for solar batteries substrate of selective emitter type, under the electrode of sensitive surface side, form concentration of dopant higher than the diffusion layer in other region.In order to form the region of the diffusion layer of this high concentration, can use mask formation composition of the present invention.In addition, in the solar cell device of two-sided illuminated, at two-sided formation finger electrode (finger bar) and main grid line electrode (bus bar), as electrode, in the one side of semiconductor substrate, form n +type diffusion layer, and form p at another side +type diffusion layer.For regioselectivity form this n +type diffusion layer and p +type diffusion layer, can be used mask formation composition of the present invention.
In (1) of Fig. 1, to giving aqueous slkali as the silicon substrate of N-shaped semiconductor substrate 10, remove damage layer, and utilize etching to obtain texture structure.
Particularly, utilize the damage layer on the silicon substrate surface that 20 quality % caustic soda produce when cutting into slices from ingot casting to remove.Then, utilize the mixed liquor of 1 quality % caustic soda and 10 quality % isopropyl alcohols to carry out etching, on N-shaped semiconductor substrate 10, form texture structure (record of omit texture structure in figure).For solar cell device, by the sensitive surface at silicon substrate (surface) side, form texture structure, thereby promote to fall into luminous effect, and realize high efficiency.
In (2) of Fig. 1, on the surface of N-shaped semiconductor substrate 10 (being sensitive surface) and the back side contrary with this sensitive surface, give mask formation composition 11 of the present invention.Adding method in the present invention is not particularly limited, and comprises print process, spin-coating method, spread coating, spraying process, scraper plate method, rolling method, ink-jet method etc., preferably uses print process or ink-jet method.
As aforementioned mask, form the amount of giving with composition, be not particularly limited, for example, be preferably made as 0.01g/m 2～100g/m 2, be preferably 0.1g/m 2～20g/m 2.Aforementioned mask forms and is not particularly limited with the coating thickness of composition, is preferably 0.1 μ m～50 μ m, more preferably 1 μ m～30 μ m.
In addition, according to mask, form the composition with composition, sometimes need to after giving, carry out for making the drying process of the contained decentralized medium volatilization of composition.Now, at the temperature of 80 ℃～300 ℃ of left and right, make it dry, in the situation that using heating plate, make its dry 1 minute～10 minutes, in the situation that using drying machine etc., make its dry about 10 minutes～30 minutes.This drying condition depends on mask and forms the containing ratio with the decentralized medium of composition, is not defined as especially in the present invention above-mentioned condition.
It should be noted that, the in the situation that of print process, ink-jet method etc., can form the mask that obtain pattern-like with composition 11 by give mask according to pattern form.On the other hand, the in the situation that of spin-coating method, spread coating, spraying process, scraper plate method, rolling method etc., mask is formed and is applied to after whole with composition 11, utilize etching etc. that it is partly removed, can obtain thus the mask of pattern-like.
Then,, in (3) of Fig. 1, coating is used to form n +type diffusion layer and p +the diffusion material 12,13 for coating of type diffusion layer.Then, in (4) of Fig. 1, carry out thermal diffusion, at the interior formation of N-shaped semiconductor substrate 10 n +type diffusion layer 14 and p +type diffusion layer 15.By the heat treatment for thermal diffusion, make coating become the burned material 12 ', 13 ' of diffusion material for coating with diffusion material 12,13, and conventionally form glassy layer.As for carrying out the heat treatment temperature of thermal diffusion, be not particularly limited, but preferably at the temperature of 750 ℃～1050 ℃ and under the condition of 1 minute～300 minutes, heat-treat.
Herein, although illustrate and form n simultaneously +type diffusion layer 14 and p +the method of type diffusion layer 15, but also can spread respectively.That is, also can first be coated with and be used to form p +the coating of type diffusion layer 15 is with diffusion material 13 and make its thermal diffusion, and after coating is removed by the burned material 13 ' of diffusion material, coating is used to form n +the coating of type diffusion layer 14 is with diffusion material 12 and make its thermal diffusion, then coating is removed by the burned material 12 ' of diffusion material.
