CN101299446A - Selenide forerunner thin film and method for producing film cell through rapid selenium vulcanizing thermal treatment - Google Patents

Abstract

The invention relates to a method of a low cost selenide van thin film and the fast selenium sulfuration heat treatment to prepare the solar cell, which can be used in the nm selenide paint roll coating or the electrodeposit method to prepare the selenide van film, through the vacuum flash selenium sulfuration heat treatment, the high efficiency cadmium-free thin film solar cell or the photovoltaic integrated module. The thin film cell adsorption layer band gap is in the v-shaped distribution, and the flash selenium sulfuration heat treatment causes the CuSe in the porous loose thin film fusing, soaking, liquid phase serving the reaction growth of the CIGS film crystal and the self densification of the film with the In4Se3, reactive sputtering In2Se3 or In2S3 to neutralize the excessive CuxSe adsorbed by the film surface layer, going on splashing the micro excessive In2S3 to generate n-high-ohmic resistor Cu(In<1-y>Gay)<3>(SxSe<1-x>)<5> thin film cell shallow burying, then reacting the splashing deposit n-type In(OH,S)/ZnS(O,OH)/Zno(S) buffer layer with the i-layer, linking the slashing transparent conductive film/and laserprocessing collecting ellectrode to complete the preparation of the thin film cell.

Description

Selenides precursor thin film and rapid selenium heat of vulcanization Processing of Preparation hull cell method

Technical field

The present invention relates to the compound semiconductor film preparation of devices, more particularly, relate to antivacuum low-cost legal system and be equipped with Cu-In-Ga-Se-S [Cu (In _0.7, Ga _0.3) Se _2-xS _XBe abbreviated as CIGS] the selenides precursor thin film of thin film solar cell, and it is carried out after vacuum rapid selenium heat of vulcanization handles, directly, serialization prepare the method for thin film solar cell or photovoltaic integrated package.

Background technology

The solar cell power generation mode is reproducible energy technology, produces in the process of electric energy the environmental impact minimum.Solar energy generation technology will be obtained coml success, must make solar cell have higher efficient, lower cost, better weather resistance, and does not increase other environmental problem.The development of conventional crystal silicon solar cell technology has benefited from the continuous technological progress of electronic silicon semi-conducting material, make it and need polycrystalline silicon material in the monocrystalline silicon upstream materials, the economic value added of crystal silicon solar energy battery is not high, it is a kind of product that obtains income by long-term accumulated, the utilization material source of industry of having shunted the Si semiconductor electricity on a large scale, certainly will further aggravate the shortage of global resource, impel its price costliness more; From another point of view, the crystal-silicon solar cell product of today and technology are also in occupation of dominant position, it can satisfy the multinomial requirement that above-mentioned solar cell technology is mentioned substantially, but can not produce solar cell in low-cost mode, its in process of production the waste of silicon materials up to 70%, and need to consume a large amount of primary energy, certainly will cause adverse influence to environment; Comparatively speaking, the energy resource consumption of producing crystal-silicon solar cell needs the generating more than 3 years to reclaim, even the manufacturing cost of every watt of energy output of the most cheap crystal silicon solar energy battery is also wanted 3 dollars, the maximum bottleneck of present stage restriction solar cell development is the too high cost of raw material and production cost.

The solar cell of based thin film technology is a technology that is in developing stage, the engineering feasibility that they provide a kind of solar cell cost to reduce significantly.The raw material of making silicon-film solar-cell are consistent with the used raw material of electronics monocrystalline silicon fabrication of semiconductor device, and its source is the middle gaseous product in the polysilicon purification process, and the stock utilization of making the silicon-film solar-cell process is higher; But the low and poor durability (performance degradation in the use) of the photoelectric conversion efficiency of silicon-film solar-cell though alleviated this defective by technological progress, can't thoroughly be effected a radical cure.Based compound semiconductor Cu (In, Ga) Se ₂Thin film solar cell is a very promising solar cell technology, and the band gap width of CIGS film can change in the scope of 1.04～1.68eV according to Ga content; To the absorption coefficient of visible light up to 10 ⁵/ cm, the film that 1-2 μ m is thick just can absorb most sunlight, is suitable for the absorbed layer as cheap solar cell.The CIGS thin film solar cell has characteristics such as no decline, radioresistance, life-span be long, and peak efficiency has reached 19.9%, near the high-photoelectric transformation efficiency of polycrystalline silicon solar cell 20.3%, is the highest in all thin film solar cells.And it can be deposited on the base materials such as large tracts of land inexpensive substrate-glass, stainless steel, titanium foil or PI plastic film, compare with crystal-silicon solar cell, reduced production process, thereby aspect reducing cost, has special advantages, if vacuum coevaporation and splash-proofing sputtering metal initialization layer technology path reach the production designing requirement, its cost has only 1/3～1/2 of crystal silicon cell.Through the research and development of two more than ten years, the CIGS thin film solar cell has been realized industrialization substantially.

Though the CIGS thin film solar cell has potentiality cheaply, but, two more than ten years, efficient CIGS hull cell development technique all was based on vacuum equipment, the selenizing technology only is in order to reduce the control difficulty of coevaporation behind the vacuum sputtering metal initialization layer, be suitable for the uniformity of large-area preparation hull cell and be easy to industrialization producing continuously and succeeding in developing, lower, the required vacuum manufacturing equipment of the relative utilance of its raw material is more.Because the selenizing method all is based on vacuum equipment after evaporation and the sputter, equipment is huge, involve great expense, and the early investment of setting up the hull cell production line is big.And the utilization rate of raw materials of deposit film only is 30～60%, and its film preparation becomes this part just to account for 45.3% of total cost with target.Having offset the low price advantage that the CIGS thin film solar cell can be prepared into film, also is that present CIGS hull cell cost does not reach the so low main cause of people's expection.

The main purpose that low-cost legal system is equipped with the CIGS hull cell is that a large amount of the minimizing used expensive vacuum equipment, reduces in the manufacture process primary energy consumption and improve raw-material utilance.At present, antivacuum legal system is equipped with the CIGS film and mainly contains two kinds of approach, and a kind of is earlier the Cu-In-Ga-Se feedstock production to be become nano paint, uses wet coating drying and forming-film on suitable substrate again, heat-treats then; Another kind is heat treatment again behind the water-bath prepared by electrodeposition CIGS film.These two kinds of technological approaches have common characteristic, all are the initialization layers that obtains the CIGS film from water-soluble material, heat reprocessing then; Common advantage is: (1) equipment is simple, investment is little, cost is low; (2), utilization rate of raw materials is up to more than 95%; (3) can large tracts of land, continuously, low temperature process deposit film predecessor.This method has obtained bigger breakthrough at present, has had a plurality of companies to begin industrialization process abroad.But also there is the film quality porous in this method, is mingled with, and occurs phenomenons such as crackle after the heating selenizing is handled.

Cladding process is that Cu-In-Ga-Se is mixed and made into the different nano particle coating of forming in certain proportion, adopts different paint-on techniques dry precursor thin film that forms on substrate again.The people such as V.K.Kapur of American I SET company press CuIn with the required Cu of final film, In, Ga element _0.7Ga _0.3Se ₂Cu/ (In+Ga) the mixed thing of chemical formula metering is dissolved in the acid solution, add the aqueous slkali neutralization reaction and form metal hydroxides, accessory substance is removed in the water flushing again, drying is made metal oxide nanoparticles, form nano paint with water and dispersant, on the Mo/ glass substrate, applies film forming and drying with mode such as printing roller coating etc., then at 500～550 ℃ H ₂And N ₂Carry out reduction reaction in the mixed atmosphere, obtain fine and close Cu-In-Ga alloy firm, again at 420～450 ℃ H ₂Se and N ₂Selenizing forms the CIGS film in the mixed atmosphere.The about 12 μ m of wet-film thickness that apply, the membrane structure that dry back forms is loose porous, the about 6 μ m of thickness, about 2 μ m are thick after hydrogen reducing and selenizing processing.Peak efficiency on Zhi Bei the CIGS hull cell glass substrate is 13.6% (0.08cm in this way ²), on the flexible substrate Mo paper tinsel is 13.0% ^[1], area is 65cm ²Battery component efficient be 8% ^[2,3]Its U.S.'s patent of invention is US5985691.

U.S. Nanosolar company is found in 2002, and the antivacuum legal system of the main research and development of decision in 2003 is equipped with the CIGS thin film technique.They utilize different chemical reactions, adopt methods such as organo-metallic compound thermal decomposition method, spraying coprecipitation, sol-gel process to prepare the nano particle of various non-oxidized substances, as CuInSe ₂, CuGaSe, CuSe, In ₂Se ₃, control the size of nano particle by the condition of control course of reaction.With CuSe and In ₂Se ₃For making selenide nanometer particle behind the nuclear parcel pure selenium, and be deployed into liquid phase coating with water-soluble solvent, with its wet coating (silk screen printing or roller coating print process) drying and forming-film on the aluminium foil of sputtering sedimentation Mo film, after heated volatile falls organic solvent, forerunner's selenide thin film is prepared PV (photovoltaic) level thin-film material through rapid thermal treatment (RTP), and it has utilized 180 ℃ of low temperature fusing points and the Cu of pure Se in forerunner's selenide thin film _xThe liquid phase feature of warm fusing point in 523 ℃ of Se, the physical and chemical processes such as liquid phase assisting growth of densification, binary selenides synthetic reaction and the crystal of porosity and looseness selenides precursor thin film Fast Heating have been carried out, prepare the big crystal grain CIS absorption layer of thin film solar cell of column densification, the monomer (0.470cm of glass substrate ²) peak efficiency of CIGS thin film solar cell reaches 14.5% ^[4]The application of Nanosolar company has United States Patent (USP) 50 multinomial, is that (technical descriptioon: CuSe represents the selenium-enriched nano microcrystal grain to US20070092648, and CuxSe represents the general name of all kinds of copper selenide compositions in the film, Cu with above-mentioned relevant patent ₂Se represents real chemical analysis in the film).

In Japan, people such as T.Wada adopt ball-milling method that the mixture of powders of simple substance Cu, In, Ga and Se is ground, and their reactions generate nanometer Cu (In, Ga) Se in the process of lapping ₂Powder mixes forming nano particle coating again with organic solvent, be applied on the Mo/ glass substrate film, by heating organic solvent is removed; At following normal atmospheric inertia N ₂Heat treated in the gaseous environment makes that this selenide thin film is heated to 550～570 ℃ on the glass substrate, and porous initialization layer selenide thin film sinters fine and close polycrystal film into, and the battery conversion efficiency of preparation is 2.7% ^[5,6]

The K.Yoon of Korea S national energy research institute ^[7]Leader's research group with CuI, InI ₃And GaI ₃Be dissolved in the pyrimidine Na ₂Se is dissolved in the methyl alcohol, and hybrid reaction generates the CIGS nano particle of about 15nm under the low temperature nitrogen protection.Reconcile into coating with organic solvent, be coated on the Mo substrate of substrate, carry out two-period form heating selenizing in rapid heat-treatment furnace, the hull cell efficient of preparation is 1.11%.

