CN102443290A - Transparent conductive film composition for solar cell and transparent conductive film thereof - Google Patents
Transparent conductive film composition for solar cell and transparent conductive film thereof Download PDFInfo
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- CN102443290A CN102443290A CN2011103050013A CN201110305001A CN102443290A CN 102443290 A CN102443290 A CN 102443290A CN 2011103050013 A CN2011103050013 A CN 2011103050013A CN 201110305001 A CN201110305001 A CN 201110305001A CN 102443290 A CN102443290 A CN 102443290A
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- oxide particle
- tackiness agent
- spherocolloids
- silicon oxide
- nesa coating
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Abstract
The present invention relates to a transparent conductive film composition which is used in a wet type coating method of the solar cell, and a transparent conductive film which is prepared by the composition. The transparent conductive film has the following functions: enlarging a difference between the refractivity of the transparent conductive film and the refractivity of photoelectric conversion layer, increasing reflection light of an interface between the transparent conductive film and the photoelectric conversion layer, and improving light emitting efficiency of the thin-film solar battery through the increased light that returns to the photoelectric conversion layer. The invention also provides the transparent conductive film composition which can form the transparent conductive film. The transparent conductive film composition for the solar cell is characterized by comprising the following components: conductive oxide particles, spherical colloid silicon oxide particles of which the average particle diameter is 6-45 nm, and an additive. Relative to total 100 by weight parts of conductive oxide particles and spherical colloid silicon oxide particles, the transparent conductive film composition comprises 2-35 by weight parts of spherical colloid silicon oxide particles.
Description
Technical field
The present invention relates to electrically conducting transparent film composition and nesa coating.In more detail, relate to electrically conducting transparent film composition and the nesa coating that is used for solar cell.
Background technology
At present, consider from the position of environmental protection, advancing research and development, the practicability of green energy resource, solar cell is aspect such as inexhaustible and nuisanceless and being attracted attention at the sunshine as the energy.In the past, used the block solar cell of silicon single crystal or polysilicon in the solar cell always, but because the manufacturing cost of block solar cell is high, and productivity is low, so be badly in need of developing the solar cell of save silicon amount as far as possible.
Thereby it for example is the exploitation of the semi-conductive thin-film solar cells such as non-crystalline silicon of 0.3～2 μ m that positive all one's effort is carried out used thickness.This thin-film solar cells is owing to be the structure that on glass substrate or heat-resistant plastic substrate, forms the semiconductor layer of opto-electronic conversion aequum, so have slim and advantages such as lightweight, low cost, easy big areaization.
Thin-film solar cells has cladding plate type (ス one パ one ス ト レ one ト) structure and base plate type (サ Block ス ト レ one ト) structure; Cladding plate type structure is because from light-transmitting substrate side incident sunshine, so adopt the structure with the order formation of substrate-transparency electrode-photoelectric conversion layer-backplate usually.
In this thin-film solar cells, became embrane method to form electrode or reflectance coating with the sputter equal vacuum in the past, but the usually introducing of large-scale vacuum film deposition system, keep, turning round needs great amount of cost.In order to improve this point, disclose use electrically conducting transparent film composition and conductive reflecting film with compsn with the technology (patent documentation 1) of inexpensive method of manufacturing wet type coating method formation nesa coating and conductive reflecting film more.
Patent documentation 1: the open 2009-88489 communique of Japanese Patent
Summary of the invention
Problem of the present invention is to improve the nesa coating of being made by above-mentioned wet type coating method.Discoveries such as the inventor; Improvement electrically conducting transparent film composition; Make the difference of specific refractory power of specific refractory power and the photoelectric conversion layer of the nesa coating that uses in the wet type coating method become big; Thereby the reflected light in nesa coating-opto-electronic conversion bed interface increases, and through the light that is back to photoelectric conversion layer of this increase, can improve the generating efficiency of thin-film solar cells.Same method is also applicable to base plate type solar cell or bulk si solar cell.
The present invention relates to solve the electrically conducting transparent film composition and the nesa coating that are used for solar cell of above-mentioned problem through following formation.
(1) a kind of electrically conducting transparent film composition that is used for solar cell; It is characterized in that; Comprise the electroconductive oxide particle, median size is spherocolloids silicon oxide particle and the tackiness agent of 6～45nm; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.
(2) a kind of electrically conducting transparent film composition that is used for cladding plate type thin-film solar cells; It is characterized in that; Comprise the electroconductive oxide particle, median size is spherocolloids silicon oxide particle and the tackiness agent of 6～45nm; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.
(3) according to above-mentioned (2) the described electrically conducting transparent film composition that is used for cladding plate type thin-film solar cells, tackiness agent is polymer type adhesive and/or non-polymeric tackiness agent through being heating and curing.
(4) according to above-mentioned (3) the described electrically conducting transparent film composition that is used for cladding plate type thin-film solar cells, the non-polymeric tackiness agent is to be selected from least a in metallic soap, metal complex, metal alkoxide, halogenated silanes class, 2-alkoxyethanol, beta-diketon and the alkyl acetate.
(5) a kind of nesa coating that is used for solar cell; It is characterized in that; Comprise electroconductive oxide particle, median size and be the spherocolloids silicon oxide particle of 6～45nm and solidify after tackiness agent; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.
(6) a kind of nesa coating that is used for cladding plate type thin-film solar cells; It is characterized in that; Comprise electroconductive oxide particle, median size and be the spherocolloids silicon oxide particle of 6～45nm and solidify after tackiness agent; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.
(7) according to above-mentioned (6) the described nesa coating that is used for cladding plate type thin-film solar cells, tackiness agent is polymer type adhesive and/or non-polymeric tackiness agent through being heating and curing.
(8) according to above-mentioned (7) the described nesa coating that is used for cladding plate type thin-film solar cells, the non-polymeric tackiness agent is to be selected from least a in metallic soap, metal complex, metal alkoxide, halogenated silanes class, 2-alkoxyethanol, beta-diketon and the alkyl acetate.
(9) a kind of cladding plate type thin-film solar cells comprises any described nesa coating that is used for cladding plate type thin-film solar cells in above-mentioned (6)～(8).
(10) a kind of method of manufacture of nesa coating; Method of manufacture for the nesa coating of the cladding plate type thin-film solar cells that comprises base material, transparent electrode layer, photoelectric conversion layer and nesa coating successively; After on photoelectric conversion layer, forming electrically conducting transparent and film with any described electrically conducting transparent film composition in wet type coating method coating above-mentioned (2)～(4), calcining has the base material that electrically conducting transparent films and forms nesa coating.
(11) according to the method for manufacture of above-mentioned (10) described nesa coating, the wet type coating method is spraying method, point gum machine coating method (デ ィ ス ペ Application サ one コ one テ ィ Application グ method), spin-coating method, spread coating, slot coated method, ink-jet application method, mold coating method (ダ ィ コ one テ ィ Application グ method), screen painting method, offset printing method or woodburytype.
The present invention's (1) electrically conducting transparent film composition can use the wet type coating method on photoelectric conversion layer, to be coated with, to calcine, and can reduce the specific refractory power of resulting nesa coating through the content of spherocolloids silicon oxide particle.Promptly; It is big that the difference of the specific refractory power of nesa coating and the specific refractory power of photoelectric conversion layer becomes; Increase at the reflected light of nesa coating-opto-electronic conversion bed interface, can obtain to improve the nesa coating of the generating efficiency of solar cell by the light that is back to photoelectric conversion layer of this increase easily.
