CN102544126A

CN102544126A - Back electrode strap for thin film solar cell and producing method of thin film solar cell

Info

Publication number: CN102544126A
Application number: CN2011104169320A
Authority: CN
Inventors: 米泽岳洋; 马渡芙弓; 山崎和彦
Original assignee: Mitsubishi Materials Corp
Current assignee: Mitsubishi Materials Corp
Priority date: 2010-12-14
Filing date: 2011-12-14
Publication date: 2012-07-04
Anticipated expiration: 2031-12-14
Also published as: CN102544126B

Abstract

The invention relates to a back electrode strap for a thin film solar cell and a producing method of a thin film solar cell. The invention aims to simplify and improve efficiency of the processing of the back electrode strap for a thin film solar cell, and further save a part of laser drawing process used in the production of common thin film solar cells, and speed up the producing process of thin film solar cells. Transparent electrode thin films and reflective electrode thin films are laminated, and the transparent electrode thin films have adhesiveness. Preferably the back electrode strap for the thin film solar cell of a barrier layer is further laminated at the side of the reflective electrode thin film.

Description

Thin-film solar cells is with backplate band and thin-film solar cells manufacturing approach

Technical field

The present invention relates to a kind of thin-film solar cells with the backplate band and use the manufacturing approach of the thin-film solar cells of this backplate band.More detailed, relate to the enough easy manufacturing approaches of a kind of ability and make thin-film solar cells, and the thin-film solar cells that can effectively utilize the sunlight of incident to improve the generating efficiency of thin-film solar cells is used the backplate band.

Background technology

At present, from the position of environmental protection, advancing the research and development and the practicability of green energy resource, from inexhaustible as the sunlight of the energy and be aspect such as nuisanceless, solar cell gets most of the attention.In the past, solar cell until data monocrystalline silicon or polysilicon bulk solar cell, but because the manufacturing cost of block solar cell is higher and productivity ratio is also lower, 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 amorphous 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 large tracts of landization 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) type structure and substrate (サ Block ストレ one ト) type structure; Cladding plate type structure is owing to from light-transmitting substrate side incident sunlight, therefore take the structure with the order formation of substrate-transparency electrode-photoelectric conversion layer-backplate usually.

One example of the sectional view of thin-film solar cells shown in Fig. 1.In addition, Fig. 1 is the example of cladding plate type.Among Fig. 1, on substrate 40, be formed with amorphous Si layer 61 and crystallite Si layer 62, nesa coating 10, conductive reflecting film 20 and the strengthening membrane 30 of nesa coating 50, formation photoelectric conversion layer.The position of laser scribing when the P1 of Fig. 1, P2 and P3 represent to make.Among Fig. 1, than P3 more the portion of keeping left form 1 thin-film solar cells, electrically be connected in series through nesa coating 50 and thin-film solar cells across the right side of P3 adjacency.At this, in thin-film solar cells,, so be called backplate in the lump because nesa coating 10 is formed at the opposing face of the input side of sunlight with conductive reflecting film 20 when photoelectric conversion layer is observed.

Then, in the past the manufacturing approach of general thin-film solar cells shown in Fig. 2.In addition, Fig. 2 is the example of cladding plate type.Among Fig. 2, (A) at first prepare base material 40.(B) become embrane method on base material 40, to form nesa coating 50 with the sputter equal vacuum.(C) carry out laser scribing P1 processing (dotted line is represented laser irradiating position) from above, nesa coating 50 is carried out pattern form.(D) become embrane method on the nesa coating 50 that pattern forms, to form photoelectric conversion layer 60 (corresponding) with the sputter equal vacuum with amorphous Si layer 61 and the crystallite Si layer 62 of Fig. 1.(E) carry out laser scribing P2 processing (dotted line is represented laser irradiating position) from below, photoelectric conversion layer 60 is carried out pattern form.(F) become embrane method on the photoelectric conversion layer 60 that pattern forms, to form nesa coating 10, conductive reflecting film 20 and strengthening membrane 30 with the sputter equal vacuum.(G) carry out laser scribing P3 processing (dotted line is represented laser irradiating position) from below, nesa coating 10, conductive reflecting film 20 and strengthening membrane 30 are carried out pattern form.As more than, the worker ordinal number of the manufacturing approach of general thin-film solar cells is more, thereby requires the shorteningization of worker ordinal number.

As above-mentioned; In the manufacturing approach of general thin-film solar cells; Become embrane method to form nesa coating 10,50 or conductive reflecting film 20 etc. with the sputter equal vacuum in the past, but generally importing, needing when keeping, moving large-scale vacuum film formation apparatus significant cost.In order to improve this point, disclose and used electrically conducting transparent film composition and conductive reflecting film with composition and with as more the wet type coating formation nesa coating of inexpensive method of manufacturing and the technology (patent documentation 1) of conductive reflecting film.Yet; Even according to above-mentioned wet type coating; Also can be directly on photoelectric conversion layer respectively to the electrically conducting transparent film composition with conductive reflecting film is coated with composition or curing etc.; Therefore cause the worker ordinal number of thin-film solar cells to become many, thereby hope to make worker ordinal number shorteningization, simpleization, efficient activity.Therefore in the above-mentioned wet type coating, base material in layer is coated with, backplate band of the present invention relatively therewith can be made by Role to Role continuously, can make that operation is further oversimplified, high speed.And in above-mentioned wet type coating, heat treatment step is more, might damage photoelectric conversion layer, but the backplate of the application of the invention is brought reduction heat treatment number of times, can make the further low temperatureization of the heat that puts on photoelectric conversion layer.

Patent documentation 1: the open 2009-88489 communique of Japan Patent

Summary of the invention

Problem of the present invention is to seek simpleization and the efficient activity of manufacturing process of the backplate of thin-film solar cells; And then be omitted in the part laser scribing P3 of (Fig. 2 (G) processing) of the laser scribing operation of using in the manufacturing of general thin-film solar cells, and can realize the high speed of the manufacturing process of thin-film solar cells.

The present invention relates to a kind ofly solve manufacturing approach and the thin-film solar cells of the thin-film solar cells of above-mentioned problem with backplate band, thin-film solar cells through the scheme shown in following.

[1] a kind of thin-film solar cells is used the backplate band, and wherein, range upon range of have transparent electrode thin film and a reflecting electrode film, and transparent electrode thin film has caking property.

[2] use the backplate band like above-mentioned [1] described thin-film solar cells, wherein, barrier film arranged in that the reflecting electrode film side is further range upon range of.

[3] use the backplate band like above-mentioned [1] or [2] described thin-film solar cells, wherein, carrier band arranged in that the opposing face of transparent electrode thin film is further range upon range of.

[4] use the backplate band like above-mentioned [3] described thin-film solar cells; It is that the thin-film solar cells that comprises base material, transparent electrode layer, photoelectric conversion layer, transparent electrode thin film and reflecting electrode film is used the backplate band, forms transparent electrode thin film and reflecting electrode film at itself and the opposed zone of said photoelectric conversion layer.

[5] a kind of manufacturing approach of thin-film solar cells wherein, comprises successively: (A) preparation is formed with the operation of the bonded thing of base material, transparent electrode layer and photoelectric conversion layer; (B) in the photoelectric conversion layer of said bonded thing is fitted above-mentioned [1]～[4] each described thin-film solar cells with the operation of the transparent electrode thin film of backplate band.

[6] like the manufacturing approach of above-mentioned [5] described thin-film solar cells, wherein, after (B) operation, make transparent electrode thin film and reflecting electrode film hardening again.

[7] a kind of thin-film solar cells, it comprises that each described thin-film solar cells is used the backplate band in above-mentioned [1]～[4].

Among the present invention [1], transparent electrode thin film and reflecting electrode film can be bonded on the photoelectric conversion layer of thin-film solar cells, can seek simpleization and the efficient activity of the manufacturing process of backplate, solidify after the bonding and become backplate.And; Thin-film solar cells can be formed at smooth carrier band etc. by enough wet type coatings with the backplate band; Compare when directly being coated with into the opto-electronic conversion stratiform with the wet type coating; Can form thin-film solar cells at a high speed and use the backplate band, and can seek the high speed of the manufacturing process of thin-film solar cells.

According to the present invention [4]; The part (the laser scribing P3 processing of Fig. 2 (G)) of the laser scribing operation of using in the manufacturing of thin-film solar cells can be omitted in reliably, and further simpleization and the efficient activity of the manufacturing process of thin-film solar cells can be sought.

According to the present invention [5],, therefore can make simpleization of manufacturing process and the efficient activity of thin-film solar cells owing to can make the backplate of thin-film solar cells easily.

Description of drawings

Fig. 1 is an example of the sectional view of thin-film solar cells.

Fig. 2 is the figure that representes the manufacturing approach of general in the past thin-film solar cells.

Fig. 3 is the figure of example that forms the method for transparent electrode thin film etc. on the carrier band that is illustrated in the opposed zone of photoelectric conversion layer.

Fig. 4 be the expression thin-film solar cells manufacturing approach one the example figure.

Fig. 5 be the expression thin-film solar cells manufacturing approach other one the example figure.

Symbol description

1,1a-transparent electrode thin film, 2,2a-reflecting electrode film, 3, the 3a-barrier film, 4-base material, 5-transparent electrode layer; The 6-photoelectric conversion layer, the bonded thing of 7-, 8, the 8a-carrier band, 9,9a-backplate band, 10-nesa coating; The 20-conductive reflecting film, 30-strengthening membrane, 40-base material, 50-nesa coating, 60-photoelectric conversion layer; 61-amorphous Si layer, 62-crystallite Si layer, the bonded thing of 70-, P1, P2-laser scribing position, P3-laser scribing position or slot part; 100-transparent electrode thin film etc., 101,102,103-transparent electrode thin film etc., 110, the 111-carrier thin film, the 120-slot part.

