CN104694005A - Organic mask electronic paste of SE solar battery and method for producing selective emitter - Google Patents

Organic mask electronic paste of SE solar battery and method for producing selective emitter Download PDF

Info

Publication number
CN104694005A
CN104694005A CN201510027512.1A CN201510027512A CN104694005A CN 104694005 A CN104694005 A CN 104694005A CN 201510027512 A CN201510027512 A CN 201510027512A CN 104694005 A CN104694005 A CN 104694005A
Authority
CN
China
Prior art keywords
component
slurry
acid
hydroxy
rosin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510027512.1A
Other languages
Chinese (zh)
Other versions
CN104694005B (en
Inventor
戈士勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JIANGSU RUIDE NEW ENERGY TECHNOLOGY Co Ltd
Original Assignee
JIANGSU RUIDE NEW ENERGY TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JIANGSU RUIDE NEW ENERGY TECHNOLOGY Co Ltd filed Critical JIANGSU RUIDE NEW ENERGY TECHNOLOGY Co Ltd
Priority to CN201510027512.1A priority Critical patent/CN104694005B/en
Publication of CN104694005A publication Critical patent/CN104694005A/en
Application granted granted Critical
Publication of CN104694005B publication Critical patent/CN104694005B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention relates to an organic mask electronic paste of an SE solar battery. The electronic paste comprises the following materials by mass percent: 30-50 percent of synthesized resin, 0.5-10 percent of coloring agent, 1-10 percent of additive, 5-25 parts of thickening agent and the balance of an organic solvent, wherein the pH value of the organic mask electronic paste is equal to or smaller than 7; the synthesized resin comprises components A, B and C, accounting for 10-18 percent, 12-20 percent and 8-12 percent of the mass of the electronic paste respectively; the component A is one or a mixture selected from the following components: rosin and rosin derivatives with conjugated double bonds and carboxylic groups; the component B is phenolic resin with carboxylic groups; and the component C is one or a mixture selected from the following components: modified epoxy resin with carboxylic groups, modified polyester resin with carboxylic groups, and acrylic resin. The organic mask electronic paste of the SE solar battery disclosed by the invention has the properties of acid resistance, alkali dissolution and hydrophobicity. The invention further relates to a method for producing a selective emitter of the SE solar battery.