According to the present invention (5), the reflected light in nesa coating-opto-electronic conversion bed interface increases, and through the light that is back to photoelectric conversion layer of this increase, can obtain the solar cell that generating efficiency improves easily.
According to the present invention (10), without the vacuum apparatus of great number, can form nesa coating, can make the high thin-film solar cells of generating efficiency with low cost easily.
Description of drawings
Fig. 1 uses the schematic cross-section of the cladding plate type thin-film solar cells of nesa coating for the present invention.
Fig. 2 uses the schematic cross-section of the base plate type thin-film solar cells of nesa coating for the present invention.
Nomenclature
1 cladding plate type thin-film solar cells
2 base plate type thin-film solar cells
10,20 base materials
11,21 nesa coatings
12,22 photoelectric conversion layers
13,23 transparent electrode layers
14,24 conductive reflecting films
25 through holes
26 collector layers
Embodiment
Below, specify the present invention based on embodiment.In addition, % is as long as represent especially, or the distinctive situation of numerical value is quality % in addition.
[the electrically conducting transparent film composition that is used for solar cell]
The electrically conducting transparent film composition (below be called " electrically conducting transparent film composition ") that the present invention is used for solar cell is characterised in that; Comprise the electroconductive oxide particle, median size is spherocolloids silicon oxide particle and the tackiness agent of 6～45nm; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.This electrically conducting transparent film composition is applicable to thin-film solar cells, is specially adapted to cladding plate type thin-film solar cells.
As the electroconductive oxide particle; Tin indium oxide), ATO (Antimony Tin Oxide: stannic oxide powder antimony doped tin oxide) or contain the Zinc oxide powder that is selected from least a metal among Al, Co, Fe, In, Sn and the Ti etc. preferred ITO (Indium Tin Oxide:; Al-Doped ZnO), IZO (Indium Zinc Oxide: mix indium zinc oxide), TZO (Tin Zinc Oxide: mix tin zinc oxide) wherein, more preferably ITO, ATO, AZO (Aluminum Zinc Oxide:.In addition, in order to ensure the stability in dispersion medium, the median size of electroconductive oxide particulate is preferably in the scope of 10～100nm, and is wherein, more preferably in the scope of 20～60nm, further preferred in the scope of 25～50nm.At this, the mensuration of median size is used the BET method of the specific surface mensuration of carrying out according to QUANTACHROME AUTOSORB-1.
The median size of spherocolloids silicon oxide particle is 6～45nm, is preferably 6～20nm.Median size is during less than 6nm, causes easily that because the stability of particle is not enough secondary aggregation, test portion make difficulty, and is during greater than 45nm, inapplicable owing to hinder the contact of electroconductive particle.At this, median size is assumed to ball with the spherocolloids silicon oxide particle and converts according to the specific area measuring that uses QUANTACHROME corporate system AUTOSORB-1.In addition, spherical can be is similar to the globular shape, and for example cubes or polyhedron shape are almost spherical.Be preferably ball.The aspect ratio of spherocolloids silicon oxide particle (long diameter/weak point diameter) is preferred 1～1.4, and more preferably 1～1.25.The spherocolloids silicon oxide particle can reduce the uneven thickness of film owing to good with the wettability of photoelectric conversion layer, reduces the specific refractory power of the nesa coating after solidifying.
Fig. 1 shows the schematic cross-section of the cladding plate type thin-film solar cells of using nesa coating of the present invention.Cladding plate type hull cell 1 possesses base material 10, transparent electrode layer 13, photoelectric conversion layer 12, nesa coating 11, conductive reflecting film 14 successively, and sunshine is from substrate 10 side incidents.Incident sunshine major part is back to photoelectric conversion layer 12 by conductive reflecting film 14 reflections, and efficiency of conversion is improved.At this; Sun reflection of light also takes place with the interface of photoelectric conversion layer 12 in nesa coating 11; Use the nesa coating 11 of electrically conducting transparent film composition of the present invention because specific refractory power is low; The nesa coating 11 and the reflected light at the interface of photoelectric conversion layer 12 are increased, thereby can improve the generating efficiency of thin-film solar cells.In addition, Fig. 2 shows the schematic cross-section of the base plate type thin-film solar cells of using nesa coating of the present invention.Base plate type hull cell 2 possesses base material 20, conductive reflecting film 24, nesa coating 21, photoelectric conversion layer 22, transparent electrode layer 23 successively, and sunshine is from transparent electrode layer 23 side incidents.Incident sunshine major part is back to photoelectric conversion layer 22 by conductive reflecting film 24 reflections, and efficiency of conversion is improved.Under the situation of base plate type hull cell also at the interface of photoelectric conversion layer 22 and nesa coating 21 sun reflection of light takes place; Use the nesa coating 21 of electrically conducting transparent film composition of the present invention because specific refractory power is low; The photoelectric conversion layer 22 and the reflected light at the interface of nesa coating 21 are increased, thereby can improve the generating efficiency of thin-film solar cells.And, at substrate 20 formation through holes 25, when being electrically connected conductive reflecting film 24, extract by the power of thin-film solar cells generation preferred easily with collector layer 26.
Tackiness agent preferably comprises any side or both sides' the compsn in polymer type adhesive that is heating and curing or non-polymeric tackiness agent.Polymer type adhesive can be enumerated vinyl resin, polycarbonate, polyester, Synolac, urethane, propenoic methyl carbamate, PS, polyacetal, polymeric amide, Z 150PH, Yodo Sol VC 400, Mierocrystalline cellulose and siloxane polymer etc.And, comprise the hydrolysis body of metallic soap, metal complex or the metal alkoxide of aluminium, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin in the preferred polymers type tackiness agent.The non-polymeric tackiness agent can be enumerated metallic soap, metal complex, metal alkoxide, halogenated silanes class, 2-alkoxyethanol, beta-diketon and alkyl acetate etc.And; Contained metal is preferably aluminium, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony in metallic soap, metal complex or the metal alkoxide, more preferably the alkoxide of silicon, aluminium (for example tetraethoxysilane, tetramethoxy-silicane, aluminum ethylate, aluminum isopropylate).These polymer type adhesives, non-polymeric tackiness agent solidify through heating, thereby can form the nesa coating of low haze and volume specific resistance at low temperatures.And metal alkoxide can be hydrolyzate or its dehydrate.
When metal alkoxide is solidified,, preferably contain hydrochloric acid, nitric acid, phosphoric acid (H as catalyzer with the moisture that is used to hydrolysis reaction is begun
3PO
4), acid or alkali such as ammoniacal liquor, aqueous sodium hydroxide solution such as fluoric acid, from be heating and curing rear catalyst easily volatilization be difficult for viewpoint such as residual, that an alkali metal salts such as halogen is not residual, P a little less than the water tolerance etc. is not residual, Na are not residual and consider, more preferably nitric acid.In addition, under the situation of nitric acid, even N photoelectric conversion layer (n type) residual and that be diffused into lower floor also can play a role as the alms giver, so the efficiency of conversion of photoelectric conversion layer does not only reduce, efficiency of conversion uprises on the contrary.
With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, the electrically conducting transparent film composition comprises the electroconductive oxide particle of 98～65 mass parts, preferably comprises 95～70 mass parts.This be because, when exceeding higher limit, adhesivity reduces, during less than lower value, electroconductibility reduces.