The technology that electrodeposition process prepares CIGS forerunner's selenide thin film be in acidic aqueous solution with the Mo substrate as negative electrode, direct all kinds of CIGS selenides of electro-deposition precursor thin film.The people such as Bhattacharya in American National regenerative resource laboratory (NREL) are in the chloride solution system, obtained rich Cu selenides precursor thin film with direct each element of electro-deposition CIGS of one-step method, under vacuum selenium atmosphere, it is heat-treated, concurrently vapour depositing accounts in the film total amount proportioning that 50% In, Ga regulate the film chemical composition, make final film composition meet the requirement for preparing semiconductor device, the hull cell efficient of preparation reaches 15.4% ^[8]But, this electric depositing solution less stable, placing just had a large amount of solute precipitations to separate out in one day; In addition, the content of Ga is very low in this selenides precursor thin film of electro-deposition, the ratio of Ga/ (In+Ga) only 0.1.After adding sulfamic acid and potassium hydrogen phthalate pH cushioning liquid, effectively improved the stability of electric depositing solution, it is obtaining breakthrough aspect technology practicality ^[9]The ratio of Ga/ in the film (In+Ga) can reach 0.3～0.7, the heat treatment under vacuum selenium atmosphere of selenides precursor thin film, In, Ga that concurrently vapour depositing accounts for film total amount 5～10% regulate film composition near stoichiometric proportion, and the efficient of preparation hull cell reaches 9.4%.If electro-deposition CIGS forerunner selenide thin film is only at H ₂Heat-treat in the Se atmosphere, dissolve the Cu of rich Cu phase in the film then with KCN solution ₂Se, the thin film solar cell efficient that does not need vacuum to replenish evaporation In, Ga and Se composition reaches 6.2% ^[10]People such as Bhattacharya U. S. application with obtain multinomial patent of invention, wherein, the patent of invention that obtains in China number is: 96199008.2; The present U.S. of Bhattacharya Solopower company specializes in electro-deposition selenides precursor thin film and heat treatment prepares the exploitation of CIGS thin-film cell photovoltaic assembly Study on Production Technology, Solopower company obtains 3,000 ten thousand dollars of risk investments, has set up the electro-deposition CIGS hull cell pilot production line of 20MW.

IRDEP (

Energy Development and Research Institute photovoltaic energy developmental research institute) the joint study unit (Unit é Mixte de Recherche) as French CNRS (CNRS), Electricite De France (EDF) and the state-run high chemical university of Paris, FRA is found in 2005 years.The main technique route that the developmental research of IRDEP-photovoltaic energy is taked is electro-deposition CuInSe ₂Again its surface is vulcanized, and formation CuIn (Se, S) ₂Structure; Immediate objective is: the efficient of (1) small size battery is greater than 12%; (2) 30 * 30cm ²Component efficiency is greater than 8%.Major measure is to add Ga or S in CIS ^[11,12]They adopt sulfate system to carry out the rich Cu phase of electro-deposition CuInSe ₂The research of film is carried out heat of vulcanization again and is handled in S atmosphere, obtain the column structure thin film material of big crystal grain densification, uses the rich Cu phase of KCN solution removal then.The battery best efficiency of preparation is 11.5%, and Substrate Area is 30 * 30cm ²The time, the quality of the initialization layer of electro-deposition is even, and battery efficiency can reach more than 7%.Existing problems are: the film of deposition generally is rich Cu film, need be in KCN solution after Overheating Treatment etching or dissolve the Cu of rich Cu phase in the film ₂Se, it can influence the structure of film surface and the quality of cell p n knot.In addition, Mo and Se reaction easily forms thicker MoSe in the heat treatment process ^[13]

The people such as A.Kampmann of Germany adopt sulfate system, electrochemical deposition is studied for a long period of time, and set up coil type continuous electro-deposition pilot scale line in CISSolartechnik company.In bandwidth is to carry out the preparation of CIGS film in the winding of 100mm metal foil, technical process: Mo, Cu, steel, Thin Stainless Steel are as the substrate of hull cell, deposited barrier layer, sputtering sedimentation Mo layer, hydatogenesis Se again behind the electro-deposition Cu-In-Ga in order, the compound of hydatogenesis Na on the last Se layer, the heat treatment that is rapidly heated then forms the CIGS film, and the technology of selenizing method is similar behind its technical process and the vacuum sputtering.The CIGS battery efficiency is that 10.4% (area is 1.0cm on the stainless steel strip ²), area is 13.3cm ²Efficient be 6.6% ^[14]

We are as can be known from above document and patent specification, the coating procedure of nano paint determines it must add various organic additives, so that making nano particle can stablize, be scattered in equably in the solvent, and prevent the flocculation of nano particle, these additives can form impurity defect in semiconductive thin film, form porous, the open structure of initialization layer.After the coating coating forms film with drying, only the contact of tangent-type point between the nano particle, contact area is relatively very little, make when adding thermosetting megacryst grain dense film, its kinetics is hindered and makes situation become very complicated, thus its kinetics in many aspects with particle between the surface area sum that contacts relevant.Oxidate nano coating needs twice heating steps, once is that the oxide of open structure is reduced into fine and close metal alloy, and then heating selenizing or at H ₂Further selenizing in the Se toxic gas, light absorbing zone uniform ingredients, the semiconductor band gap of preparation are smooth, and vulcanizing treatment can form the dual-property p N-type semiconductor N film of gradient band gap and top layer high resistant on the top layer; But its high-temperature hydrogen reduction time is long, and energy resource consumption is big, has the danger of blast, and its technical know-how has been used for reference the technology that selenizing behind the vacuum sputtering metal initialization layer prepares hull cell; The preparation of selenide nanometer particle need be in organic solvent prepared in reaction, consume a large amount of organic solvents, easily cause environmental pollution, relative cost is higher; In the remelting crystallization process of antivacuum reprocessing, depend on the thin film densification mechanism of the auxiliary recrystallization process of liquid phase of low melting point component in the initialization layer, the liquid growth technology of crystal when it has used for reference polynary coevaporation vapor deposition film has finally obtained the big crystal grain film of column densification; But the coating additive of leaving in the film hole with defective such as be mingled with and be difficult to eliminate fully, the light absorbing zone composition uniformity of rapid thermal treatment preparation is relatively poor, the crystalline quality on film top layer is not high, impurity and crystal boundary are compound more and influence the quality of cell p n knot, make the open circuit voltage Voc of hull cell lower.

The characteristics of prepared by electrodeposition selenide thin film: can carry out from purification to being deposited material, can use raw material than low-purity, can change composition in the initialization layer film according to sedimentation potential, be convenient to form gradient band gap and distribute, compare its initialization layer film with cladding process fine and close.The problem that exists is: the Mo substrate the deposition initial stage chemical replacement reaction takes place and in the burn into solution solubility of solute little, the current density of electro-deposition semiconductor selenizing film is less relatively, the stability that electro-deposition compares with cladding process that the deposition velocity of film is on the low side, contain a large amount of oxygen, solution in the film still exists problem etc., only at H ₂Se or class H ₂Processing in the Se gas could be removed oxide effectively, and this has increased difficulty to the use of eliminating toxic gas.On the other hand, the stoichiometric proportion that the composition of exceedingly pursuing electro-deposition selenides precursor thin film requires to meet hull cell is inappropriate, excessive high-melting-point selenides can hinder film densification further in the electro-deposition selenides precursor thin film, even there is excessive CuSe (rich steel structure) in the film, can not produces in heating process that tangible liquid phase thing is assembled or cohesion, wrap up other particle and produce slip, deformation of thin membrane (densification) or separate out at film surface; Do not neutralize unnecessary Cu if do not deposit In, Ga ₂Se just needs KCN solution by soaking into, dissolve the Cu in the film ₂Se.

Summary of the invention

The present invention is in view of above-mentioned technology in esse problem and constituting in commercial process, and it provides a kind of low cost to prepare CIGS hull cell selenides precursor film and the rapid selenium heat of vulcanization is handled the method that directly prepares thin film solar cell.Can be used for low-cost nano paint printing roll coating process or the direct rapid selenium vulcanizing treatment of water-bath electro-deposition forerunner selenide thin film, and serialization ground carries out the production of hull cell subsequent handling, prepare efficient no cadmium CIGS thin film solar cell integrated photovoltaic assembly.The light absorbing zone of this thin film solar cell be by the vacuum rapid thermal treatment make loose or the fusion of porous crystallite precursor thin-film, particle between soak into, the auxiliary crystal synthetic reaction growth of liquid phase the time, carry out metallic target reactive sputtering In ₂Se ₃With/or In ₂S ₃, make the film integral composition change poor steel structure into, the In that trace is superfluous by rich copper ₂S ₃Generate on the surface of hull cell absorbed layer high resistant OVC (defective chalcopyrite in order) structure n-Cu (In, Ga) ₃(Se, S) ₅, constituted the pn shallow embedding knot and the dual-property light absorbing zone of low-cost preparation hull cell; Because Ga and S element all have high level or the wherein V-shaped distribution of Ga at Mo back electrode place and film top layer respectively in the selenides precursor thin film, after the rapid selenium heat of vulcanization is handled, the semiconductor band gap of this film presents the V-type distribution in the depth direction of film thickness, and film surface has pn shallow embedding knot.Along with the reduction of substrate temperature, again on light absorbing zone reactive sputter-deposition n type high resistant intrinsic i-In (OH, S)/ZnS (O, OH)/ZnO (S) transparent caching layer and i layer.The transparent n-ZnO:Al film of sputtering sedimentation low-resistance constitutes the n type conductive layer of battery subsequently, just finished this type of low-cost selenides precursor thin film and prepared the more complete pin structure of CIGS hull cell, it has presented than tangible consistency with practical structures with the CIGS hull cell theoretical model of coevaporation peak efficiency (19.9%).

Other purpose of the present invention provides a kind of manufacturing process of the CIGS of being used for thin film solar cell, compare with the vacuum method in past, can reduce the input of manufacturing equipment in early stage significantly, increase substantially the raw-material utilance of rare diffusing noble metal in the thin film solar cell manufacture process, reduced the energy resource consumption of manufacture process, shorten and simplified fabrication, integrated the technical advantage that selenizing behind coevaporation and the sputter initialization layer prepares hull cell, promoted the quality that low-cost preparation method produces hull cell, thereby reduce the raw material and the manufacturing cost of CIGS class thin film solar cell, impel solar cell to obtain to be applied even more extensively.