Description

SE solar cell etch layer electronics slurry and manufacture selective emitter method
Technical field
The present invention relates to the manufacture of SE solar cell, particularly the etch layer electronics slurry of SE solar cell; And the manufacture method of the selective emitter of SE solar cell.
Background technology
In order to improve the efficiency of conversion of battery, people are optimized emission area structure, develop selective emitter solar battery (hereinafter referred to as SE battery), namely heavy doping is carried out in metal grid lines and silicon chip contact part, light dope is carried out in position in-between the electrodes, make: (1) easily forms ohmic contact between metal grid lines and silicon chip, thus reduce the series resistance of battery; (2) photo-generated carrier is reduced in cell active area at the probability of surface recombination, also can improve the spectral response of battery to short wavelength light region simultaneously, the short-circuit current of battery and open circuit voltage just can be enhanced, and high surface levels doping easily causes surface " dead layer " and then affects transformation efficiency, light dope in cell active area can reduce the impact of " dead layer ", compared with conventional batteries, SE cell photoelectric efficiency can improve 0.3%.
Selective emitter battery has comparatively ideal raising than conventional batteries in electricity conversion, and relative to other high performance solar batteries technology, the production technique of selective emitter battery also and uncomplicated, wherein One Diffusion Process method technique is the simplest, and merely through a High temperature diffusion process, minimum to silicon chip damage, be manufacture the irreversible trend of SE battery; Specifically, comprise zone of oxidation mask diffusion-print process, laser is coated with source doping-electrochemical plating, returns lithography etc.Return the pipelining that lithography is more suitable for high yield; Concrete manufacture method is disclosed in the Chinese patent application of CN101916797A: cleaning silicon chip making herbs into wool, diffusion, and forms heavy doping, obtains lower square resistance; Then according to the grid line figure designed, starch with silk screen printing mask electronics and dry, then HF and HNO is used after removing phosphorosilicate glass in local on silicon chip 3mixed solution carry out returning and carve corrosion, then remove mask, the isolation of pn knot is removed phosphorosilicate glass, surface deposition antireflection layer simultaneously, is finally printed electrode.
The difficult point returning lithography manufacture SE battery is, adopts fluoride and oxygenant (as HF and HNO 3) mixed solution carry out returning and carve corrosion, in view of existing mask material adopts general mask slurry, acid resistance is to be improved, easy generation excessive corrosion, cause the doping below mask to reduce, transverse dispersion resistance increases, and finally causes the increase of SE cell series resistance; For this reason, returning in lithography of also having adopts the method for printing or printing spraying corrosive fluid to remove the mask in the non-electrode grid line district of corrosion to retain the mask layer under grid line, if publication number is the patent application of CN103531657A.
In addition, the method for the first many employing water of minimizing technology of mask slurry or the alcohol combination of ultrasound deionized water overflow of 50 ~ 100% removes the poor effect of mask, there is the problem that mask is difficult to eliminate, affects the deposition of antireflection layer and final SE battery performance.
Therefore the mask material developing a kind of applicable silk screen printing is necessary, it not only has good acid resistance is enough to stand the wafer thinning strong acid realized needed for light dope and embathes process and wash-out does not occur, but also the good solubility had in non acidic solvent is to facilitate removal; Preferably directly thermofixation can realize film forming, without the need to the photocuring film forming by high cost, complex process; Compactness in addition after film forming is also need to consider.
Summary of the invention
The object of the invention is to overcome the defect existed in prior art, provide a kind of etch layer material of applicable silk screen printing, it not only has good acid resistance is enough to stand wafer thinning and realizes strong acid needed for light dope as HF and HNO 3mixture embathe process and wash-out do not occur, but also there is good caustic solubility to facilitate removal; And need within tens seconds, be only curable film-forming the temperature thermofixation of about 100 DEG C.
For this reason, technical scheme of the present invention is a kind of SE solar cell etch layer electronics slurry, and its composition of raw materials is made up of the component of following mass percent: 30 ~ 50% synthetic resins, 0.5 ~ 10% tinting material, 1 ~ 10% auxiliary agent, 5 ~ 25% thickening materials, surplus are organic solvent; And the pH of described etch layer electric slurry is≤7; And synthetic resins is made up of A, B, C component, A, B, C component accounts for 10 ~ 18%, 12 ~ 20% of electronics slurry total mass respectively, 8 ~ 12%, wherein component A selects one in following group or mixture: rosin, rosin derivative with conjugated double bond and hydroxy-acid group; B component is selected: with the resol of hydroxy-acid group; Component C selects one in following group or mixture: the modified epoxy with hydroxy-acid group, the modified polyester resin with hydroxy-acid group, acrylic resin.