With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts, preferably comprise 5～30 mass parts.This be because, be lower value when following, can not make the abundant step-down of specific refractory power of the nesa coating after the curing, be higher limit when above, electroconductibility reduces.
With respect to the solid content in the electrically conducting transparent film composition (electroconductive oxide particle, spherocolloids silicon oxide particle and tackiness agent) 100 mass parts, these tackiness agents contain proportional 5～50 mass parts that are preferably, more preferably 10～30 mass parts.In addition, use metal alkoxide, when catalyzer uses nitric acid,, when nitric acid is 0.03～3 mass parts, consider and preferred as tackiness agent from the viewpoint of the residual quantity of the curing speed of tackiness agent, nitric acid with respect to metal alkoxide 100 mass parts.And, the amount of catalyzer nitric acid after a little while, the polymerization velocity of the hydrolysis body of binder metal alkoxide is slack-off, during the required water shortage of hydrolysis, may can not get firm nesa coating.In addition; If when being cured, obtain the hydrating solution of the high grid structure of the polymerization degree through calcining; Then thinking to become the form of the contact between the stress additional conductive property particle of effect when shrinking, so with respect to metal alkoxide 100 mass parts, preferably water is 10～120 mass parts.
The electrically conducting transparent film composition preferably adds coupling agent according to other component of using.This is the nesa coating that forms for the cohesiveness that improves electrically conductive microparticle, spherocolloids silicon oxide particle and tackiness agent and by this electrically conducting transparent film composition and the layers on substrates photoelectric conversion layer of pressing or the adhesivity of conductive reflecting film.Coupling agent can be enumerated silane coupling agent, aluminum coupling agent and titanium coupling agent etc.With respect to the solid content that accounts for the electrically conducting transparent film composition (electroconductive oxide particle, spherocolloids silicon oxide particle, tackiness agent and silane coupling agent etc.) 100 mass parts, preferred 0.2～5 mass parts of the content of coupling agent, more preferably 0.5～2 mass parts.
For film forming well, the electrically conducting transparent film composition preferably comprises dispersion medium.Dispersion medium can be enumerated water; Alcohols such as methyl alcohol, ethanol, Virahol, butanols; Ketones such as acetone, methylethylketone, pimelinketone, isophorone; Hydro carbons such as toluene, YLENE, hexane, hexanaphthene; N, amidess such as dinethylformamide, DMAC N,N; Glycolss such as sulfoxide classes such as DMSO 99.8MIN. or terepthaloyl moietie; Glycol ethers such as ethyl cellosolve etc.In order to obtain good film-forming properties, with respect to electrically conducting transparent film composition 100 mass parts, the content of dispersion medium is preferably 65～99 mass parts.
In addition, the component according to using preferably adds low resistance agent or water-soluble cellulose derivative etc.The low resistance agent is preferably selected from the mineral acid salt of cobalt, iron, indium, nickel, lead, tin, titanium and zinc and in the organic acid salt one or more.For example, can enumerate the mixture etc. of mixture, etheric acid titanium and cobalt octoate of mixture, indium nitrate and sugar of lead of mixture, zinc naphthenate, stannous octoate and the antimony chloride of nickelous acetate and iron(ic)chloride.With respect to electroconductive oxide powder 100 mass parts, preferred 0.2～15 mass parts of the content of these low resistance agent.Water-soluble cellulose derivative is a nonionogenic tenside; But compare with other tensio-active agent, even if a small amount of the interpolation, the ability of dispersed electro-conductive property oxide powder is also high; And, also improve the transparency of formed nesa coating through adding water-soluble cellulose derivative.Water-soluble cellulose derivative can be enumerated hydroxypropylcellulose, Vltra tears etc.With respect to electroconductive oxide powder 100 mass parts, preferred 0.2～5 mass parts of the addition of water-soluble cellulose derivative.
The electrically conducting transparent film composition can mix desirable component by coating wobbler, ball mill, sand mill, medium dispersion machine (セ Application ト リ ミ Le), three-roll mill (three ロ one Le) etc. according to usual way, and dispersions such as electroconductive oxide particle, spherocolloids silicon oxide particle are made.Certainly, also can make through common stirring operation.
[nesa coating that is used for cladding plate type thin-film solar cells]
The nesa coating (below be called nesa coating) that the present invention is used for solar cell is characterised in that; Comprise electroconductive oxide particle, median size and be the spherocolloids silicon oxide particle of 6～45nm and solidify after tackiness agent; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.This nesa coating is applicable to thin-film solar cells, is specially adapted to cladding plate type thin-film solar cells.
Electroconductive oxide particle, spherocolloids silicon oxide are with above-mentioned the same, and the tackiness agent after the curing is the tackiness agent that makes after above-mentioned tackiness agent solidifies.That is, nesa coating is the film that makes after the above-mentioned electrically conducting transparent film composition that is used for cladding plate type thin-film solar cells solidifies.
The method of manufacture of nesa coating of the present invention; Method of manufacture for the nesa coating of the cladding plate type thin-film solar cells that comprises base material, transparent electrode layer, photoelectric conversion layer and nesa coating successively; Be coated with the wet type coating method on the photoelectric conversion layer after above-mentioned electrically conducting transparent film composition forms electrically conducting transparent and film, calcining has the base material that electrically conducting transparent films and forms nesa coating.
At first, on the photoelectric conversion layer of the cladding plate type thin-film solar cells that possesses base material, transparent electrode layer, photoelectric conversion layer and nesa coating successively, be coated with above-mentioned electrically conducting transparent film composition with the wet type coating method.This coating is so that the thickness of the nesa coating after the calcining is 0.03～0.5 μ m, and the mode that is preferably the thickness of 0.05～0.2 μ m is carried out.Then, this is filmed in 20～120 ℃ of temperature, preferred 25～60 ℃ of following dryings 1～30 minute, preferred 2～10 minutes.So handling the formation electrically conducting transparent films.At this, it is that the reason of the scope of 0.03～0.5 μ m is that coating electrically conducting transparent film composition makes the thickness of the nesa coating after the calcining, and the thickness after the calcining is less than 0.03 μ m, or when exceeding 0.5 μ m, can't fully obtain increasing reflecting effect.
Above-mentioned base material can use any one of the light-transmitting substrate that formed by glass, pottery or macromolecular material, perhaps is selected from the two or more light transmission lamination body in glass, pottery, macromolecular material and the silicon.Polymeric substrate can be enumerated the film substrate that is formed by organic polymers such as polyimide resin, polyvinyl resin, PET (polyethylene terephthalate) resin, polybutylene terephthalate resin, epoxy resin.Photoelectric conversion layer can enumerate monocrystalline type or the polymorphic of crystal system, armorphous, compound type, or with the mixed type of monocrystalline type or polymorphic and armorphous combination etc.Transparent electrode layer can use ITO, White tin oxide etc.On base material, form not special qualification of method of transparent electrode layer, photoelectric conversion layer, can be known method of use such as vacuum film formation method.In addition, as shown in Figure 1, when on nesa coating 11, forming conductive reflecting film 24, conductive reflecting film 14 reflections are back to photoelectric conversion layer 12, thereby can improve efficiency of conversion from base material 10 side incident sunshines.When this conductive reflecting film is Ag nanoparticle sintered compact, the conductive reflecting film that preferably comprises the Ag nanoparticle with wet type coating method coating with compsn after, can form through calcining, but also can be with formation such as vacuum film formation methods.