In addition, to using coating to be illustrated by the situation of diffusion material 12,13, but also can similarly be applied in, use POCl herein 3gas, BBr 3in the method for gas.Now, first will in N-shaped semiconductor substrate 10, form p +the presumptive area of type diffusion layer 15, as peristome, is utilized mask to form and with composition, beyond the region of this peristome, is formed mask.Then on the N-shaped semiconductor substrate 10 corresponding with this peristome, form p +type diffusion layer 15, removes mask afterwards.Then, will form n +the presumptive area of type diffusion layer 14, as peristome, is utilized mask to form and with composition, beyond the region of this peristome, is formed mask.Then, on the N-shaped semiconductor substrate 10 corresponding with this peristome, form n +type diffusion layer 14.
Then, in (5) of Fig. 1, mask is formed with composition 11 and coating and removed by the burned material 12 ', 13 ' of diffusion material, obtain used for solar batteries substrate.As the above-mentioned method of removing, can enumerate to be immersed in and contain the medium method of aqueous acid, preferably according to mask, form with composition 11 and be used to form n +type diffusion layer 14 and p +for the coating of type diffusion layer 15, the burned material 12 ' of diffusion material, 13 ' composition decide.Particularly, preferably include following operation: utilize the aqueous solution that contains hydrofluoric acid to carry out etching to the glassy layer generating by heat diffusion treatment on semiconductor substrate.More particularly, can enumerate following method: for example, after utilizing hydrochloric acid (the HCl aqueous solution of 10 quality %) that alkaline including earth metal or alkali-metal metallic compound are removed, wash, recycling hydrofluoric acid aqueous solution (for example HF aqueous solution of 2.5 quality %) carries out etching to coating by the burned material 12 ', 13 ' of diffusion material, washes afterwards.
Then, in (6) of Fig. 1, as the surface of sensitive surface, giving antireflection film 16, and giving overleaf passivating film 17.The composition of antireflection film 16 and passivating film 17 can be identical or different.As antireflection film 16, can enumerate for example silicon nitride film, as passivating film 17, can enumerate for example silicon oxide film.The thickness of antireflection film and passivating film is not particularly limited, but is preferably made as 10nm～300nm, is more preferably made as 30nm～150nm.
Then,, in (7) of Fig. 1, on passivating film 17, to forming the position of electrode, opening is set.The method that opening is set is not particularly limited, such as can for example, by utilizing ink-jet method etc. the position coating etching solution (solution that comprises hydrofluoric acid, ammonium fluoride or phosphoric acid) of opening is set and it is heat-treated to arrange opening wanting.
Then, in (8) of Fig. 1, at n +type diffusion layer 14 and p +on type diffusion layer 15, form respectively n electrode 18 and p electrode 19.In the present invention, the material of electrode 18,19, formation method are not particularly limited.The electrode of the metal that for example can contain aluminium, silver or copper by coating forms with paste and makes its dry electrode 18,19 that forms.Then, electrode 18,19 is burnt till, thereby complete solar cell device.
It should be noted that, the paste comprise frit if use is as above-mentioned electrode formation paste, can omit the operation that opening is set shown in (7) of Fig. 1.If by the electrode that comprises frit form with paste be coated on passivating film 17 and with the scope of 600 ℃～900 ℃ burn till several seconds～several minutes, frit makes passivating film 17 meltings of rear side, and the metallic in paste (for example silver particles) forms contact site and solidifies with silicon substrate 10.Thus, make formed surface electrode 18,19 and silicon substrate 10 conductings.This is called as burning logical (fire through).
< solar cell >
Solar cell comprises a kind of above above-mentioned solar cell device and laying-out and wiring material and forming on the electrode of solar cell device.Solar cell can also link a plurality of solar cell devices by wiring material as required and utilizes encapsulant to seal and form.
As above-mentioned wiring material and encapsulant, be not particularly limited, can from the normally used material in this area, suitably select.
It should be noted that, for the disclosure of No. 2012-002633, Japanese publication, as with reference to it is all incorporated in this specification.
Whole documents, patent application and the technical standard in this specification, recorded, with the situation of specifically and respectively having recorded each document, patent application and technical standard with degree as with reference to quoting in this specification.
Embodiment
Below, embodiments of the invention are described more specifically, but the present invention is not subject to the restriction of these embodiment.It should be noted that, in case of no particular description, raw material is all used reagent.In addition, " % " refers to " quality % " in case of no particular description.