In this formula, the conjugated double bond of the rosin of component A or the derivative of rosin and resol generation addition reaction, realize film-forming, and wherein the derivative of rosin or rosin gives the good slipperiness of mask layer and glossiness, acid etching solution is avoided to cause the stripping of mask layer from the hole infiltration of rete; And B component and component C generation etherificate or esterification are improved the fragility of resol and reduced the cure shrinkage of resol, after preventing film forming from drying, cooling produces tiny crack and provides passage for acid liquid corrosion and add in mask electronics slurry solvability in a solvent and improve mask layer adhesiveproperties.This electronics slurry be coated to silicon chip gate electrode line district, solidify as after mask, carrying out HF and HNO 3mixing acid in when carrying out reduction processing, A, B, component C all have acidic-group, and after solidification, rete is stable in acid solution solution; And when carrying out lift-off mask layer in alkali lye, the acidic-group of the A in rete, B, component C and alkali lye generation neutralization reaction, thus produce numerous microchannel in the mask, passage is provided for mask layer corrodes into fine powder in alkali lye, alkali lye can be corroded to mask inside by rapid permeability, wherein B component resol alkali resistance is poor, makes mask layer corrode into fine powder by disintegrating phenol-formaldehyde resin matrix.Compare and starch with the mask electronics of photocuring, fine powder can be peeled off in alkali lye after this mask electronics slurry film forming, avoid traditional mask layer and be difficult to stripping or become block ground mode to peel off in flakes easily make overburden block flushing channel and then need the problem of external human assistance.
In order to improve thermofixation efficiency, preferably, the acid number of described synthetic resins is 120 ~ 300.The high acid value of synthetic resins carries sour environment for the etherificate and/or esterification realizing autocatalysis B, component C in acid condition provides, thus make electric slurry can realize thermofixation, without the need to additional crosslink agent or catalyzer in tens seconds at about 100 DEG C temperature; And the raising of acid number also contributes to the caustic solubility of mask layer, but acid number is not easily too high, otherwise affects the stability of synthetic resins and carrying out smoothly of addition reaction.
Component A is given mask high gloss, is consolidated soon, mineral oil solvability.The conjugated double bond that rosin and listed rosin derivative have can with resol generation addition reaction, realize solidification.In the selection of component A, selectable rosin is a kind of renewable natural resin, and its main component is various resinous acid, and resinous acid has three ring skeleton structures, and major part is containing conjugated double bond and a carboxyl two kinds of active centre.In addition, can be able to be westvaco rosin, nilox resin, polymerized rosin as the rosin derivative of component A, and the rosin ester with residual carboxylic groups, the westvaco rosin ester with residual carboxylic groups, the nilox resin ester with residual carboxylic groups, the polymerized rosin ester with residual carboxylic groups.Listed rosin ester, westvaco rosin ester, nilox resin ester, polymerized rosin ester can be modified rosin and the polyvalent alcohol of rosin or correspondence, as the partial esterification products of glycerine, tetramethylolmethane etc., by controlling reaction ratio, the content controlling residual carboxylic groups can obtain.
B component gives the skeleton of mask solidification, it is acidproof not alkaline-resisting, therefore to coordinate when alkali cleaning lift-off mask layer in synthetic resins in hydroxy-acid group and alkali lye with the numerous small hole produced, alkali lye penetrates into mask layer inside gradually, and then be the phenol-formaldehyde resin matrix decomposition of mask layer, mask layer corrodes into chip thus peels off.In the selection of B component, the mask layer formed after starching solidification to make electronics can be more fine and close, preferably selects with hydroxy-acid group and by the linear phenolic resin of phenolic hydroxyl group end-blocking; It is in the presence of acidic, a kind of novolac resin obtained by excessive phenol and formaldehyde condensation polymer, has good solubility in a solvent, thus can be that after the solidification of electronics slurry, the mask layer of formation is more fine and close, without hole, thus more tolerate acid liquid corrosion.
Its condensation reaction of component C and B component generation esterification or etherificate, and the effect mainly playing fragility and shrinking percentage and the adhesiveproperties improving mask layer.Modified epoxy with hydroxy-acid group can be that epoxy resin is obtained by suitable chemical modification method, and it is introduced method of hydroxy-acid group and does not limit, such as can be epoxy resin and anhydride reaction thus introduce hydroxy-acid group in epoxy molecule chain; The method that modified polyester resin introduces hydroxy-acid group is not also limit, can be for example in interior acid and dibasic alcohol generation esterification containing polyprotonic acid more than triprotic acid, its esterification products is with residual carboxylic groups, and and for example the carboxylate of triprotic acid and dibasic alcohol is with participating in carboxylic acid group.