Embodiment

Below, according to execution mode the present invention is specified.In addition, short ofly illustrate especially, and except the intrinsic situation of numerical value, % is quality %.

Thin-film solar cells of the present invention is characterised in that with the backplate band, and range upon range of have transparent electrode thin film and a reflecting electrode film, and transparent electrode thin film has caking property.Thin-film solar cells of the present invention can be used in various thin-film solar cells with the backplate band, but is particularly suited for cladding plate type thin-film solar cells.

[transparent electrode thin film]

Transparent electrode thin film has caking property, has (1) transparent electrode thin film itself to have close-burning situation and (2) are formed with tack coat on the surface of transparent electrode thin film situation.

For transparent electrode thin film itself or form the binding agent of tack coat, the state when forming transparent electrode thin film or tack coat (below be called initial condition) be required to be liquid or with its approximate flow-like, its pattern mainly can be enumerated following 4.

< 1>response class

Initial condition is liquid for what be the main body with the composition before the generation chemical reaction, is divided into through monomer beginning to react the chemical reaction type of also polymerization reaction take place, moisture absorption, condensation reaction etc. and the thermohardening type that solidifies, bonds through heating with the external factors such as perhaps hot or airborne moisture of mixing of effect promoter.Can enumerate crylic acid resin, polyurethanes, cellulose family, olefines, epoxy resin, cyanoacrylate, silicone, polyimide, polybenzimidazoles class and polyvinyl butyral resin class.

< 2>solution class

Initial condition is that polymeric solid compositions such as synthetic resin or rubber are dissolved in liquid in water or the solvents such as alcohol or organic solvent, bonds through the residual solute in solvent gasification back is solidified.Kind according to solvent is divided into solvent based or water class etc.Can enumerate polyesters, polystyrene type, cellulose family, olefines, polyvinyl chloride-base, rubber-like and plexiglass class.

< 3>aqueous dispersion class

Initial condition is the aqueous suspension of polymerization macromolecule solid constituent in water.The macromolecule that is colloidal state is by emulsification and can state soluble in water, and solidifies through aqueous vaporization and solute and to bond.Can enumerate crylic acid resin, polyurethanes, polyvinyl alcohol, polyvinyl acetate class, epoxy resin and rubber-like.

< 4>solid

Initial condition is powder or pellet or film or solid such as netted, heats the state that is thawing through the solid binder to the thermoplastic resin composition and gives being coated with on the basis of flowability (heat is melted) and cooling off and be cured, bond.Can enumerate polyurethanes, polyamide-based, polyvinyl acetate class and olefines.

At this, have close-burning transparent electrode thin film following situation is arranged, promptly (A) is bonded in situation (above-mentioned < 1 >, < 2 >, < 3>on the substrate through the adherence of transparent electrode thin film itself.Below be called (A) type) and (B) non-adhesiveness of transparent electrode thin film own, but the right and wrong adhesive waits the close-burning situation (above-mentioned < 4>that manifests through heating after fitting.Below be called (B) type).

" (1) transparent electrode thin film itself has close-burning situation "

Can form transparent electrode thin film with composition from transparent electrode thin film, can enumerate the composition that comprises electroconductive oxide particle and adhesive with composition as transparent electrode thin film.

Indium tin oxide), ATO (Antimony doped 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 comprises B, Al, Co, Fe, In, Ga and Ti etc. be preferably ITO (Indium Tin Oxide: as the electroconductive oxide particle; Aluminium-doped zinc oxide), IZO (Indium doped Zinc Oxide: the indium doping zinc-oxide), GZO (Garium dopedZinc Oxide: Ga-doped zinc oxide) wherein, ITO, ATO, AZO (Aluminum doped Zinc Oxide: more preferably.And the average grain diameter of electroconductive oxide particulate is in order in decentralized medium, to keep stability, preferably in the scope of 10～100nm, wherein more preferably in the scope of 20～60nm.At this, the average grain diameter utilization is based on measuring according to the BET method of the specific area measuring of QUANTACHROMEAUTOSORB-1 or according to the dynamic light scattering method that the hole field makes the LB-550 of manufacturing.Under the situation that is not having special record, utilize based on BET method and measure according to the specific area measuring of QUANTACHROME AUTOSORB-1.

Preferred adhesive is polymer type adhesive or arbitrary side in the non-polymeric adhesive or both sides' the composition that comprises through being heating and curing.More preferably do not comprise to photoelectric conversion layer bring bad influence moisture or acid, make the alkali metal that the characteristic of above-mentioned electroconductive oxide particle descends or the adhesive of alkaline-earth metal and ion thereof.

As polymer type adhesive, can enumerate crylic acid resin, polymethyl methacrylate (PMMA) type, polycarbonate-based, polyesters, alkyd resins class, polyurethanes, acroleic acid polyurethane class, polystyrene type, polyacetals, polyamide-based, polyvinyl alcohol (PVA), polyvinyl acetate class, cellulose family, olefines, ethylene-vinyl acetate copolymer (EVA) type and type siloxane polymer etc.Wherein, Even it is because, so preferred from operating aspect as the polyurethanes of the typical example of solid binder, polyamide-based, polyvinyl acetate class, olefines or as can after than disposable full solidification tack coats such as the polyvinyl alcohol of the thermoplastic resin of lower temperature injected moulding, polystyrene, ethylene-vinyl acetate copolymer, polymethyl methacrylates, also can boning through heating.

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 adhesive.As the non-polymeric adhesive, can enumerate metallic soap, metal complex, metal alkoxide, silicon halide alkanes, 2-alkoxyethanol, beta-diketon and alkyl acetate etc.And; The metal that is comprised in metallic soap, metal complex or the metal alkoxide is preferably aluminium, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony; The alkoxide of silicon, aluminium (for example, tetraethoxysilane, tetramethoxy-silicane, aluminium ethylate, aluminium isopropoxide) more preferably.These polymer type adhesives, non-polymeric adhesive solidify through heating, and can form the transparency electrode of mist degree and specific insulation lower under the low temperature thus.In addition, metal alkoxide can be hydrolysate or its dehydrate.

Transparent electrode thin film comprises the electroconductive oxide particle of 98～50 mass parts with respect to transparent electrode thin film with the solid constituent in the composition (electroconductive oxide particle and adhesive etc.) 100 mass parts with composition, preferably comprises 90～70 mass parts.This be because, if surpass higher limit, then adhesiveness descends, if less than lower limit, then conductivity descends.

Preferred these adhesives to contain proportional be 2～50 mass parts with respect to transparent electrode thin film with the solid constituent in the composition (electroconductive oxide particle and adhesive etc.) 100 mass parts, more preferably 10～30 mass parts.And when using metal alkoxide as adhesive and when using nitric acid as catalyst, from the viewpoint of the remaining quantity of the curing rate of adhesive, nitric acid, preferably the metal alkoxide with respect to 100 mass parts is the nitric acid of 0.03～3 mass parts.In addition, then slack-off if less as the polymerization speed of the hydrolysis body of the metal alkoxide of adhesive as the amount of the nitric acid of catalyst, 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 degree of polymerization when solidifying if consider; The form that then is the stress additional conductive property particle contact each other that applies when shrinking; Therefore consider that from the viewpoint that can become the photoelectric conversion layer worsening reason owing to excessive adding preferably the metal alkoxide with respect to 100 mass parts is the water of 0.1～1.0 mass parts.

Transparent electrode thin film preferably adds coupling agent according to employed other compositions with composition.This is in order to improve and the associativity of electrically conductive microparticle and adhesive and the transparent electrode thin film that is formed with composition by this transparent electrode thin film and be laminated in photoelectric conversion layer or the adhesiveness between the reflecting electrode film on the base material.Can enumerate silane coupler, 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 transparent electrode thin film with solid constituent shared in the composition (electroconductive oxide particle, adhesive and silane coupler etc.) 100 mass parts, more preferably 0.5～2 mass parts.

For film forming well, the preferably clear electrode film comprises decentralized medium with composition.As decentralized medium, can enumerate: water; Alcohols such as methyl alcohol, ethanol, isopropyl alcohol, butanols; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, isophorone; Hydro carbons such as toluene, xylenes, hexane, cyclohexane; N, dinethylformamide, N, amide-types such as N-dimethylacetylamide; Glycols such as sulfoxide classes such as dimethyl sulfoxide (DMSO) or ethylene glycol; And gylcol ether such as ethyl cellosolve etc.In order to obtain good film forming, the content of preferred decentralized medium is 80～99 mass parts with respect to the transparent electrode thin film use composition of 100 mass parts.

In addition, according to employed composition, preferably add low-resistance agent (low opposingization drug) or water-soluble cellulose derivative etc.As the low-resistance agent, be preferably selected from the group of the inorganic acid salt that comprises cobalt, iron, indium, nickel, lead, tin, titanium and zinc and acylate more than a kind or 2 kinds.For example, can enumerate the mixture etc. of mixture, acetyl group acetic acid titanium and cobalt octoate of mixture, indium nitrate and lead acetate of mixture, zinc naphthenate, tin octoate and the antimony chloride of nickel acetate and iron chloride.The content of preferred these low-resistance agent is 0.2～15 mass parts with respect to the electroconductive oxide powder of 100 mass parts.Water-soluble cellulose derivative is the non-ionized surfactant; Even but add the amount that is less than other surfactants, 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 hydroxypropyl cellulose, hydroxypropyl methylcellulose etc.The addition of preferred water-soluble cellulose derivative is 0.2～5 mass parts with respect to the electroconductive oxide particle of 100 mass parts.

Transparent electrode thin film with composition in the scope of not damaging the object of the invention and can cooperate filler, stress moderator and other additives etc. as required.