And then; Above-mentioned wet type coating method is preferably any one in spraying method, point gum machine coating method, spin-coating method, spread coating, slot coated method, ink-jet application method, screen painting method, offset printing method or the mold coating method; But be not limited to these coating methods, all methods capable of using.
Spraying method is to make the electrically conducting transparent film composition become vaporific being coated on the base material through pressurized gas; Perhaps to nesa coating with composition itself pressurization and become vaporific and be coated on the method on the base material; The point gum machine coating method is for example the electrically conducting transparent film composition to be packed in the syringe; Through pushing the piston of this syringe, the electrically conducting transparent film composition is discharged from the minute nozzle of syringe front end and be coated on the method on the base material.Spin-coating method is that the electrically conducting transparent film composition is dripped on the base material of rotation; The electrically conducting transparent film composition that will drip through its cf-is diffused into the peripheral method of base material; Spread coating is that the base material that the front end with scraper separates predetermined gap is arranged to and can be moved in the horizontal direction; By this scraper the electrically conducting transparent film composition is supplied on the base material of upstream side, make the base material method that moves horizontally of side downstream.The slot coated method is to make the electrically conducting transparent film composition flow out and be coated on the method on the base material from slit, and the ink-jet application method is electrically conducting transparent film composition, the method for on base material, carrying out ink jet printing of in the print cartridge of commercially available ink-jet printer, filling.The screen painting method is to use screen cloth to indicate material as pattern, makes electrically conducting transparent film composition transfer to method base material on through the half tone image of making above that.The offset printing method is not make the electrically conducting transparent film composition that is attached on the hectograph directly be attached on the base material; But be transferred on the sheet rubber from hectograph is disposable, again from the sheet rubber printing process of water-repellancy of electrically conducting transparent film composition of having transferred to utilization on the base material.The mold coating method is to use manifold that the electrically conducting transparent film composition that supplies in the mold is distributed, and is expressed on the film method that the substrate surface that moves is coated with from slit.The mold coating method has bar seam coating method or slip coating method, curtain coating mode.
At last, will have base material that electrically conducting transparent films in atmosphere or in the inactive gas atmosphere such as nitrogen, argon gas, under 130～400 ℃, preferred 150～350 ℃ temperature, keep calcining in 5～60 minutes, preferred 15～40 minutes.
It is because during less than 130 ℃, produce the bad problem that the sheet resistance value of nesa coating becomes too high that the calcining temperature that will have a base material of filming is located at 130～400 ℃ scope.In addition, when exceeding 400 ℃, can not bring into play the advantage in the production of so-called low temperature process, promptly manufacturing cost increases, and productivity reduces.In addition, particularly non-crystalline silicon, microcrystal silicon or the mixed type silicon solar cell that uses them to heat a little less than, so efficiency of conversion reduces because of calcination process.
To have scope that the calcination time of the base material of filming was located at 5～60 minutes and be because calcination time is during less than lower value, produces the bad problem that the sheet resistance value of nesa coating becomes too high.When calcination time exceeded higher limit, manufacturing cost was increased to more than the necessary cost, and productivity reduces, and also produced the bad problem of the efficiency of conversion reduction of solar battery cell.
Through more than, can form nesa coating of the present invention.Like this, method of manufacture of the present invention can be got rid of as far as possible and use vacuum vapour deposition, sputtering method equal vacuum to become the operation of embrane method, so can make nesa coating more at an easy rate through using the wet type coating method.
[embodiment]
Below, specify the present invention through embodiment, but the present invention is not limited to these embodiment.
With the composition shown in table 1～3 (numeric representation mass parts), put into 100cm to amount to 60g
3Vial in, utilize diameter for the zirconia balls of 0.3mm (MICROHYCA, clear make) 100g with the Shell Oil Co., with coating whisking appliance dispersion 6 hours, make the electrically conducting transparent film composition of embodiment 1～23, comparative example 1～5 thus.At this, as the SiO of tackiness agent use
2Sticker 1～7 is made as follows.
[SiO
2Sticker 1]
Use 500cm
3The glass four-hole boiling flask, add 140g tetraethoxysilane and 140g ethanol, in the time of stirring, disposable adding in the solution of 120g pure water, is reacted 60% nitric acid dissolve of 1.7g 3 hours down and is made at 50 ℃ afterwards.
[SiO
2Sticker 2]
Use 500cm
3The glass four-hole boiling flask, add 85g tetraethoxysilane and 100g ethanol, in the time of stirring, at room temperature use and manage pump and in 10～15 minutes time, drop into 60% nitric acid dissolve with 0.09g in the solution of 110g pure water.Afterwards, in resulting mixing solutions, use the pipe pump in 10～15 minutes time, to drop into 45g ASBD and the 60g alcoholic acid mixing solutions that is pre-mixed placement.After at room temperature stirring about 30 minutes, make 50 ℃ of following reactions 3 hours.
[SiO
2Sticker 3]
Use 500cm
3The glass four-hole boiling flask, add 115g tetraethoxysilane and 175g ethanol, in the time of stirring, disposable adding in the solution of 110g pure water, is reacted 35% dissolving with hydrochloric acid of 1.4g 3 hours down and is made at 45 ℃ afterwards.
[SiO
2Sticker 4]
Use 500cm
3The glass four-hole boiling flask, add 130g tetraethoxysilane and 145g ethanol, in the time of stirring, disposable adding in the solution of 124g pure water, is reacted 30% ammonia solvent of 1.25g 3 hours down and is made at 45 ℃ afterwards.
[SiO
2Sticker 5]
Use 500cm
3The glass four-hole boiling flask, add 90g tetraethoxysilane and 100g ethanol, in the time of stirring, under room temperature state in 10～15 minutes time input with 60% nitric acid dissolve of 0.9g in the solution of 110g pure water.Afterwards, in resulting mixing solutions, in 10～15 minutes time, drop into 40g ASBD and the 60g alcoholic acid mixing solutions that is pre-mixed placement.After at room temperature stirring about 30 minutes, make 50 ℃ of following reactions 3 hours.
[SiO
2Sticker 6]
Use 500cm
3The glass four-hole boiling flask, add 125g tetraethoxysilane and 160g ethanol, in the time of stirring, disposable adding in the solution of 115g pure water, is reacted 60% nitric acid dissolve of 0.6g 3 hours down and is made at 50 ℃ afterwards.
[SiO
2Sticker 7]
Use 500cm
3The glass four-hole boiling flask, add 145g tetraethoxysilane and 140g ethanol, in the time of stirring, disposable adding in the solution of 115g pure water, is reacted 60% nitric acid dissolve of 0.015g 3 hours down and is made at 50 ℃ afterwards.
[coupling agent]
Silane coupling agent has used vinyltriethoxysilane.Titanium coupling agent has used the titanium coupling agent with dialkyl group pyrophosphorous acid ester group shown in the formula (1).
[mixed solvent]
Mixed solvent 1 has used Virahol, ethanol and N, and the mixed solution of dinethylformamide (mass ratio 4: 2: 1), mixed solvent 2 have used the mixed solution (mass ratio 98: 2) of ethanol and butanols.
[non-polymeric tackiness agent]
[embodiment 1～23]
Among the embodiment 1; At first shown in following table 1; In dispersion medium IPA, the mixed with 98 to 2 as the median size of electroconductive oxide powder be the colloidal silica spherical particle made of the ito powder of 25nm and daily output chemical industry (strain) that median size is 10nm (trade(brand)name: ST-O), in addition; The solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 1.