For solving above-mentioned problem, the invention provides the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of antivacuum low-cost thin films battery, be primarily characterized in that: (1) is sequential applications nanometer selenides coating and drying and forming-film on the molybdenum electrode film of rigid substrate substrate, or order plating (or electro-deposition) different component nano microcrystalline selenides precursor thin film, this selenides precursor thin film composition with structure is respectively: (CuGaSe ₂+ CuSe), (Ga ₂Se ₃+ CuSe), In ₄Se ₃(or In ₂Se ₃+ CuInSe ₂), CuSe[or (CuSe+Ga ₂Se ₃), (CuSe+CuGaSe ₂)] order choice formula combination; (2) the one pile of rigid substrates that has prepared this selenides precursor thin film is placed in the airtight space in the vacuum chamber, by from room temperature to 290 ℃ high vacuum heating, injection hydrogen, be evacuated to high vacuum and the first hydrogenation pretreatment process of the multi-pass operation of injecting hydrogen again with last injection argon gas+hydrogen; (3) second selenizings are handled, and with this pile substrate from top to bottom or from bottom to top parallel moving, push another relative airtight space respectively blocks ofly, start the heating of substrate bottom earlier, and import class H to second airtight space ₂Se gas, keeping enough selenium air pressure (20～80kPa) time, the fixed form heating that substrate in moving is carried out Fast Heating up and down or the heating of top scan-type and bottom moving with substrate, heat up, substrate itself remains at 350 ℃～580 ℃, the substrate top layer is because the movable type scanning heating of high power radiant heat source, forerunner's selenide thin film can be rapidly heated 350 ℃～1100 ℃, impels Cu in the selenides precursor thin film _xSe/ and In ₄Se ₃Be heated mutually and melt (523 ℃ of liquefaction) fast, the densification of auxiliary CIGS film crystal liquid phase reactor growth and film self, after the CIGS film of big crystal grain densification generated, its top layer can be oozed out trace or adsorb unnecessary liquid Cu _xSe; (4) the 3rd selenium vulcanizing treatment, base substrate are transferred to the sputter position with the substrate motion when 520 ℃～580 ℃ preference temperatures, regulate airtight space air pressure to 0.3～25Pa, by reactive sputtering In ₂Se ₃Or In ₂S ₃Neutralization reaction is fallen the unnecessary liquid Cu in substrate top layer _xSe, strict control substrate surface CIGS film composition is transformed into In in the poor steel structure process by rich copper ₂Se ₃Or In ₂S ₃The sputter amount; (5) the 4th selenizings are handled, and after reactive sputtering finishes, increase airtight space and import class H ₂The Se gas flow, when making its environment selenium air pressure reach 20～80kPa, the high power radiant heat source carries out the heat scan of faster speed to substrate; (6) the 5th high temperature vulcanized processing, emptying class H ₂Behind the Se gas, refill reactive sputtering gas H ₂S+Ar keeps air pressure at 0.3～25Pa, and substrate carries out reactive sputtering In after moving to the sputter position ₂S ₃, it generates n type Cu (In on the film top layer _1-xGa _x) SSe or Cu (In _1-yGa _y) ₃(Se _1-xS _x) ₅Resistive formation; Vulcanize in the heat treated operating process at above-mentioned rapid selenium, second airtight space alternately charges into class H ₂Se gas or H ₂S+Ar gas, high vacuum exhaustion was carried out in the centre, and its air pressure has to rise to have and falls; (7) will be transferred to the 3rd airtight cooling space through the substrate after the processing of rapid selenium heat of vulcanization; Like this, the whole pile of substrate in first space is included into the 3rd cooling space after handling through the rapid selenium heat of vulcanization, and this space is injected with Ar+H ₂The S mist guarantees that base substrate drops in 110 ℃ of processes by 580 ℃ gradually, and the selenium element sulphur does not run off in the CIGS thin-film material; (8) substrate after the cooling is pushed into the 4th airtight space respectively, carry out the high resistant eigen I n (OH of metallic target reactive sputter-deposition hull cell, S)/and ZnS (O, OH)/ZnO (S) resilient coating and i layer, the material of two or three pairs of simple metal sputtering targets and the collocation of reacting gas are: In/ (Ar, H ₂S and H ₂O), Zn/ (Ar, H ₂S and H ₂O) and Zn/ (Ar, H ₂S and O ₂Or CO ₂), the temperature of base substrate is controlled at 110 ℃～350 ℃ in the sputter procedure; Airtight space was pumped down to high vacuum state after sputter was finished, and started the quick scanning substrate of high power radiant heat source surface; (9) with reactive sputter-deposition the substrate behind the high resistant resilient coating be included into the 5th cooling space respectively; Operation that substrate cooling back just can change that next laser processing is handled or the electrode of the battery integrated package of machinery line is connected in series over to, or deposit the low-resistance transparent conducting ZnO: Al film operation.

According to the present invention as can be known, forerunner's selenide thin film is to apply in certain sequence or roller coating nanometer selenides coating and drying and forming-film, or water-bath prepared by electrodeposition nano microcrystalline selenides precursor thin film obtains in proper order, and the composition of these selenides precursor thin films is respectively: CuGaSe ₂, Ga ₂Se ₃, CuInSe ₂, CuSe, In ₄Se ₃Or In ₂Se ₃Permutation and combination, wherein only rich selenium CuSe and poor selenium In ₄Se ₃Can be the selenides of low melting point (523 ℃), they be indispensable or indispensable compositions in the selenides precursor thin film, determining allow after the loose selenide thin film process rapid selenium heat of vulcanization processing, directly prepare the absorbed layer film of big crystal grain densification.That is to say, must be by carrying out synthetic reaction between multiple binary (containing a small amount of ternary) the selenides microcrystal grain, just can make forerunner's selenide thin film finally generate PV (photovoltaic) the level film of quaternary column, big crystal grain densification, wherein all will utilize in the synthetic reaction process than low melting point binary selenides CuSe and/or In ₄Se ₃The solid-liquid phase crystal of (523 ℃) reaction growth mechanism, and can not allow high-melting-point solid phase selenides (Ga in forerunner's selenide thin film ₂Se ₃, CuInSe ₂, CuGaSe ₂, In ₂Se ₃) stop low melting point selenides microcrystal grain fusing in the film, infiltration, liquid phase to be wrapped in that thin sight slip, microcosmic hole that refractory grain causes are filled and led up or the plastic history and the densification process of film such as obstruction.

In the present invention, be mingled with macromolecule organic unavoidably in the precursor thin film of the coating of nanometer selenides, roller coating, be mingled with about oxide more than 15% in the water-bath electro-deposition selenide thin film, they all need to be evacuated to high vacuum and the first hydrogenation pretreatment process of the multi-pass operation operation of injecting hydrogen with last injection argon gas+hydrogen by from room temperature to 290 ℃ high vacuum heating, injection hydrogen; The selenides precursor thin film is when 290 ℃ of temperature are following, its inner generation synthetic reaction probability is less, the surface and the inner crystallite adsorbed gas that help porous membrane are reduced by desorption, partial oxide, it all is necessary that heating makes technological measures such as the organic substance volatilization that is mingled with or desorption, and selenides precursor thin film material is modulated onto the high pure state of electron level before formal Fast Heating the recrystallization of subsequent thin film is prepared semiconductor device is very useful.Second airtight space imports class H ₂Be pumped down to 1 * 10 before the Se gas ^-3The high vacuum that Pa is above, with the first airtight space air pressure balance after, open the slide valve between two Room, first indoor a slice substrate is pushed the airtight space in the rapid selenium heat of vulcanization process chamber and closes slide valve, continue to import class H ₂Behind the air pressure of Se gas to 50～80kPa, just can carry out the second selenium vulcanizing treatment operation; Class H ₂Consisting of of Se gas ingredients: 30%～50% argon gas, 25%～35% hydrogen, 15%～45%H ₂Se.Under the prerequisite that keeps enough selenium atmosphere, substrate in mobile is got on, get off or scan-type heating and intensification fast simultaneously up and down, substrate self remains on 350 ℃～580 ℃ temperature range, the high power radiant heat source makes forerunner's selenide thin film on substrate top layer be rapidly heated 350 ℃～1100 ℃, impels selenides precursor thin film middle crystallite CuSe and/or In ₄Se ₃The liquid phase reactor growth of the auxiliary CIGS film crystal of the thawing (523 ℃ of liquefaction) of being heated fast, film self is experiencing the remelting and the densification process of crystallization again, Fast Heating has promoted chemosynthesis reaction takes place in forerunner's selenide thin film, finally generates the CIGS film of high-melting-point, big crystal grain densification.Because during preparation selenides precursor thin film composition being strict with is rich steel structure, more crystallite CuSe is arranged on the top layer consciously, and micro-liquid Cu can be oozed out in the top layer after the Fast Heating _xSe, this moment, substrate base should maintain 520 ℃～580 ℃, and the substrate bottom heater is in permanent power state of a control.When whole substrate generated the big crystal grain dense film of CIGS fully, unnecessary liquid Cu can adsorbed in its surface ₂Se reduces selenium air pressure to 0.3～15Pa in the environment, and substrate is transferred to the reactive sputtering zone, carries out reactive sputtering In ₂Se ₃Or In ₂S ₃, the unnecessary liquid Cu in strict monitoring substrate top layer ₂Copper content was reduced to 24.5% o'clock when Se is neutralized by reaction or in the film, and very obvious variation can appear in the physical state of permanent power heating condition subtegulum film surface, and promptly the CIGS film composition is transformed into sputter In in the process of poor steel structure by rich copper ₂Se ₃Or In ₂S ₃Amount need accurately monitoring.

Because the selenides precursor thin film itself is an open structure, the performance of its conduction heat is limited; The present invention preferred earlier from the bottom heating with heat up, in the selenides precursor thin film near the CuGaSe of molybdenum film ₂+ CuSe and Ga ₂Se ₃380 ℃ of beginning synthetic reactions, a small amount of CuGaSe in the film ₂As the young crystalline substance of high-melting-point selenides, induce Cu _xSe and Ga ₂Se ₃Reaction generates broad-band gap CuGaSe around it ₂Big crystal grain film, the molybdenum film that causes substrate is by big crystal grain CuGaSe ₂Interconnect in flakes and cover; On the other hand, CuGaSe ₂Middle trace gallium and molybdenum react the generation metallic compound easily, greatly improve the engaging force between CIGS film and the back electrode molybdenum film, stop the back electrode molybdenum element to continue and excessive selenium reaction generation MoSe.If the high power radiant heat source on top this moment (or outside) scans the selenides precursor thin film fast, its surface will produce between melting, particle to be soaked into, subsides or phenomenon such as contraction, high-melting-point Cu (In, Ga) Se ₂Crystallite can be induced the low melting point liquid Cu _xSe and In ₄Se ₃With Ga ₂Se ₃Reaction grows into CIGS megacryst film around it, the crystal boundary of each big product intergranular is melted, precursor thin film bottom and top layer Ga and the counterdiffusion mutually of In element form level and smooth composition gradient naturally in big crystal grain depth of film direction and distribute and the semiconductor gradient band gap unnecessary or excessive liquid Cu ₂Se is adsorbed on the top layer of big product grain CIGS film, by the In of sputter subsequently ₂Se ₃Or In ₂S ₃Neutralization reaction is fallen; Strengthen and inject class H ₂The amount of Se gas when making ambient pressure reach 20～80kPa, starts the quick scanning substrate of high power radiant heat source surface once more, and the film Flashmelt on substrate top layer has eliminated each big intercrystalline crystal boundary, intragranular Cu ₂Se, In ₂Se ₃Dissolved Deng the dephasign thing, low-lying place and the floating lug boss of big grain surface have been filled and led up between the crystal boundary, make the crystal of CIGS thin-membrane section very complete, the microcosmic surface of film is also very level and smooth, reduced that effectively crystal boundary is compound in the hull cell, improved battery open circuit voltage Voc; Emptying class H ₂Refill H behind the Se gas ₂S gas, sputtering sedimentation In ₂S ₃After the film top layer generate n type Cu (In _1-xGa _x) SSe or Cu (In _1-yGa _y) ₃(Se _1-X, S _X) ₅Resistive formation, the about 20～40nm of its thickness forms hull cell homogeneity shallow embedding knot or dual-property light absorbing zone, has improved the hull cell junction characteristic and has suppressed leakage current, has improved the hull cell photoelectric conversion efficiency.In like manner, natural cooling along with substrate CIGS film, start the n type intrinsic high resistant In (OH of sputter battery resilient coating, S)/ZnS (O, OH)/ZnO (S) film after, after the 4th airtight space is evacuated to high vacuum, start the quick scanning substrate of high power radiant heat source surface, make the more closely knit and zinc element sulphur of desorbing gas, film intercrystalline in the sputtering sedimentation cushioning layer material to the diffusion of p type CIGS film top layer, improved the quality in hull cell pn knot internal electric field district.

In the present invention's first hydrogenation preprocessing process, also can add blocking hydrogen and supply with the vacuum exhaust operation of opening the airtight space valve fast; By this vacuum exhaust operation, airtight space temporarily can become high vacuum state, heating volatilizees or desorption the organic substance that is mingled with in the selenides precursor thin film with high vacuum once more, refill hydrogen and make active high hydrogen and the reaction of the oxide in the selenides precursor film, make selenides precursor thin film material be reduced into the high pure state of electron level as much as possible, thoroughly eliminate organic being mingled with in the film, reduce the existence of oxide.In like manner, second and third, equally also be provided with vacuum exhaust mechanism in the vacuum chamber of four airtight spaces, can carry out the vacuum exhaust operation sequence, it is used to adjust some state in the film.

Therefore, the low-cost selenides precursor thin film of making by the present invention passes through the CIGS thin film solar cell of rapid selenium heat of vulcanization Processing of Preparation, can obtain the distinctive photoelectric conversion efficiency of chalcopyrite thin-film solar cell reliably, constantly perfect along with technology, its performance will reach the level that the vacuum coevaporation prepares hull cell.