Transparent electrode thin film can be through mixing desirable composition according to common method and by coating blender, ball mill, puddle mixer, centrifugal mill, triple-roller mill etc. with composition, and dispersed electro-conductive property oxide particle, spherical colloid silica dioxide granule wait and make.Certainly, also can make through common stirring operation.In addition, can also use the transparent conductivity adhesive as transparent electrode thin film with composition.

Then, on substrate, be coated with transparent electrode thin film with the wet type coating and use composition, and make its drying, curing etc., have close-burning transparent electrode thin film thereby can make.

In the substrate that above-mentioned base material can use glass, pottery, be made up of metal or macromolecular material any perhaps is selected from the duplexer more than 2 kinds in these groups.Although can not bring influence, more preferably have higher raw material such as flexibility and weatherability, moisture-proof, thermal endurance according to the workability when the bonded thing bonding etc. to the characteristic of thin-film solar cells through these base materials.

In addition; Above-mentioned wet type coating is preferably any in spraying process, point gum machine rubbing method (デイスペ Application サ one コ one テイ Application グ method), spin-coating method, knife coating, slot coated method, ink-jet application method, screen painting method, hectographic printing method or the mold rubbing method; But be not limited to this, can utilize all methods.

Spraying process is the method that makes transparent electrode thin film be vaporific with composition and coat on the substrate or dispersion itself is pressurizeed and coated on the substrate with vaporific through compressed air; The point gum machine rubbing method is the piston that for example transparent electrode thin film is injected syringe with composition and push this syringe, makes dispersion spue and coat the method on the substrate from the minute nozzle of syringe front end thus.Spin-coating method is that the transparent electrode thin film that on the substrate of rotation, drips is used method for compositions with composition and through its centrifugal force to this transparent electrode thin film that drips of substrate periphery expansion; Knife coating is the substrate that separates predetermined gap with the front end of scraper to be set movably to horizontal direction; Use composition to supplying with transparent electrode thin film on more near the substrate of upstream side, move horizontally the method for substrate towards the downstream than this scraper.The slot coated method is to make transparent electrode thin film flow out and coat the method on the substrate from narrow slit with composition, and the ink-jet application method is to be filled in the print cartridge of commercially available ink-jet printer with composition transparent electrode thin film and the method for on substrate, 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 substrate transfer transparent electrode thin film above that.The hectographic printing method is that the transparent electrode thin film that invests on the version directly is attached on the substrate with composition, but from the disposable film that is transferred to of version, and transfers to again from film and to utilize the printing process of transparent electrode thin film with the water proofing property of composition on the substrate.The mold rubbing method is to distribute the transparent electrode thin film be supplied in the mould to be extruded on the film with composition and through slit through manifold, the surface of the substrate of advancing is carried out the method for coating.The mold rubbing method has slotted coating method or slidingtype coating method, curtain formula coating method.

At last, carry out drying with the substrate of filming of composition or burn till having transparent electrode thin film in atmosphere or in the inactive gas atmosphere such as nitrogen or argon gas.Under the situation of (A) type; This drying or burn till that to make transparent electrode thin film be exercisable intensity; And residue in transparent electrode thin film in adherence and get final product under with the condition in the composition, for example for transparent electrode thin film is got final product with the degree of the drying of the solvent in the composition.And, under the situation of (B) type, but also intensive drying.At this, dry or burn till after transparent electrode thin film be preferably the scope of 0.03～0.5 μ m, more preferably 0.05～0.1 μ m with the thickness of composition.This be because dry or burn till after transparent electrode thin film with the thickness of composition during less than 0.03 μ m, the uniformity of film descends, and adhesiveness descends, if surpass 0.5 μ m, the then transparency and conductivity decline.At this, if the transparent electrode thin film after above-mentioned drying or the curing has flexibility, then preferable operability when photoelectric conversion layer adhered film used for solar batteries backplate band is therefore preferred.

" (2) form the situation of tack coat on the surface of transparent electrode thin film "

Transparent electrode thin film be except using drying or solidifying the film of above-mentioned transparent electrode thin film with composition, can also use the film that becomes ITO that embrane method or spray heating decomposition form, AZO, GZO, ATO etc. through sputter, MBE, PLD, vapor deposition equal vacuum.The thickness of transparent electrode thin film at this moment is preferably 0.001～10 μ m, considers 0.01～0.1 μ m more preferably from the viewpoint of the transparency, saving resource, operation.

As tack coat, can enumerate epoxy resin, acrylic resin, silicone resin, silica sol-gel etc., their type of latex is also preferred.The thickness of tack coat is preferably 0.005～1 μ m, more preferably 0.01～0.1 μ m.This is in order not only to have caking property but also to keep the contact with photoelectric conversion layer.

[reflecting electrode film]

Because the diffuse reflectance that reflection electrode layer is had relatively high expectations; Therefore when the reflecting electrode film is metal forming; Can enumerate the alloy or the alloys such as nichrome or stainless steel of the higher metal of reflectivity (metals such as silver, iron, chromium, tantalum, molybdenum, nickel, aluminium, cobalt or titanium) or these metals, especially preferred silver, aluminium.When for the film that becomes the formation of embrane method or plating method with sputter, vapor deposition, ion plating, MBE equal vacuum etc.; Can enumerate the alloy or the alloys such as nichrome or stainless steel of the higher metal of reflectivity (metals such as silver, iron, chromium, tantalum, molybdenum, nickel, aluminium, cobalt or titanium) or these metals, especially preferred silver, aluminium.The reflecting electrode film is except using these metal formings or by the film of vacuum film formation method or plating method film forming etc., can also making through the reflecting electrode film is carried out the wet type coating with composition.

Be used for preferably comprising metal nanoparticle with composition through the reflecting electrode film of wet type coating manufacturing; As metal nanoparticle; Can enumerate to be selected from and form or alloy composition mixing more than a kind or 2 kinds in the group that comprises silver, gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese, consider to be preferably silver and gold from the viewpoint of reflectivity, conductivity.The average grain diameter of metal nanoparticle is preferably 10～50nm.At this, the average grain diameter utilization is measured based on the BET method according to the specific area measuring of QUANTACHROME AUTOSORB-1.Consider that from dispersed, reflexive viewpoint being shaped as of preferable alloy nano particle is spherical, tabular.In addition, in order to prevent cohesion, preferably use polyvinylpyrrolidone (PVP) or protective agent coating metal nano granules such as polyvinyl alcohol (PVA), citric acid.

Consider that from adhesiveness, reflexive viewpoint the reflecting electrode film preferably comprises additive with composition.As additive, consider more preferably to comprise at least a kind that is selected from the group that comprises organic polymer, metal oxide, metal hydroxides, organo-metallic compound and silicone oil from reflectivity, adhering viewpoint.

As as the organic polymer of additive, consider from reflexive viewpoint, be preferably at least a kind in the group that is selected from the copolymer that comprises polyvinylpyrrolidone, polyvinylpyrrolidone and water-soluble cellulose.As the copolymer of polyvinylpyrrolidone, can enumerate PVP-methylmethacrylate copolymer, PVP-styrol copolymer, PVP-vinyl acetate co-polymer etc.And, can enumerate cellulose ethers such as hydroxypropyl methylcellulose, methylcellulose, HEMC as water-soluble cellulose.

Metal oxide as as additive is preferably and contains at least a kind oxide or the composite oxides that are selected from the group that comprises aluminium, silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.As composite oxides, particularly can enumerate above-mentioned ITO, ATO, IZO, AZO etc.

Metal hydroxides as as additive is preferably and contains at least a kind the hydroxide that is selected from the group that comprises aluminium, silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

Organo-metallic compound as as additive is preferably and contains the hydrolysate that is selected from least a kind metallic soap, metal complex, metal alkoxide or metal alkoxide in the group that comprises silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin.For example, metallic soap can be enumerated chromic acetate, formic acid manganese, ironic citrate, cobaltous formate, nickel acetate, silver citrate, Schweinfurt green, copper citrate, tin acetate, zinc acetate, zinc oxalate, acetic acid molybdenum etc.And metal complex can be enumerated acetylacetone,2,4-pentanedione zinc complex, acetylacetone,2,4-pentanedione chromium complex, acetylacetone,2,4-pentanedione nickel complex etc.And metal alkoxide can be enumerated titanium isopropoxide, methyl silicate, NCO propyl trimethoxy silicane, TSL 8330 etc.

As silicone oil, can use straight chain type silicone oil and modified silicone oil both sides as additive.Modified silicone oil can also use the part of the side chain of polysiloxanes import organic group structure (side chain type), import the structure (single tip type) of organic group and in the part of the side chain of polysiloxanes and the structures (side chain two tip type) of two terminal importing organic groups two terminal arbitrary sides that import in the structure (two tip type) of organic groups, two ends of polysiloxanes at polysiloxanes.Modified silicone oil responding property silicone oil and non-reacted silicone oil, but its two kinds all can be used as additive of the present invention.In addition; That the reactive silicone oil meter shows is amino modified, epoxide modified, carboxy-modified, methyl alcohol modification, sulfhydryl modified and xenogenesis functional group modification (epoxy radicals, amino, polyether-based), that non-reacted silicone oil is represented is polyether-modified, the modification of methyl styrene base, alkyl-modified, higher fatty acids is ester modified, fluorine modification and the special modification of hydrophily.

The reflecting electrode film that contains proportional removal decentralized medium with respect to 100 mass parts of additive is used composition, is preferably 0.1～25 mass parts, more preferably 0.2～10 mass parts.If more than 0.1 mass parts, then good with the cohesive force of nesa coating, if below 25 mass parts, the film when then being difficult for producing film forming is uneven.

