CN102464941A - Composition for transparent conductive film, for solar cell, and transparent conductive film - Google Patents

Composition for transparent conductive film, for solar cell, and transparent conductive film Download PDF

Info

Publication number
CN102464941A
CN102464941A CN2011103397372A CN201110339737A CN102464941A CN 102464941 A CN102464941 A CN 102464941A CN 2011103397372 A CN2011103397372 A CN 2011103397372A CN 201110339737 A CN201110339737 A CN 201110339737A CN 102464941 A CN102464941 A CN 102464941A
Authority
CN
China
Prior art keywords
silsesquioxane
particle
tackiness agent
nesa coating
electroconductive oxide
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.)
Pending
Application number
CN2011103397372A
Other languages
Chinese (zh)
Inventor
日向野怜子
泉礼子
山崎和彦
林年治
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.)
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Materials Corp
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
Priority claimed from JP2011196299A external-priority patent/JP2012114408A/en
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Publication of CN102464941A publication Critical patent/CN102464941A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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

  • Paints Or Removers (AREA)

Abstract

The invention relates to a composition for a transparent conductive film, for a solar cell, and a transparent conductive film manufactured via the composition, wherein the composition is used in a wet coating method. The reflected light on the interface between a transparent conductive film and a photoelectric conversion layer is enhanced through an increase of difference on the index of refraction between the transparent conductive film and the photoelectric conversion layer. The enhanced light is returned to the photoelectric conversion layer, so that the transparent conductive film helps to improve the generation efficiency of a film solar cell, thereby forming the composition for the transparent conductive film. The composition for a transparent conductive film, which is used for a solar cell, is characterized by comprising conductive oxide particles, silsesquioxane particles and a bonding agent, wherein the average diameter of each silsesquioxane particle is 1-50nm, and the composition comprises, by mass, 2-35 parts of silsesquioxane particles, corresponding to 100 parts of conductive oxide particles and silsesquioxane particles together.