Contriver finds, for further increasing compactness, the acid liquid corrosion resistibility of electronics slurry solidification rear one-tenth mask layer, preferably, described component C is selected with hydroxy-acid group and by hydroxy-end capped unsaturated polyester resin.Except condensation reaction, the double bond in unsaturated polyester can with the derivative generation addition of the rosin of component A or rosin, further increase the compactness of film forming.
For realizing the viscosity that can increase system in acid system, making it be more suitable for silk screen printing, in system, adding thickening material.Described thickening material selects one in following group or mixture: methylcellulose gum, ethyl cellulose, aerosil, organobentonite.Wherein, methylcellulose gum, ethyl cellulose are nonionic thickening material, can play thickening power in acid condition, avoid conventional anion thickening material and are added in acid mask electronics slurry system not normal; Although traditional way is nonionic thickening material and cationic thickening is composite can obtain better thickening effectiveness in acid system, but after mask electronics slurry film forming, need to possess hydrophobicity angle, only select nonionic thickening material to improve the viscosity of system.By contrast, inorganic thickening agent is as aerosil, organobentonite, attapulgite, clay, more more outstanding than methylcellulose gum, ethyl cellulose in thickening and antiacid corrosion.Particularly contriver finds, aerosil is except as thickening material, and it can make the finer and close refinement of film surface in the present invention's formula, tinting material is uniformly distributed, greatly can improves smooth finish, contribute to improving the rotproofness of mask layer to acid solution.
Mask layer color given by tinting material, is convenient to silk screen printing electronics slurry, is solidified into whether mask layer post-equalization mask layer is aimed at positive pole grid line, convenience checks.Otherwise do not have tinting material, slurry may be colourless or very slight color, and operator do not see printing effect, and such as whether half tone is aimed at, and whether slurry is printed on the region of regulation, comprise after having printed oven dry and also will check side-play amount.In the selection of tinting material, for improving the acid-resistant corrosion of the rear film forming of electronics slurry solidification, preferably, described tinting material is acid proof stain, thus avoids because tinting material forms micropore on mask layer surface and aggravate acid liquid corrosion.
Tinting material is divided into dyestuff and pigment.In dyestuff, preferably described tinting material is matching stain.What the acidity of dyestuff and alkalescence referred to is not its pH value, and refers to the electronegative or positive charge of its auxochrome group, and the positively charged staining agent of auxochrome group is basic stain, otherwise is then acid stain.Wherein matching stain is as methyl green, pyrrole Luo Hong, and that green chance water strong is soluble, easily makes mask layer produce porous and meets acid solution and peel off; Basic dyestuff meets sour salify, its solvability lower than matching stain, preferred basic dyestuff for this reason, as aceto-camine, Viola crystallina etc.Matching stain acid and alkali corrosion; Otherwise the ion band positive charge that basic dyestuff ionization produces and acidic substance salify and be dissolved in acid solution, cause mask layer to fade and lose the correct functioning of silicon chip after acid solution dipping is thinning, the corrosion of acid solution in mask layer that be dissolved as of more serious dyestuff provides passage.
By contrast, preferred described tinting material is pigment.Pigment is water insoluble, and has good solvent resistance, not easily makes mask produce hole in acid liquid corrosion process; Particularly preferably acidproof stable pigment dyestuff, phthalocyanine pigment as stable in azo pigment (azophloxine, permanent bordeaux, permanent yellow, permanent violet), acid and alkali-resistance (phthalocyanine red, phthalocyanine green, phthalocyanine blue), anthraquinone (anthraquinone red, anthraquinone blue), polycyclic pigment, the fragrant methane series pigment etc. such as indigoids, quinacridone, dioxazines, it is stable that it meets acid, and the hydrophobicity had further suppress mask layer peeling off in acid solution washing process.And mineral dye is as oxide compound, chromic salt, vitriol, silicate, borate, molybdate, phosphoric acid salt, vanadate, ferricyanate, oxyhydroxide, sulfide, metal etc., meet acid dissolve in acid solution, cause fading and correct functioning after losing wafer thinning, and generation porous, for the corrosion of acid solution in mask layer provides passage.
As long as the selection of auxiliary agent is in order to the quality of the manufacturability and film forming of improving silk screen printing.Described auxiliary agent comprises at least one in wetting dispersing agent, defoamer, thixotropic agent, flow agent.