Metal nanoparticle is used composition with respect to the reflecting electrode film of 100 mass parts, considers to be preferably more than 75 mass parts from the viewpoint of reflectivity, conductivity, more preferably more than 80 mass parts.And, consider with the adhering viewpoint of composition from the reflecting electrode film, be preferably below 95 mass parts, more preferably more than 80 mass parts.

And for film forming well, the reflecting electrode film preferably comprises decentralized medium with composition.Identical with transparent electrode thin film about the reflecting electrode film with the situation of composition with the decentralized medium in the composition.

The reflecting electrode film with composition in the scope of not damaging the object of the invention and can cooperate filler, stress moderator and other additives etc. as required.

Then, according to wet type coating coating reflecting electrode film with dry after the composition or burn till, thereby can make the reflecting electrode film.Using coating layer to form through the coating of wet type coating and heat, burn till thickness afterwards the reflecting electrode film is 0.05～2.0 μ m, preferably becomes the thickness of 0.1～1.5 μ m.This is that the sheet resistance value of the electrode that solar cell is required is not very abundant because during less than 0.05 μ m.According to wet type coating coating, dry or to burn till the reflecting electrode film identical with the situation of composition with transparent electrode thin film with method for compositions; But because the reflecting electrode film need not caking property; Therefore about dry or burn till, keep burning till in 5 minutes～1 hour, preferred 15～40 minutes with 130～400 ℃, preferred 150～350 ℃ temperature in atmosphere or in the inactive gas atmosphere such as nitrogen or argon gas.The reflecting electrode film with the heating-up temperature of coating layer be made as 130～400 ℃ scope be because; Metal nanoparticle sintering each other is not very abundant during less than 130 ℃, and the protective agent of metal nanoparticle is difficult to break away from or decompose (separating or burning) through heating.If the reflecting electrode film after above-mentioned drying or the curing has flexibility, then preferable operability when photoelectric conversion layer adhered film used for solar batteries backplate band is therefore preferred.In addition, carry out drying with transparent electrode thin film with the situation of composition identically or burn till, make the reflecting electrode film keep caking property to get final product.

[thin-film solar cells is used the backplate band]

The method of range upon range of transparent electrode thin film and reflecting electrode film can be used the method for well known to a person skilled in the art; Can enumerate the method for carrying out drying or curing after transparent electrode thin film being coated on the opposing party's reflecting electrode film or the transparent electrode thin film with the arbitrary side in the composition with composition or reflecting electrode film according to the wet type coating etc., have at transparent electrode thin film and carry out range upon range of getting final product under the close-burning state.

Thin-film solar cells with the backplate band preferably at the further lamination barrier film of reflecting electrode film side.And, preferably at the further range upon range of carrier band of the opposing face of transparent electrode thin film.Below, barrier film and carrier band are described successively.

[barrier film]

For barrier film, if use composition, then can reduce the operating cost of manufacturing equipment with easy operation with wet type coating barrier-coated film on the reflecting electrode film, therefore preferred.

Barrier film comprises through heating the arbitrary side or the both sides of the mineral-type basic material of organic type or mineral-type basic material or the non-polymeric adhesive that come cured polymer type adhesive after ultraviolet irradiation or heating or the ultraviolet irradiation with composition.Solidify these polymer type adhesives, non-polymeric adhesive through heating after ultraviolet irradiation or heating or the ultraviolet irradiation, thereby can form the barrier film of the densification that shows weatherability, resistance to water, moisture-proof, thermal endurance etc.

Organic type of basic material of polymer type adhesive preferably include in the group that is selected from the polymer that comprises acrylic compounds, epoxies, polyurethanes, acroleic acid polyurethane class, propylene oxide acids, cellulose family and type siloxane more than a kind or 2 kinds.Use as acrylic adhesives and in acrylic monomer, to add Photoepolymerizationinitiater initiater, and the acrylic polymer that its photopolymerization is obtained to this mixture irradiation ultraviolet radiation (UV).Can enumerate to be selected from as acrylic monomer and comprise 1; 6-hexanediyl ester, trimethylolpropane triacrylate, neopentylglycol diacrylate, tetramethylol methane tetraacrylate, two trimethylolpropane tetra-acrylate, 1, single monomer more than a kind or 2 kinds or mix monomer in the group of 9-nonanediol diacrylate, tripropylene glycol diacrylate, peroxidating cyanuric acid triacrylate and tetramethylol methane tetraacrylate.1-methoxyl group-2-propyl alcohol), PGMEA (propylene glycol monomethyl ether acetate: equal solvent 1-methoxyl group-2-propanol acetate ester) preferably in these monomers, add MIBK (methyl iso-butyl ketone (MIBK)), PGME (propylene glycol monomethyl ether:.But; If can dissolve the common organic solvents of above-mentioned monomer, then can use ethanol, methyl alcohol, benzene,toluene,xylene, NMP (N-methyl pyrrolidone), acrylonitrile, acetonitrile, THF (oxolane), ethyl acetate, MEK (methyl ethyl ketone), BC, BC acetate, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, ethyl carbitol acetate, IPA (isopropyl alcohol), acetone, DMF (dimethyl formamide), DMSO (dimethyl sulfoxide (DMSO)), piperidines, phenol etc.And can enumerate 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl]-phenyl as Photoepolymerizationinitiater initiater }-2-methyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone etc.Acrylic monomer can and be adjusted to the viscosity that is prone to coating with respect to above-mentioned any solvent dilution and use.Photoepolymerizationinitiater initiater adds 0.1～30 mass parts with respect to the acrylic monomer of 100 mass parts.This is that if surpass 30 mass parts, then cured film (backplate strengthening membrane) variable color or residual stress and causing adheres to bad because the addition of Photoepolymerizationinitiater initiater solidifies during less than 0.1 mass parts insufficiently with respect to the acrylic monomer of 100 mass parts.So the mixed liquor that in acrylic monomer, adds solvent and Photoepolymerizationinitiater initiater and stirring and obtain is used the composition basal liquid as barrier film.In addition, under the uneven situation of mixed liquor that obtains when in acrylic monomer, adding solvent and Photoepolymerizationinitiater initiater and stirring, can heat to about 40 ℃.

As epoxy adhesive, can use in epoxylite, adding solvent and stir, and in this mixed liquor, add thermal curing agents and stir, thus obtained mixed liquor is heated and the epoxide polymer that obtains.Can enumerate biphenyl type epoxy resin, cresol-novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, naphthalene type epoxy resin etc. as epoxylite.And can enumerate BCA (BC acetate), ECA (ethyl carbitol acetate), BC (BC) etc. as solvent.But so long as can dissolve above-mentioned epoxylite common organic solvents, just can use ethanol, methyl alcohol, benzene,toluene,xylene, PGME (propylene glycol monomethyl ether), PGMEA (propylene glycol monomethyl ether acetate), NMP (N-methyl pyrrolidone), MIBK (hexone), acrylonitrile, acetonitrile, THF (oxolane), ethyl acetate, MEK (methyl ethyl ketone), BC, BC acetate, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, ethyl carbitol acetate, IPA (isopropyl alcohol), acetone, DMF (dimethyl formamide), DMSO (dimethyl sulfoxide (DMSO)), piperidines, phenol etc.Can enumerate 2-ethyl-4-methylimidazole, boron fluoride MEA, DICY (dicyanodiamine), diethylaminopropylamine, IPD, diaminodiphenyl-methane, piperidines, 2 as thermal curing agents; 4; 6-three-(dimethylaminomethyl) phenol, glyoxal ethyline, HHPA, 7; 11-18 carbon dialkylenes-1,18-two carbohydrazides etc.Epoxylite can and be adjusted to the viscosity that is prone to coating by above-mentioned any solvent dilution and use.Thermal curing agents adds 0.5～20 mass parts with respect to the epoxylite of 100 mass parts.This is because the addition of thermal curing agents solidifies during less than 0.5 mass parts insufficiently with respect to the epoxylite of 100 mass parts, if surpass 20 mass parts, produces big internal stress when then solidifying and causes that adhesiveness is bad.The mixed liquor that so interpolation solvent and thermal curing agents in epoxylite is also stirred and obtain is as the basal liquid of barrier film with composition.In addition, about can heating to 40 ℃ under the uneven situation of mixed liquor that obtains adding solvent and stirring in the epoxylite.

The cellulose family adhesive can be to adding solvent and stirring and in this mixed liquor, add gelatin and stir and the mixed liquor that obtains heats and obtains in cellulosic polymer.Can enumerate hydroxypropyl cellulose as water-soluble cellulose derivative, hydroxypropyl methylcellulose, methylcellulose, HEMC etc. as cellulosic polymer.And can enumerate IPA (isopropyl alcohol), ethanol, methyl alcohol, PGME (propylene glycol monomethyl ether), PGMEA (propylene glycol monomethyl ether acetate), MIBK (hexone), acetone etc. as solvent.Cellulosic polymer can and be adjusted to the viscosity that is prone to coating by above-mentioned any solvent dilution and use.Gelatin adds 0.1～20 mass parts with respect to the cellulosic polymer of 100 mass parts.This be because if the addition of gelatin with respect to the cellulosic polymer of 100 mass parts less than 0.1 mass parts or surpass 20 mass parts, then can't obtain the viscosity that is suitable for being coated with.The mixed liquor that so interpolation solvent and gelatin in cellulosic resin is also stirred and obtain is as the basal liquid of strengthening film composition.In addition, make mixed liquor even through in cellulosic polymer, adding solvent and gelatin and being heated into to stir about 30 ℃.