Among the embodiment 2; In dispersion medium ethanol; Mixed with 95 to 5 is the colloidal silica spherical particle (trade(brand)name: ST-O-40) of the ATO powder of 40nm and daily output chemical industry (strain) manufacturing that median size is 15nm as the median size of electroconductive oxide powder; In addition, the solids 90 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 10 quality % non-polymeric tackiness agent 1 as tackiness agent.
Among the embodiment 3; In dispersion medium IPA; Mixed with 92 to 8 is the colloidal silica spherical particle (trade(brand)name: LUDOX CL-P) of the TZO powder of 30nm and グ レ one ス ジ ャ パ Application (strain) manufacturing that median size is 12nm as the median size of electroconductive oxide powder; In addition, the solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 2.
Among the embodiment 4; In dispersion medium ethanol; Mixed with 92 to 8 is the colloidal silica spherical particle (trade(brand)name: ST-O) of the ito powder of 30nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 75 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 25 quality % SiO as tackiness agent
2Sticker 7.
Among the embodiment 5; In mixed solvent 1 as dispersion medium; Mixed with 90 to 10 is the colloidal silica spherical particle (trade(brand)name: ST-OXS) of the ito powder of 35nm and daily output chemical industry (strain) manufacturing that median size is 6nm as the median size of electroconductive oxide powder; In addition, the solids 80 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 20 quality % SiO as tackiness agent
2Sticker 6.
Among the embodiment 6; In dispersion medium ethanol; Mixed with 90 to 10 is the colloidal silica spherical particle (trade(brand)name: LUDOX TMA) of the ito powder of 40nm and グ レ one ス ジ ャ パ Application (strain) manufacturing that median size is 20nm as the median size of electroconductive oxide powder; In addition, the solids 80 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 20 quality % SiO as tackiness agent
2Sticker 2.
Among the embodiment 7; In dispersion medium ethanol; Mixed with 85 to 15 is the colloidal silica spherical particle (trade(brand)name: ST-OXS) of the ito powder of 25nm and daily output chemical industry (strain) manufacturing that median size is 6nm as the median size of electroconductive oxide powder; In addition; Solids 70 quality % with respect to electroconductive oxide particle and colloidal silica particle total; With the ratio mixed of 30 quality % non-polymeric tackiness agent 1, further with respect to formation film the electroconductive oxide particle of the solid ingredient after forming and the compsn 99.5 quality % of colloidal silica particle and binder ingredients total, with the titanium coupling agent shown in the ratio mixed chemical formula (1) of 0.5 quality % with dialkyl group pyrophosphorous acid ester group as tackiness agent.
Among the embodiment 8; In mixed solvent 2 as dispersion medium; Mixed with 85 to 15 is the colloidal silica spherical particle (trade(brand)name: LUDOX CL-P) of the ATO powder of 50nm and グ レ one ス ジ ャ パ Application (strain) manufacturing that median size is 12nm as the median size of electroconductive oxide powder; In addition; The solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % non-polymeric tackiness agent 2 as tackiness agent.
Among the embodiment 9; In mixed solvent 1 as dispersion medium; Mixed with 85 to 15 is the colloidal silica spherical particle (trade(brand)name: IPA-ST) of the ATO powder of 30nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 85 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 15 quality % SiO as tackiness agent
2Sticker 3.
Among the embodiment 10; In mixed solvent 2 as dispersion medium; Mixed with 82 to 18 is the colloidal silica spherical particle (trade(brand)name: ST-OXS) of the ito powder of 40nm and daily output chemical industry (strain) manufacturing that median size is 6nm as the median size of electroconductive oxide powder; In addition, the solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 4.
Among the embodiment 11; In mixed solvent 2 as dispersion medium; Mixed with 82 to 18 is the colloidal silica spherical particle (trade(brand)name: LUDOX TMA) of the ito powder of 35nm and グ レ one ス ジ ャ パ Application (strain) manufacturing that median size is 20nm as the median size of electroconductive oxide powder; In addition, the solids 75 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 25 quality % SiO as tackiness agent
2Sticker 5.
Among the embodiment 12; In dispersion medium ethanol; Mixed with 80 to 20 is the colloidal silica spherical particle (trade(brand)name: IPA-ST) of the ito powder of 30nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 75 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 25 quality % SiO as tackiness agent
2Sticker 6; Further with respect to formation film electroconductive oxide particle and the colloidal silica particle of the solid ingredient after forming and the compsn 99.3 quality % that binder ingredients amounts to, with the ratio mixed silane coupling agent (KBE-1003 of SHIN-ETSU HANTOTAI's シ リ コ one Application (strain) manufacturing) of 0.7 quality %.
Among the embodiment 13; In dispersion medium IPA; Mixed with 80 to 20 is the colloidal silica spherical particle (trade(brand)name: LUDOX TMA) of the IZO powder of 25nm and グ レ one ス ジ ャ パ Application (strain) manufacturing that median size is 20nm as the median size of electroconductive oxide powder; In addition, the solids 75 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 25 quality % SiO as tackiness agent
2Sticker 1.
Among the embodiment 14; In the dispersion medium butanols; Mixed with 80 to 20 is the colloidal silica spherical particle (trade(brand)name: LUDOX TMA) of the ito powder of 25nm and グ レ one ス ジ ャ パ Application (strain) manufacturing that median size is 20nm as the median size of electroconductive oxide powder; In addition, the solids 90 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 10 quality % non-polymeric tackiness agent 3 as tackiness agent.
Among the embodiment 15; In dispersion medium IPA; Mixed with 80 to 20 is the colloidal silica spherical particle (trade(brand)name: ST-O) of the IZO powder of 25nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 75 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 25 quality % SiO as tackiness agent
2Sticker 3.
Among the embodiment 16; In mixed solvent 1 as dispersion medium; Mixed with 78 to 22 is the colloidal silica spherical particle (trade(brand)name: ST-O-40) of the IZO powder of 25nm and daily output chemical industry (strain) manufacturing that median size is 15nm as the median size of electroconductive oxide powder; In addition, the solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 5.
Among the embodiment 17; In mixed solvent 1 as dispersion medium; Mixed with 77 to 23 is the colloidal silica spherical particle (trade(brand)name: LUDOX CL-P) of the TZO powder of 30nm and グ レ one ス ジ ャ パ Application (strain) manufacturing that median size is 12nm as the median size of electroconductive oxide powder; In addition; The solids 85 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 15 quality % non-polymeric tackiness agent 2 as tackiness agent.
Among the embodiment 18; In mixed solvent 1 as dispersion medium; Mixed with 70 to 30 is the colloidal silica spherical particle (trade(brand)name: IPA-ST) of the ito powder of 50nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 85 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 15 quality % SiO as tackiness agent
2Sticker 2.
Among the embodiment 19; In dispersion medium IPA; Mixed with 65 to 35 is the colloidal silica spherical particle (trade(brand)name: LUDOX CL-P) of the ATO powder of 40nm and グ レ one ス ジ ャ パ Application (strain) manufacturing that median size is 12nm as the median size of electroconductive oxide powder; In addition, the solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 7.
Among the embodiment 20; In dispersion medium IPA; Mixed with 92 to 8 is the colloidal silica spherical particle (trade(brand)name: IPA-ST-L) of the ito powder of 25nm and daily output chemical industry (strain) manufacturing that median size is 45nm as the median size of electroconductive oxide powder; In addition, the solids 75 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 25 quality % SiO as tackiness agent
2Sticker 6.