In addition, the alkaline including earth metal in embodiment or the volume average particle size of alkali-metal metallic compound are used laser diffraction and scattering method granularity particle size distribution analyzer (Beckman Coulter, Inc. LS 13 320 processed) to measure particle diameter with dispersity.
< embodiment 1>
(mask forms the preparation with composition 1)
Tetraethoxysilane (the chemical industry system of rubbing, ethyl orthosilicate) 10g, water 4g, nitric acid 0.1g and ethanol are mixed and stirred more.Then, utilize mortar to mix magnesium oxide (with the pure pharmaceutical worker of light industry system, volume average particle size 0.2 μ m, amorphous particle) 10g, be prepared into mask and form with composition 1.It is 0.2Pas in the viscosity under 25 ℃, 5rpm that this mask forms with composition 1.In addition, viscosity is made as 0.5ml and measures by utilizing E type viscosimeter (Tokyo gauge system) and mask being formed to sampling amount with composition.
(preparation of phosphorus diffusion liquid)
Prepare the ammonium dihydrogen phosphate 20 quality % aqueous solution of (with the pure pharmaceutical worker of light industry system), use the saturated ammonium dihydrogen phosphate aqueous solution of supernatant to spread liquid as phosphorus.
(thermal diffusion and etching work procedure)
On N-shaped silicon substrate after section (also claiming below " N-shaped silicon substrate ") surface, utilize spin coater (MIKASA company system, MS-A100) (rotating speed 1000rpm) to form with composition 1 whole spin coating mask of one side, make it on the heating plate of 200 ℃, be dried 5 minutes.Then, prepare other silicon substrate, with 500rpm spin coating phosphorus diffusion liquid, and be dried at 200 ℃.
Under the opposed state of distance that makes above-mentioned two silicon substrates with 1mm, 950 ℃ of heating 10 minutes, phosphorus is diffused into and is coated with mask formation with in the silicon substrate of composition 1.Then, by being coated with mask formation, with the silicon substrate of composition 1, in the 10 quality %HCl aqueous solution, flood 5 minutes, wash afterwards, then flood 5 minutes in the 2.5 quality %HF aqueous solution.After its washing being dried, to being coated with mask formation, by the part of composition 1, carried out following evaluation.
(mensuration of film resistor)
Use the Loresta-EP MCP-T360 processed of Mitsubishi Chemical's (strain) type low-resistivity meter, utilize four probe method to measure and be coated with the film resistor that mask forms the part of using composition 1.Being coated with mask formation is 190 Ω/ with the film resistor of the part of composition 1.
It should be noted that, as reference sample, the N-shaped silicon substrate after section is flooded 5 minutes in the 2.5 quality %HF aqueous solution, after its washing being dried, film resistor is measured, result is 240 Ω/.
< embodiment 2>
Except replacing the magnesium oxide in embodiment 1, use calcium oxide (with the pure pharmaceutical worker of light industry system, volume average particle size 2.5 μ m, amorphous particle) 10g, prepared similarly to Example 1 mask and formed with composition 2.With composition 2, the viscosity at 25 ℃ is 0.15Pas in this mask formation.
Except replacing the mask formation in embodiment 1 to use mask to form with composition 2 with composition 1, evaluate similarly to Example 1.Being coated with mask formation is 150 Ω/ with the film resistor of the part of composition 2.
< embodiment 3>
Tetraethoxysilane (the chemical industry system of rubbing, ethyl orthosilicate) 10g, water 4g and nitric acid 0.1g are mixed and stirred more.Then, utilize mortar to mix calcium carbonate (high-purity chemical system, volume average particle size 2.0 μ m, amorphous particle) 10g, be dissolved with α-terpineol (Terpene Chemical Co. of the ethyl cellulose (DowChemical Company system, STD200) of 15 quality %, Ltd. make) 20g and α-terpineol 5g, fully stir, be prepared into mask and form with composition 3.With composition 3, the viscosity at 25 ℃ is 0.2Pas in this mask formation.
Mask is formed and is spin-coated on N-shaped silicon substrate with composition 3, at 150 ℃, be dried.Carried out similarly to Example 1 its later operation and evaluated.Being coated with mask formation is 180 Ω/ with the film resistor of the part of composition 3.