Be prepared as follows the polyurethane binding that uses the Thermocurable polyurethane resin.At first, making with toluene di-isocyanate(TDI) (TDI), diphenylmethane isocyanate (MDI) etc. is that the excessive polyisocyanate compounds of representative reacts the urethane prepolymer that obtains to contain terminal active isocyanate base with the polyalcohols composition that is representative with polyol compounds such as trimethylolpropane or neopentyl glycols.Then, make as the phenols that with the sylvan is representative, as with β-butyrolactam be representative lactams or as methyl ethyl ketone oxime be that the block agent such as ketoxime class of representative are reacted with the urethane prepolymer that contains this end active isocyanate base.Can use ketone, alkyl benzene, cellosolve class, ester class, alcohols etc. as solvent.Object lesson as ketone can be enumerated acetone, methyl ethyl ketone etc., can enumerate benzene, toluene etc. as the object lesson of alkyl benzene.And the object lesson as the cellosolve class can be enumerated methyl cellosolve, butyl cellosolve etc., can enumerate butyl cellosolve acetate, butyl acetate etc. as the object lesson of ester class, can enumerate isopropyl alcohol, butanols etc. as the object lesson of alcohols.On the other hand, can use polyamine as thermal curing agents (reactant).Can enumerate N-octyl group-N-aminopropyl-N '-aminopropyl propane diamine, N-lauroyl-N-aminopropyl-N '-aminopropyl propane diamine, N-myristyl-N-aminopropyl-N '-aminopropyl propane diamine, N-octyl group-N-aminopropyl-N ' as the object lesson of polyamine, N '-two (aminopropyl) propane diamine etc.The urethane prepolymer that contains terminal active isocyanate base that obtains making the reaction of above-mentioned polyol component and isocyanate compound is implemented the blockization according to the block agent, makes block polyisocyanate.The amino that polyamine had is preferably (0.7～1.1 scope) about 1 with respect to the equivalent proportion of the NCO that this block polyisocyanate had.This be because if amino that polyamine had with respect to the equivalent proportion of the NCO that block polyisocyanate had less than 0.7 or surpass 1.1, more than then the arbitrary side in block polyisocyanate and the polyamine can become and react insufficient, so solidify insufficient.Polyether polyols with reduced unsaturation can and be adjusted to the viscosity that is prone to coating by above-mentioned any solvent dilution and use.

As acroleic acid polyurethane class adhesive; Can enumerate and comprise the urethane acrylate quasi-oligomer, the ultraviolet light UV-3310B or ultraviolet light UV-6100B (Japanese Synesis Company makes) or EBECRYL4820 or EBECRYL284 (Daicel-Cytec manufactured), U-4HA or the UA-32P acroleic acid polyurethane base polymers such as (manufacturings of Xin Zhong village chemical industrial company) that solidify through irradiation ultraviolet radiation (UV).And can improve curable through being added on the Photoepolymerizationinitiater initiater (for example 1-hydroxy-cyclohexyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone etc.) that uses in the esters of acrylic acid as required.And, can use ketone, alkyl benzene, cellosolve class, ester class, alcohols etc. as solvent.Object lesson as ketone can be enumerated acetone, methyl ethyl ketone etc., can enumerate benzene, toluene etc. as the object lesson of alkyl benzene.And the object lesson as the cellosolve class can be enumerated methyl cellosolve, butyl cellosolve etc., can enumerate butyl cellosolve acetate, butyl acetate etc. as the object lesson of ester class, can enumerate isopropyl alcohol, butanols etc. as the object lesson of alcohols.Can be as required in the scope of 0.1～30 mass parts, add Photoepolymerizationinitiater initiater with respect to the acroleic acid polyurethane base polymer of 100 mass parts.This be because the addition of Photoepolymerizationinitiater initiater solidify during less than 0.1 mass parts insufficient, if surpass 30 mass parts then internal stress become big and adhesiveness is bad.And acroleic acid polyurethane base polymer (containing oligomer) can and be adjusted to the viscosity that is prone to coating with above-mentioned any solvent dilution and use.

Can use the propylene oxide base polymer as propylene oxide class adhesive.(for example can enumerate bisphenol-a epoxy acrylate as the propylene oxide base polymer; The NKOligo EA-1020 that Xin Zhong village chemical industrial company makes) or 1,6-hexanediol diglycidyl ether diacrylate (for example Xin Zhong village chemical industrial company make NK Oligo EA-5521) etc.And can use Neopor8318 or Neopor8355 of Japanese U-PICA manufactured etc.Can use ketone, alkyl benzene, cellosolve class, ester class, alcohols etc. as solvent.Object lesson as ketone can be enumerated acetone, methyl ethyl ketone etc., can enumerate benzene, toluene etc. as the object lesson of alkyl benzene.And the object lesson as the cellosolve class can be enumerated methyl cellosolve, butyl cellosolve etc.Object lesson as the ester class can be enumerated butyl cellosolve acetate, butyl acetate etc.Object lesson as alcohols can be enumerated isopropyl alcohol, butanols etc.Can in the propylene oxide base polymer, add thermal curing agents or Photoepolymerizationinitiater initiater as required.And be heating and curing or UV solidifies or UV is heating and curing after solidifying through thermal curing agents or Photoepolymerizationinitiater initiater.And the propylene oxide base polymer can and be adjusted to the viscosity that is prone to coating with above-mentioned any solvent dilution and use.

Can use the type siloxane polymer as the type siloxane adhesive.Can enumerate dimethyl silicone polymer, polymethyl hydrogen siloxane, PSI etc. as the type siloxane polymer.And can use straight chain type silicone oil and modified silicone oil both sides as type siloxane polymer in this expression.As modified silicone oil can also use the part of the side chain of polysiloxanes import organic group structure (side chain type), import the structure (single tip type) of organic group and in the part of the side chain of polysiloxanes and the structures (side chain two tip type) of two terminal importing organic groups etc. two terminal arbitrary sides that import in the structure (two tip type) of organic groups, two ends of polysiloxanes at polysiloxanes.Modified silicone oil responding property silicone oil and non-reacted silicone oil, but its both sides can be used.In addition; That the reactive silicone oil meter shows is amino modified, epoxide modified, carboxy-modified, methyl alcohol modification, sulfhydryl modified or xenogenesis functional group modification (epoxy radicals, amino, polyether-based), that non-reacted silicone oil is represented is polyether-modified, the modification of methyl styrene base, alkyl-modified, higher fatty acids is ester modified, fluorine modification or the special modification of hydrophily.And, can use ketone, alkyl benzene, cellosolve class, ester class, alcohols etc. as solvent.Object lesson as ketone can be enumerated acetone, methyl ethyl ketone etc.Object lesson as alkyl benzene can be enumerated benzene, toluene etc.And the object lesson as the cellosolve class can be enumerated methyl cellosolve, butyl cellosolve etc.Object lesson as the ester class can be enumerated butyl cellosolve acetate, butyl acetate etc.Object lesson as alcohols can be enumerated isopropyl alcohol, butanols etc.Add thermal curing agents or Photoepolymerizationinitiater initiater as required in the type siloxane polymer, even but do not add thermal curing agents, also need not thermal curing agents during cured film.And the type siloxane polymer can and be adjusted to the viscosity that is prone to coating with above-mentioned any solvent dilution and use.

The mineral-type basic material of polymer type adhesive preferably comprise in the group that is selected from the hydrolysis body that comprises metallic soap, metal complex and metal alkoxide more than a kind or 2 kinds.The mineral-type basic material of these polymer type adhesives is for becoming the material of mineral-type basic material from organic class through heating.Promptly can be through burning till the film that forms character with mineral-type basic material.And in the hydrolysis body of above-mentioned metallic soap, metal complex or metal alkoxide contained metal be preferably be selected from the group that comprises aluminium, silicon, titanium, zirconium and tin more than a kind or 2 kinds.Can enumerate chromic acetate, formic acid manganese, ironic citrate, cobaltous formate, nickel acetate, silver citrate, Schweinfurt green, copper citrate, tin acetate, zinc acetate, zinc oxalate, acetic acid molybdenum etc. as above-mentioned metallic soap.And can enumerate acetylacetone,2,4-pentanedione zinc complex, acetylacetone,2,4-pentanedione chromium complex, acetylacetone,2,4-pentanedione nickel complex etc. as metal complex.Can enumerate titanium isopropoxide, methyl silicate, NCO propyl trimethoxy silicane, aminopropyltriethoxywerene werene etc. as metal alkoxide in addition.

On the other hand, can enumerate SiO as the mineral-type basic material of non-polymeric adhesive ₂Bond.This SiO ₂Bond is made like the example shown in following.At first, HCl is dissolved in the pure water, the preparation HCl aqueous solution.Then, mix tetraethoxysilane and alcohol, the above-mentioned HCl aqueous solution of adding heats afterwards and reacts in this mixed liquor.Make SiO thus ₂Bond.And the non-polymeric adhesive preferably comprise in the group that is selected from the hydrolysis body, halogenated silanes class, 2-alkoxyethanol, beta-diketon and the alkyl acetate that comprise metallic soap, metal complex, metal alkoxide more than a kind or 2 kinds.The hydrolysis body of this metal alkoxide comprises sol-gel.And in the hydrolysis body of above-mentioned metallic soap, metal complex or metal alkoxide contained metal be preferably be selected from the group that comprises aluminium, silicon, titanium, zirconium and tin more than a kind or 2 kinds.Can enumerate chromic acetate, formic acid manganese, ironic citrate, cobaltous formate, nickel acetate, silver citrate, Schweinfurt green, copper citrate, tin acetate, zinc acetate, zinc oxalate, acetic acid molybdenum etc. as above-mentioned metallic soap; Acetylacetone,2,4-pentanedione zinc complex, acetylacetone,2,4-pentanedione chromium complex, acetylacetone,2,4-pentanedione nickel complex etc. can be enumerated as metal complex, titanium isopropoxide, methyl silicate, NCO propyl trimethoxy silicane, aminopropyltriethoxywerene werene etc. can be enumerated as metal alkoxide.And can enumerate chlorosilane, bromo-silicane, silicon fluoride etc. as the halogenated silanes class.Can enumerate 2-methyl cellosolve, cellosolvo, butoxy ethanol etc. as the 2-alkoxyethanol.Can enumerate 2 as beta-diketon, 4-pentane diketone, 1,3-hexichol-1,3-propane diketone etc.Can enumerate ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate etc. as the alkyl acetate in addition.