The part of other purpose of the present invention, advantage and new feature will be stated in the following description, and this part to one skilled in the art, be to understand easily by the research to following description of drawings, specific implementation method and case.

Description of drawings

Shown in Figure 1 is the sketch of general each layer of CIGS class thin film solar cell structure;

Fig. 2 is the thin-film solar cell structure sketch of low-cost forerunner's selenide thin film of the present invention and the preparation of rapid selenium vulcanizing treatment;

Shown in Figure 3 is the principle sketch that low-cost selenides precursor thin film of the present invention carries out the light absorbing zone of rapid selenium heat of vulcanization Processing of Preparation CIGS thin film solar cell;

The present invention of being shown in Figure 4 prepares the main flow sketch of CIGS thin film solar cell photovoltaic integrated package production process.It is little, and Fig. 4 (a) reactive sputtering metallic silicon, titanium target prepare alkali barrier layers such as SiO, TN and SiN; Fig. 4 (b) sputter prepares the Mo electrode layer; Fig. 4 (c) laser cutting molybdenum film is divided equally the electrode that back of the body electric field prepares each sub-battery; Roller coating preparation of Fig. 4 (d) nano paint order or order prepared by electrodeposition selenides precursor thin film; Fig. 4 (e) selenides precursor thin film hydrogenation preliminary treatment; The remelting crystallization again in the selenium atmosphere of Fig. 4 (f) selenides precursor thin film; Fig. 4 (g) liquid Cu ₂Se is by reactive sputtering In ₂Se ₃Or In ₂S ₃The height convex-concave surface that neutralize, the high power radiant heat source scans back remelting elimination intercrystalline crystal boundary and floating film fast, sputter In then ₂S ₃Generate high resistant n type Cu (InGa) ₃(SeS) ₅Fig. 4 (h) reactive sputtering indium zinc target prepare In (OH, S)/ZnS (O, OH)/resilient coating of ZnO (S) hull cell; Contact electrode is handled in Fig. 4 (i) laser radiation; Fig. 4 (j) sputter transparent conducting ZnO: Al layer; The anti-quick-fried die-cut transparent electrode layer that cuts of Fig. 4 (k) laser radiation; Fig. 4 (l) CIGS thin-film cell photovoltaic integrated package contact conductor, encapsulation.

It shown in Fig. 5 (a) the theory structure sketch that nano paint printing roll coating process or water-bath electrodeposition process prepare forerunner's selenide thin film rapid selenium heat of vulcanization Processing of Preparation hull cell light absorbing zone, resilient coating and i bed device; Fig. 5 (b) selenides precursor thin film is by the principle sketch of (the inventive method is made) in-line arrangement rapid selenium heat of vulcanization processing unit; The surface of Fig. 5 (c) hull cell light absorbing zone prepares high resistant resilient coating and intrinsic i layer continuously; Fig. 5 (b), Fig. 5 (c) are respectively the enlarged drawings of 32a and two parts of 34a in the big system and device of Fig. 5 (a).

Specific implementation method

Low-cost forerunner's selenide thin film solar cell (shown in Figure 2) that the present invention makes is identical with the basic structure (shown in Figure 1) of traditional chalcopyrite class CIGS thin film solar cell, only on manufacturing approach or method, there are some differences, prepare the selenides precursor thin film earlier with antivacuum cost effective method, carry out the processing of vacuum rapid selenium heat of vulcanization again and directly produce hull cell p type light absorbing zone (shown in Figure 3), the resilient coating in hull cell pn interface and i layer, just can change the crossed process (battery floor electrode and face electrode are connected in series) that the intraconnected electrode of thin film solar cell integrated package is connected in series over to, or continue the transparent Window layer ZnO:Al of deposition n type low-resistance, prepare Routine Test Lab detection monomer film solar cell.

When the relatively poor common sodium calcium float glass of service quality uniformity or batch difference, the uneven glass of quality, glass surface alkali composition is seriously uneven, carrying out along with hull cell preparation technology, have other impurity and in light absorbing zone 1d, spread, influence the quality of light absorbing zone and the uniformity of large tracts of land crystallization by Mo mea layers 1c; In addition, the enforcement of battery process can cause the alkali of glass surface quick-fried, adhesion between Mo electrode layer film and the light absorbing zone is weakened, cause separating and coming off of hull cell absorbed layer and Mo film, influence the photoelectric conversion efficiency and the fill factor, curve factor FF of hull cell.In order to obtain homogeneous, good thin-film cell photovoltaic integrated package, the present invention preferably (also claims common soda-lime glass at soda lime glass, english abbreviation SLG) substrate 1a goes up sequential aggradation alkali barrier layer 1b and Mo electrode thin film layer 1c, and the alkali barrier layer prepares SiO, TiN, SiN etc. by reactive sputtering metallic silicon or metal titanium targets and constitutes; Another reason is to contain CIGS Film Optics absorbed layer needed sodium salt in the remelting recrystallization process in the selenides precursor thin film of the present invention, and to diffuse into absorbed layer by the Mo electrode thin film layer be not very essential to sodium in the SLG substrate.

Fig. 3 represents the structure of the order roller coating of the preferred nano paint of the present invention or each layer of electrochemistry layer by layer deposition selenides precursor thin film, and the rapid selenium heat of vulcanization is when handling, and the selenides precursor thin film remelting principle sketch of crystallization again that is heated is relevant with Fig. 4 (f).

SLG substrate behind the prefabricated selenides precursor thin film of Fig. 5 (a) expression is put into the principle of device sketch that rapid selenium heat of vulcanization processing unit carries out hull cell light absorbing zone and resilient coating and the preparation of i layer, with Fig. 4 (e), Fig. 4 (f), Fig. 4 (g) is corresponding with the forerunner's selenide thin film rapid selenium heat of vulcanization treatment process shown in Fig. 4 (h), be via slide valve 320,321,340,341 with the 31a of hydrogenation pretreatment chamber, rapid selenium heat of vulcanization process chamber 32a, storage sheet cooling chamber 33a, sputtering settling chamber 34a, get the principle sketch of the in-line arrangement rapid selenium heat of vulcanization processing unit that sheet chamber 35a is communicated with respectively, each the chamber 31a on this device, 32a, 33a, connecting not shown vacuum exhaust mechanism on the 34a respectively.If connect the vacuum equipment of Fig. 4 (i), Fig. 4 (j) and Fig. 4 (k) again, just can prepare the photovoltaic integrated package of hull cell continuously.

31a device among Fig. 5 (a) is corresponding with the pretreatment process of forerunner's selenide thin film hydrogenation shown in Fig. 4 (e), carrying in the inside of the 31a of hydrogenation pretreatment chamber and can take in batch being a plurality of substrate 3a of unit, but substrate 3a is placed on the supporting device that oscilaltion, integral body be handled upside down (not shown), bearing support is placed in the airtight space 312, airtight space outside having heaters 311 and heat radiation screening plate 310, and substrate delivery device 313, in airtight space, also have hydrogen, the shared ingress pipe of argon gas and controlled drain tap (not shown).The one pile of substrate 3a that is accommodated in the hydrogenation pretreatment chamber has carried out the order roller coating and the oven dry of the nanometer selenides precursor thin film on the Mo electrode thin film layer, or electrochemistry order electro-deposition selenides precursor thin film, wherein Mo hearth electrode film has been laser-cut into the film monomer of being divided equally; Be among the substrate 3a of unit to criticize, be stored on the liftable operation of substrate, the barrow that level is shelved (not shown) through the hydrotreated substrate 3a of heating, it can push substrate 3a to the dolly 323 of rapid selenium heat of vulcanization process chamber 32a via slide valve 320 one by one by under substrate delivery device 313 and the common collaboration situation of lifting supporting device.

Fig. 5 (b) is that rapid selenium heat of vulcanization of the present invention is handled the principle sketch that the selenides precursor thin film prepares hull cell absorbed layer device, and it and Fig. 4 (f) forerunner selenide thin film carry out remelting Crystallization Procedure and Fig. 4 (g) reactive sputtering In again in the selenium atmosphere ₂Se ₃Or In ₂S ₃Neutralize the remelting Adsorption of Cu on crystallization absorbed layer surface again _xSe and sputter In ₂S ₃Generate high resistant n-Cu (In _1-xGa _x) SSe or Cu (In _1-yGa _y) ₃(Se _1-xS _x) ₅Operation corresponding.In rapid selenium heat of vulcanization process chamber 32a, placing substrate 3b on the dolly 323 of may command displacement, speed, it is many to thermocouple to arrange evenly under the substrate 3b that resistive heating device contacts with substrate 3b, can carry out the heating of substrate backside controllable temperature or permanent power mode; The high power infrared source 324 of may command displacement, speed and power can carry out quick scan-type heating to substrate 3b surface; In moveable carriage 323 both sides fixing H is installed ₂Se or class H ₂The Se gas introduction tube, at gas introduction tube near the nozzle bore that is provided with a plurality of even layouts on the one-sided wall of dolly 323, H ₂Se or class H ₂Se gas flows to the surface (not shown) of the substrate 3b that moves from nozzle bore; Pair of metal indium reactive sputtering target 325 is installed in the 32a chamber, is separately installed with two cover gas circuits of argon gas and sputter reacting gas ingress pipe above it; Said apparatus all is positioned in the airtight space 326, is equipped with on the airtight space 326 can open exhaust fast or regulate the valve of air pressure and the vacuum nude gauge pipe (not shown) of detected gas pressure.Open slide valve 321, substrate 3b stored up in the sheet cooling chamber 33a get sheet mechanism 331 include in can the substrate bearing mechanism 333 of horizontal lifting on (not shown).

In storage sheet cooling chamber 33a, the selenides precursor thin film on the substrate 3c is through heating, sputter In ₂Se ₃/ In ₂S ₃Successful transformation becomes the optical absorbing layer of poor copper, big crystal grain densification, and 540 ℃～580 ℃ that the temperature of its substrate 3c will be when changing over to are reduced to 100 ℃ gradually, are filled with the H of 0.5～30Pa in the storage sheet cooling chamber all the time ₂S+Ar gas, the last optical absorbing layer of assurance substrate 3c can not be volatilized in temperature decline process or escape and be lost the selenium element sulphur; 3c increases gradually along with substrate, when slide valve 321 closed conditions, opens slide valve 340, utilizes substrate delivery device 332 that substrate 3c is pushed to the dolly 342 of sputtering settling chamber 34a.

Fig. 5 (c) is the principle sketch of sputtering sedimentation resilient coating and i floor chamber 34a device, on the CIGS hull cell absorbed layer of it and Fig. 4 (h) directly reactive sputtering indium metal zinc target prepare In (OH, S)/and ZnS (O, OH)/ZnO (S) resilient coating is corresponding with the operation of i layer.In sputtering settling chamber 34a, the dolly 343 of may command displacement, speed is identical with dolly 323 basic structures of rapid selenium heat of vulcanization process chamber, place following even resistive heating device and two pairs of temperature thermocouples arranged of substrate 3d, by soft braided wire it is connected with the vacuum chamber controller outside, when substrate surface is carried out resilient coating and the sputter of i layer, substrate temperature is controlled in 80 ℃～350 ℃, preferred 100 ℃～180 ℃; Two～three pairs of midfrequent AC or DC pulse reactive sputtering metallic target 343,345 and 346 are installed in the 34a chamber, they are respectively high purity indium and zinc metal pair target, be separately installed with two cover gas circuit pipelines on every pair of target, sputter that supply work is required and reacting gas, the sputtering sedimentation district is covered by expanded metal, be connected with ground wire separately and do not link to each other with casing, its effect is the plasma sputter between shielding two targets, prevents charged ion bombardment substrate 3d and destroys the structure of hull cell pn knot; Equally, fixed high power radiant heat source 344 is installed in sputtering chamber 34a, they also are positioned in the airtight space 347, and the controllable valve that can open exhaust fast or regulate air pressure is installed on the airtight space 347, and the vacuum nude gauge pipe (not shown) of detected gas pressure.After resilient coating and the sputter of i layer are finished, the substrate 3d that carries out after the rapid thermal treatment on high vacuum top layer is got on the support of getting 351 income substrate bearing mechanisms (not shown) 352 of sheet mechanism in the 35a of sheet chamber via slide valve 341, in getting sheet chamber 35a, be equipped with the substrate transportable supporting device identical with the structure of the 31a of hydrogenation pretreatment chamber, can will be equivalent to batch being that a plurality of substrate 3e of unit are accommodated on the level frame of supporting device, open the gate that vacuum is got sheet chamber 35a, with regard to available transportation fork-truck by the gross the supporting device of substrate 3e get from vacuum and directly transport the sheet chamber, change down the road production process over to.