Description

The electrically conducting transparent film composition and the nesa coating of used for solar batteries
Technical field
The present invention relates to a kind of electrically conducting transparent film composition and nesa coating.More in detail, the electrically conducting transparent film composition and the nesa coating that relate to a kind of used for solar batteries.
Background technology
At present, from the position of environment protection, advancing the research and development and the practicability of green energy resource, from inexhaustible as the sunshine of the energy and be aspect such as nuisanceless, solar cell gets most of the attention.In the past, solar cell until data silicon single crystal or polysilicon bulk solar cell, but because the manufacturing cost height and the productivity of block solar cell are also low, therefore be badly in need of developing the solar cell of the silicon amount that practices every conceivable frugality.
Therefore, endeavour to develop the semi-conductive thin-film solar cells that thickness for example is the non-crystalline silicon etc. of 0.3～2 μ m.Therefore this thin-film solar cells has slim and advantages such as light weight, low cost and easy big areaization owing to be the structure that on glass substrate or heat-resistant plastic substrate, forms the semiconductor layer of the required amount of opto-electronic conversion.
Thin-film solar cells has cladding plate (ス one パ one ス ト レ one ト) structure and substrate (サ Block ス ト レ one ト) structure; Cladding plate type structure is owing to from light-transmitting substrate side incident sunshine, therefore take the structure with the order formation of substrate-transparency electrode-photoelectric conversion layer-backplate usually.
In the past, in this thin-film solar cells, electrode or reflectance coating became embrane method to form with the sputter equal vacuum, but were generally importing, needing when keeping and moving large-scale vacuum film formation apparatus significant cost.In order to improve this point, disclose utilize electrically conducting transparent film composition and conductive reflecting film with compsn to form the technology (patent documentation 1) of nesa coating and conductive reflecting film as the wet type coating method of inexpensive method of manufacturing more.
Patent documentation 1: the open 2009-88489 communique of Japanese Patent
Summary of the invention
Problem of the present invention is improveing through the nesa coating of above-mentioned wet type coating method manufacturing.Discoveries such as the inventor; The difference of the specific refractory power through the electrically conducting transparent film composition being improved and strengthened the nesa coating that in the wet type coating method, uses and the specific refractory power of photoelectric conversion layer increases nesa coating-photoelectric conversion layer reflected light at the interface, and can improve the generating efficiency of thin-film solar cells through the light that is back to photoelectric conversion layer of this increase.Identical method also can be applicable to base plate type thin-film solar cells or bulk si solar cell.
The present invention relates to a kind of electrically conducting transparent film composition and nesa coating that solves the used for solar batteries of above-mentioned problem through the scheme shown in following.
(1) a kind of electrically conducting transparent film composition of used for solar batteries; It is characterized in that; Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the tackiness agent of 1～50nm; Add up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprise the silsesquioxane particle of 2～35 mass parts.
(2) the electrically conducting transparent film composition used of a kind of cladding plate type thin-film solar cells; It is characterized in that; Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the tackiness agent of 1～50nm; Add up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprise the silsesquioxane particle of 2～35 mass parts.
(3) the electrically conducting transparent film composition of using like above-mentioned (2) described cladding plate type thin-film solar cells, wherein, tackiness agent is polymer type adhesive and/or non-polymeric tackiness agent through being heating and curing.
(4) the electrically conducting transparent film composition of using like above-mentioned (3) described cladding plate type thin-film solar cells; Wherein, the non-polymeric tackiness agent is to be selected from least a in the group that is made up of metallic soap, metal complex, metal alkoxide, halogenated silanes class, 2-alkoxyethanol, beta-diketon and alkyl acetic ester.
(5) a kind of nesa coating of used for solar batteries; It is characterized in that; Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the solidified tackiness agent of 1～50nm; Add up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprise the silsesquioxane particle of 2～35 mass parts.
(6) nesa coating used of a kind of cladding plate type thin-film solar cells; It is characterized in that; Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the solidified tackiness agent of 1～50nm; Add up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprise the silsesquioxane particle of 2～35 mass parts.
(7) nesa coating of using like above-mentioned (6) described cladding plate type thin-film solar cells, wherein, tackiness agent is polymer type adhesive and/or non-polymeric tackiness agent.
(8) nesa coating of using like above-mentioned (7) described cladding plate type thin-film solar cells; Wherein, 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 acetic ester.
(9) a kind of cladding plate type thin-film solar cells, it comprises the nesa coating that each described cladding plate type thin-film solar cells is used in above-mentioned (6)～(8).
(10) a kind of method of manufacture of nesa coating; It is the method for manufacture of the nesa coating of the cladding plate type thin-film solar cells that possesses base material, transparent electrode layer, photoelectric conversion layer and nesa coating successively; Wherein, on photoelectric conversion layer, be coated with each described electrically conducting transparent film composition in above-mentioned (2)～(4), after the formation electrically conducting transparent is filmed through the wet type coating method; Burn till and have the base material that electrically conducting transparent is filmed, the formation nesa coating.
(11) like the method for manufacture of above-mentioned (10) described nesa coating; Wherein, the wet type coating method is spraying method, point gum machine coating method (デ イ ス ペ Application サ one コ one テ イ Application グ method), spin-coating method, spread coating, slot coated method, ink-jet application method, mold coating method, screen painting method, offset printing method or woodburytype.
The present invention's (1) electrically conducting transparent film composition can be coated with on photoelectric conversion layer, burn till with the wet type coating method, and can reduce the specific refractory power of the nesa coating that obtains through silsesquioxane particulate content.That is the difference of specific refractory power that, can simply obtain specific refractory power and the photoelectric conversion layer of nesa coating becomes big, nesa coating-photoelectric conversion layer reflected light at the interface increases and can improve the nesa coating of the generating efficiency of thin-film solar cells with the light that is back to photoelectric conversion layer of this increase.
According to the present invention (5), can obtain simply that nesa coating-photoelectric conversion layer reflected light at the interface increases and improve the solar cell of generating efficiency through the light that is back to photoelectric conversion layer of this increase.
According to the present invention (10), do not utilize the vacuum apparatus of high price, just can form nesa coating, and can simply make the higher thin-film solar cells of generating efficiency with low cost.
Description of drawings
Fig. 1 is the synoptic diagram in cross section that utilizes the cladding plate type thin-film solar cells of nesa coating of the present invention.
Fig. 2 is the synoptic diagram in cross section that utilizes the base plate type thin-film solar cells of nesa coating of the present invention.
Nomenclature
10,20-base material, 11,21-nesa coating, 12,22-photoelectric conversion layer, 13,23-transparent electrode layer, 14,24-conductive reflecting film, 25-through hole, 26-collector layer.
Embodiment
Below, according to embodiment the present invention is specified.In addition, short ofly illustrate especially, perhaps except numerical value inherent situation, % is quality %.
[the electrically conducting transparent film composition of used for solar batteries]
The electrically conducting transparent film composition of used for solar batteries of the present invention (below; Be called " electrically conducting transparent film composition "; It is characterized in that; Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the tackiness agent of 1～50nm, adds up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprises the silsesquioxane particle of 2～35 mass parts.This electrically conducting transparent film composition is fit to thin-film solar cells, especially is fit to cladding plate type thin-film solar cells.
Indium tin oxide), ATO (Antimony Tin Oxide: stannic oxide powder antimony-doped tin oxide) or contain Zinc oxide powder that is selected from least a metal in the group that constitutes by Al, Co, Fe, In, Sn and Ti etc. be preferably ITO (Indium Tin Oxide: as the electroconductive oxide particle; Aluminium-doped zinc oxide), IZO (Indium Zinc Oxide: the indium doping zinc-oxide), TZO (Tin Zinc Oxide: tin mixed with zinc oxide) wherein, ITO, ATO, AZO (Aluminum Zinc Oxide: more preferably.And the median size of electroconductive oxide particulate in the scope of 10～100nm, wherein, if in the scope of 20～60nm, then for more preferably, if in the scope of 25～50nm, then is further preferred preferably in order in dispersion medium, to keep stability.At this, the median size utilization is measured based on the BET method according to the specific area measuring of QUANTACHROME AUTOSORB-1.
Silsesquioxane is the silicon-containing polymer that is made up of siloxane bond, is with following formula (1):
Figure BDA0000104401480000051
(in the formula, R representes alkyl, according to circumstances comprises oxygen) is as the general name of the ZGK 5 of basic structural unit.The structure of silsesquioxane can be enumerated, by the random structure of formula (2) expression,
Figure BDA0000104401480000052
By the ladder structure of formula (3) expression,
Figure BDA0000104401480000053
Cage structure by formula (4)～(6) expression.
Figure BDA0000104401480000061
At this,, be preferably and comprise alkyl such as being selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl and dodecyl as the R of formula (2)～(6); Naphthenic base such as cyclohexyl; Aralkyl such as 2-hydrocinnamyl; Aryl such as phenyl, tolyl; And at least a functional group in the thiazolinyls such as vinyl, allyl group etc., from the viewpoint of easy manufacturing particulate, more preferably methyl, ethyl, propyl group, butyl, amyl group, hexyl, vinyl or phenyl.
Silsesquioxane particulate median size is 1～50nm, is preferably 6～15nm.This be because, if median size is less than 1nm, then lack particulate stability, therefore cause secondary aggregation easily and be difficult to make test portion, if greater than 50nm, then hinder the contact of conductive particle, therefore be not suitable for.At this, median size is by the specific area measuring that utilizes QUANTACHROME manufactured AUTOSORB-1, and hypothesis silsesquioxane particle is that proper sphere converts.That the silsesquioxane coating of particles can be enumerated is spherical, ring-type and the flat sugared shape of gold etc., preferably spherical.Silsesquioxane particulate aspect ratio (major diameter/minor axis) is preferably 1～1.4, and more preferably 1～1.25.The wettability of silsesquioxane particle and photoelectric conversion layer is better, can reduce the uneven thickness of film, reduces the specific refractory power of the nesa coating after solidifying.Fig. 1 illustrates the synoptic diagram in the cross section of the cladding plate type thin-film solar cells of utilizing nesa coating of the present invention.Cladding plate type thin-film solar cells possesses successively base material 10 is arranged, transparent electrode layer 13, photoelectric conversion layer 12, nesa coating 11 and conductive reflecting film 14, from substrate 10 side incident sunshines.Institute's incident sunshine by conductive reflecting film 14 reflections, is back to photoelectric conversion layer 12 mostly, improves efficiency of conversion.At this; The sunshine that also causes at the interface at nesa coating 11 and photoelectric conversion layer 12 reflects; Utilize the specific refractory power of nesa coating 11 of electrically conducting transparent film composition of the present invention lower; Therefore can increase the reflected light at the interface of nesa coating 11 and photoelectric conversion layer 12, improve the generating efficiency of thin-film solar cells.And expression utilizes the synoptic diagram in cross section of the base plate type thin-film solar cells of nesa coating of the present invention among Fig. 2.Base plate type thin-film solar cells 2 possesses successively base material 20 is arranged, conductive reflecting film 24, nesa coating 21, photoelectric conversion layer 22 and transparent electrode layer 23, from transparent electrode layer 23 side incident sunshines.Institute's incident sunshine by conductive reflecting film 24 reflections, is back to photoelectric conversion layer 22 mostly, improves efficiency of conversion.When being the base plate type thin-film solar cells; Also the sunshine that causes at the interface at photoelectric conversion layer 22 and nesa coating 21 reflects; Utilize the specific refractory power of nesa coating 21 of electrically conducting transparent film composition of the present invention lower; Therefore can increase the reflected light at the interface of photoelectric conversion layer 22 and nesa coating 21, improve the generating efficiency of thin-film solar cells.In addition,, then take out the electric power that produces from thin-film solar cells easily if on substrate 20, form through hole 25 and be electrically connected conductive reflecting film 24 and collector layer 26, therefore preferred.