Preferably add coupling agent at barrier film in composition according to other compositions that use.This is in order to improve and adhesiveness as the reflecting electrode film of lower floor.Can enumerate silane coupler, aluminum coupling agent and titanium coupling agent etc. as coupling agent.

And barrier film preferably includes metal oxide microparticle or the flat particle more than a kind or 2 kinds that is selected from the group that comprises cataloid, aerosil particle, silica dioxide granule, mica particles and montmorillonite particle with composition.Add these metal oxide microparticles or flat particle to barrier film with in the composition, can be prevented the steric effect that moisture immerses thus, therefore when using the adhesive of organic type of basic material, improve resistance to water, water proofing property especially effectively.

Cataloid is SiO ₂Or the colloid of its hydrate, average grain diameter is 1～100nm, is preferably 5～50nm and does not have fixing structure.The aerosil particle is through making the silicon chloride gasification and in thermal-flame, generating with the gas phase state oxidation, and average grain diameter is 1～50nm, is preferably 5～30nm.Silica dioxide granule is that average grain diameter is 1～100nm, is preferably the particle of 5～50nm.Mica particles is the particle of 10～50000nm for the average grain diameter of using the synthetic method manufacturing, and being preferably average diameter is that 1～20 μ m and average thickness are the flat particle of 10～100nm.The montmorillonite particle for constitute by ionic bond etc., surface a kind of with the ion exchangeable laminar silicic acid salt compound of the parallel overlapping crystal structure of more weak bonding force each other; And for average grain diameter is the particle of 10～100000nm, being preferably average diameter is that 1～20 μ m and average thickness are the flat particle of 10～100nm.Barrier film comprises cataloid and aerosil particle etc. with composition, thereby can further increase the hardness of barrier film.At this, average grain diameter is meant with laser diffraction/diffuse transmission type particle size distribution device (the hole field makes manufacturing LA-950) mensuration and with size grade scale and is made as the 50% average grain diameter (D that number is carried out computing ₅₀).The value of the number standard average grain diameter of measuring through this laser diffraction/diffuse transmission type particle size distribution device its average grain diameter when in through the image of scanning electron microscope (S-4300SE and the S-900 of Hitachi's tip science and technology (HitachiHigh-Technologies) manufacturing) observation, any 50 particles being carried out the practical measurement particle diameter is roughly consistent.And the average diameter of above-mentioned flat particle and average thickness or after also the value of average diameter and average thickness of each flat particulate of stating for measure same as described abovely.

In addition, it is because colloid is unstable and be prone to cohesion during less than 1nm that the average grain diameter of above-mentioned cataloid is limited to 1～100nm scope, if surpass 100nm then particle diameter can become dispersion liquid more greatly and not.And with the size of above-mentioned aerosil particle, silica dioxide granule, mica particles, montmorillonite particle be limited to above-mentioned scope be because its for obtainable particle size, or do not compare with the film thickness of lower floor and can become big size range.

And barrier film preferably includes with composition and contains the metal more than a kind or 2 kinds that is selected from the group that comprises gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium, manganese and aluminium or the particulate or the flat particulate of their metal oxide.Through adding these particulates or flat particulate, can obtain prevent the steric effect that moisture immerse identical with metal oxide microparticle or flat particle.The size of these particulates and addition can be identical with the size and the addition of the particulate of in aforesaid reinforcement film composition, putting down in writing.

In addition, add additive such as above-mentioned essential particle, particulate, flat particulate and make these additives be scattered in method in the basal liquid can to use and mix above-mentioned transparent electrode thin film in the basal liquid of composition at barrier film with the identical method of the method for the composition in the composition.

Barrier film preferably replaces the barrier film of mineral-type basic material that overlapping use contains mineral-type basic material or the non-polymeric adhesive of polymer type adhesive and forms with the organic type barrier layer 1 layer or 2 layer or more of the barrier film that uses the organic type of basic material that contains polymer type adhesive with composition with the mineral-type barrier layer more than 1 layer or 2 layers of composition.More preferably replace overlapping mineral-type barrier layer and organic type of barrier layer in addition and form 3～5 layers a plurality of range upon range of.Thus can be through a plurality of range upon range of barrier films that form of different nature.Barrier film through containing the mineral-type basic material is higher with the moisture-proof and the thermal endurance on the mineral-type barrier layer of composition formation; And can expect to obtain the excellent effect in aspect of hard films and so on, but cause the unfavorable condition that in film, produces the hole that becomes defective easily.On the other hand, excellent with the resistance to water and the resistance to impact on organic type of barrier layer of composition formation, still higher relatively poor aspect the moisture-proof through the barrier film that contains organic type of basic material because of water vapour permeability.Therefore through remedying mutual shortcoming, and can obtain as closely and the effect that plays a role of the excellent barrier films of various characteristics such as resistance to water, moisture-proof, weatherability, resistance to impact, thermal endurance by a plurality of range upon range of barrier films that form of different nature.If more than 6 layers, though then there is not the unfavorable condition on the characteristic, can waste material and increase process number and manufacturing cost increases, therefore not preferred.

Then, use composition through wet type coating barrier-coated film.The wet type coating can use and the identical method of putting down in writing in composition at above-mentioned transparent electrode thin film of method.

Single or the multilayer irradiation ultraviolet radiation that the barrier-coated film is obtained with composition or preferably be heated to 120～400 ℃, more preferably be heated to and preferably be heated to 120～400 ℃ after 120～200 ℃ or the irradiation ultraviolet radiation, more preferably be heated to 120～200 ℃ and form barrier film.At this, if the barrier film after above-mentioned drying or the curing has flexibility, then preferable operability when photoelectric conversion layer adhered film used for solar batteries backplate band is therefore preferred.Heating-up temperature is during less than 120 ℃, the nubbin of solvent etc. hinder the curing in the backplate strengthening membrane and solidify insufficient, if surpass 400 ℃ of advantages in the production that then can't produce low temperature process and so on.Promptly cause manufacturing cost to increase and productivity ratio decline.When especially after fitting in photoelectric conversion layer, solidifying, might or utilize the optical wavelength zone of the opto-electronic conversion in these mixed type (many maqting type) silicon solar cell module to bring influence to amorphous silicon, microcrystal silicon.And the thickness of formed barrier film preferably is made as 0.2～20 μ m.The thickness of barrier film is during less than 0.2 μ m, when the situation that produces defective etc., is difficult to keep sufficient weatherability, resistance to water, moisture-proof etc., although then do not have special unfavorable condition waste material if surpass 20 μ m.Wherein more preferably the thickness of barrier film is made as 0.2 μ m～10 μ m.

[carrier band]

Carrier band keeps transparent electrode thin film and reflecting electrode film, according to circumstances keeps barrier film.Especially a kind of used for solar batteries backplate band that comprises base material, transparent electrode layer, photoelectric conversion layer, transparent electrode thin film and reflecting electrode film; Forming transparent electrode thin film and reflecting electrode film with the opposed zone of said photoelectric conversion layer; When according to circumstances forming barrier film, prevent that transparent electrode thin film from separating with reflecting electrode film etc.

Can enumerate substrate that forms by polyimides or PET organic polymers such as (PETs) etc. as carrier band.When the transparent electrode thin film of attaching film used for solar batteries backplate band on photoelectric conversion layer, then operability is good if carrier band has flexibility, and is therefore preferred.

If through the wet type coating on this carrier band, be coated with successively the reflecting electrode film with composition, transparent electrode thin film with composition perhaps successively the barrier-coated film form thin-film solar cells with composition, transparent electrode thin film with composition with composition, reflecting electrode film and use the backplate band; Then can simply change manufacturing process, therefore preferred.

Will with the carrier band in the opposed zone of above-mentioned photoelectric conversion layer on form transparent electrode thin film and reflecting electrode film, the example that according to circumstances forms the method for barrier film (below be called transparent electrode thin film etc.) is shown in Fig. 3.At this; Be meant the part that constitutes each thin-film solar cells like the left part of the P3 of Fig. 1 with the opposed zone of photoelectric conversion layer; Also comprise the part that do not form photoelectric conversion layer (part of laser scribing P2 processing) among Fig. 1, but do not comprise the slot part P3 of the nesa coating of a plurality of battery blocks that only are formed on matrix, electrically being connected in series.In addition, the dotted line of Fig. 3 is corresponding with the position of the P3 of Fig. 1.At first, enumerate the method that the backplate band that pattern is formed is bonded to bonded thing.As the method that pattern forms, at first can enumerate as Fig. 3 (A) be coated with 1 row transparent electrode thin film etc. 100 with the width of photoelectric conversion layer on the carrier thin film that is shown in 110 and repeat this and be coated with the method that forms multiple row transparent electrode thin film etc. 100.And, can enumerate as Fig. 3 (B) form on the carrier thin film that is shown in 111 after the transparent electrode thin film etc. 101 of multiple row amount (several column branch), cutting apart the method that forms multiple row transparent electrode thin film etc. 102 by the part of single-point line expression.At this, the method for cutting apart transparent electrode thin film etc. 101 can enumerate with punching press such as mould or mechanically line etc. remove the method for slot part 120; On carrier thin film 111, form the transparent electrode thin film etc. of multiple row amount, and only solidify after the part of multiple row transparent electrode thin film etc. 102 method through removal slot parts 120 such as etchings with uncured mode; Method through the formation of print process patterns such as flexographic printing, hectographic printing, screen painting; Cut into method with the width in the opposed zone of photoelectric conversion layer etc. by each carrier band.And can the backplate band is bonded to after the bonded thing laser scribing or mechanically ream, but, therefore preferably backplate band itself be carried out pattern and form because operation becomes miscellaneous.