Among the embodiment 21; In mixed solvent 1 as dispersion medium; Mixed with 90 to 10 is the colloidal silica spherical particle (trade(brand)name: ST-O-L) of the ito powder of 35nm and daily output chemical industry (strain) manufacturing that median size is 45nm as the median size of electroconductive oxide powder; In addition, the solids 80 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 20 quality % SiO as tackiness agent
2Sticker 7.
Among the embodiment 22; In dispersion medium IPA; Mixed with 85 to 15 is the colloidal silica spherical particle (trade(brand)name: IPA-ST-L) of the ATO powder of 30nm and daily output chemical industry (strain) manufacturing that median size is 45nm as the median size of electroconductive oxide powder; In addition, the solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 1.
Among the embodiment 23; In dispersion medium IPA; Mixed with 85 to 15 is the colloidal silica spherical particle (trade(brand)name: ST-O) of the ito powder of 25nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 7.
[comparative example 1～5]
In the comparative example 1, in dispersion medium IPA, the median size of mixing as the electroconductive oxide powder is the ito powder of 25nm, in addition with respect to electroconductive oxide particle 70 quality %, with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 1.
In the comparative example 2; In dispersion medium IPA; Mixed with 99 to 1 is the colloidal silica spherical particle (trade(brand)name: IPA-ST) of the ito powder of 25nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 75 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 25 quality % SiO as tackiness agent
2Sticker 1.
In the comparative example 3; In dispersion medium IPA; Mixed with 63 to 37 is the colloidal silica spherical particle (trade(brand)name: ST-O) of the ito powder of 25nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 1.
In the comparative example 4; In dispersion medium ethanol; Mixed with 50 to 50 is the colloidal silica spherical particle (trade(brand)name: IPA-ST) of the ito powder of 25nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 75 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 25 quality % SiO as tackiness agent
2Sticker 1.
In the comparative example 5; In mixed solvent 1 as dispersion medium; Mixed with 80 to 20 is the colloidal silica spherical particle (trade(brand)name: ST-OYL) of the ito powder of 25nm and daily output chemical industry (strain) manufacturing that median size is 70nm as the median size of electroconductive oxide powder; In addition, the solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 1.
[the specific refractory power evaluation of electrically conducting transparent film composition]
For the specific refractory power evaluation; After the known glass substrate of optical constant formed ELD with wet type coating method (spin-coating method, mold coating method, spraying method, offset printing method) with the electrically conducting transparent film composition shown in embodiment 1～23, the comparative example 1～5; Calcining 20～60 minutes down at 160～220 ℃, is the nesa coating of 0.05～0.2 μ m thereby form thickness.(M-2000 that J.A.Woollam Japan (strain) makes) measures this film with the elliptically polarized light spectral apparatus, to transparency electrode partial analysis data, obtains optical constant.According to the optical constant of analyzing, with the value of 633nm as specific refractory power.These results have been shown in table 1～3.
[evaluation of electrically conducting transparent film composition in cladding plate type thin-film solar cells]
As shown in Figure 1, at first, prepare to form the SiO of thickness 50nm as substrate 10 at the interarea of a side
2The glass substrate of layer (not shown) is at this SiO
2Surface electrode layer (the SnO that on the layer surface is had the thickness 800nm of Z-Correct bump mapping Z-correct and doped F (fluorine)
2Film) forms transparent electrode layer 13.This transparent electrode layer 13 forms array-like through carry out patterning with laser processing method, and has formed the distribution that they are electrically connected each other.Then, on transparent electrode layer 13, form photoelectric conversion layer 12 with plasma CVD method.This photoelectric conversion layer 12 is obtained by the film of p type α-Si:H (amorphous unit price silicon), i type α-Si (non-crystalline silicon) and n type μ c-Si (crystallite silit) formation from substrate 10 sides lamination successively in the present embodiment.Use laser processing method with above-mentioned photoelectric conversion layer 12 patternings.It is used for the electrically conducting transparent film composition evaluation shown in the embodiment as carrying out film forming cladding plate type thin-film solar cells unit.
Is after the mode of 0.01～0.5 μ m is coated with the electrically conducting transparent film composition shown in embodiment 1～23, the comparative example 1～5 to carrying out film forming cladding plate type thin-film solar cells unit with the thickness of wet type coating method (spin-coating method, mold coating method, spraying method, offset printing method) after with calcining, is low temperature dry 5 minutes formation nesa coatings 11 down of 25～60 ℃ in temperature.In table 1～3 coating process has been shown.In addition, thickness after the calcining of nesa coating 11 has been shown in table 1～3.At this, thickness is measured through the cross-section that the scanning electron microscope made from the Ha ィ テ of Hitachi Network ノ ロ ジ one ズ (SEM, device name: S-4300, SU-8000) carries out.
Then; Thickness after using the wet type coating method on this nesa coating 11 with calcining be the mode of 0.05～2.0 μ m be coated with conductive reflecting film by following method preparation with compsn after, be low temperature dry 5 minutes formation conductive reflecting films 14 down of 25～60 ℃ in temperature.Then, calcined 20～60 minutes down at 160～220 ℃, thereby on solar battery cell, form composite package.And conductive reflecting film is following with the preparation of compositions method.
At first, Silver Nitrate is dissolved in the deionized water preparation metals ion aqueous solution.In addition, be the sodium citrate aqueous solution of 26 weight % Trisodium Citrate is dissolved in preparing concentration in the deionized water.In this sodium citrate aqueous solution, in remaining 35 ℃ stream of nitrogen gas, directly add granular ferrous sulfate and make it dissolving, preparation contains the reductive agent aqueous solution of citrate ions and ferrous ion with 3: 2 mol ratio.Then; Above-mentioned stream of nitrogen gas is being remained under 35 ℃ the state; The stirrer of magnetic stirring apparatus is put into the reductive agent aqueous solution; When making stirrer stir the above-mentioned reductive agent aqueous solution with the rotation of the speed of rotation of 100rpm, this reductive agent aqueous solution above-mentioned aqueous metal salt that drips is synthesized.At this, aqueous metal salt thinks that to the addition of the reductive agent aqueous solution mode below 1/10 of the water-soluble liquid measure of reductive agent adjusts the concentration of each solution, thereby even the aqueous metal salt of the room temperature of dripping also makes temperature of reaction remain on 40 ℃.In addition, to be adjusted to the equivalent of the ferrous ion that adds as reductive agent be 3 times of metal ion equivalent to the ratio of mixture of the above-mentioned reductive agent aqueous solution and aqueous metal salt.Aqueous metal salt further continues to mix liquid 15 minutes after dripping of the reductive agent aqueous solution finished, thereby at the inner metallics that produces of mixed solution, obtains metallics dispersive metallics dispersion liquid.The pH of metallics dispersion liquid is 5.5, and the stoichiometry growing amount of the metallics in the dispersion liquid is 5g/L.The dispersion liquid that obtains is through at room temperature placing the metallics deposition that makes in the dispersion liquid, through the condensation prod of the metallics behind the decantation precipitation separation.Isolating metal condensation prod is added deionized water as dispersion-s, carry out desalting treatment through ultrafiltration after, and then clean with the methyl alcohol displacement, the content that makes metal (silver) is 50 quality %.Afterwards, use separating centrifuge, the cf-particle separation diameter of adjusting this separating centrifuge exceeds the big silver particles of 100nm, thereby preparation contains the Nano silver grain of the primary particle size of mean number more than 71% in 10～50nm scope.That is, to make the Nano silver grain of primary particle size in 10～50nm scope be that mean number is more than 71% with respect to all silver nano-grain 100% shared ratios in adjustment.Resulting Nano silver grain is the protective material chemically modified of organic main chain of 3 by the carbonatoms of carbon skeleton.