The silsesquioxane particle obtains through following method: the monomer that trimethylammonium methoxy silane etc. is had the silica-based trifunctional of tri-alkoxy; Be that organotrialkoxysilane is put into as after in the alcohol such as methyl alcohol of solvent; Stir; Utilize ion exchanged water and the conduct suitably acid (nitric acid, hydrochloric acid, fluoric acid and organic acid etc.) or the alkali (ammonia etc.) of catalyzer therein, in 0～70 ℃ of scope, carry out hydrolysis in 2～6 hours and polycondensation.
As organotrialkoxysilane; Can enumerate methyltrimethoxy silane, Union carbide A-162, methyl three isopropoxy silane, methyl three (methoxy ethoxy) silane, ethyl trimethoxy silane, vinyltrimethoxy silane, vinyl three (methoxy ethoxy) silane, phenyltrimethoxysila,e etc., from easy manufacturing particulate viewpoint preferable methyl Trimethoxy silane, Union carbide A-162 and phenyltrimethoxysila,e.As the organic acid that catalyzer utilizes, can enumerate formic acid, acetic acid, propionic acid, oxalic acid and Hydrocerol A etc., from easy manufacturing particulate viewpoint preferable formic acid, acetic acid.Ion exchanged water, pure water preferably are used in hydrolysis.With respect to 1 mole organotrialkoxysilane, catalyzer is preferably 1 * 10 -3～1 * 10 -1Mole, water is preferably 2～10 moles.
As the alkali that utilizes for the polycondensation that promotes hydrolyzed solution, can enumerate sodium hydroxide, Pottasium Hydroxide, ammonia, Monomethylamine, monoethylamine etc., from can control particle diameter and can control the viewpoint of particle size range, preferred ammonia, monoethylamine narrowlyer.For example, when using ammonia, mixture 100 mass parts with respect to water and water and organic solvent are preferably about 0.01～1 mass parts.
As the organic solvent that uses in the reaction; Can enumerate methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, terepthaloyl moietie, Ucar 35, ethylene glycol monomethyl ether, acetone, dme, diethyl ether, phenyl ether, THF, diacetone alcohol etc., particular methanol, ethanol, Virahol, acetone, phenyl ether, diacetone alcohol.Organic solvent can be a kind, also can mix more than 2 kinds.
As concrete example, can enumerate following (1)～(4).(1) through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 140g trimethylammonium methoxy silane and 140g methyl alcohol, when stirring, disposable adding is reacted the solution of 60% nitric acid dissolve in the 120g pure water of 1.7g 3 hours down at 50 ℃ afterwards.(2) through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 140g three basic first and second TMOSs and 140g methyl alcohol, when stirring, disposable adding is dissolved in the solution in the 120g pure water with 1.5g formic acid, afterwards at 50 ℃ of reactions 3 hours down, acquisition hydrolyzed solution A.In addition, utilize hose pump in hydrolyzed solution A, to drop into alkaline solution through about 60 minutes, this alkaline solution is for to make an addition to the solution in 30g pure water and the 70g alcoholic acid mixed solution with 0.1g ammoniacal liquor.(3) through following method manufacturing: utilize 200cm 34 mouthfuls of flasks of glass; Add 0.5g methyltrimethoxy silane, 2.3g phenyltrimethoxysila,e and 80g ethanol, when stirring, disposable adding is dissolved in 0.03g formic acid the solution of 8g pure water; Reacted 1 hour down at 20 ℃ afterwards, thereby obtain hydrolyzed solution B.Utilize 500cm 34 mouthfuls of flasks of glass, add the solution that 0.25g Pottasium Hydroxide is dissolved in the 100g ion exchanged water, keep 20 ℃ when stirring, and utilize hose pump cost 2 hours to its hydrolyzed solution B that drips, after dripping, further stirred 2 hours.Afterwards, utilize hose pump to add 0.2g formic acid is added the mixed solution in the 100g ethanol through 20 minutes.(4) through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 100g phenyltrimethoxysila,e and 140g phenyl ether, when stirring, keep 25 ℃ and obtain mixed solution.In addition, utilize hose pump to drip in about 1 hour 0.1g Pottasium Hydroxide is dissolved in the solution in the 120g pure water to the mixed solution cost.
Preferred adhesive is polymer type adhesive or arbitrary side in the non-polymeric tackiness agent or both sides' the compsn that comprises through being heating and curing.As polymer type adhesive, can enumerate vinyl resin, polycarbonate, polyester, Synolac, urethane, vinylformic acid urethane, PS, polyacetal, polymeric amide, Z 150PH, PVA, Mierocrystalline cellulose and siloxane polymer etc.And the hydrolysis body that comprises 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.As the non-polymeric tackiness agent, can enumerate metallic soap, metal complex, metal alkoxide, halogenated silanes class, 2-alkoxyethanol, beta-diketon and alkyl acetic ester 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; The more preferably alkoxide of silicon, aluminium (for example, tetraethoxysilane, tetramethoxy-silicane, aluminum ethylate, aluminum isopropylate).These polymer type adhesives, non-polymeric tackiness agent can form the mist degree lower under the low temperature and the nesa coating of volume specific resistance thus through being heating and curing.In addition, metal alkoxide can be hydrolyzate or its dehydrate.
When metal alkoxide is solidified, preferably together contain hydrochloric acid, nitric acid, phosphoric acid (H as catalyzer with the moisture that is used to begin hydrolysis reaction 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 remaining, the not more weak P of residual halogens, not residual water tolerance etc., not viewpoints such as an alkali metal salt such as residual Na, more preferably nitric acid.And when being nitric acid, even suppose remaining N and diffuse to the photoelectric conversion layer (n type) of bottom, owing to play a role as donor, the efficiency of conversion of photoelectric conversion layer can not reduce yet, and can improve efficiency of conversion on the contrary.
The electrically conducting transparent film composition adds up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprises the electroconductive oxide particle of 98～65 mass parts, preferably comprises 95～70 mass parts.This is that electroconductibility descends during less than lower value because if surpass higher limit, then adhesivity descends.
Add up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprise the silsesquioxane particle of 2～35 mass parts, preferably comprise 5～30 mass parts.This is because when lower value is following, can't fully reduce the specific refractory power of the nesa coating after the curing, and when higher limit was above, electroconductibility descended.
Preferred these tackiness agents to contain proportional be 5～50 mass parts with respect to the solids content in the electrically conducting transparent film composition (electroconductive oxide particle, silsesquioxane particle and tackiness agent) 100 mass parts, more preferably 10～30 mass parts.And, when using metal alkoxide,, be preferably the nitric acid of 0.03～3 mass parts with respect to 100 mass parts metal alkoxides from the viewpoint of the remaining quantity of the curing speed of tackiness agent, nitric acid as tackiness agent and when using nitric acid as catalyzer.In addition, then slack-off if less as the polymerization velocity of the hydrolysis body of the metal alkoxide of tackiness agent as the amount of the nitric acid of catalyzer, during the required water shortage of hydrolysis, might can't obtain firm nesa coating.And; Take through burning till the hydrating solution of the higher eyed structure of the polymerization degree when solidifying if consider; Then become the situation of the stress additional conductive property particle contact each other that applies when shrinking, therefore preferred metal alkoxide with respect to 100 mass parts is the water of 10～120 mass parts.
The electrically conducting transparent film composition preferably adds coupling agent according to employed other compositions.This is to reach the nesa coating that forms through this electrically conducting transparent film composition and be laminated in the photoelectric conversion layer of base material or the adhesivity between the conductive reflecting film for the associativity that improves electrically conductive microparticle, silsesquioxane particle and tackiness agent.Can enumerate silane coupling agent, aluminum coupling agent and titanium coupling agent etc. as coupling agent.The content of preferred coupling agent is 0.2～5 mass parts with respect to solid content shared in the electrically conducting transparent film composition (electroconductibility oxidation particle, silsesquioxane particle, tackiness agent and silane coupling agent etc.) 100 mass parts, more preferably 0.5～2 mass parts.
For film forming well, preferably transparent conduction film composition comprises dispersion medium.As dispersion medium, can enumerate: water; Alcohols such as methyl alcohol, ethanol, Virahol, butanols; Ketones such as acetone, methyl ethyl ketone, pimelinketone, isophorone; Hydro carbons such as toluene, YLENE, hexane, hexanaphthene; N, amines such as dinethylformamide, DMAC N,N; Glycolss such as sulfoxide classes such as DMSO 99.8MIN. or terepthaloyl moietie; Reach gylcol ethers such as ethyl cellosolve.In order to obtain good film-forming properties, the content of preferred dispersion medium is 65～99 mass parts with respect to the electrically conducting transparent film composition of 100 mass parts.
In addition, according to employed composition, preferably add low resistance agent or water-soluble cellulose derivative etc.As the low resistance agent, be preferably selected from the group that mineral acid salt and the organic acid salt of cobalt, iron, indium, nickel, lead, tin, titanium and zinc form more than a kind or 2 kinds.For example, can enumerate the mixture etc. of mixture, ethanoyl acetic acid titanium and cobalt octoate of mixture, indium nitrate and plumbic acetate of mixture, zinc naphthenate, stannous octoate and the antimony chloride of nickel acetate and iron(ic)chloride.The content of preferred these low resistance agent is 0.2～15 mass parts with respect to electroconductive oxide powder 100 mass parts.Water-soluble cellulose derivative is the non-ionized tensio-active agent; Even but add the amount that is less than other tensio-active agents, the ability of dispersed electro-conductive property oxide powder is also high, in addition; Through adding water-soluble cellulose derivative, also improve the transparency of formed nesa coating.As water-soluble cellulose derivative, can enumerate hydroxypropylcellulose, Vltra tears etc.The addition of preferred water-soluble cellulose derivative is 0.2～5 mass parts with respect to electroconductive oxide powder 100 mass parts.
The electrically conducting transparent film composition can mix desirable composition according to domestic method through coating whisking appliance, ball mill, sand mill, centrifugal mill, triple-roller mill etc., and dispersed electro-conductive property oxide particle, silsesquioxane particle wait and make.Certainly, also can make through common stirring operation.
[nesa coating of used for solar batteries]
The nesa coating of used for solar batteries of the present invention (below; Be called nesa coating); It is characterized in that; Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the solidified tackiness agent of 1～50nm, adds up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprises the silsesquioxane particle of 2～35 mass parts.This nesa coating is fit to thin-film solar cells, especially is fit to cladding plate type thin-film solar cells.
Relevant electroconductive oxide particle, silsesquioxane particle be for as stated, and the solidified tackiness agent is meant the tackiness agent that solidifies behind the above-mentioned tackiness agent.That is, nesa coating is meant the film that solidifies behind the above-mentioned electrically conducting transparent film composition.
The method of manufacture of nesa coating of the present invention is the method for manufacture of the nesa coating of the cladding plate type thin-film solar cells that possesses base material, transparent electrode layer, photoelectric conversion layer and nesa coating successively; This method is coated with above-mentioned electrically conducting transparent film composition through the wet type coating method on photoelectric conversion layer; Form after electrically conducting transparent films, burn till and have the base material that electrically conducting transparent films and form 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 through the wet type coating method.In the coating here, the thickness that makes the nesa coating after burning till is 0.03～0.5 μ m, preferably becomes the thickness of 0.05～0.2 μ m.Then, this is filmed under 20～120 ℃ of temperature, preferably under 25～60 ℃, dry 1～30 minute, preferred 2～10 minutes.Forming electrically conducting transparent like this films.At this, the reason that is coated with the electrically conducting transparent film composition in the mode of 0.03～0.5 mu m range with the thickness of the nesa coating after burning till be because, if the thickness after burning till less than 0.03 μ m or surpass 0.5 μ m, then can't fully obtain to increase reflecting effect.