The example of structure of thin-film solar cells with the backplate band is shown in following (1)～(8), and still thin-film solar cells of the present invention is not limited to following with the structure of backplate band.In addition, do not comprise barrier film in the following example, but can make each self-structure comprise barrier film certainly.

(1) possesses the transparent electrode thin film film, reflecting electrode film, the combination of carrier band of tack coat based on the metallic film of vapor phase method;

(2) have close-burning transparent electrode thin film, reflecting electrode film, a combination of carrier band with what the wet type coating formed based on the metallic film of vapor phase method;

(3) possesses the combination of reflecting electrode film of transparent electrode thin film film, the metal forming of tack coat;

The combination of the reflecting electrode film that (4) forms with the wet type coating with close-burning transparent electrode thin film, metal forming;

(5) have close-burning transparent electrode thin film, reflecting electrode film, a combination of carrier band with what the wet type coating formed with the metallic film of wet type coating formation;

The reflecting electrode film of the metallic film that (6) possess the transparent electrode thin film film of tack coat, forms with the wet type coating, the combination of carrier band;

(7) possess the transparent electrode thin film film, reflecting electrode film, the combination of carrier band of tack coat based on the metallic film of plating method; And

(8) have close-burning transparent electrode thin film, reflecting electrode film, a combination of carrier band with what the wet type coating formed based on the metallic film of plating method.

[manufacturing approach of thin-film solar cells]

The manufacturing approach of thin-film solar cells of the present invention is characterised in that, comprises that successively (A) prepares to be formed with the operation and (B) operation of above-mentioned thin-film solar cells with the transparent electrode thin film of backplate band of on the photoelectric conversion layer of said bonded thing, fitting of the bonded thing of base material, transparent electrode layer and photoelectric conversion layer.Preferably after (B) operation, make transparent electrode thin film and reflecting electrode film hardening again.Below, an example of the manufacturing approach of thin-film solar cells is shown, but the present invention is not limited to following manufacturing approach.

One example of the manufacturing approach of thin-film solar cells shown in Fig. 4.In addition, the symbol in Fig. 4 (B) 9 stacks gradually the example of barrier film, reflecting electrode film, transparent electrode thin film from carrier band with backplate band (below be called the backplate band) for thin-film solar cells.Shown in Fig. 4 (A), at first prepare to be formed with successively the bonded thing 7 of base material 4, transparent electrode layer 5 and photoelectric conversion layer 6.On base material 4, form the method for transparent electrode layer 5 and photoelectric conversion layer 6 such as (A)～(E) of Fig. 2 successively.

Shown in Fig. 4 (B), then, on the photoelectric conversion layer 6 of bonded thing 7, the transparent electrode thin film 1 of backplate band 9 is fitted shown in Fig. 4 (C).This backplate band 9 has stacked gradually transparent electrode thin film 1, reflecting electrode film 2, barrier film 3 and carrier band 8.

Shown in Fig. 4 (D), peel off carrier band 9 and form the slot part P3 shown in Fig. 4 (E) afterwards.The method that forms this slot part P3 can be enumerated the method that removes slot part P3 with punching presses such as moulds; Uncured backplate band 9 is fitted in after the photoelectric conversion layer 6, and the backplate band 9 that only solidifies the part corresponding with photoelectric conversion layer 6 is afterwards with the method for removal slot part P3 such as etching; Mechanically ream the method that removes and method of laser scribing etc.

Other examples of the manufacturing approach of thin-film solar cells shown in Fig. 5.In addition, Fig. 5 also stacks gradually the example of barrier film, reflecting electrode film, transparent electrode thin film from carrier band for the backplate band.This example is formed with the transparent electrode thin film 1a, reflecting electrode film 2a and the barrier film 3a that carry out pattern formation with the corresponding insulation tank of P3 line trace in the structure in the past the zones corresponding with photoelectric conversion layer 6 (removing the zone of slot part P3).Shown in Fig. 5 (A), at first prepare to be formed with successively the bonded thing 7 of base material 4, transparent electrode layer 5 and photoelectric conversion layer 6.

Shown in Fig. 5 (B), the transparent electrode thin film 1 that then makes backplate band 9 carries out the applying shown in Fig. 5 (C) with the contraposition that the photoelectric conversion layer 6 of bonded thing 7 carries out slot part P3.In (D) of Fig. 5, remove carrier band, but this carrier band itself uses higher raw material such as weatherability, thermal endurance, moisture-proof, resistance to water, therefore need not to remove this carrier band, and then increase reliability, therefore more preferably.

When the manufacturing approach of Fig. 4, arbitrary thin-film solar cells illustrated in fig. 5, all preferably include to attach and comprise transparent electrode thin film and reflecting electrode film, the backplate band that according to circumstances comprises barrier film makes the operation of its curing afterwards.

The thin-film solar cells of using the manufacturing approach manufacturing of these thin-film solar cells is and representes the identical structure of Fig. 1 of thin-film solar cells in the past.Yet the advantage of thin-film solar cells of the present invention is; Owing to use the backplate band; Therefore simpleization and the efficient activity of the manufacturing process of backplate can be sought, and the part of the laser scribing operation of using in the manufacturing of general thin-film solar cells can be omitted.And be also advantageous in that through the shortening heat processing procedure and because low temperatureization alleviates the fire damage to photoelectric conversion layer, improve conversion efficiency thus.

[embodiment]

Below, according to embodiment the present invention is elaborated, but the present invention is not limited to these.And in evaluation of the present invention, use many bonding films silicon solar cell, but can use solar cell of the present invention is not limited to this.Like following mensuration conversion efficiency.With many maqting type thin film silicon solar cell, distribution lead on the substrate behind the on-line machining solar cell piece uses solar simulator and digital source table to the evaluation after the electrode making, obtains irradiation AM:1.5,100mW/cm ²The I-V of light time (current-voltage) curve.In addition, through the current value (I) in I-V (current-voltage) curve that obtains is obtained J-V curve (current density-voltage) divided by the surface area of solar cell piece.Be 2 limits with voltage axis and current density axis in this J-V curve, the output in the area with the rectangular area that links the point on initial point and the J-V curve and depict during for maximum is made as the highest output density (mW/cm ²), will [the highest output density (mW/cm ²)]/[100 (mW/cm ²)] * 100 be made as conversion efficiency (%).Table 1, these results shown in 2.

< embodiment 1 >

Utilize Fig. 2 (A)～(E) that the method for making bonded thing is described, operation afterwards utilizes Fig. 5 to describe.At first, shown in Fig. 2 (B), transparency carrier 40 preparation length and width 10cm are square, thickness is the glass plate of 4mm, use SnO as nesa coating 50 ₂At this moment the thickness of nesa coating 50 is 800nm, and sheet resistance is 10 Ω/, and mist degree is 15～20%.

Then; Shown in Fig. 2 (C); Utilize plasma CVD method from the nesa coating 50 that proceeds to laser scribing P1 processing with 300nm thickness film forming amorphous silicon layer 61; Then utilize plasma CVD method on amorphous silicon layer 61 with 1.7 μ m thickness film forming microcrystal silicon layers 62, form the silicon class photoelectric conversion layer 60 shown in Fig. 2 (D) thus.Shown in Fig. 2 (E), this photoelectric conversion layer 60 is implemented laser scribing P2 processing, with this as bonded thing 70.Represent bonded thing by symbol 7 in Fig. 5 (A).

On the other hand; In order to make backplate band 9a as shown in Figure 5; With the thickness of mold apparatus for coating after PET (PET) system carrier band 8a goes up coating heat treatment is that the methylcellulose of 1 μ m is as barrier film 3a, and 120 ℃ of following heat treatments 10 minutes.The Ag film that passes through spatter film forming 100nm on this basis is as reflecting electrode film 2a.

Then, use with the ITO target of atomic ratio measuring, through the transparent electrode thin film 1a of spatter film forming 10nm thickness as Sn/ (Sn+In)=0.05.On this basis acrylic resin is adjusted to the thickness after the heat treatment of 10nm, carries out coating, form tack coat with the mold apparatus for coating.This tack coat is implemented the laser scribing P3 processing shown in Fig. 5 (B), make backplate band 9a.

Then, shown in Fig. 5 (C), utilize contact panel bonding process device accurate contraposition backplate band 9a and bonded thing 7, after applying backplate band 9a and the bonded thing 7 120 ℃ of following cured 10 minutes.

< embodiment 2～23 >

Except being set as the condition shown in the table 1, use with embodiment 1 identical method to make an experiment.At this, the silica sol-gel that in embodiment 2 grades, uses uses the SB-10A of the MATERIAL of Mitsubishi manufactured.And, make the reflecting electrode film that in the wet type coating, uses of embodiment 12 grades as follows and use composition.