Then, the interpolation of the metal nanoparticle that obtains 10 mass parts is mixed in mixing solutions 90 mass parts that comprise water, ethanol and methyl alcohol, thereby makes its dispersion.And then it is 95 quality % that the silver citrate that this dispersion liquid is added Vinylpyrrolidone polymer and the 1 quality % of 4 quality % as additive makes the ratio of metal nanoparticle, uses compsn thereby obtain conductive reflecting film.
Then; As solar cell when estimating generating efficiency; On the solar battery cell that is formed up to conductive reflecting film, be coated with the enhancing film composition as reinforcing membrane with the mold apparatus for coating on the conductive reflecting film 14; And make that to strengthen the thickness of film composition after calcining be 350nm, through vacuum-drying from reinforcing membrane with after removing solvent the coated film, in hot-air drying stove, make solar battery cell 180 ℃ of maintenances 20 minutes down; Make reinforcing membrane use the coated film thermofixation, use reinforcing membrane thereby obtain conductive reflecting film.And reinforcing membrane is following with the preparation of compositions method.
At first; The median size as the electroconductive oxide particulate of mixing 8 quality % be the ITO particle of 25nm, 2 quality % as the titanium coupling agent with dialkyl group pyrophosphorous acid ester group of coupling agent and 90 quality % as the methyl alcohol of dispersion medium and the mixed solution of butanols (mass ratio 98: 2), at room temperature the speed of rotation with 800rpm stirred 1 hour.Then, this mixture 60g is put into the vial of 100cc, (clearly make with the Shell Oil Co., MICROHYCA) 100g with coating whisking appliance dispersion 6 hours, prepares ITO dispersion of particles liquid thus for the zirconia balls of 0.3mm to utilize diameter.At this, have shown in the chemical formula (1) that the titanium coupling agent of dialkyl group pyrophosphorous acid ester group enumerated by above-mentioned embodiment.In addition, SiO
2Sticker and above-mentioned SiO
2Sticker 1 is adjusted equally.Then, ITO dispersion of particles liquid 4 quality % with after ethanol 86 quality % as dispersion medium mix, are further mixed the SiO of 10 quality %
2Sticker 1; Be enhanced behind the base fluid of film composition; Mix this base fluid of 95 quality % and the fumed silica dispersion liquid of 5 quality % as additive; With ultrasonic vibrator at room temperature dispersing and mixing made mixture whole fused in 10 minutes, thereby preparation is as the masking liquid that strengthens film composition.
Be formed up to conductive reflecting film and with laser processing method nesa coating 11, conductive reflecting film 14 and the conductive reflecting film of photoelectric conversion layer 12 and formation above that implemented patterning with reinforcing membrane with the solar battery cell of reinforcing membrane.
Evaluation method as solar battery cell; Use laser processing method on the substrate after the processing of implementing patterning, to implement the lead-in wire distribution; Output characteristic when having confirmed the IV rational curve and as the value of short-circuit current (Jsc); The photoelectric conversion layer that the method for manufacture identical with use and embodiment obtains, the cladding plate type solar battery cell that all uses sputtering method to form nesa coating, conductive reflecting film, reinforcing membrane are to export evaluation at 100 o'clock relatively.These results have been shown in table 1～3.
At this, as shown in Figure 1 for the cladding plate type solar battery cell that all forms by sputtering method, at first, prepare to form the SiO of thickness 50nm as substrate 10 at the interarea of a side
2The glass substrate of layer (not shown) is at this SiO
2Form the surface electrode layer (SnO that the surface has the thickness 800nm of Z-Correct bump mapping Z-correct and doped F (fluorine) on the layer
2Film) 13.When this transparent electrode layer 13 forms array-like through carry out patterning with laser processing method, form the distribution that they are electrically connected each other.Then, on transparent electrode layer 13, form photoelectric conversion layer 12 with plasma CVD method.This photoelectric conversion layer 12 is obtained by the film of p type α-Si:H (non-crystalline silicon, thickness 40nm), i type α-Si (non-crystalline silicon, thickness 200nm) and n type μ c-Si (microcrystal silicon, thickness 40nm) formation from substrate 10 sides lamination successively in the present embodiment.
After using laser processing method with above-mentioned photoelectric conversion layer 12 patternings, use magnetic control tandem sputter equipment on photoelectric conversion layer 12, to form the nesa coating (ZnO layer) 11 of thickness 80nm and the conductive reflecting film (silver electrode layer) 14 of thickness 200nm successively.
When nesa coating contains median size and is the fine spherocolloids silicon oxide particle of 6～45nm, because adhesivity may reduce, so carried out the adhesivity evaluation.For the adhesivity evaluation; Use method based on tape test (JIS K-5600); Electrically conducting transparent film composition shown in embodiment 1～23, the comparative example 1～5 to after carrying out film forming solar battery cell formation nesa coating 11 and conductive reflecting film 14, was calcined 20～60 minutes down at 160～220 ℃, thereby formed on the solar battery cell on the basis of composite package; This film is adhered to adhesive tape; Through when peeling off, the film of formation is peeled off or the degree of roll-up state, estimates with excellent, good, bad Three Estate.Do not form thing in the adhesive tape side with film; Be excellent when only having peeled off adhesive tape; Peeling off and mixing as the state that the photoelectric conversion layer 12 of base material exposes of adhesive tape is good when existing, and is bad when peeling off whole the showing out that makes as photoelectric conversion layer 12 surfaces of base material through the traction of adhesive tape.These results have been shown in table 1～3.
[table 1]
[table 2]
[table 3]
[table 4]
Can know that by table 1～3 embodiment 1～23 is that specific refractory power is low, good adhesion, the obvious height of generating efficiency is 105～123% relatively, short-circuit current is also high relatively is 102～105%.Particularly the relative generating efficiency of embodiment 23 is with short-circuit current is the highest relatively, and adhesivity might as well.Relative therewith, at the comparative example that does not contain the colloidal silica particle 1 with only contain in the comparative example 2 of colloidal silica particle of 1 mass parts, specific refractory power is high, and generating efficiency is about 100% with short-circuit current relatively relatively.The comparative example of the colloidal silica particle that contains 37 mass parts 3 with contain in the comparative example 4 of 50 mass parts, generating efficiency is with short-circuit current is all low relatively relatively.In the big comparative example 5 of the median size of colloidal silica particle, the adhesivity deterioration, generating efficiency is with short-circuit current is all low relatively relatively.
< embodiment 24 >
Among the embodiment 24; At first; In dispersion medium IPA, the mixed with 98 to 2 as the median size of electroconductive oxide powder be the colloidal silica spherical particle made of the ito powder of 25nm and daily output chemical industry (strain) that median size is 10nm (trade(brand)name: ST-O), in addition; The solids 70 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 30 quality % SiO as tackiness agent
2Sticker 1.At this, dispersion medium (IPA) uses with the ratio of 72.3 quality % with respect to the electrically conducting transparent film composition.