Embodiment 1

When making CuInSe with nanometer selenides coating _2-xS _xDuring thin film solar cell, the SLG substrate surface is sputter alkali barrier layer and Mo back electrode film respectively, implements roller coating selenides coating CuSe, In respectively at this substrate surface ₄Se ₃(or In ₂Se ₃) and CuSe is respectively once, the In of the preferred poor selenium of the present invention ₄Se ₃(520 ℃ of fusing points) nano paint; Oven dry immediately behind each roller coating coating, the selenides precursor thin film presents CuSe/In ₄Se ₃(or In ₂Se ₃)/CuSe structure, the total Cu/In of film＞1.06, surface C uSe＞bottom CuSe, best than 1.1～1.5, about 4～7 μ m of oven dry back gross thickness (requiring final rapid selenium heat of vulcanization to handle about 0.9～1.8 μ m of absorber thickness of back preparation), the constituent structure of three layers of selenide thin film was than about 4: 10: 6.1, before the last oven dry of forerunner's selenide thin film, need evenly a certain amount of sodium salt of spray, it can obtain big crystal grain dense film when auxiliary selenides precursor thin film rapid selenium heat of vulcanization is handled under the low condition.With the oven dry after forerunner's selenide thin film substrate 3a in accordance with regulations the sheet number be encased on the support of horizontal bearing mechanism in the hydrogenation pretreatment chamber shown in Fig. 5 (a), close the door of vacuum chamber.

Forerunner's selenide thin film rapid selenium heat of vulcanization of the present invention is handled the standard technology program: the valve of opening the hydrogenation 31a of pretreatment chamber vacuum pumping hardware and its interior airtight space 312, simultaneously, heater 311 rises to 290 ℃ with the airtight space internal temperature from room temperature, the preferred range of nanometer forerunner's selenides or electro-deposition forerunner selenides is respectively: 30 ℃～180 ℃ and 30 ℃～290 ℃, be evacuated to high vacuum 1 * 10 ^-3After Pa is above, close the valve of airtight space, injecting hydrogen maintains between 30～60kPa the air pressure of airtight space, keep emptying after 3～5 minutes, refill hydrogen after being evacuated to high vacuum, circulate 3～5 times, make the thorough desorption of organic additive and volatilization or hydrogenation decomposition (15%～18% oxide is by partial reduction in the electro-deposition forerunner selenide thin film) in the nanometer selenides coating, material in the selenides precursor thin film is the pure pure level of electronics, injects Ar+H after the last emptying ₂Gas (is respectively: 50～70% and 30～50%), air pressure to the 0.3～20Pa in the close space of spirit falls, and with the air pressure balance of 32a chamber after open slide valve 320, substrate 3a is pushed on the dolly 323 of rapid selenium heat of vulcanization process chamber 32a, close slide valve 320.

After being positioned on the dolly 323, the pretreated substrate 3a of over hydrogenation just renames as 3b, start dolly substrate 3b back heater, be warming up to 350～550 ℃ (or 450～580 ℃ for containing the preferred of Ga selenides), open the valve of dolly both sides gas circuit simultaneously, inject class H ₂Se gas, selenium atmosphere maintains under the air pressure of 30～80kPa in the airtight space 326, dolly moves back startup high power radiant heat source substrate 3b is carried out scan-type rapid selenium heat-transmission processing, the temperature of glass substrate is controlled at 530～580 ℃, the selenides of substrate surface is rapidly heated to 550 ℃～1100 ℃, the selenides precursor thin film is fully reacted CIS (or CIGS) film that generates big crystal grain densification, because the selenides precursor thin film self is rich steel structure, the rear surface is handled in the rapid selenium heat-transmission can adsorb unnecessary liquid Cu ₂Se closes class H ₂Se gas piping valve is opened the drain tap of airtight space, reduces environment selenium air pressure to 0.5～25Pa, and dolly 323 moves to the position of reactive sputtering target, and the substrate 3b bottom heater on the dolly 323 is in permanent power state of a control.On substrate 3b, carry out reactive sputtering In ₂Se ₃Or In ₂S ₃Neutralization reaction is fallen liquid Cu ₂During Se, the substrate 3b many variations to the thermocouple difference in bottom on the monitoring dolly 323 are by its decision reactive sputtering In ₂Se ₃Or In ₂S ₃Unit power or the deposition on the unit are, and the translational speed of accurately controlling dolly 323; Strict control substrate 3b surface selenide thin film is because reactive sputter-deposition In ₂Se ₃Or In ₂S ₃, the film integral composition is transformed into the sudden change of this thin film physics state (probe temperature) in the poor steel structure process by rich copper, and just copper accounts for the crucial change point of film composition than≤24.5% o'clock.Dolly substrate 3b keeps appropriate translational speed and sputter In all the time ₂Se ₃Or In ₂S ₃Suitable deposition has just been finished the absorbed layer that whole substrate 3b surface evenly, fully is transformed into the CIGS hull cell, closes shielding power supply, Sputtering Ar and reacting gas H ₂Se or H ₂S closes the heater of dolly 323, and it is moved, returns high power radiant heat source place, opens the valve of dolly both sides gas circuit, injects class H ₂Se gas to 30～80kPa, again opening the high power radiant heat source scans more quickly to substrate 3b surface, dolly 323 is carrying out relative motion simultaneously with high power radiant heat source device 324, the crystal boundary of big crystal grain CIS in substrate 3b surface or CIGS and grain surface lug boss are by remelting, it is compound and dissolved the dephasign in the crystal to have reduced effective crystal boundary of hull cell, reaches the purpose that hull cell open circuit voltage Voc is enhanced.Substrate moves near the sputter position, reduces air pressure to the 0.5～25Pa of airtight space, and replacing sputter reacting gas is H ₂S starts dolly heating power supply, travel mechanism and reactive sputtering power supply, reactive sputtering In ₂S ₃Deposit equably to substrate 3b top layer, substrate 3b surface generates high resistant n-CuInS ₂Or n-CuIn ₃(Se _1-x, S _x) ₅, the about 20～40nm of thickness, this moment, the temperature of substrate 3b was approximately 480 ℃～550 ℃.Open slide valve 321, the substrate 3b that selenium vulcanizing treatment is finished sends on the carrying support of storage sheet cooling chamber 33a, at the Ar+H of 0.5～30Pa ₂Natural cooling under the S atmosphere protection.

The substrate 3c that is cooled to below 100 ℃ is transported on the dolly 342 of sputtering settling chamber 34a, the heater on the unlatching dolly 342 and the drain tap of confined space 347, substrate 3c is heated to 80 ℃～350 ℃, and preferred 100 ℃～180 ℃, airtight space is pumped down to high vacuum 1 * 10 ^-3More than the Pa, open the reacting gas on each reactive sputtering target and the valve of Sputtering Ar, keep the air pressure of airtight space, regulate that reaction is appropriate proportioning and flow with sputter gas on each target at 0.2～25Pa, the target of the first sputter target position is the simple metal indium, reacting gas H ₂S+H ₂O, sputter product are that (OH S), wherein comprises a spot of In to In ₂O ₃The material of second and third sputter target position all is the pure zinc of metal, and reacting gas is respectively H ₂S+H ₂O and H ₂S+O ₂Or CO ₂, the sputter product be respectively ZnS (O, OH) with ZnO (S), the reacting gas H on two, three target position ₂The flow of S is different, and sputtering power is also inequality; The resilient coating sputter is in proper order: and In (OH, S)/ZnS (O, OH)/ZnO (S), they can not be reversed or produce other combination.Dolly substrate 3c opens shielding power supply before near each sputter target position, the resilient coating of sequential sputtering hull cell and i layer film, and its thickness is respectively: 15～25nm, 20～30nm and 50～75nm add up to about 90～130nm; Substrate surface is closed the heating power supply on the dolly 342 after all having deposited each layer film, opens the pneumatic control valve on the airtight space 347 fully, is evacuated to high vacuum 1 * 10 ^-3Behind the Pa, open the telecontrol equipment and the high power radiant heat source 344 of dolly, CIS film, resilient coating and i layer to substrate surface carry out flash heat treatment, the zone of its thermal impact only accounts for 1～2 μ m of film skin depth, impels the more closely knit and zinc element sulphur of adsorbed gas desorption, product intergranular in the sputtered film to spread to the top layer of CIS film.Open slide valve 341, the sheet mechanism 351 of getting that substrate 3c is got in the 35a of sheet chamber takes on the support of substrate bearing mechanisms 352, and after substrate reached some, whole carrier was removed vacuum chamber, and substrate changes next operational sequence over to.

Embodiment 1 can prepare two types of thin film solar cells, uses In ₂S ₃In and liquid Cu _xThe open circuit voltage Voc of the CuInSeS hull cell of Se is relative with photoelectric conversion efficiency higher.

Embodiment 2

When making CuIn with nanometer selenides coating _0.7Ga _0.3Se _2-xS _xDuring thin film solar cell, need four kinds of nanometer selenides coating, they are respectively: (CuSe+CuGaSe ₂), Ga ₂Se ₃, In ₄Se ₃(or In ₂Se ₃+ CuInSe ₂), CuSe, modulate them respectively to appropriate viscosity, roller coating and oven dry are implemented in continuity ground on substrate Mo film, four kinds of disposable serially film forming of selenides coating, its forerunner's selenide thin film is configured to: (CuSe+CuGaSe ₂)/Ga ₂Se ₃/ In ₄Se ₃(or In ₂Se ₃+ CuInSe ₂)/CuSe, the total Cu/ of film (In+Ga)＞1.06, the atomic structure ratio of four-level membrane composition is: (4+4): 1: 3.5: 12.1, about 4～7 μ m of forerunner's selenide thin film thickness, wherein in the film each elementary composition than Ga/ (In+Ga) 〉=0.3, Se/M＜I, surface C uSe＞bottom CuSe.The characteristics of this kind CIGS hull cell are that gallium element concentrates on bottom in the selenides precursor thin film, and the indium selenium compound of poor selenium is on gallium selenium compound phase, and rapid selenium heat of vulcanization treatment process is substantially the same manner as Example 1; The high power radiant heat source is restarted after the heating in advance in the substrate bottom, because the thermal conduction characteristic of selenides precursor thin film and the difference of indium gallium element diffusion coefficient, the preferential CGS semiconductive thin film that generates high gallium of bottom, carry out the counterdiffusion between the indium gallium element again, the indium gallium element is not even distribution at thickness direction in the final CIGS film, naturally form the Gradient distribution of gallium element and the back of the body electric field of hull cell, the formation of back of the body electric field has improved the collection and the battery conversion efficiency of hull cell charge carrier, add the formed shallow embedding knot of top layer doping element sulphur, the V-shaped distribution of absorbed layer semiconductor band gap of CIGS hull cell, the hull cell of making is compared with embodiment 1, has increased substantially its cost performance.