For example described wetting agent can be chosen as polyethylene wax, polyvinylpyrrolidone, in system of the present invention, particularly have the polyoxyethylene glycol of better Miscibility.
Described defoamer can be selected Laurate alcohol ester phenylacetate, polydimethylsiloxane, in system of the present invention, particularly have the polyether-modified silicon defoaming agent of better Miscibility.
Described thixotropic agent can be selected polyamide wax, in system of the present invention, particularly have the hydrogenated castor oil of better Miscibility.
Described flow agent can select end group modified organic silicon flow agent, esters of acrylic acid flow agent, particularly well substrate wetting, the fluorin modified crylic acid ester class flow agent that anti-shrinkage cavity ability is strong, significantly can improve the surface smoothness after the solidification of electronics slurry, improve tolerance acid liquid corrosion.
Solvent plays regulation system viscosity in system, with the effect of applicable silk screen printing.Solvent described here is during can be selected from following group at least one or mixture: Terpineol 350, turps, butyl carbitol acetic ester, diethylene glycol monobutyl ether, dibutyl phthalate.
The present invention also provides a kind of manufacture method of SE solar battery selective emitter structure, and this manufacture method comprises the following steps: (1) chemistry removes silicon chip surface energy affected layer, cleaning and texturing; (2) adopt One Diffusion Process technique to carry out heavy doping to silicon chip, form PN junction; (3) on silicon chip, silk screen printing mask electronics slurry, oven dry form consistent with grid line pattern but slightly wide compared with the grid line width mask layer that thickness is 20 ~ 300nm; (4) bite is without mask layer region, and rinse, dry formed shallow doped region; (6) remove mask layer by alkali cleaning, and rinse, dry, namely obtain selective emitting electrode structure.
Preferably, the mask electronics slurry in described step (3) is adopt above-mentioned etch layer electronics slurry.
Compared with prior art, the invention has the advantages that,
(1) mask electronics slurry of the present invention only needs within tens seconds, can realize solidification by drying 100 more, and cost is lower, and technique is simpler;
(2) mask electronics slurry of the present invention can realize silk screen printing, and can realize the precise calibration of silk screen printing, and the secondary contraposition precision of later stage silk screen printing is higher, overcomes the shortcoming that existing photocuring mask material is difficult to realize accurate contraposition.
(3) mask electronics of the present invention slurry can semiconductor bond firm, smooth surface, good toughness, after solidifying to form mask, acid resistance is extremely strong, and silicon chip can soak thinning and then realize light dope in acid solution; Wash-out can be realized easily by dipping by lye, and mask layer alkali liquid corrosion can be become smalls shape, and then without the need to human assistance blowdown, can discharging of waste liquid tube drainage be passed through.
(4) selective emitting electrode structure of the present invention is formed coloured mask layer by screen printing sizing agent very ripe in solar cell manufacture, is realized light dope by acid liquid corrosion, by alkali liquid corrosion lift-off mask layer, boundary lake town, only need increase the printing drying plant of a set of mask electronics slurry, the gain that electricity conversion has about 0.3% efficiency can be reached, have very large meaning to the benefit improving enterprise.
Embodiment
Below in conjunction with embodiment and comparative example, the specific embodiment of the present invention is further described.Following embodiment only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
The invention provides a kind of preparation method and etch layer electronics used slurry of SE solar battery selective emitter structure.This preparation method comprises the following steps: (1) chemistry removes silicon chip surface energy affected layer, cleaning silicon chip making herbs into wool; (2) adopt One Diffusion Process technique to carry out heavy doping to silicon chip, form PN junction, obtain lower square resistance; (3) according to the grid line figure designed, on silicon chip, silk screen printing one deck mask electronics slurry, oven dry form consistent with grid line pattern but slightly wide compared with the grid line width mask layer that thickness is 20 ~ 300nm, drying the temperature of namely solidifying is 140 ~ 150 DEG C of temperature, and set time is 20s; (4) use as HF and HNO 3mixed solution bite without mask layer region, reduce the doping in unmasked overlay area and cell activation district, improve this region sheet resistance, and rinse, dry and form shallow doped region; (6) remove mask layer by alkali cleaning, and rinse, dry, thus highly doped and low square resistance when having made mask protection region retain diffusion, namely obtain selective emitting electrode structure.Subsequently again dephosphorization silex glass, flushing, sputtering passivation layer and antireflection layer, print electrode, make efficient SE battery.
Mask electronics slurry wherein used has good hydrophobicity, acid resistance and caustic solubility.In step (5), the volume of each component in acid solution can be selected to be: HNO 3: HF:H 2o=9:1:18, different according to the requirement of light dope degree, soak 60s-120s; In step (6), be enough to slough mask layer within 5%KOH solution soaking 30s can be selected here.