Above-mentioned base material can use any in the light-transmitting substrate that is made up of glass, pottery or macromolecular material or be selected from the range upon range of body of light transmission more than 2 kinds in glass, pottery, macromolecular material and the silicon.As polymeric substrate, can enumerate the film substrate that forms by organic polymers such as polyimide resin, polyvinyl resin, PET (polyethyleneterephthalate) resin, polybutylene terephthalate resin, epoxy resin.As photoelectric conversion layer, can enumerate monocrystalline type or the polymorphic of crystal system, armorphous, compound type or combination monocrystalline type or polymorphic and armorphous mixed type etc.Transparent electrode layer can use ITO, White tin oxide etc.The method that on base material, forms transparent electrode layer, photoelectric conversion layer does not have special qualification, and known method such as vacuum film formation method get final product.And as shown in Figure 1, if on nesa coating 11, form conductive reflecting film 24, then conductive reflecting film 14 reflections are back to photoelectric conversion layer 12 from base material 10 side incident sunshines, can improve efficiency of conversion.If this conductive reflecting film is an Ag nano particle sintered compact, the conductive reflecting film that the enough wet type coating method coatings of then preferred ability comprise the Ag nano particle form through burning till, but also vacuum available becomes formation such as embrane method with after the compsn.
Above-mentioned in addition wet type coating method is preferably any 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 this, can utilize all methods.
Spraying method is to make the electrically conducting transparent film composition be vaporific and coat perhaps nesa coating to be pressurizeed with composition itself on the base material through pressurized air to be vaporific and to coat the method on the base material; The point gum machine coating method is for example through the electrically conducting transparent film composition being injected syringe and push the piston of this syringe, from spue electrically conducting transparent film composition and coat the method on the base material of the minute nozzle of syringe front end.Spin-coating method is the electrically conducting transparent film composition and use method for compositions to this nesa coating that drips of base material circumferential expansion through its cf-of on the base material of rotation, dripping; Spread coating is the base material that separates predetermined gap with the front end of scraper to be set movably to horizontal direction; To supplying with the electrically conducting transparent film composition on more near the base material of upstream side, move horizontally the method for base material towards the downstream side than this scraper.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 narrow slit, and the ink-jet application method is to be filled in the print cartridge of commercially available ink-jet printer the electrically conducting transparent film composition and the method for on base material, carrying out ink jet printing.The screen painting method is to utilize yarn to use method for compositions as pattern indication material and through the domain picture that makes to base material transfer nesa coating above that.The offset printing method is not make the electrically conducting transparent film composition that invests on the version directly be attached to base material, but from the disposable film that is transferred to of version, and transfers to the printing process of the water-repellancy of utilizing the electrically conducting transparent film composition on the base material again from film.The mold coating method is to distribute the electrically conducting transparent film composition be supplied in the mould and be extruded on the film through slit through manifold, the surface of the base material of advancing is carried out the method for coating.The mold coating method has slotted coating method or sliding type coating method, curtain formula coating method.
At last, in atmosphere or in the inactive gas atmosphere such as nitrogen or argon, will have base material that electrically conducting transparent films with 130～400 ℃, preferred 150～350 ℃ temperature kept 5～60 minutes, preferably kept burning till in 15～40 minutes.
The firing temperature that will have a base material of filming is located in 130～400 ℃ the scope, and if this is because less than 130 ℃, then can produce the unfavorable condition that the sheet resistance value of nesa coating becomes too high.And be because, if surpass 400 ℃, then can not bring into play the advantage in the production of so-called low temperature process, promptly cause manufacturing cost to increase, productivity reduces.And especially non-crystalline silicon, microcrystal silicon or utilize these mixed type silicon solar cell relatively To Be Protected from Heat are because of the firing process efficiency of conversion descends.
The firing time that will have a base material of filming is located in 5～60 minutes the scope, and this is because the unfavorable condition that the sheet resistance value of nesa coating becomes too high during less than lower value, can take place firing time.And be because above higher limit, then manufacturing cost increases to the above and productivity reduction of necessity, and the unfavorable condition of the efficiency of conversion reduction of generation solar battery cell as if firing time.
Through more than, can form nesa coating of the present invention.Like this, therefore method of manufacture of the present invention can cheaply more make nesa coating owing to can get rid of the technology of utilizing vacuum vapour deposition or sputtering method equal vacuum to become embrane method as far as possible through using the wet type coating method.
[embodiment]
Below, through embodiment the present invention is elaborated, but the present invention is not limited to these.
To become the mode of the composition shown in table 1～3 (numeric representation mass parts), put into 100cm to add up to 60g 3Vial in, utilize the 100g diameter for the zirconium oxide bead of 0.3mm (MICROHYCA, clear with Royal Dutch Shell system), with coating whisking appliance dispersion 6 hours, thereby produce the electrically conducting transparent film composition of embodiment 1～24, comparative example 1～6.Table 4 illustrates employed silsesquioxane particulate median size.At this, the silsesquioxane spherical particle 1～6 (SQ1～6) that uses as the silsesquioxane particle, the SiO that uses as tackiness agent 2Wedding agent 1～7 as following making.
[silsesquioxane spherical particle 1 (SQ1)]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 140g trimethylammonium methoxy silane and 140g methyl alcohol, when stirring, disposable adding is reacted the solution of 60% nitric acid dissolve in the 120g pure water of 1.7g 3 hours down at 50 ℃ afterwards.
[silsesquioxane spherical particle 2 (SQ2)]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add trimethylethoxysilane and the 140g methyl alcohol of 140g, when stirring, disposable adding is dissolved in the solution in the 120g pure water with 1.5g formic acid, afterwards at 50 ℃ of reaction 3 hours and acquisition hydrolyzed solution A down.In addition, utilize hose pump in hydrolysis reaction liquid, to drop into alkaline solution through about 60 minutes, this alkaline solution is for to make an addition to the alkaline solution in 30g pure water and the 70g alcoholic acid mixed solution with 0.1g ammoniacal liquor.
[silsesquioxane spherical particle 3 (SQ3)]
Through following method manufacturing: utilize 200cm 34 mouthfuls of flasks of glass; Add 0.5g methyltrimethoxy silane, 2.3g phenyltrimethoxysila,e and 80g ethanol, when stirring, disposable adding is dissolved in 0.03g formic acid the solution in the pure water of 8g; Reacted 1 hour down at 20 ℃ afterwards, and obtain hydrolyzed solution B.Utilize 500cm 34 mouthfuls of flasks of glass, add the solution that 0.25g Pottasium Hydroxide is dissolved in the 100g ion exchanged water, keep 20 ℃ when stirring, and utilize hose pump cost 2 hours to its hydrolyzed solution B that drips, further stirred 2 hours after dripping.Afterwards, utilize hose pump to add 0.2g formic acid is added the mixed solution in the 100g ethanol through 20 minutes.
[silsesquioxane spherical particle 4 (SQ4)]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 100g phenyltrimethoxysila,e and 140g phenyl ether, maintenance obtains mixed solution for 25 ℃ when stirring.In addition, utilize hose pump cost about 1 hour to drip 0.1g Pottasium Hydroxide is dissolved in the solution in the 120g pure water to above-mentioned mixed solution.
[silsesquioxane spherical particle 5 (SQ5)]
Through following method manufacturing: utilize 200cm 34 mouthfuls of flasks of glass; Add 0.5g methyltrimethoxy silane, 2.3g phenyltrimethoxysila,e and 80g ethanol, when stirring, disposable adding is dissolved in 0.05g formic acid the solution of 8g pure water; Reacted 1 hour down at 20 ℃ afterwards, thereby obtain hydrolyzed solution B.Utilize 500cm 34 mouthfuls of flasks of glass, add the solution that 0.4g Pottasium Hydroxide is dissolved in the 100g ion exchanged water, keep 20 ℃ when stirring, and utilize hose pump cost 2 hours to its hydrolyzed solution B that drips, after dripping, further stirred 2 hours.Afterwards, utilize hose pump to add 0.2g formic acid is added the mixed solution in the 100g ethanol through 40 minutes.
[silsesquioxane spherical particle 6 (SQ6)]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 100g phenyltrimethoxysila,e and 140g phenyl ether, maintenance obtains mixed solution for 35 ℃ when stirring.In addition, utilize hose pump cost about 1 hour to drip 0.1g Pottasium Hydroxide is dissolved in the solution in the 120g pure water to above-mentioned mixed solution.
[SiO 2Wedding agent 1]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 140g tetraethoxysilane and 140g ethanol, when stirring, disposable adding is reacted the solution of 60% nitric acid dissolve in the 120g pure water of 1.7g 3 hours down at 50 ℃ afterwards.
[SiO 2Wedding agent 2]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 85g tetraethoxysilane and 100g ethanol, when stirring at room temperature, utilize 10～15 fens clock time inputs of hose pump warp with 60% nitric acid dissolve of 0.09g in the solution of 110g pure water.Afterwards, at the 45g tri sec-butoxy aluminum and the 60g alcoholic acid mixing solutions that utilize hose pump in the mixing solutions that is obtained, to be pre-mixed through 10～15 fens clock time inputs.After at room temperature stirring about 30 minutes, reacted 3 hours down at 50 ℃.
[SiO 2Wedding agent 3]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 115g tetraethoxysilane and 175g ethanol, when stirring, disposable adding is reacted the solution of 35% dissolving with hydrochloric acid in the 110g pure water of 1.4g 3 hours down at 45 ℃ afterwards.
[SiO 2Wedding agent 4]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 130g tetraethoxysilane and 145g ethanol, when stirring, disposable adding is reacted the solution of 30% ammonia solvent in the 124g pure water of 1.25g 3 hours down at 45 ℃ afterwards.
[SiO 2Wedding agent 5]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 90g tetraethoxysilane and 100g ethanol, when stirring under room temperature state, 10～15 fens clock time inputs of warp with 60% nitric acid dissolve of 0.9g in the solution of 110g pure water.Afterwards, the 40g tri sec-butoxy aluminum and the 60g alcoholic acid mixing solutions that in the mixing solutions that is obtained, are pre-mixed through 10～15 fens clock time inputs.After at room temperature stirring about 30 minutes, reacted 3 hours down at 50 ℃.
[SiO 2Wedding agent 6]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 125g tetraethoxysilane and 160g ethanol, when stirring, disposable adding is reacted the solution of 60% nitric acid dissolve in the 115g pure water of 0.6g 3 hours down at 50 ℃ afterwards.
[SiO 2Wedding agent 7]
Through following method manufacturing: utilize 500cm 34 mouthfuls of flasks of glass, add 145g tetraethoxysilane and 140g ethanol, disposable adding is reacted the solution of 60% nitric acid dissolve in the 115g pure water of 0.015g 3 hours down at 50 ℃ afterwards when stirring.
[coupling agent]
Silane coupling agent utilizes vinyl triethoxysilane.The titanium coupling agent utilization has by general formula (7):
Figure BDA0000104401480000171
The titanium coupling agent of the dialkyl group pyrophosphorous acid ester group of expression.
[mixed solvent]
Mixed solvent 1 has utilized Virahol, ethanol and N, and the mixed solution of dinethylformamide (mass ratio is 4: 2: 1), mixed solvent 2 have utilized the mixed solution (mass ratio is 98: 2) of ethanol, butanols.
[non-polymeric tackiness agent]
Non-polymeric tackiness agent 1 has utilized 2-n-butoxy ethanol and 3-sec.-propyl-2; The mixed solution of 4-diacetylmethane; Non-polymeric tackiness agent 2 has utilized 2; 2-dimethyl--3, the mixed solution of 5-hexanedione and sec.-propyl acetic ester (mass ratio is 1: 1), non-polymeric tackiness agent 3 have utilized the mixture (mass ratio is 4: 1: 1) of 2-isobutoxy ethanol and 2-hexyloxy ethanol and n-propyl acetic ester.
[embodiment 1～22]
Among the embodiment 1; At first; Be shown among the IPA that becomes dispersion medium like 1 of following table, the mixed with 98 to 2 is the ito powder of 25nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder, and; With respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 30 quality % 2Wedding agent 1 is as tackiness agent.
Among the embodiment 2; In becoming the ethanol of dispersion medium; Mixed with 95 to 5 is the ATO powder of 40nm and the silsesquioxane spherical particle 2 that median size is 15nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 90 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed non-polymeric tackiness agent 1 of 10 quality % as tackiness agent.