Embodiment 3

Electrochemical deposition selenides precursor thin film prepares CuInSe _2-xS _xThin film solar cell.The proportioning of its electric depositing solution composition is: 2.6mMolL ^-1CuCl ₂2H ₂O, 9.6mMolL ^-1InCl ₃With 5.5mM olL ^-1H ₂SeO ₃, LiCl0.236MolL ^-1And the ph=3 buffer of interpolation Potassium Hydrogen Phthalate and sulfamic acid composition, three electrode constant potential system is adopted in PH～2.6 that record electroplating solution, and reference electrode is saturated calomel electrode (SCE).With sputtering sedimentation the SLG substrate of alkali barrier layer and Mo back electrode film put into above-mentioned electroplating solution, anticipated substrate Mo back electrode film 1 minute at-0.5V, substrate takes out the back and dries up with deionized water rinsing and high pure nitrogen, after shelving certain hour, put into electroplating solution once more and carry out electro-deposition, 5～8 minutes Cu of elder generation-0.2V pre-deposition _2-xSe is-0.5V deposition 15 minutes ,-0.6V deposition 45 minutes, again-0.2V deposition 5～8 minutes; The substrate that takes out is rinsed the back well and is dried up with high pure nitrogen, and the surface of selenides predecessor film is silver gray, has smooth, fine and close outward appearance, about 1.8～2.4 μ m of thickness, and the film composition structure is: Cu _2-xSe/CuInSe ₂/ Cu _2-xSe, Cu/In＞1.06, oxygen content is about 15% in the film, top layer Cu _2-xSe＞bottom Cu _2-xSe, substrate is put into a certain amount of sodium salt of spray before the 31a of hydrogenation pretreatment chamber of rapid selenium heat of vulcanization processing unit of Fig. 5, carry out according to embodiment 1 standard technology program, the substrate that obtains prepares contact electrode through the electrode series connection attended operation-laser scribing heat treatment of integrated battery, processes such as the anti-quick-fried punching press divisional plane electrode of sputter ZnO:Al low-resistance transparent window layer and laser, the just basic integrated package that obtains the CIS hull cell of calculating, the periphery of cleaning large area film battery and welding electrode lead-in wire, just can carry out the test of large tracts of land assembly photoelectric conversion efficiency, carry out the packaging technology operation of photovoltaic module.

Embodiment 4

Electrochemical deposition selenides precursor thin film prepares CuInGaSe _2-xS _xThin film solar cell, wherein forerunner's selenide thin film only is that the composition and the semiconductor band gap that depend in the sedimentation potential control film are V-shaped, film is that one-step method obtains rich Cu selenides precursor thin film.The proportioning of its electric depositing solution composition is: 2.0mMolL ^-1CuCl ₂, 10.0mMolL ^-1InCl ₃, 15.0mM olL ^-1GaCl ₃With 5.0mM olL ^-1H ₂SeO ₃, 0.236MolL ^-1LiCl adds Potassium Hydrogen Phthalate and sulfamic acid ph=3 buffer, and three electrode constant potential system is adopted in PH～2.6 that record solution in the electrolysis tank, and reference electrode is saturated calomel electrode (SCE).Substrate is immersed earlier in the special-purpose preliminary treatment cell liquid, anticipated on the substrate back electrode Mo film 1 minute at-0.5V, Cu in Mo and the solution _xThe chemical replacement reaction takes place in Se, and the thin one deck Cu of deposition _xSe takes out the back and dries up with deionized water rinsing and high pure nitrogen, shelve certain hour after, put into the electrolysis special tank liquor once more and carry out electro-deposition; 5～8 minutes (Cu of elder generation-0.2V current potential pre-deposition _2-xSe+CuGaSe ₂), obtained high gallium [Cu in 25 minutes in-0.75V current potential deposition _2-xSe+Cu (In _0.5, Ga _0.5) Se ₂],-0.5V current potential deposition 35 minutes, again-0.2V current potential deposition 5 minutes and-0.8V current potential deposition 3 minutes, the selenides precursor thin film is high gallium content at bottom and surface, because containing the gallium selenides all is high-melting-point solid formations, the Ga elemental diffusion is relatively difficult in the film, has determined it to play the framework effect in the remelting recrystallization process of selenides precursor thin film; It is clean that the disposable electro-deposition substrate of control sedimentation potential takes out afterflush, dry up and place in the baking oven with high pure nitrogen and dry, this electrodeposited film surface presents smooth, fine and close silver gray outward appearance, about 1.8～2.4 μ m of thickness, and the layer structure of film composition is distributed as: (Cu _2-xSe+CuGaSe ₂)/[Cu (In _0.5, Ga _0.5) Se ₂]/Cu (In _0.8Ga _0.2) Se ₂/ (Cu _2-xSe+CuGaSe ₂)/CuIn _0.4Ga _0.6Se, Cu/ in the film (In+Ga)＞1.06, Se/M＜1, total composition CuSe+CuIn _0.7Ga _0.3Se ₂, its mesexine CuSe＞bottom CuSe, superficial layer Ga element＜bottom Ga element, oxygen content about 15～17% in the film; Standard technology program according to embodiment 1 is carried out, and just can obtain the high-quality CIGS thin film solar cell of fine and close big crystal grain, the V-shaped distribution of band gap.

Embodiment 5

Electrochemical deposition selenides precursor thin film prepares two-sided light-permeable type CuInGaSe _2-xS _xThin film solar cell.Select for use commercial ito glass substrate to carry out the electro-deposition of selenides precursor thin film.Ito glass ultrasonic cleaning 10min and carry out the operation that nesa coating is cut apart in laser scribing in isopropyl alcohol before the deposition, select sulfate electrochemical deposition system for use, reference electrode be saturated mercuric sulfate electrode (current potential of MSE relative standard hydrogen electrode for+650mV), 80 ℃, do not have to stir, constant potential electro-deposition Ga in the aqueous solution of high pure nitrogen deoxygenation ₂Se ₃And CuIn _0.7Ga _0.3Se ₂The thick Ga of electro-deposition 0.2～0.3 μ m on ITO of elder generation ₂Se ₃, sedimentation potential is-1.1V (with respect to saturated calomel electrode MSE) that solution composition is: the SeO of 1mM ₂, the Ga of 1mM ₂(SO ₄) ₃And 0.3MK ₂SO ₄, the pH value is transferred to 2.4 with sulfuric acid.Deposit CIGS again, depositing operation: solution ratio: 0.3MK ₂SO ₄(pH2.4, H ₂SO ₄Regulate), 1.0mMCuSO ₄, 3.0mMIn ₂(SO ₄) ₃, 3.0mMGa ₂(SO ₄) ₃And 1.7mMSeO ₂Sedimentation potential is-0.9V, and film thickness is about 1.8～2.4, Cu/ in the film (In+Ga)＞1.06, Se/M＜1, top layer Cu _2-xSe＞bottom Cu _2-xSe, top layer Ga element＜bottom Ga element.Carry out according to embodiment 1 standard rapid selenium heat of vulcanization treatment process program, the substrate that obtains prepares contact electrode, sputter ZnO:Al low-resistance transparent window layer, the anti-quick-fried punching press of laser through the electrode attended operation-laser scribing heat treatment of integrated battery and cuts apart electrode and technological operation programs such as contact conductor and encapsulation, the glass generating curtain wall parts of special purpose CIS hull cell integrated package have just been obtained, its positive transmission generating by solar, reverse side is accepted the infrared light of scattering, the optical energy power of stackable two-sided absorption.

Embodiment 6

Present embodiment is that nanometer selenides coating is made CuIn _0.7Ga _0.3Se _2-xS _xPreferred version in the thin film solar cell.The method of it and embodiment 2 is basic identical, also needs four kinds of nanometer selenides coating, implements roller coating and oven dry on substrate Mo electrode film, can the disposable film forming in substep continuity ground, and four kinds of selenides coating are respectively: CuSe+CuGaSe ₂, Ga ₂Se ₃, In ₄Se ₃(or In ₂Se ₃+ CuInSe ₂), (CuSe+CuGaSe ₂); Its precursor thin film is configured to: (CuSe+CuGaSe ₂)/Ga ₂Se ₃/ In ₄Se ₃/ (CuSe+CuGaSe ₂), the Cu/ (In+Ga)＞1.06 that film is total, the atomic structure ratio is in the four-level membrane composition: (4+3): 1: 3.5: (12.1+1), about 4～7 μ m of forerunner's selenide thin film thickness, wherein in the film each essential element composition than Ga/ (In+Ga) 〉=0.3, Se/M＜1, top layer CuSe＞bottom CuSe, top layer Ga element＜bottom Ga element.Its rapid selenium heat of vulcanization treatment process is identical with embodiment 2, and the open circuit voltage Voc of hull cell is than the height that lacks of embodiment 2, the V-shaped distribution of semiconductor band gap of hull cell.

Embodiment 7

Three step electro-deposition (Cu _2-xSe+CuGaSe ₂)/In ₄Se ₃/ Cu _2-xSe selenides precursor thin film prepares CuInGaSe _2-xS _xThin film solar cell, the three-electrode system of standard is adopted in electro-deposition, and positive electrode adopts flow cell channel structure capable of circulation with graphite fiber cloth, reference electrode Ag/AgCl electrode, and electrolyte uses circulating pump to supply with and form circulation.The solution ratio of first step deposition: 0.3MK ₂SO ₄, 1.0mMCuSO ₄, 5.0mMGa ₂(SO ₄) ₃And 1.7mMSeO ₂, H ₂SO ₄Regulate pH=2.2 ± 0.2; Deposition is by the constant potential process control, with respect to the sedimentation potential of Ag/AgCl electrode be-0.75～-1.0V, the ratio of scalable [Cu]/[Ga] is rich Cu or poor Cu; The solution ratio of the second step deposition: the SeO of 1mM ₂, the In of 1mM ₂(SO ₄) ₃, 0.3MK ₂SO ₄With suitable organic additive, the pH value is transferred to 2.2 with sulfuric acid, deposits the In of poor selenium ₄Se ₃The additive that depends on ppm amount in the solution is controlled; The 3rd step was changed electric depositing solution, carried out Cu _2-xThe electro-deposition of Se.Selenides precursor thin film Cu/ (In+Ga)＞1.06, Se/M≤1, Ga/ (Ga+In)=0.3～0.36, top layer Cu _2-xSe＞bottom Cu _2-xSe, top layer Ga element＜bottom Ga element, oxygen content is about more than 15% in the film.Carry out the rapid selenium heat of vulcanization of selenides precursor thin film according to embodiment 1 standard technology program and handle, carry out follow-up other depositing operation and operation again, just can obtain the CIGS thin film solar cell similar, if the 3rd step electrodeposition process interpolation Ga to embodiment 2 ₂(SO ₄) ₃, just can obtain the hull cell of embodiment 6.

Embodiment 8

The cell substrate of forerunner's selenide thin film noted earlier all is that horizontal positioned is carried out associative operations such as processing of rapid selenium heat of vulcanization and sputtering sedimentation, scope according to core technology of the present invention, equipment that also can the vertical placement substrate of design and fabrication, respectively with substrate upright operation in Fig. 4 photovoltaic module production process main flow and Fig. 5 in-line arrangement rapid selenium heat of vulcanization processing unit, miscellaneous equipment is made corresponding adjustment, and it does not exceed the scope of core technology of the present invention.