Following examples 1-10 schematically illustrates the formula composition of mask electronics slurry used respectively.Compare its acid resistance and caustic solubility simultaneously, the results are shown in Table 1.
Acid resistance relatively in, by each mask slurry of same weight according in above-mentioned method (1) (2) (3) formed mask layer, the volume then silicon chip being put into each component is: HNO 3: HF:H 2hF and HNO of O=9:1:18 3mixed solution in soak 60s, then rinse well rapidly with deionized water, dry, calculate the rate of weight loss soaked before and after acid solution.
Acid soak mass loss rate=[soaking the silicon chip weight loss before and after acid solution]/[after applying slurry, silicon chip increases weight].
Caustic solubility relatively in, each mask slurry of same weight is formed mask layer according to (1) (2) (3) in above-mentioned method, then silicon chip is put into the KOH solution 20s of 5% mass percent, then rinse well rapidly with deionized water, dry, calculate the rate of weight loss soaked before and after alkali lye.
Dipping by lye mass loss rate=[soaking the weight loss before and after alkali lye]/[after applying slurry, silicon chip increases weight].
embodiment 1
The composition of raw materials of this etch layer electronics slurry is made up of the component of following mass percent: 10% nilox resin, 12% is organic solvent diethylene glycol monobutyl ether with hydroxy-acid group and by the linear phenolic resin of phenolic hydroxyl group end-blocking, 8% acrylic resin, 0.5% permanent violet, 1% fluorin modified crylic acid ester class flow agent, 25% aerosil, surplus, the pH of slurry is≤7, acid number 120 ~ 300.
embodiment 2
The composition of raw materials of this etch layer electronics slurry is made up of the component of following mass percent: 18% polymerized rosin, 20% is organic solvent butyl carbitol acetic ester with hydroxy-acid group and by the linear phenolic resin, 12% of phenolic hydroxyl group end-blocking with the modified polyester resin of hydroxy-acid group, 10% phthalocyanine blue, 10% polyoxyethylene glycol, 5% aerosil, surplus, the pH of slurry is≤7, acid number 120 ~ 300.
embodiment 3
The composition of raw materials of this etch layer electronics slurry is made up of the component of following mass percent: 15% is organic solvent turps with hydroxy-acid group and by the linear phenolic resin, 9% of phenolic hydroxyl group end-blocking with the chemical modification epoxy resin of hydroxy-acid group, 3% permanent bordeaux, 3% polyether-modified silicon defoaming agent, 8% aerosil, surplus with the rosin ester, 18% of residual carboxylic groups, the pH of slurry is≤7, acid number 120 ~ 300.
embodiment 4
The composition of raw materials of this etch layer electronics slurry is made up of the component of following mass percent: 8% rosin, 8% is organic solvent Terpineol 350 with the rosin ester, 16% of residual carboxylic groups with hydroxy-acid group and by the linear phenolic resin, 10% of phenolic hydroxyl group end-blocking with hydroxy-acid group and by hydroxy-end capped unsaturated polyester resin, 5% azophloxine, 4% hydrogenated castor oil, 9% aerosil, surplus, the pH of slurry is≤7, acid number 120 ~ 300.
embodiment 5
The composition of raw materials of this etch layer electronics slurry is made up of the component of following mass percent: 12% rosin, 17% is dibutyl phthalate with hydroxy-acid group and by the linear phenolic resin, 11% of phenolic hydroxyl group end-blocking with hydroxy-acid group and by hydroxy-end capped unsaturated polyester resin, 6% permanent yellow, 2% polyoxyethylene glycol, 1% polyether-modified silicon defoaming agent, 1% hydrogenated castor oil, 1% fluorin modified crylic acid ester class flow agent, 12% aerosil, surplus, the pH of slurry is≤7, acid number 120 ~ 300.
embodiment 6
As different from Example 5, in the present embodiment, aerosil changes ethyl cellulose into.
embodiment 7
As different from Example 5, in the present embodiment, aerosil changes methylcellulose gum into.
embodiment 8
As different from Example 5, in the present embodiment, aerosil changes organobentonite into.
embodiment 9
As different from Example 5, in the present embodiment, tinting material permanent yellow changes aceto-camine into.
embodiment 10
As different from Example 5, in the present embodiment, tinting material permanent yellow changes iron oxide red into.
comparative example 1
as different from Example 5, do not add unsaturated polyester resin in this comparative example, rosin content changes 17% rosin into, linear phenolic resin content changes 23% into, and all the other are identical with embodiment 5.Test it equally in acid solution, to soak rear mass loss rate and in alkali lye, soak rear mass loss rate to weigh its acid resistance and caustic solubility, the results are shown in Table 1.
comparative example 2
As different from Example 5, do not add rosin in this comparative example, linear phenolic resin content changes 23% into, and unsaturated polyester resin content changes 17% into, all the other are identical with embodiment 5.Test it equally in acid solution, to soak rear mass loss rate and in alkali lye, soak rear mass loss rate to weigh its acid resistance and caustic solubility, the results are shown in Table 1.
Table 1.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (10)