Among the embodiment 3; In becoming the IPA of dispersion medium; Mixed with 92 to 8 is the TZO powder of 30nm and the silsesquioxane spherical particle 2 that median size is 15nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 30 quality % 2Wedding agent 2 is as tackiness agent.
Among the embodiment 4; In becoming the ethanol of dispersion medium; Mixed with 92 to 8 is the ito powder of 30nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 75 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 25 quality % 2Wedding agent 7 is as tackiness agent.
Among the embodiment 5; In the mixed solvent that becomes dispersion medium 1; Mixed with 90 to 10 is the ito powder of 35nm and the silsesquioxane spherical particle 3 that median size is 6nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 80 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 20 quality % 2Wedding agent 6 is as tackiness agent.
Among the embodiment 6; In becoming the ethanol of dispersion medium; Mixed with 90 to 10 is the ito powder of 40nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 80 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 20 quality % 2Wedding agent 2 is as tackiness agent.
Among the embodiment 7; In becoming the ethanol of dispersion medium; Mixed with 85 to 15 is the ito powder of 25nm and the silsesquioxane spherical particle 3 that median size is 6nm as the median size of electroconductive oxide powder; And; With respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed non-polymeric tackiness agent 1 of 30 quality % as tackiness agent, and; Become the electroconductive oxide particle and the compsn 99.5 quality % of silsesquioxane spherical particle and binder constituents of the solids component after forming of filming with respect to total, the titanium coupling agent of representing by chemical formula (1) with the ratio mixed of 0.5 quality % with dialkyl group pyrophosphorous acid ester group.
Among the embodiment 8; In the mixed solvent that becomes dispersion medium 2; Mixed with 85 to 15 is the ATO powder of 50nm and the silsesquioxane spherical particle 2 that median size is 15nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed non-polymeric tackiness agent 2 of 30 quality % as tackiness agent.
Among the embodiment 9; In the mixed solvent that becomes dispersion medium 1; Mixed with 85 to 15 is the ATO powder of 30nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 85 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 15 quality % 2Wedding agent 3 is as tackiness agent.
Among the embodiment 10; In the mixed solvent that becomes dispersion medium 2; Mixed with 82 to 18 is the ito powder of 40nm and the silsesquioxane spherical particle 3 that median size is 6nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 30 quality % 2Wedding agent 4 is as tackiness agent.
Among the embodiment 11; In the mixed solvent that becomes dispersion medium 2; Mixed with 82 to 18 is the ito powder of 35nm and the silsesquioxane spherical particle 2 that median size is 15nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 75 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 25 quality % 2Wedding agent 5 is as tackiness agent.
Among the embodiment 12; In becoming the ethanol of dispersion medium; Mixed with 80 to 20 is the ito powder of 30nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 75 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 25 quality % 2Wedding agent 6 is as sticker; And; Become film the electroconductive oxide particle of the solids component after forming and the compsn 99.3 quality % of silsesquioxane spherical particle and binder constituents with respect to total, with the ratio mixed silane coupling agent (SHIN-ETSU HANTOTAI's シ リ コ one Application (strain) system KBE-1003) of 0.7 quality %.
Among the embodiment 13; In becoming the IPA of dispersion medium; Mixed with 80 to 20 is the IZO powder of 25nm and the silsesquioxane spherical particle 2 that median size is 15nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 75 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 25 quality % 2Wedding agent 1 is as tackiness agent.
Among the embodiment 14; In becoming the butanols of dispersion medium; Mixed with 80 to 20 is the ito powder of 25nm and the silsesquioxane spherical particle 2 that median size is 15nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 90 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed non-polymeric tackiness agent 3 of 10 quality % as tackiness agent.
Among the embodiment 15; In becoming the IPA of dispersion medium; Mixed with 80 to 20 is the IZO powder of 25nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 75 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 25 quality % 2Wedding agent 3 is as tackiness agent.
Among the embodiment 16; In the mixed solvent that becomes dispersion medium 1; Mixed with 78 to 22 is the IZO powder of 25nm and the silsesquioxane spherical particle 2 that median size is 15nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 30 quality % 2Wedding agent 5 is as tackiness agent.
Among the embodiment 17; In the mixed solvent that becomes dispersion medium 1; Mixed with 77 to 23 is the TZO powder of 30nm and the silsesquioxane spherical particle 2 that median size is 15nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 85 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed non-polymeric tackiness agent 2 of 15 quality % as tackiness agent.
Among the embodiment 18; In the mixed solvent that becomes dispersion medium 1; Mixed with 70 to 30 is the ito powder of 50nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 85 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 15 quality % 2Wedding agent 2 is as tackiness agent.
Among the embodiment 19; In becoming the IPA of dispersion medium; Mixed with 65 to 35 is the ATO powder of 40nm and the silsesquioxane spherical particle 2 that median size is 15nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 30 quality % 2Wedding agent 7 is as tackiness agent.
Among the embodiment 20; In becoming the IPA of dispersion medium; Mixed with 98 to 2 is the ito powder of 25nm and the silsesquioxane spherical particle 5 that median size is 1nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle 5, with the ratio mixed SiO of 30 quality % 2Wedding agent 1 is as tackiness agent.
Among the embodiment 21; In becoming the IPA of dispersion medium; Mixed with 92 to 8 is the ito powder of 25nm and the silsesquioxane spherical particle 6 that median size is 50nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 75 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle 6, with the ratio mixed SiO of 25 quality % 2Wedding agent 1 is as tackiness agent.
Among the embodiment 22; In becoming the IPA of dispersion medium; Mixed with 85 to 15 is the ito powder of 25nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 75 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle 1, with the ratio mixed SiO of 25 quality % 2Wedding agent 2 is as tackiness agent.
[comparative example 1～5]
In the comparative example 1, in becoming the IPA of dispersion medium, be the ito powder of 25nm as electroconductive oxide powder median size, and with respect to electroconductive oxide particle 70 quality %, with the ratio mixed SiO of 30 quality % 2Wedding agent 1 is as tackiness agent.
In the comparative example 2; In becoming the IPA of dispersion medium; Mixed with 99 to 1 is the ito powder of 25nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 75 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 25 quality % 2Wedding agent 1 is as tackiness agent.
In the comparative example 3; In becoming the IPA of dispersion medium; Mixed with 63 to 37 is the ito powder of 25nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 30 quality % 2Wedding agent 1 is as tackiness agent.
In the comparative example 4; In becoming the ethanol of dispersion medium; Mixed with 50 to 50 is the ito powder of 25nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 75 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 25 quality % 2Wedding agent 1 is as tackiness agent.
In the comparative example 5; In the mixed solvent that becomes dispersion medium 1; Mixed with 80 to 20 is the ito powder of 25nm and the silsesquioxane spherical particle 4 of median size 70nm as the median size of electroconductive oxide powder; And, with respect to the solid particulate 70 quality % that add up to electroconductive oxide particle and silsesquioxane spherical particle, with the ratio mixed SiO of 30 quality % 2Wedding agent 1 is as tackiness agent.
[the specific refractory power evaluation of electrically conducting transparent film composition]
About the specific refractory power evaluation; With regard to the electrically conducting transparent film composition shown in embodiment 1～22, the comparative example 1～5; After the glass substrate formation ELD of wet type coating method (spin-coating method, mold coating method, spraying method, offset printing method) to the known optical constant; Under 160～220 ℃, burnt till 20～60 minutes, and formed the nesa coating that thickness is 0.05～0.2 μ m thus.Utilize elliptically polarized light spectral device (J.A.Woollam Japan (strain) makes M-2000) that this film is measured, the transparency electrode membrane portions is carried out data analysis, obtain optical constant.From the optical constant of analyzing, the value of 633nm is made as specific refractory power.In table 1～3 these results are shown.
[evaluation in the cladding plate type thin-film solar cells of electrically conducting transparent film composition]
As shown in Figure 1, at first, prepare to be formed with the SiO that thickness is 50nm at a side interarea 2The glass substrate of layer (not shown) is as substrate 10, at this SiO 2Being formed on the thickness that the surface has Z-Correct bump mapping Z-correct and doped F (fluorine) on the layer is the surface electrode layer (SnO of 800nm 2Film) as transparent electrode layer 13.On this transparent electrode layer 13 through utilizing laser processing method to carry out forming their distribution of mutual electrical connection when patterning is array-like.Then, utilize plasma CVD method, on transparent electrode layer 13, form photoelectric conversion layer 12.Among this embodiment, this photoelectric conversion layer 12 is through stacking gradually (uncrystalline silicon, thickness: 40nm), i type a-Si (uncrystalline silicon, thickness: 200nm) and n type μ c-Si (microcrystal silicon, thickness: the film that 40nm) constitutes and obtaining by p type a-Si:H from substrate 10 sides.Utilize laser processing method that above-mentioned photoelectric conversion layer 12 is carried out patterning.With these as carrying out during the electrically conducting transparent film composition of film forming cladding plate type thin-film solar cells unit by using shown in an embodiment estimate.
With regard to the electrically conducting transparent film composition shown in embodiment 1～22, the comparative example 1～5; The mode that is become 0.01～0.5 μ m by wet type coating method (spin-coating method, mold coating method, spraying method, offset printing method) with the thickness after burning till is to carry out after film forming solar battery cell is coated with; Drying is 5 minutes under the low temperature of 25～60 ℃ of temperature, forms nesa coating 1.At coating method shown in table 1～3.And, the thickness after burning till nesa coating 11 shown in table 1～3.At this, thickness is through (SEM, the device name: S-4300, cross-section SU-8000) is measured based on Hitachi High-Technologies system scanning electron microscope.
Then; On this nesa coating 1; The mode that becomes 0.05～2.0 μ m with the thickness after burning till by the wet type coating method is coated with conductive reflecting film by following method preparation with after the compsn; Drying is 5 minutes under the low temperature of 25～60 ℃ of temperature, then under 160～220 ℃, burns till 20～60 minutes, forms conductive reflecting film 14 thus.In addition, conductive reflecting film use preparation of compositions method is as follows.
At first, Silver Nitrate is dissolved in deionized water, the preparation metals ion aqueous solution.And, Trisodium Citrate is dissolved in deionized water, preparation concentration is the sodium citrate aqueous solution of 26 weight %.In the oxide gas air-flow of 35 ℃ of maintenances, directly add the granulous ferrous sulfate and make its dissolving to this sodium citrate aqueous solution, preparation contains the reductive agent aqueous solution of citrate ions and ferrous ion with 3: 2 mol ratio.Then; Under state with 35 ℃ of above-mentioned oxide gas air-flow maintenances; The stirrer of magnetic stirring apparatus is put into the reductive agent aqueous solution; And with the rotating speed of 100rpm rotation stirrer, when stirring the above-mentioned reductive agent aqueous solution, to drip above-mentioned aqueous metal salt and synthesizing of this reductive agent aqueous solution.At this, the amount of adding aqueous metal salt to the reductive agent aqueous solution thinks that the mode below 1/10 of the water-soluble liquid measure of reductive agent adjusts the concentration of each solution, thereby even if the aqueous metal salt of the room temperature of dripping, temperature of reaction also keeps 40 ℃.And the ratio of mixture of the above-mentioned reductive agent aqueous solution and aqueous metal salt is adjusted into, and the equivalent of the ferrous ion that adds as reductive agent becomes 3 times of metal ion equivalent.Finish aqueous metal salt after the dripping of the reductive agent aqueous solution, continue to stir 15 minutes mixed solutions again, thus at the inner metallic particles dispersion liquid that produces metallic particles and obtain to be dispersed with metallic particles of mixed solution.The pH of metallic particles dispersion liquid is 5.5, and the stoichiometry growing amount of the metallic particles in the dispersion liquid is the 5g/ litre.The dispersion liquid that obtains is placed on room temperature, precipitates the metallic particles in the dispersion liquid thus, the condensation prod of the metallic particles through the decantation precipitation separation.Add deionized water as dispersion-s to isolating metal condensation prod, carry out further replacing cleaning by methyl alcohol after the desalting treatment through ultrafiltration, the content with metal (silver) is made as 50 quality % thus.Afterwards, utilize separating centrifuge that the cf-of this separating centrifuge is adjusted and particle separation diameter surpasses the bigger silver-colored particle of 100nm, contain 71% thereby the silver nano-grain in primary particle size 10～50nm scope is adjusted in number average.That is, be adjusted in the silver nano-grain of number average primary particle size in the scope of 10～50nm and become 71% with respect to the ratio of all silver nano-grains 100%.The silver nano-grain that obtains is the protective material chemically modified of organic main chain of carbonatoms 3 by carbon skeleton.