Like this, substrate in the first hydrogenation pretreatment chamber all is vertical type and places, hydrogenation pretreatment chamber can push two selenides precursor thin film substrates at every turn and enter the second rapid selenium vulcanizing treatment chamber, substrate frame on the second Room dolly also is vertical type and places, settle heater in the middle of the substrate frame, can toast the substrate of both sides external, and arrange many thermocouple, can measure simultaneously the temperature value of multiple spot on the substrate of both sides, than the higher and saving energy of operating efficiency of horizontal positioned; The both sides of substrate frame dolly are two of symmetrical placement high power radiant heat source movably respectively, and they can be opened simultaneously and move; The other high pure metal indium reactive sputtering target pair devices of settling two symmetries to place of removable radiant heat source, they are according to towards the vertical installation of the symmetric position of dolly substrate frame; The goalkeeper that the slide valve of corresponding each chamber is opened is wideer, once has two substrates to pass in and out simultaneously, gets, feeding mechanism will carry out operation simultaneously to two substrates.In like manner, the 3rd substrate cooling chamber, the 4th sputtering chamber and the 5th are got the sheet chamber and are all done corresponding change with first, second chamber, and inner is plumbness from the horizontal operation Status Change; Wherein, need acquire nearly one times of device in the 4th sputtering chamber, have four to six pairs of metal reaction sputters to target, they present symmetry settles with vertical, and a pair of high power radiant heat source also is symmetry and plumbness, and substrate is presented horizontal portable scanning.It is basic identical that the selenides precursor thin film rapid selenium heat of vulcanization of its operation sequence and technology and embodiment 1 is handled standard technology, its operating efficiency doubles than the operating type of horizontal positioned base wafer assembly, is more suitable in the manufacturing of big substrate or super large substrate membrane cell photovoltaic assembly.

Industrial utilizability

The present invention is applicable to by coating roller coating of nanometer selenides or water-bath electrochemical deposition and prepares the selenides precursor thin film, handle by rapid selenium heat of vulcanization the selenides precursor thin film, can directly, serialization prepare CIGS hull cell optical absorbing layer, resilient coating and i layer, again by follow-up cell electrode series connection ways of connecting (intraconnected integrated package), be utilized with regard to can be used as the high large tracts of land photovoltaic module of photoelectric conversion efficiency, be used for generating electricity by way of merging two or more grid systems of photovoltaic plant or architecture-integral.

Although the present invention explains with reference to preferred embodiment and Figure of description and embodiment, to one skilled in the art, various uses of the present invention and distortion can not depart from essence of the present invention and scope and finish.Therefore, can think that at this detailed specification and accompanying drawing be not limiting the scope of the invention, it can derive from claims of front, and they are equivalent legally.

Description of reference numerals

Code	Explanation	Code	Explanation	Code	Explanation
						1a	Common soda-lime glass	2a	CuGaSe 2+CuSe	20	Vacuum chamber
1b	Alkali barrier layer (SiO, SiN, TiN)	2b	CuSe		21							Alkali barrier layer sputtering target
						1c	Mo back electrode film	2c	Ga 2Se 3	22	Mo back electrode thin film sputtering target
1d	The poor copper absorbed layer of hull cell	2d	In 4Se 3(or In2Se 3)	23	Laser cutting Mo device
						1e	The hull cell cushion	2e	CuSe(+Ga 2Se 3)	24	Rapid selenium heat of vulcanization process chamber
1f	The electrically conducting transparent Window layer	2f	Liquid CuXSe	25	The high power radiant heat source
						1g	Rich copper contact electrode	2g	Rich copper absorbed layer	26	The pure indium reactive sputtering of metal target
3a	Selenides precursor thin film substrate	31a	Hydrogenation preliminary treatment vacuum chamber	27	The pure zinc reactive sputtering of metal target

3b	Selenium vulcanizing treatment substrate	32a	Rapid selenium heat of vulcanization process chamber	28	The pure zinc reactive sputtering of metal target
						3c	CIGS absorbed layer substrate	33a	The stocker cooling chamber	29	The pure indium reactive sputtering of metal target
3d	Sputter cushion substrate	34a	The cushion sputtering chamber	30	Vacuum chamber
						3e	Treat laser treatment or substrate to be rule	35a	Vacuum is got the sheet chamber	31	Laser prepares rich copper contact electrode
310	The heat radiation screening cover	311	Heater	32	ZnO:Al conductive window sputtering target
						312	Hydrogenation preliminary treatment airtight space	313	The substrate delivery device	33	The anti-quick-fried divisional plane electrode that rushes of laser
320	Slide valve	321	Slide valve	323	Can control mobile/heating dolly
						324	Removable high power infrared source	325	The pure indium reactive sputtering of metal is to target	326	Rapid selenium vulcanizing treatment airtight space
331	Get sheet mechanism	332	The substrate delivery device	333	Substrate bearing mechanism
						340	Slide valve	341	Slide valve	342	Can control mobile/heating dolly
343	The pure indium reactive sputtering of metal is to target	344	Fixed high power infrared source	345	The pure zinc reactive sputtering of metal is to target
						346	The pure zinc reactive sputtering of metal is to target	347	Cushion sputter airtight space
351	Get sheet mechanism	352	Substrate bearing mechanism

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[10]Calixto?ME，Dobson?KD，McCandless?BE，et?al.Controlling?growth?chemistry?and?morphology?ofsingle-bath?electrodeposited?Cu(In，Ga)Se ₂thin?films?for?photovoltaic?application.Journal?of?the?ElectrochemicalSociety?2006；153(6)：521-528.

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Claims (10)

1. an antivacuum low-cost legal system is equipped with the selenides precursor thin film and the rapid selenium sulfuration heat-treating methods of CIGS thin film solar cell, it is characterized in that, comprise: (1) is sequential applications nanometer selenides coating and drying and forming-film on the molybdenum electrode film of rigid substrate substrate, or order plating (or electro-deposition) different component nano microcrystalline selenides precursor thin film, this selenides precursor thin film composition with structure is respectively: (CuGaSe ₂+ CuSe), (Ga ₂Se ₃+ CuSe), In ₄Se ₃(or In ₂Se ₃+ CuInSe ₂), CuSe[or (CuSe+Ga ₂Se ₃), (CuSe+CuGaSe ₂)] order choice formula combination; (2) the one pile of rigid substrate that has prepared this selenides precursor thin film is placed in the airtight space in the vacuum chamber, by heating, inject hydrogen from room temperature to 290 ℃ high vacuum, be evacuated to high vacuum and the multi-pass operation of injecting hydrogen, the first hydrogenation preliminary treatment of the argon gas+hydrogen that reinjects at last again; (3) second selenizings are handled, and with this pile substrate from top to bottom or from bottom to top parallel moving, push another relative airtight space respectively blocks ofly, start the heating of substrate bottom earlier, and import class H to second airtight space ₂Se gas, keeping enough selenium air pressure (20～80kPa) time, substrate in moving carried out the fixed form heating of Fast Heating up and down or the heating of top scan-type and bottom moving with substrate and heat up, substrate itself remains at 350 ℃～580 ℃, the substrate top layer is because the movable type scanning heating of high power radiant heat source, forerunner's selenide thin film can be rapidly heated 350 ℃～1100 ℃, impels Cu in the selenides precursor thin film _xSe/ and In ₄Se ₃Be heated mutually and melt (523 ℃ of liquefaction) fast, the densification of auxiliary CIGS film crystal liquid phase reactor growth and film self, after the CIGS film of big crystal grain densification generated, its top layer can be oozed out trace or adsorb unnecessary liquid Cu _xSe; (4) the 3rd selenium vulcanizing treatment, base substrate are transferred to the sputter position with the substrate motion when 520 ℃～580 ℃ preference temperatures, regulate airtight space air pressure to 0.3～25Pa, by reactive sputtering In ₂Se ₃Or In ₂S ₃Neutralization reaction is fallen the unnecessary liquid Cu in substrate top layer _xSe, strict control substrate surface CIGS film composition is transformed in the poor steel structure process reactive sputtering In by rich copper ₂Se ₃Or In ₂S ₃Amount; (5) the 4th selenizings are handled, and reactive sputtering finishes the back and increases airtight space importing class H ₂The Se gas flow, when making its environment selenium air pressure reach 20～80kPa, the high power radiant heat source carries out the heat scan of faster speed to substrate; (6) the 5th high temperature vulcanized processing, emptying class H ₂Behind the Se gas, refill reactive sputtering gas H ₂S+Ar keeps air pressure at 0.3～25Pa, and substrate carries out reactive sputtering In after moving to the sputter position ₂S ₃, In ₂S ₃Generate n type Cu (In on the top layer of film _1-xGa _x) SSe or Cu (In _1-yGa _y) ₃(Se _1-xS _x) ₅Resistive formation; Vulcanize in the heat treated operating process at above-mentioned rapid selenium, second airtight space alternately charges into class H ₂Se gas or H ₂S+Ar gas carried out high vacuum exhaustion operation in the middle of it, and air pressure has to rise to have and falls; (7) will be transferred to the 3rd airtight cooling space through the substrate after the processing of rapid selenium heat of vulcanization; Like this, the whole pile of substrate in first space is included into the 3rd cooling space after through the rapid selenium vulcanizing treatment, and this space is injected with Ar+H ₂The S mist guarantees that base substrate drops in 110 ℃ of processes by 580 ℃ gradually, and the selenium element sulphur does not run off in the CIGS thin-film material; (8) substrate after the cooling is pushed into the 4th airtight space respectively, carry out the high resistant eigen I n (OH of metallic target reactive sputter-deposition hull cell, S)/and ZnS (O, OH)/ZnO (S) resilient coating and i layer, the target of two or three pairs of simple metal sputtering targets and the collocation of reacting gas foot: In/ (Ar, H ₂S and H ₂O), Zn/ (Ar, H ₂S and H ₂O) and Zn/ (Ar, H ₂S and O ₂Or CO ₂), the temperature of base substrate is controlled at 110 ℃～350 ℃ in the sputter procedure; Airtight space was pumped down to high vacuum state after sputter was finished, and started the quick scanning substrate of high power radiant heat source surface; (9) with reactive sputter-deposition the substrate behind high resistant resilient coating and the i layer be included into the 5th cooling space respectively; Operation that substrate cooling back just can change that next laser processing is handled or the electrode of the battery integrated package of machinery line is connected in series over to, or deposit the low-resistance transparent conducting ZnO: Al film operation.

2. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, the order that its selenides precursor thin film can adopt six kinds of nano microcrystalline selenides coating to make up is accepted or rejected and is constituted composition and each layer structure that applies selenides precursor thin film material, promptly sequential applications and drying are made the selenides precursor thin film on substrate Mo back electrode film, it is characterized in that, have the CuSe layer (phase) of rich selenium or/and the In of poor selenium in the selenides precursor thin film ₄Se ₃The layer (phase), this low melting point CuSe or/with In ₄Se ₃Nanometer selenide material shared volume ratio＞30% in the selenides precursor thin film; Cu/ in the selenides precursor film (In+Ga)=1.01～1.3, preferred Ga/ (Ga+In)=0.15～0.35, Se/M≤1; The CuSe of selenides precursor thin film mesexine＞bottom CuSe, best than 1.1～1.5, can not lack CuSe near molybdenum electrode film place; Bottom Ga element＞surface Ga element in the selenides precursor thin film, best than 9.0～10.0, or the Ga element only is distributed in the film place near molybdenum electrode.

3. the selenides precursor thin film of narrating according to claim 1 and the method for rapid selenium heat of vulcanization Processing of Preparation thin film solar cell, the structural feature of its electro-deposition selenides precursor thin film is: can adopt the step order electro-deposition of control sedimentation potential or the substep order electro-deposition of replacing different electrolytes composition to prepare the selenides precursor thin film, have independently Cu in the film _2-xThe Se phase allows directly to deposit in the electro-deposition selenides precursor thin film a certain amount of quaternary CuInGaSe ₂Microcrystal grain, Cu/ in the electrodeposited film (In+Ga)=1.01～1.3, preferred Ga/ (Ga+In)=0.15～0.35, Se/M≤1; Electro-deposition selenides precursor thin film mesexine Cu _2-xSe＞bottom Cu _2-xSe, best than 1.1～1.5, should not lack Cu near molybdenum electrode film place _2-xSe, low melting point Cu _2-xVolume ratio＞20% of the shared selenides precursor thin film of Se.

4. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, it is characterized in that, rapid selenium heat of vulcanization treatment process all carries out in the airtight space in vacuum chamber, and it is equipped with blocking class H ₂Se gas or Ar+H ₂The valve that S gas is supplied with, the operational sequence that can carry out vacuum exhaust in the airtight space.

5. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, it is characterized in that the class H that selenizing heat treatment is used ₂Consisting of of Se gas ingredients: (30%～50%) Ar+ (25%～35%) H ₂+ (15%～45%) H ₂Se; Reactive sputtering In ₂Se ₃Sputter gas be argon gas, reacting gas is H ₂Se or class H ₂Se gas; Reactive sputtering In ₂S ₃Sputter gas be argon gas, reacting gas is H ₂S gas; The selenides precursor thin film and be transformed into fine and close big crystal grain fully, when poor slightly steel structure CIGS film begins flash heat treatment, selenium air pressure in its airtight space environment maintains 20～80kPa, but when the resilient coating of heat treatment CIGS hull cell and i layer, but be in the high vacuum environment and carry out.

6. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, the selenides precursor thin film is rich steel structure, the size of copper content all can not be accurately controlled in the film, need the rapid selenium heat of vulcanization to handle and accurately adjust copper content final in the film, make it be suitable for preparing the requirement of high efficiency CIGS hull cell semiconductor device, copper content should the strict scope of controlling be 20%～24.0% in its absorbed layer.It is characterized in that the selenides precursor thin film can ooze out or adsorb micro-liquid Cu through the top layer after the Fast Heating _xSe, the base substrate temperature maintenance is at 520 ℃～580 ℃, when the heating of bottom is in permanent power state of a control, by reactive sputter-deposition In ₂Se ₃Or In ₂S ₃With film top layer liquid Cu _xThe method of Se neutralization reaction is controlled the copper content in the film composition; Strict monitoring substrate membrane surface liquid Cu _xSe be neutralized react away or film composition in copper content descend when crossing the theoretical copper content 24.5% of CIGS semi-conducting material feature, bottom probe temperature value with permanent power heating condition subtegulum selenide thin film occurs significantly sporting sign, is accurately determining by heat treatment and sputtering sedimentation In ₂Se ₃Or In ₂S ₃Required In when making the selenides precursor thin film be transformed into the CIGS absorbed layer thin-film material of slightly poor steel structure fully ₂Se ₃Or In ₂S ₃Amount.

7. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, selenides precursor thin film on the back electrode molybdenum film is handled the place one's entire reliance upon heating in vacuum mode of uniqueness of the present invention of the fine and close PV of big crystal grain (photovoltaic) level film crystal that is transformed into by the rapid selenium heat of vulcanization, it is characterized in that, the substrate of selenides precursor thin film bottom adopts the mode of following the fixed heater that substrate moves all the time to heat, or does not follow substrate and move and but keep the lower heating amount even all the time, the mode of large tracts of land balanced heating heats; The top of selenides precursor thin film or the outside high power radiant heat source that adopts relative motion or pulse mode scan selenide thin film or the heating of dynamical fashion, the heating that the one dimension direction is arranged is uniform all the time, the heating of another dimension direction of motion is pulse or dynamic all the time, the heat that adds up of its large tracts of land heating should be uniform, when top or the heating of outside high power radiant heat source, selenide thin film is different with the residing temperature of substrate in most cases, exist evident difference, the pulse of top or outside or the heat that adds of scan mode only have very big influence to selenide thin film, and be less relatively to the influence of substrate; The bottom of substrate exists the point for measuring temperature more than three all the time, and the orientation of point for measuring temperature is consistent with the substrate direction of motion, and the temperature value that obtains is used to carry out the control of substrate bottom heated condition, or the control of other and this film related physical quantity.

8. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, the selenides precursor thin film in the atmosphere that high selenium is pressed by remelting crystallization again, top layer absorption or the liquid Cu of oozing out _xSe is by the In of reactive sputtering ₂Se ₃Or In ₂S ₃Neutralization reaction is fallen, and it is characterized in that the top layer liquid Cu _xSe is by the In of reactive sputtering ₂Se ₃Or In ₂S ₃When neutralization reaction is fallen, tangible flex point can appear in the temperature test curve of control substrate bottom heating power, illustrate that this selenide thin film is transformed into the semi-conducting material that meets stoichiometric proportion, is poor slightly steel structure fully, meet the essential condition of preparation hull cell absorbed layer fully; The In of sputtering sedimentation ₂Se ₃Make selenide thin film top layer semiconductor band gap smoothly descend the In of sputtering sedimentation ₂S ₃Selenide thin film top layer semiconductor band gap is smoothly risen, the about 40～60nm of its thickness; Subsequently, film surface continues reactive sputtering In ₂S ₃, will generate n type high resistant Cu (In on the top layer of selenide thin film _1-yGa _y) ₃(SxSe _1-x) ₅Thin-film material, form the homogeneity shallow embedding will prepare hull cell and tie the about 20～40nm of its thickness.

9. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, after handling through the rapid selenium heat of vulcanization, the selenides precursor thin film has been transformed into the PV level film crystal of big crystal grain densification, and then the resilient coating of deposit film battery and i layer continuously again, the pn knot that guarantees hull cell is not exposed to formation contaminating impurity and surface oxidation in the atmosphere, influence the device quality of hull cell, it is characterized in that, the absorbed layer surface of CIGS hull cell directly, reactive sputter-deposition In (OH continuously, S)/ZnS (O, OH)/thin-film material of three kinds of compositions of ZnO (S) constituted the resilient coating and the i layer of hull cell, its thickness is respectively: 15～25nm, 20～30nm and 50～75nm, add up to about 85～130nm, the sedimentary sequence of each thin-film material can not change, the boundary of material composition can be fuzzyyer, and wherein sulfur content reduces gradually, oxygen content increases gradually; Two or the three pairs of reactive sputterings are respectively pure indium of metal and pure zinc to the target of target, the reactive sputtering mode adopt the plane to target or bicylindrical shape rotating magnetron to target, shielding power supply adopts the power supply of DC pulse or midfrequent AC working method, the porous metals gauze screen covers this working region to the target sputtering sedimentation, and uncharged deposit passes thin thin wire netting and is deposited on formation resilient coating and i layer on the absorbed layer.

10. the antivacuum low-cost legal system of narrating according to claim 1 is equipped with the method for the selenides precursor thin film and the rapid selenium heat of vulcanization Processing of Preparation thin film solar cell of CIGS thin film solar cell, can set up the substrate that deposits the selenides precursor thin film through the continuous processing in the rapid selenium heat of vulcanization processing unit according to this method, directly prepare CIGS thin film solar cell optical absorbing layer, the first mode of manufacture line of resilient coating and i layer, and big substrate, behind roller coating of super large substrate or the electro-deposition selenides precursor thin film, enter rapid selenium heat of vulcanization processing unit in the upright mode of double-basis sheet, sputter prepares resilient coating and i layer and the integrated integrated apparatus that connects processing and sputter transparent conductive film of vacuum chamber inner laser electrode, a direct step is finished the second mode of manufacture line of CIGS thin-film cell photovoltaic integrated package all process steps, it is characterized in that (1) first kind of mode of manufacture line structure is: 1. hydrogenation pretreatment chamber, 2. rapid selenium heat of vulcanization process chamber, 3. store up the sheet cooling chamber, 4. sputter resilient coating and i floor chamber and 5. get five relatively independent working cells such as sheet chamber and be connected in series by slide valve and form; Wherein, but the supporting device of 1. settling oscilaltion, integral body to be handled upside down in the airtight space in the hydrogenation pretreatment chamber, and there are heater and heat radiation screening plate in the outside, but the mechanism of gas introduction tube, valve and vacuum exhaust; 2. the dolly of may command displacement and speed is installed in the airtight space of rapid selenium heat of vulcanization process chamber, place pending substrate on the dolly, it is many to thermocouple that dolly substrate bottom is arranging that equably resistive heating device contacts with substrate, the mode that can carry out substrate backside controllable temperature or firm power heats, dolly top is installed with may command displacement, the high power radiant heat source of speed and energy, it can carry out quick scan-type heating to substrate upper epidermis film, the dolly both sides are equipped with fixing gas introduction tube, ingress pipe offers the nozzle bore of a plurality of even layouts on the tube wall of dolly direction, gas flows to the substrate upper surface that moves from nozzle bore, and dolly top also is equipped with two circuits of a group reaction sputter target pair device and sputter and reacting gas; 4. be equipped with equally in the airtight space of sputter resilient coating and i floor chamber with rapid selenium heat of vulcanization process chamber in the dolly of same size, two circuits of two or three group reaction sputters to target and sputter and reacting gas are installed on dolly top in proper order, the material of sputtering target is respectively pure indium of metal and pure zinc, and sputter is installed with fixed high power radiant heat source to the centre of target is forward.(2) second kinds of mode of manufacture line structures are: 1. hydrogenation pretreatment chamber, 2. rapid selenium heat of vulcanization process chamber, 3. store up the sheet cooling chamber, 4. sputter resilient coating and i floor chamber, 5. the laser Integrated electrode connects processing and sputter transparent conductive film chamber and 6. gets six relatively independent working cells such as sheet chamber and is connected in series by slide valve and forms; Wherein, 1. the substrate in the hydrogenation pretreatment chamber all is vertical placement, but the supporting device that the vertical substrate of move left and right, integral body can be handled upside down is installed in its airtight space, and other parts are corresponding with being provided with of aforementioned hydrogenation pretreatment chamber; 2. the dolly of may command displacement and speed is installed in the airtight space in the rapid selenium heat of vulcanization process chamber, erect on the dolly and placing two pending back-to-back substrates, substrate presents the setting placement by frame on the dolly, substrate on end resistive heating device and the both sides substrate is contacted many to thermocouple by the frame intermediate arrangement, can carry out the heating of controllable temperature or firm power mode simultaneously to the back of both sides substrate, the moveable carriage both sides also respectively symmetry may command displacement is installed, two high power radiant heat source of speed and energy, can carry out vertically evenly the surface film of dolly substrate simultaneously by the substrate on the frame, the laterally heating of scan-type fast, the dolly both sides be separately installed with fixing gas introduction tube up and down, ingress pipe is near the nozzle bore that offers a plurality of even layouts on the tube wall of dolly substrate direction, gas flows to the surface of mobile substrate from nozzle bore, the nozzle pipeline of two road selenium gases is installed before and after the direction of motion of removable high power radiant heat source equally, guarantee the Fast Heating zone effectively, the supply of selenium element equably, dolly also is equipped with the reactive sputtering target pair device of two symmetrical high pure metal indium targets of placing and two circuits of sputter and reacting gas by the both sides of horse, and they are according to the installation of leaning on the vertical mode of symmetric position of frame substrate towards dolly; 4. the indoor dolly of sputter resilient coating and i layer equally also is that vertical is placed by frame, close with the dolly function of rapid selenium heat of vulcanization process chamber, dolly is installed four, six groups by the both sides of frame substrate in the setting mode and is faced substrate direction, the reactive sputtering target pair device of symmetry placement and two circuits of sputter and reacting gas, to middle forward two the high power radiant heat source fixtures that are installed with in vertical mode towards substrate that have of target; 5. the laser Integrated electrode connects that processing and sputter transparent conductive film are indoor dolly equally, what dolly was upright does not heat and temperature measuring equipment by having on the frame, but up and down two laser processing devices of fast moving and the accurate stepping of adaptive control are installed the bilateral symmetry of vacuum chamber, transparent window by vacuum chamber wall, laser can carry out the preliminary treatment of contact electrode and the processing of anti-quick-fried die-cut face electrode film to substrate surface, dolly is equipped with the vertical sputter of placing with symmetry of many groups to target by the substrate both sides of frame, can carry out the sputter of the transparent conductive film of ZnO:Al ceramic target; The many groups of manipulators that can carry out the propelling movement of two substrates or fetch, shift are simultaneously arranged in the middle of this mode of manufacture line.

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