1. a SE solar cell etch layer electronics slurry, it is characterized in that, its composition of raw materials is made up of the component of following mass percent: 30 ~ 50% synthetic resins, 0.5 ~ 10% tinting material, 1 ~ 10% auxiliary agent, 5 ~ 25% thickening materials, surplus are organic solvent; And the pH of described etch layer electric slurry is≤7; And synthetic resins is made up of A, B, C component, A, B, C component accounts for 10 ~ 18%, 12 ~ 20% of electronics slurry total mass respectively, 8 ~ 12%, wherein component A selects one in following group or mixture: rosin, rosin derivative with conjugated double bond and hydroxy-acid group; B component is selected: with the resol of hydroxy-acid group; Component C selects one in following group or mixture: the modified epoxy with hydroxy-acid group, the modified polyester resin with hydroxy-acid group, acrylic resin.
2. SE solar cell etch layer electronics slurry as claimed in claim 1, it is characterized in that, the acid number of described synthetic resins is 120 ~ 300.
3. SE solar cell etch layer electronics slurry as claimed in claim 1, it is characterized in that, the described rosin derivative with conjugated double bond and hydroxy-acid group comprises westvaco rosin, nilox resin, polymerized rosin, and with rosin ester, westvaco rosin ester, nilox resin ester, the polymerized rosin ester of residual carboxylic groups.
4. SE solar cell etch layer electronics slurry as claimed in claim 1, it is characterized in that, described B component is selected: with hydroxy-acid group and by the linear phenolic resin of phenolic hydroxyl group end-blocking.
5. SE solar cell etch layer electronics slurry as claimed in claim 1, it is characterized in that, described component C is selected with hydroxy-acid group and by hydroxy-end capped unsaturated polyester resin.
6. the SE solar cell etch layer electronics slurry as described in claim 1 to 5 any one, it is characterized in that, described tinting material is acid proof stain.
7. SE solar cell etch layer electronics slurry as claimed in claim 6, is characterized in that, described thickening material selects one in following group or mixture: methylcellulose gum, ethyl cellulose, aerosil, organobentonite; Described auxiliary agent comprises at least one in wetting dispersing agent, defoamer, thixotropic agent, flow agent; Described solvent is during to be selected from following group at least one or mixture: Terpineol 350, turps, butyl carbitol acetic ester, diethylene glycol monobutyl ether, dibutyl phthalate.
8. SE solar cell etch layer electronics slurry as claimed in claim 7, it is characterized in that, described auxiliary agent comprises wetting dispersing agent, defoamer, thixotropic agent, flow agent; Wherein, described wetting agent is polyoxyethylene glycol; Described defoamer is polyether-modified silicon defoaming agent; Described thixotropic agent is hydrogenated castor oil; Described flow agent is fluorin modified crylic acid ester class flow agent.
9. a manufacture method for SE solar battery selective emitter structure, is characterized in that, this manufacture method comprises the following steps: (1) chemistry removes silicon chip surface energy affected layer, cleaning and texturing; (2) adopt One Diffusion Process technique to carry out heavy doping to silicon chip, form PN junction; (3) on silicon chip, silk screen printing mask electronics slurry, oven dry form consistent with grid line pattern but slightly wide compared with the grid line width mask layer that thickness is 20 ~ 300nm; (4) bite is without mask layer region, and rinse, dry formed shallow doped region; (6) remove mask layer by alkali cleaning, and rinse, dry, namely obtain selective emitting electrode structure.
10. a manufacture method for SE solar battery selective emitter structure as claimed in claim 9, is characterized in that, the mask electronics slurry in described step (3) is the SE solar cell etch layer electronics slurry described in claim 1 to 8 any one.
CN201510027512.1A 2015-01-20 2015-01-20 SE solar cell etch layer electronics slurry and manufacture selective emitter method Active CN104694005B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510027512.1A CN104694005B (en) 2015-01-20 2015-01-20 SE solar cell etch layer electronics slurry and manufacture selective emitter method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510027512.1A CN104694005B (en) 2015-01-20 2015-01-20 SE solar cell etch layer electronics slurry and manufacture selective emitter method