Then, through being added to mix to the mixing solutions that comprises water, ethanol and methyl alcohol 90 mass parts, the metal nanoparticle that is obtained 10 mass parts disperse.In addition, in this dispersion liquid, add the Vinylpyrrolidone polymer of 4 quality % and the silver citrate of 1 quality % makes the ratio of metal nanoparticle become 95 quality %, use compsn thereby obtain conductive reflecting film as additive.
Then; When estimating generating efficiency as solar battery cell; On the conduction reflectance coating,, strengthen film composition, become the mode of 350nm to burn till the thickness of strengthening behind the film composition through the coating on the solar battery cell of film forming to conductive reflecting film of mold apparatus for coating as strengthening membrane; Through vacuum-drying from strengthening membrane removes solvent with coated film after; In hot-air drying stove, solar battery cell was kept 20 minutes down at 180 ℃, strengthening membrane is carried out thermofixation with coated film, obtain conductive reflecting film and use strengthening membrane.In addition, strengthening membrane use preparation of compositions method is as follows.
At first; The median size as the electroconductive oxide particulate of mixing 8 quality % be the ITO particle of 25nm, 2 quality % the titanium coupling agent as coupling agent, 90 quality % with dialkyl group pyrophosphorous acid ester group as the ethanol of dispersion medium and the mixed solution of butanols (mass ratio is 98: 2), at room temperature the rotating speed with 800rpm stirred 1 hour.Then, 60g puts into the 100cc vial with this mixture, and (clear and Royal Dutch Shell system: MICROHYCA) 100g with coating whisking appliance dispersion 6 hours, prepares ITO particulate dispersion liquid thus for the zirconium oxide bead of 0.3mm to utilize diameter.At this, the titanium coupling agent with dialkyl group pyrophosphorous acid ester group is represented by the chemical formula of enumerating in the above-described embodiment (7).And, SiO 2Wedding agent and above-mentioned SiO 2Wedding agent 1 is adjusted identically.Then, ITO particulate dispersion liquid 4 quality % with after ethanol 86 quality % as dispersion medium mix, are further mixed SiO with 10 quality % 2Wedding agent 1; Obtain to strengthen after the basal liquid of film composition; Mix this basal liquid of 95 quality % and the aerosil dispersion liquid of 5 quality % as additive; Through ultrasonic vibrator dispersing and mixing 10 minutes at room temperature, mixture is fused in integral body, preparation is as the masking liquid of strengthening film composition.
About being formed up to the solar battery cell of conductive reflecting film, utilize laser processing method that photoelectric conversion layer 12 and film forming nesa coating 11, conductive reflecting film 14 and conductive reflecting film are on it implemented patterning with strengthening membrane with strengthening membrane.
Evaluation as solar battery cell; On the substrate that utilizes after laser processing method is implemented the processing of patterning, carry out the lead distribution; And affirmation IV rational curve; About the output characteristic of this moment and as the value of short-circuit current (Jsc), carry out utilizing the photoelectric conversion layer that obtains by the method for manufacture identical and being made as 100 o'clock relative output evaluation by the cladding plate type solar battery cell that sputtering method forms nesa coating, conductive reflecting film, strengthening membrane with embodiment.These results shown in table 1～3.
At this, the cladding plate type solar cell module unit that forms by sputtering method refers to that as shown in Figure 1 at first the preparation is formed with the SiO that thickness is 50nm at a side interarea 2The glass substrate of layer (not shown) is as substrate 10, at this SiO 2Being formed on the thickness that the surface has Z-Correct bump mapping Z-correct and doped F (fluorine) on the layer is the surface electrode layer (SnO of 800nm 2Film) 13.On this transparent electrode layer 13 through utilizing laser processing method to carry out forming their distribution of mutual electrical connection when patterning is array-like.Then, utilize plasma CVD method, on transparent electrode layer 13, form photoelectric conversion layer 12.Among this embodiment, this photoelectric conversion layer 12 is through stacking gradually (uncrystalline silicon, thickness: 40nm), i type a-Si (uncrystalline silicon, thickness: 200nm) and n type μ c-Si (microcrystal silicon, thickness: the film that 40nm) constitutes and obtaining by p type a-Si:H from substrate 10 sides.Utilize laser processing method that above-mentioned photoelectric conversion layer 12 is carried out after the patterning; Utilize magnetron straight-line type sputter equipment, on photoelectric conversion layer 12, form nesa coating (the ZnO layer) 11 of thickness 80nm and the conductive reflecting film (silver electrode layer) 14 of thickness 200nm successively.
If in nesa coating, contain the trickle silsesquioxane particle that median size is 1～50nm, then might reduce adhesivity, therefore carry out the adhesivity evaluation.About the adhesivity evaluation; Utilization is based on the method for adhesive tape test (JIS K-5600); To the electrically conducting transparent film composition shown in embodiment 1～22, the comparative example 1～5, form after nesa coating 11 and the conductive reflecting film 14 carrying out film forming solar battery cell, under 160～220 ℃, burnt till 20～60 minutes; Forming on the solar battery cell on the basis of composite package thus; This film is adhered to adhesive tape and when peeling, peel off or the degree of roll-up state, estimate with excellent, qualified, defective these 3 stages according to the film that forms.Be not stained with that film forms thing and the situation of having only adhesive tape to come off is made as excellent in the adhesive tape side; Adhesive tape comes off and becomes situation that state that the photoelectric conversion layer 12 of base material exposes mixes and is made as qualifiedly, and the whole situation about showing out that become photoelectric conversion layer 12 surfaces of base material because of peeling of adhesive tape are made as defective.In table 1～3 these results are shown.
[table 1]
Figure BDA0000104401480000271
[table 2]
Figure BDA0000104401480000281
[table 3]
Figure BDA0000104401480000291
[table 4]
Figure BDA0000104401480000301
Can know that like table 1～3 in all embodiment 1～22, specific refractory power is lower, good adhesion, generating efficiency is obviously up to 111～125% relatively, and short-circuit current is also up to 103～106% relatively.Especially the relative generating efficiency of embodiment 22 and relative short-circuit current are the highest, and adhesivity is also good.With respect to this, do not comprise silsesquioxane particulate comparative example 1, only comprise in the silsesquioxane particulate comparative example 2 of 1 mass parts, specific refractory power is higher, relatively generating efficiency, short-circuit current density is roughly 100% relatively.The silsesquioxane particulate comparative example 3 that comprises 37 mass parts with comprise in the comparative example 4 of 50 mass parts, relatively generating efficiency, short-circuit current density is all lower relatively.In the bigger comparative example 5 of silsesquioxane particulate median size, poor adhesion, relatively generating efficiency, short-circuit current density is all lower relatively.
< embodiment 23 >
Among the embodiment 23; At first; In becoming the IPA of dispersion medium, the mixed with 98 to 2 is the ito powder of 25nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder, and; With respect to adding up to electroconductive oxide particle and silsesquioxane particulate solid particulate 70 quality %, with the ratio mixed SiO of 30 quality % 2Wedding agent 1 is as tackiness agent.At this, dispersion agent (IPA) uses with the ratio of 72.3 quality % with respect to the electrically conducting transparent film composition.
< embodiment 24 >
Among the embodiment 24; At first; In becoming the ethanol of dispersion medium, the mixed with 92 to 8 is the ito powder of 30nm and the silsesquioxane spherical particle 1 that median size is 10nm as the median size of electroconductive oxide powder, and; With respect to adding up to electroconductive oxide particle and silsesquioxane particulate solid particulate 75 quality %, with the ratio mixed SiO of 25 quality % 2Wedding agent 7 is as tackiness agent.At this, dispersion agent (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, in becoming the IPA of dispersion medium, the ito powder that mixes median size and be 25nm is as the electroconductive oxide powder, and with respect to 70 quality % electroconductive oxide particles, with the ratio mixed SiO of 30 quality % 2Wedding agent 1 is as tackiness agent.At this, dispersion medium (IPA) uses with the ratio of 72.3 quality % with respect to the electrically conducting transparent film composition.
[evaluation in the base plate type thin-film solar cells of electrically conducting transparent film composition]
As shown in Figure 2, prepare vertical 100mm, laterally the film substrate of the polyimide resin system of 100mm, thickness 50 μ m forms the through hole 25 of diameters 100 μ m as base material 20 at this film substrate 20.At first through the sputtering method collector layer 26 (thickness: 200nm) that formation is made up of Ag below the film substrate.Also fill the energized components that Ag be made up of at through hole 25 this moment.Then; Through wet type coating method (screen painting method) on base material 20 the coating conductive reflecting film with compsn after; The film substrate is put into recirculation furnace; Keep burning till conductive reflecting film 24 in 30 minutes with 200 ℃ temperature, make and carry out film forming base plate type thin-film solar cells unit.In addition, the thickness of the conductive reflecting film 24 after burning till is 200nm.
Then; On conductive reflecting film 24, with spin-coating method to after the electrically conducting transparent film composition that carries out film forming base plate type thin-film solar cells unit coating embodiment 23 and 24, comparative example 6, with 50 ℃ of temperature dryings 5 minutes; Then; Burnt till 30 minutes with 180 ℃, thus, on solar battery cell, form nesa coating 21.Nesa coating 21 burn till the back thickness be 0.1 μ m in embodiment 23, be 0.13 μ m in embodiment 24, be 0.1 μ m in comparative example 6.
On formed nesa coating 21 and conductive reflecting film 24, be array-like and form the distribution that can be electrically connected them each other through utilizing laser processing method to carry out patterning.Then, utilize plasma CVD method, on nesa coating 21, form photoelectric conversion layer 22.This photoelectric conversion layer 22 is through stacking gradually (microcrystal silicon, thickness: 40nm), i type a-Si (uncrystalline silicon, thickness: 200nm) and p type a-Si:H (uncrystalline silicon, thickness: the film that 40nm) constitutes and obtaining by n type μ c-Si from base material 20 sides.Utilize laser processing method that above-mentioned photoelectric conversion layer 22 is carried out patterning.
In addition, on photoelectric conversion layer 22, be formed on the surface electrode layer (SnO that the surface has the thickness 800nm of Z-Correct bump mapping Z-correct and doped F (fluorine) 2Film) as transparent electrode layer 23.On this transparent electrode layer 23, be array-like and form the distribution that can be electrically connected them each other, and obtain the base plate type thin-film solar cells through utilizing laser processing method to carry out patterning.
Relative generating efficiency and the short-circuit current (Jsc) of base plate type thin-film solar cells that makes acquisition is identical with cladding plate type solar cell and estimate.At this, will be made as 100 by the base plate type thin-film solar cells unit that sputtering method is made base material 20, conductive reflecting film 24, nesa coating 21, photoelectric conversion layer 22 and transparent electrode layer 23, export evaluation relatively.
Among the embodiment 23, generating efficiency is 112% relatively, short-circuit current density is 103% relatively, all is improved.Among the embodiment 24, generating efficiency is 114% relatively, short-circuit current density is 104% relatively, all is improved.The opposing party is relative generating efficiency 98%, short-circuit current density 101% relatively in the comparative example 6, is lower than the result of embodiment 23 and 24.
As more than, electrically conducting transparent film composition of the present invention can be coated with on photoelectric conversion layer, burn till by enough wet type coating methods, the specific refractory power of the nesa coating that can be obtained according to the content adjustment of silsesquioxane.Therefore, can simply obtain to improve the nesa coating of the generating efficiency of thin-film solar cells.