< embodiment 4>
Tetraethoxysilane (the chemical industry system of rubbing, ethyl orthosilicate) 10g, water 4g and nitric acid 0.1g are mixed and stirred more.Then, utilize mortar to mix calcium sulfate (with the pure pharmaceutical worker of light industry system, volume average particle size 1.5 μ m, amorphous particle) 10g, be dissolved with α-terpineol (Terpene ChemicalCo. of the ethyl cellulose (Dow Chemical Company system, STD200) of 15 quality %, Ltd. make) 20g and α-terpineol 5g, fully stir, be prepared into mask and form with composition 4.With composition 4, the viscosity at 25 ℃ is 0.2Pas in this mask formation.
Mask is formed and is spin-coated on N-shaped silicon substrate with composition 4, at 150 ℃, be dried.Carried out similarly to Example 1 its later operation and evaluated.Being coated with mask formation is 220 Ω/ with the film resistor of the part of composition 4.
< embodiment 5>
Tetraethoxysilane (the chemical industry system of rubbing, ethyl orthosilicate) 10g, water 4g and nitric acid 0.1g are mixed and stirred more.Then, utilize mortar to mix magnesium oxide (with the pure pharmaceutical worker of light industry system, volume average particle size 0.2 μ m, amorphous particle) 10g, be dissolved with α-terpineol (Terpene ChemicalCo. of the ethyl cellulose (Dow Chemical Company system, STD200) of 15 quality %, Ltd. make) 20g and α-terpineol 5g, fully stir, be prepared into mask and form with composition 5.With composition 5, the viscosity at 25 ℃ is 0.2Pas in this mask formation.
Mask is formed and is spin-coated on N-shaped silicon substrate with composition 5, at 150 ℃, be dried.Carried out similarly to Example 1 its later operation and evaluated.Being coated with mask formation is 200 Ω/ with the film resistor of the part of composition 5.
< embodiment 6>
Calcium oxide (with the pure pharmaceutical worker of light industry system, volume average particle size 2.5 μ m, amorphous particle) 40g and butyl carbitol (with the pure pharmaceutical worker of light industry system, diethylene glycol single-butyl ether) 60g are mixed, use planetary ball mill, utilize 3mm stabilized zirconia pearl with 600rpm, pulverize and disperse, be prepared into and disperse liquid 1.
Then, tetraethoxysilane (the chemical industry system of rubbing, ethyl orthosilicate) 10g, water 4g and nitric acid 0.1g mixed and stirred more, being prepared into solution of silane 1.5g dispersion liquid 1 and 5g solution of silane 1 are mixed, be prepared into mask and form with composition 6.With composition 6, the viscosity at 25 ℃ is 0.1Pas in this mask formation.
Mask is formed and is spin-coated on N-shaped silicon substrate with composition 6, at 150 ℃, be dried.Carry out similarly to Example 1 its later operation and evaluate.Being coated with mask formation is 240 Ω/ with the film resistor of the part of composition 6.
< embodiment 7>
The 1g dispersion liquid 1 making in embodiment 6 and 9g solution of silane 1 are mixed, be prepared into mask and form with composition 7.With composition 7, the viscosity at 25 ℃ is 80mPas in this mask formation.
Mask is formed and is spin-coated on N-shaped silicon substrate with composition 7, at 150 ℃, be dried.Carry out similarly to Example 1 its later operation and evaluate.Being coated with mask formation is 140 Ω/ with the film resistor of the part of composition 7.
< embodiment 8>
The 0.1g dispersion liquid 1 making in embodiment 6 and 9.9g solution of silane 1 are mixed, be prepared into mask and form with composition 8.With composition 8, the viscosity at 25 ℃ is 55mPas in this mask formation.
Mask is formed and is spin-coated on N-shaped silicon substrate with composition 8, at 150 ℃, be dried.Carried out similarly to Example 1 its later operation and evaluated.Being coated with mask formation is 90 Ω/ with the film resistor of the part of composition 8.
< embodiment 9>
By being dissolved with the solution of silane 1 making in the dispersion liquid 1 that makes in butyl carbitol 2g, the 5g embodiment 6 of 20 quality % ethyl celluloses (Dow Chemical Company system, STD200) and 3g embodiment 6, mix, be prepared into mask and form with composition 9.With composition 9, the viscosity at 25 ℃ is 8Pas in this mask formation.