At first, silver nitrate is dissolved in the deionized water preparation metal ion aqueous solution.And, natrium citricum is dissolved in the deionized water, preparation concentration is the sodium citrate aqueous solution of 26 quality %.In the nitrogen air-flow of 35 ℃ of maintenances, directly add granular ferrous sulfate and make its dissolving to this sodium citrate aqueous solution, preparation contains the reducing agent aqueous solution of citrate ions and ferrous ion with 3: 2 mol ratio.Then; Under state, the stirrer of magnetic stirring apparatus is put into the reducing agent aqueous solution, with the rotating speed rotation stirrer of 100rpm with 35 ℃ of above-mentioned nitrogen air-flow maintenances; When stirring the above-mentioned reducing agent aqueous solution, to drip above-mentioned aqueous metal salt and synthesizing of this reducing agent aqueous solution.At this, about adding the amount of aqueous metal salt to the reducing agent aqueous solution, the concentration of each solution is adjusted into below 1/10 of the water-soluble liquid measure of reducing agent, thereby even if the aqueous metal salt of the room temperature of dripping, reaction temperature also keeps 40 ℃.And the mixing ratio of the above-mentioned reducing agent aqueous solution and aqueous metal salt is adjusted into, and the equivalent of the ferrous ion that adds as reducing agent becomes 3 times of metal ion equivalent.End continues to stir 15 minutes mixed liquors again after the reducing agent aqueous solution drips aqueous metal salt, thus at the inner metallic particles dispersion liquid that produces metallic particles and obtain to be dispersed with metallic particles of mixed liquor.The pH of metallic particles dispersion liquid is 5.5, and the stoichiometry growing amount of the metallic particles in the dispersion liquid is 5g/dm ³The dispersion liquid that obtains is placed on room temperature, precipitates the metallic particles in the dispersion liquid thus, the condensation product of the metallic particles through the decantation precipitation separation.Add deionized water as dispersion to the metal condensation product that separated, carry out replacing cleaning with methyl alcohol again after the desalting processing, thus metal (silver) content is made as 50 quality % through ultrafiltration.Afterwards, utilize centrifugal separator that the centrifugal force adjustment of this centrifugal separator is separated the silver-colored particle above the greater particle size of 100nm, to contain 71% primary particle size in number average be the silver nano-grain in 10～50nm scope thereby be adjusted into.That is, be adjusted into the silver nano-grain that primary particle size accounts in 10～50nm scope and become 71% in number average with respect to the ratio of all silver nano-grains 100%.Silver nano-grain to obtaining is the protective agent chemical modification of organic main chain of carbon number 3 by carbon skeleton.

Then, be mixed in the metal nanoparticle that is obtained that disperses 10 mass parts in the mixed solution that comprises water, ethanol and methyl alcohol of 90 mass parts through interpolation.In addition, in this dispersion liquid, add the polyvinylpyrrolidone of 4 mass parts and the silver citrate of 1 mass parts,, use composition thereby obtain the reflecting electrode film so that the ratio of metal nanoparticle becomes 95 mass parts as additive.With the wet type coating with embodiment 1 be identically formed on the barrier film on PET (PET) system carrier band the mode that becomes the thickness shown in the table 1 with the thickness after burning till be coated with the reflecting electrode film that obtained with composition after; Under 180 ℃ (heat resisting temperature that derives from PET system carrier band is 200 ℃ a temperature), condition below 60 minutes, burn sticking filming, thereby form the reflecting electrode film.

Among the embodiment 13, through sputtering at the transparent electrode thin film of film forming 1nm thickness on the formed reflecting electrode film.On this basis acrylic resin is adjusted to the thickness after the heat treatment of 100nm, carries out coating, form tack coat with the mold apparatus for coating.This tack coat is mechanically implemented the laser scribing P3 processing shown in Fig. 5 (B), make the backplate band.

< embodiment 24 >

Utilize Fig. 5 to describe.Bonded thing 7 shown in Fig. 5 (a) uses the bonded thing of in embodiment 1, making.Then, make the last mode coating silica sol-gel that becomes 1 μ m with the thickness after the heat treatment of carrier band 8a as barrier film 3a at PET (PET) with the mold apparatus for coating, and 120 ℃ of following heat treatments 10 minutes.The Ag film that passes through spatter film forming 800nm on this basis is as reflecting electrode film 2a.

Then, be prepared as follows the transparent electrode thin film that uses when forming transparent electrode thin film 1a and use composition.As electrically conductive microparticle, what add 50 mass parts is that Al/ (Al+Zn)=0.02, particle diameter are the AZO powder of 0.03 μ m with the atomic ratio measuring, adds IPA as decentralized medium, thereby integral body is made as 100 mass parts.The zirconium oxide bead that uses the 0.3mm diameter makes the microparticulate in the mixture to 2 hours horizontal mills (horizontal ball mill) of this mixture running.In this dispersion liquid, count AZO so that become mass ratio as adhesive mixed silica sol-gel: silica sol-gel=7: 3, be diluted to AZO with ethanol again and be scaled 2 mass parts, obtain transparent electrode thin film and use composition.The thickness that uses composition to be adjusted to after the heat treatment this transparent electrode thin film is 50nm, carries out coating with the mold apparatus for coating.This is mechanically implemented the laser scribing P3 processing shown in (B) of Fig. 5, make backplate band 9a.

In addition, about the method for the average grain diameter of measuring above-mentioned electrically conductive microparticle for as below, and calculate according to number average.Use the dynamic light scattering determination of making the LB-550 of manufacturing based on the hole field, also confirm particle diameter from electron micrograph.About employed electron microscope, suitably separately use SEM or TEM according to the kind of size, powder.

< embodiment 25～45 >

Except being set as the condition shown in the table 2, use with embodiment 24 identical methods to make an experiment.

< comparative example 1 >

Utilize Fig. 2 to describe.The bonded thing that carries out laser scribing P2 processing 70 shown in Fig. 2 (E) uses the bonded thing of in embodiment 1, making.The electrically conducting transparent film composition that uses when being prepared as follows the nesa coating 10 that forms the inside side.As electrically conductive microparticle; What add 1.0 mass parts is that Sn/ (Sn+In)=0.1, particle diameter are the ito powder of 0.03 μ m with the atomic ratio measuring; The silica sol-gel that adds 0.05 mass parts as adhesive; Further add the ethanol of 98.95 mass parts as decentralized medium, thereby integral body is made as 100 mass parts.In addition, about the method for the average grain diameter of measuring above-mentioned electrically conductive microparticle for like 24 records of embodiment.

Use the zirconium oxide bead of 0.3mm diameter,, make the microparticulate in the mixture, thereby obtain the electrically conducting transparent film composition 2 hours horizontal mills (horizontal ball mill) of this mixture running.

Then, become 80nm, burn sticking filming 30 minutes down, form nesa coating 10 thus at 200 ℃ through the thickness of spin-coating method after on the photoelectric conversion layer 60 nesa coating of above-mentioned preparation to be used composition coating be to burn till.Thickness after burning till is measured through the photo of being taken the cross section by SEM.Particulate in the nesa coating 10 that burns till and obtain is the microdot/adhesive ratio with the ratio of adhesive: 2/1.In addition, the temperature about burning when sticking is measured 4 temperature at the angle of 10cm square glass plate, be made as mean value design temperature ± condition in 5 ℃ of scopes.

In addition, be scattered in the Ag nanometer ink of ethanol solvent through the Ag colloid of spin-coating method coating 0.03 μ m average grain diameter on the side nesa coating 10 of formed the inside, so that the thickness after burning till becomes 200nm; And under 200 ℃, burn to glue and filmed 30 minutes; Thereby form conductive reflecting film 20, the backplate band of the no strengthening membrane of (F) of construction drawing 2 is followed thus; Shown in Fig. 2 (G), carry out laser scribing P3 processing, obtain to estimate with many maqting type thin film silicon solar cell.In addition, the Ag colloid that consists of 10 mass parts of employed Ag nanometer ink and the ethanol of 90 mass parts.

[table 1]

[table 2]

As knowing from table 1,2, in all embodiment 1～45, all can use the backplate band to make thin-film solar cells, conversion efficiency is up to 7.23～7.87%.With respect to this, in comparative example 1, promptly use more complicated step making than embodiment 1～45, conversion efficiency also is lower than embodiment 1～45.Owing in embodiment 1～45, shortens the heat treatment process in the manufacturing process, and realize low temperatureization, so conversion efficiency uprises.

As more than, backplate that can the application of the invention is brought simpleization and the efficient activity of the manufacturing process that seeks backplate.And can omit the part of the laser scribing operation that is used to make general thin-film solar cells.And can improve conversion efficiency thus through the shortening heat processing procedure and because low temperatureization alleviates the fire damage to photoelectric conversion layer.

Claims

1. a thin-film solar cells is used the backplate band, it is characterized in that,

Range upon range of have transparent electrode thin film and reflecting electrode film, and transparent electrode thin film has caking property.

2. thin-film solar cells as claimed in claim 1 is used the backplate band, wherein,

Barrier film arranged in that the reflecting electrode film side is further range upon range of.

3. according to claim 1 or claim 2 thin-film solar cells is used the backplate band, wherein,

Carrier band arranged in that the opposing face of transparent electrode thin film is further range upon range of.

4. thin-film solar cells as claimed in claim 3 is used the backplate band,

It is that the thin-film solar cells that comprises base material, transparent electrode layer, photoelectric conversion layer, transparent electrode thin film and reflecting electrode film is used the backplate band, and it is forming transparent electrode thin film and reflecting electrode film with the opposed zone of said photoelectric conversion layer.

5. the manufacturing approach of a thin-film solar cells is characterized in that,

Comprise successively: (A) preparation is formed with the operation of the bonded thing of base material, transparent electrode layer and photoelectric conversion layer; (B) in the photoelectric conversion layer applying claim 1～4 of said bonded thing each described thin-film solar cells with the operation of the transparent electrode thin film of backplate band.

6. the manufacturing approach of thin-film solar cells as claimed in claim 5, wherein,

After (B) operation, make transparent electrode thin film and reflecting electrode film hardening again.

7. thin-film solar cells, it comprises that each described thin-film solar cells is used the backplate band in the claim 1～4.