Claims (11)

1. the electrically conducting transparent film composition of a used for solar batteries is characterized in that,
Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the tackiness agent of 1～50nm, adds up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprises the silsesquioxane particle of 2～35 mass parts.
2. electrically conducting transparent film composition that cladding plate type thin-film solar cells is used; It is characterized in that; Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the tackiness agent of 1～50nm; Add up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprise the silsesquioxane particle of 2～35 mass parts.
3. the electrically conducting transparent film composition that cladding plate type thin-film solar cells as claimed in claim 2 is used, wherein, 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 cladding plate type thin-film solar cells as claimed in claim 3 is used; Wherein, 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 acetic ester.
5. a used for solar batteries nesa coating is characterized in that,
Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the solidified tackiness agent of 1～50nm, adds up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprises the silsesquioxane particle of 2～35 mass parts.
6. the nesa coating that cladding plate type thin-film solar cells is used is characterized in that,
Comprise the electroconductive oxide particle, median size is silsesquioxane particle and the solidified tackiness agent of 1～50nm, adds up to 100 mass parts with respect to electroconductive oxide particle and silsesquioxane particulate, comprises the silsesquioxane particle of 2～35 mass parts.
7. the nesa coating that cladding plate type thin-film solar cells as claimed in claim 6 is used, wherein,
Tackiness agent is polymer type adhesive and/or non-polymeric tackiness agent.
8. the nesa coating that cladding plate type thin-film solar cells as claimed in claim 7 is used, wherein,
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 acetic ester.
9. a cladding plate type thin-film solar cells comprises the nesa coating that each described cladding plate type thin-film solar cells is used in the claim 6～8.
10. the method for manufacture of a nesa coating is the method for manufacture of the nesa coating of the cladding plate type thin-film solar cells that possesses base material, transparent electrode layer, photoelectric conversion layer and nesa coating successively, wherein,
On photoelectric conversion layer, be coated with each described electrically conducting transparent film composition in the claim 2～4 through the wet type coating method, form after electrically conducting transparent films, burn till and have the base material that electrically conducting transparent is filmed, form nesa coating.
11. the method for manufacture of nesa coating as claimed in claim 10, wherein,
The wet type coating method is 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.
CN2011103397372A 2010-11-01 2011-11-01 Composition for transparent conductive film, for solar cell, and transparent conductive film Pending CN102464941A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2010-245179 2010-11-01
JP2010245179 2010-11-01
JP2011-196299 2011-09-08
JP2011196299A JP2012114408A (en) 2010-11-01 2011-09-08 Composition for transparent conductive film of solar cell and transparent conductive film