Mask is formed and is spin-coated on N-shaped silicon substrate with composition 9, at 150 ℃, be dried.Carry out similarly to Example 1 its later operation and evaluate.Being coated with mask formation is 190 Ω/ with the film resistor of the part of composition 9.
< embodiment 10>
By being dissolved with the solution of silane 1 making in the dispersion liquid 1 that makes in butyl carbitol 1g, the 8g embodiment 6 of 20 quality % ethyl celluloses (Dow Chemical Company system, STD200) and 1g embodiment 6, mix, be prepared into mask and form with composition 10.With composition 10, the viscosity at 25 ℃ is 10Pas in this mask formation.
Utilize silk screen printing (MT-320T, Microtech system) mask to be formed to a surperficial part of coating N-shaped silicon substrate with composition 10, make it dry after 5 minutes on the heating plate of 150 ℃, on the heating plate of 500 ℃, be dried 1 minute.Carry out similarly to Example 1 its later operation and evaluate.Being coated with mask formation is 230 Ω/ with the film resistor of the part of composition 10.
< embodiment 11>
Prepare to be similarly to Example 10 coated with mask and form the N-shaped silicon substrate with composition 10.
Then, prepare another silicon substrate, and on this substrate with 200rpm spin coating B 2o 3saturated aqueous solution, at 200 ℃, be dried.
Under the opposed state of distance that makes above-mentioned two silicon substrates with 1mm, limit passes into nitrogen limit heats 30 minutes at 950 ℃, boron is diffused into and is coated with mask formation with in the silicon substrate of composition 10.Then, by being coated with mask formation, with the silicon substrate of composition 10, in the 10 quality %HCl aqueous solution, flood 5 minutes, wash afterwards, then flood 5 minutes in the 2.5 quality %HF aqueous solution.After its washing being dried, to being coated with mask formation, with part and the formation of uncoated mask of composition 10, by the part of composition 10, measured film resistor.
Being coated with mask formation is 240 Ω/ with the film resistor of the part of composition 10, and on the other hand, it is 55 Ω/ that uncoated mask forms with the film resistor of the part of composition 10.
< embodiment 12>
Polyvinyl alcohol (weight average molecular weight 10000, partly-hydrolysed type and the pure pharmaceutical worker of light industry system) is water-soluble, be prepared into 10% polyvinyl alcohol water solution.With automatic mortar kneading device by this solution 8g, calcium oxide (with the pure pharmaceutical worker of light industry system, volume average particle size 2.5 μ m, amorphous particle) 1.5g, pyrogenic silica (Nippon Aerosil Co., Ltd. R200 processed, average aggregate particle size 5.0 μ m) and surfactant SH28PA (silicone-based surfactant, Dow ComingToraySilicone (strain) system) 0.2g mix, be prepared into mask and form and use composition 11.Form with silicon compound contains pyrogenic silica, and this pyrogenic silica also has the effect as thickener and thixotropy imparting agent.Use GPC (eastern Cao UV-8220 processed) and use METHYLPYRROLIDONE as solvent, the weight average molecular weight of polyvinyl alcohol is measured.With composition 11, the viscosity at 25 ℃ is 17mPas in this mask formation.
Utilize the membrane filter of aperture 30 μ m to form and filter and remove foreign matter with composition 11 mask, be supplied to piezoelectric ink jet device (MICROJET Co., Ltd. system, the trade name: Nanoprinter1000) of the shower nozzle that is equipped with bore 50 μ m.Use this ink discharge device (Seiko Epson Corporation's system), on the N-shaped silicon substrate surface after section, give mask and form with composition 11, make it form the linear pattern of live width 50 μ m, length 40mm.Then, make it on the heating plate of 150 ℃, be dried 5 minutes, evaluate similarly to Example 1 afterwards.Being coated with mask formation is 200 Ω/ with the film resistor of the part of composition 11.
< comparative example 1>
(preparation of comparative example composition 1)
Except do not add magnesium oxide in embodiment 1, prepared similarly to Example 1 comparative example composition 1.The viscosity of comparative example composition 1 at 25 ℃ is 6Pas.