< embodiment 25 >
Among the embodiment 25; In dispersion medium ethanol; Mixed with 92 to 8 is the colloidal silica spherical particle (trade(brand)name: ST-O) of the ito powder of 30nm and daily output chemical industry (strain) manufacturing that median size is 10nm as the median size of electroconductive oxide powder; In addition, the solids 75 quality % that amount to respect to electroconductive oxide particle and colloidal silica particle are with the ratio mixed of the 25 quality % SiO as tackiness agent
2Sticker 7.At this, dispersion medium (IPA) uses with the ratio of 72.3 quality % with respect to the electrically conducting transparent film composition.
< comparative example 6 >
In the comparative example 6, the median size of in dispersion medium IPA, mixing as the electroconductive oxide powder is the ito powder of 25nm, in addition, and with respect to electroconductive oxide particle 70 quality %, with the ratio mixed of 30 quality % SiO as tackiness agent
2Sticker 1.At this, dispersion medium (IPA) uses with the ratio of 72.3 quality % with respect to the electrically conducting transparent film composition.
[evaluation of electrically conducting transparent film composition in the base plate type thin-film solar cells]
As shown in Figure 2, prepare the film substrate of the polyimide resin system of long 100mm, wide 100mm, thickness 50 μ m as base material 20, at the through hole 25 of these film substrate 20 formation diameters 100 μ m.At first, below film substrate 20, form the collector layer 26 (thickness 200nm) that forms by Ag with sputtering method.At this moment, also filled the conductive part material that constitutes by Ag in the through hole 25.Then; On base material 20 with wet type coating method (screen painting method) coating conductive reflecting film with compsn after; Film substrate is put into recirculation furnace; Under 200 ℃ temperature, keep 30 minutes calcining conductive reflecting films 24, as carrying out film forming base plate type thin-film solar cells unit.And the thickness of the conductive reflecting film 24 after the calcining is 200nm.
Then; On the conductive reflecting film 24 with spin-coating method to the electrically conducting transparent film composition that carries out film forming base plate type thin-film solar cells unit coating embodiment 24 and 25, comparative example 6 after; Following dry 5 minutes 50 ℃ of temperature; Then, calcined 30 minutes down, thereby on solar battery cell, form nesa coating 21 at 180 ℃.For thickness after the calcining of nesa coating 21, embodiment 24 is 0.1 μ m, and embodiment 25 is 0.13 μ m, and comparative example 6 is 0.1 μ m.
When the transparent electrode layer 21 after the formation is patterned to array-like with conductive reflecting film 24 through using laser processing method, the distribution that formation can be electrically connected them each other.Then, on transparent electrode layer 21, form photoelectric conversion layer 22 with plasma CVD method.This photoelectric conversion layer 22 is obtained by the film of n type μ c-Si (crystallite silit), i type α-Si (non-crystalline silicon) and p type α-Si:H (amorphous unit price silicon) formation from substrate 20 sides lamination successively.Use laser processing method with above-mentioned photoelectric conversion layer 22 patternings.
And then, on photoelectric conversion layer 22, the surface had the surface electrode layer (SnO of the thickness 800nm of Z-Correct bump mapping Z-correct and doped F (fluorine)
2Film) forms transparent electrode layer 23.When this transparent electrode layer 23 is patterned to array-like through using laser processing method, forms the distribution that they are electrically connected each other, thereby obtain the base plate type thin-film solar cells.
Likewise estimate the relative generating efficiency and the short-circuit current (Jsc) of the base plate type thin-film solar cells that obtains with cladding plate type solar cell.At this, base material 20, conductive reflecting film 24, nesa coating 21, photoelectric conversion layer 22, transparent electrode layer 23 all are made as 100 with the base plate type thin-film solar cells unit that sputtering method is made, export evaluation relatively.
Among the embodiment 24, generating efficiency is 108% relatively, and short-circuit current density is 104% relatively, and any one is all improved.Among the embodiment 25, generating efficiency is 110% relatively, and short-circuit current density is 103% relatively, and any one is all improved.On the other hand, in the comparative example 6, relatively generating efficiency is 98%, and short-circuit current density is 101% relatively, draws the low result that compares with embodiment 24 and 25.
As stated, electrically conducting transparent film composition of the present invention can use the wet type coating method on photoelectric conversion layer, to be coated with, to calcine, the specific refractory power of the nesa coating that can obtain through the content adjustment of spherocolloids silicon oxide particle.Therefore, can obtain to improve the nesa coating of the generating efficiency of thin-film solar cells simply.
Claims (11)
1. electrically conducting transparent film composition that is used for solar cell; It is characterized in that; Comprise the electroconductive oxide particle, median size is spherocolloids silicon oxide particle and the tackiness agent of 6～45nm; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.
2. electrically conducting transparent film composition that is used for cladding plate type thin-film solar cells; It is characterized in that; Comprise the electroconductive oxide particle, median size is spherocolloids silicon oxide particle and the tackiness agent of 6～45nm; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.
3. the electrically conducting transparent film composition that is used for cladding plate type thin-film solar cells according to claim 2, tackiness agent is polymer type adhesive and/or non-polymeric tackiness agent through being heating and curing.
4. the electrically conducting transparent film composition that is used for cladding plate type thin-film solar cells according to claim 3, non-polymeric tackiness agent are to be selected from least a in metallic soap, metal complex, metal alkoxide, halogenated silanes class, 2-alkoxyethanol, beta-diketon and the alkyl acetate.
5. nesa coating that is used for solar cell; It is characterized in that; Comprise electroconductive oxide particle, median size and be the spherocolloids silicon oxide particle of 6～45nm and solidify after tackiness agent; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.
6. nesa coating that is used for cladding plate type thin-film solar cells; It is characterized in that; Comprise electroconductive oxide particle, median size and be the spherocolloids silicon oxide particle of 6～45nm and solidify after tackiness agent; With respect to total 100 mass parts of electroconductive oxide particle and spherocolloids silicon oxide particle, comprise the spherocolloids silicon oxide particle of 2～35 mass parts.
7. the nesa coating that is used for cladding plate type thin-film solar cells according to claim 6, tackiness agent are polymer type adhesive and/or non-polymeric tackiness agent.
8. the nesa coating that is used for cladding plate type thin-film solar cells according to claim 7, non-polymeric tackiness agent are to be selected from least a in metallic soap, metal complex, metal alkoxide, halogenated silanes class, 2-alkoxyethanol, beta-diketon and the alkyl acetate.
9. a cladding plate type thin-film solar cells comprises any described nesa coating that is used for cladding plate type thin-film solar cells in the claim 6～8.
10. the method for manufacture of a nesa coating; Method of manufacture for the nesa coating of the cladding plate type thin-film solar cells that comprises base material, transparent electrode layer, photoelectric conversion layer and nesa coating successively; After on photoelectric conversion layer, forming electrically conducting transparent and film with any described electrically conducting transparent film composition in the wet type coating method coating claim 2～4, calcining has the base material that electrically conducting transparent films and forms nesa coating.
11. the method for manufacture of nesa coating according to claim 10, wet type coating method are spraying method, point gum machine coating method, spin-coating method, spread coating, slot coated method, ink-jet application method, mold coating method, screen painting method, offset printing method or woodburytype.
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| JP2011192185A JP2012094830A (en) | 2010-09-30 | 2011-09-03 | Transparent conductive film composition for solar battery and transparent conductive film |
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