Publications (1)

Publication Number Publication Date
CN102464941A true CN102464941A (en) 2012-05-23

Family

ID=46069080

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011103397372A Pending CN102464941A (en) 2010-11-01 2011-11-01 Composition for transparent conductive film, for solar cell, and transparent conductive film

Country Status (1)

Country Link
CN (1) CN102464941A (en)

Similar Documents

Publication Publication Date Title
TWI509048B (en) Composition for antireflection film of solar battery, antireflection film of solar battery, method for manufacturing antireflection film of solar battery, and solar battery
CN102443287A (en) Transparent conductive film composition for solar cell and transparent conductive film thereof
CN101803037B (en) Composite membrane for super straight solar cell, process for producing the composite membrane for super straight solar cell, composite membrane for substraight solar cell, and process for producing the composite membrane for substraight solar cell
CN102649330B (en) Joint layered product and conjugant
CN105513670A (en) Transparent electroconductive film for solar cell, composition for transparent electroconductive film and multi-junction solar cell
CN102201274A (en) Conductive film forming composition, solar cell composite film and forming method thereof
CN102646726B (en) Transparency carrier and its manufacture method with composite membrane used for solar batteries
CN102738254A (en) Composition of transparent conductive film for thin-film solar battery and transparent conductive film
CN102675947A (en) Composition for transparent conductive film used for solar cell, and transparent conductive film
CN102702803A (en) Composition for transparent conductive film of solar cell and transparent conductive film
CN102637749B (en) Composite membrane used for solar batteries and manufacture method thereof
CN102464941A (en) Composition for transparent conductive film, for solar cell, and transparent conductive film
CN102732150A (en) Composition for transparent conducting film of solar cell and transparent conducting film
CN102443288A (en) Transparent conductive film composition for solar cell and transparent conductive film thereof
CN102443289A (en) Transparent conductive film composition for solar cell and transparent conductive film thereof
CN102443290A (en) Transparent conductive film composition for solar cell and transparent conductive film thereof
CN102610667A (en) Transparent conductive film composition for solar cell and transparent conductive film
CN102097513A (en) Conductive reflective film and producing method thereof
JP2012094830A (en) Transparent conductive film composition for solar battery and transparent conductive film
CN102263158A (en) Preparation method of composite film used for solar cell and composite film prepared by same
CN102544126B (en) Thin-film solar cells back electrode strap and thin-film solar cells manufacture method
CN103296100A (en) Composite film for solar cell and manufacture method thereof, and solar cell
JP2012094828A (en) Transparent conductive film composition for solar battery and transparent conductive film
JP2012114408A (en) Composition for transparent conductive film of solar cell and transparent conductive film
CN103258864A (en) Conductive reflective film and method of manufacturing same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20120523