Except replacing the mask in embodiment 1 to form with composition 1 use comparative example composition 1, evaluate similarly to Example 1.The film resistor that is coated with the part of comparative example composition 1 is 25 Ω/.
< comparative example 2>
Not sheltering on the N-shaped silicon substrate in embodiment 1, evaluate similarly to Example 1.The film resistor of N-shaped silicon substrate is 10 Ω/.
< comparative example 3>
Except replacing the magnesium oxide in embodiment 1, use silica (high-purity chemical system, volume average particle size 1 μ m), prepared similarly to Example 1 comparative example composition 3.The viscosity of comparative example composition 3 at 25 ℃ is 0.18Pas.
Except replacing the mask in embodiment 1 to form with composition 1 use comparative example composition 3, evaluate similarly to Example 1.The film resistor that has been coated with the part that has comparative example composition 3 is 30 Ω/.
As known from the above, the mask formation composition that contains silicon compound, alkaline including earth metal or alkali-metal metallic compound and decentralized medium by use, can prevent the diffusion of donor element and recipient element fully.

Claims (15)

1. a mask formation composition, it contains silicon compound, alkaline including earth metal or alkali-metal metallic compound and decentralized medium.
2. mask formation composition as claimed in claim 1, wherein, the described alkaline including earth metal in nonvolatile component or the gross mass ratio of alkali-metal metallic compound are that 5 quality % are above and lower than 100 quality %.
3. mask formation composition as claimed in claim 1 or 2, wherein, it is above as metallic element that described alkaline including earth metal or alkali-metal metallic compound comprise a kind of being selected from magnesium, calcium, sodium, potassium, lithium, rubidium, caesium, beryllium, strontium, barium and radium.
4. the mask formation composition as described in any one in claim 1～3, wherein, described alkaline including earth metal or alkali-metal metallic compound comprise be selected from magnesium oxide, calcium oxide, magnesium carbonate, calcium carbonate, magnesium sulfate, calcium sulfate, calcium nitrate, magnesium hydroxide and calcium hydroxide more than a kind.
5. the mask formation composition as described in any one in claim 1～4, wherein, described alkaline including earth metal or alkali-metal metallic compound are to be the particle of solid at normal temperatures, the volume average particle size of described particle is below 30 μ m.
6. the mask formation composition as described in any one in claim 1～5, wherein, described silicon compound comprises silicone resin.
7. the mask formation composition as described in any one in claim 1～6, wherein, described silicon compound is the silicone resin that alkoxy silane hydrolytic condensation is obtained.
8. the mask formation composition as described in any one in claim 1～7, wherein, described silicon compound is by the silicone resin that is selected from a kind of above compound hydrolysis condensation in tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four butoxy silanes and obtains.
9. the mask formation composition as described in any one in claim 1～8, wherein, described decentralized medium comprise be selected from water, alcohol series solvent, ethylene glycol mono-ether series solvent and terpenic series solvent more than a kind.
10. the mask formation composition as described in any one in claim 1～9, it also comprises organic bond.
11. mask formation compositions as claimed in claim 10, wherein, described organic bond comprise be selected from acrylic resin and celluosic resin more than a kind.
12. mask formation compositions as described in any one in claim 1～11, it also contains thixotropic agent.
The manufacture method of 13. 1 kinds of used for solar batteries substrates, it comprises following operation:
Mask described in any one in claim 1～12 is formed with composition and is imparted on semiconductor substrate and the operation of formation mask according to pattern form; And
To the part doping donor element that does not form mask on described semiconductor substrate or recipient element, at described semiconductor-based intralamellar part, divide the operation that forms diffusion layer.
The manufacture method of 14. used for solar batteries substrates as claimed in claim 13, wherein, giving described mask formation is print process or ink-jet method by the method for composition.
The manufacture method of 15. 1 kinds of solar cell devices, it is included in the operation that forms electrode on the diffusion layer that utilizes the used for solar batteries substrate that the manufacture method described in claim 13 or 14 obtains.
CN201380005060.6A 2012-01-10 2013-01-10 Mask-forming composition, method for producing solar cell substrate, and method for producing solar cell element Pending CN104067395A (en)

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