Publications (2)

Publication Number Publication Date
CN104694005A true CN104694005A (en) 2015-06-10
CN104694005B CN104694005B (en) 2016-11-23

Family

ID=53341571

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510027512.1A Active CN104694005B (en) 2015-01-20 2015-01-20 SE solar cell etch layer electronics slurry and manufacture selective emitter method

Country Status (1)

Country Link
CN (1) CN104694005B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106384634A (en) * 2016-10-11 2017-02-08 西安宏星电子浆料科技有限责任公司 Lead-free mask slurry for chip resistor
CN106563894A (en) * 2016-10-20 2017-04-19 长沙理工大学 Strippable welding flux mask layer composition
CN106847938A (en) * 2017-02-20 2017-06-13 浙江晶科能源有限公司 A kind of preparation method of SE batteries
CN109037079A (en) * 2018-07-13 2018-12-18 无锡天杨电子有限公司 A kind of graphic method of rail traffic chip nitride ceramics copper-clad plate
CN112242457A (en) * 2019-07-16 2021-01-19 单伶宝 Patterning method of ITO film for double-sided heterojunction photovoltaic cell

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101958361A (en) * 2009-07-13 2011-01-26 无锡尚德太阳能电力有限公司 Method for etching transparent thin-film solar cell component
CN102544198A (en) * 2011-12-14 2012-07-04 青岛吉阳新能源有限公司 Selective emitter junction crystalline silicon solar cell preparation method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106384634A (en) * 2016-10-11 2017-02-08 西安宏星电子浆料科技有限责任公司 Lead-free mask slurry for chip resistor
CN106563894A (en) * 2016-10-20 2017-04-19 长沙理工大学 Strippable welding flux mask layer composition
CN106847938A (en) * 2017-02-20 2017-06-13 浙江晶科能源有限公司 A kind of preparation method of SE batteries
CN109037079A (en) * 2018-07-13 2018-12-18 无锡天杨电子有限公司 A kind of graphic method of rail traffic chip nitride ceramics copper-clad plate
CN112242457A (en) * 2019-07-16 2021-01-19 单伶宝 Patterning method of ITO film for double-sided heterojunction photovoltaic cell

Also Published As

Publication number Publication date
CN104694005B (en) 2016-11-23

Similar Documents

Publication Publication Date Title
CN104694005A (en) Organic mask electronic paste of SE solar battery and method for producing selective emitter
CN103045015A (en) Liquid photo-imageable alkali developable and anodizing resistant ink and preparation method thereof
CN102993823B (en) Water-based ink used in inkjet printing direct-to-plate, and preparation method thereof
TWI525390B (en) Black hardening resin composition
TWI502031B (en) Etch-resistant composition and its application
CN106274122B (en) A kind of lithographic plate and its preparation method and application
CN105733361A (en) Etching-resistant jet ink and application thereof
CN104710871A (en) Alkaline-developable photosensitive solder resist ink for FPC, preparation method, application and product
CN106867314A (en) A kind of high accuracy RFID antenna electrically conductive ink and its preparation, printing process
CN101958361A (en) Method for etching transparent thin-film solar cell component
CN106816200A (en) A kind of silicon solar cell front electrode silver slurry and preparation method thereof
WO2021196736A1 (en) Water-based glass coating material resistant to boiling in boiling water, and preparation method therefor
EP2698831A2 (en) Inkjet printable etch resist
CN104845499A (en) Preparation method for waterborne epoxy paste paint
CN107513309A (en) Three-dimensionally shaped photocuring transparent ink composition and its preparation method and application
CN102002281A (en) Thermocuring ink for ink printing plate as well as preparation method and application thereof
CN103226989A (en) Corrosive carrier, preparation method thereof, crystalline silicon solar battery front/back side silver conductive paste and preparation method thereof
EP2920809B1 (en) Compositions and processes for fabrication of rear passivated solar cells
CN106366906A (en) Solar photovoltaic glass antireflection coating and preparation method thereof
CN104325802A (en) Novel plate material using water-based printing ink
CN109321099B (en) Black water-based automobile chassis paint and preparation method thereof
CN101587291B (en) Method of screen printing fine mask on silicon chip surface based on UV curing process
CN105504971A (en) Epoxy-resin-modified UV (ultraviolet) raw lacquer ink for digital jet printing and preparation method thereof
CN103131003B (en) Functionalized soybean oil compounds, and coating compositions comprising the same
CN103376653B (en) Photosensitive water development welding resistance composition and photosensitive water development dry film solder mask

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP02 Change in the address of a patent holder
CP02 Change in the address of a patent holder

Address after: 214400 west side of Dongfeng Road, Zhouzhuang Town, Jiangyin City, Wuxi, Jiangsu, China

Patentee after: Jiangsu Ruide New Energy Technology Co., Ltd.

Address before: 214400 Dongfeng Road, Zhouzhuang Town, Jiangyin, Wuxi, Jiangsu (21 Dongfeng Road)

Patentee before: Jiangsu Ruide New Energy Technology Co., Ltd.