CN101159298A - Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer - Google Patents

Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer Download PDF

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CN101159298A
CN101159298A CNA2007101779145A CN200710177914A CN101159298A CN 101159298 A CN101159298 A CN 101159298A CN A2007101779145 A CNA2007101779145 A CN A2007101779145A CN 200710177914 A CN200710177914 A CN 200710177914A CN 101159298 A CN101159298 A CN 101159298A
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film
cu
thin
alloy
se
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CN100466305C (en
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果世驹
聂洪波
王延来
王义民
杨霞
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北京科技大学
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/52Manufacturing of products or systems for producing renewable energy
    • Y02P70/521Photovoltaic generators

Abstract

The invention provides a method of preparing an In-enriched light absorption layer for a CuInSe2 thin-film solar battery, belonging to the preparation of CuInSe2 semiconductor thin films. The method adopts coating-sintering process, and uses Cu-In alloy, Cu-In alloy and Se powder as raw material. The method comprises mixing Cu-In alloy, Cu-In alloy and Se powder with a molar ratio of 1:(1.1-1.25):2:(2-2.2), ball milling the mixture for 36-72 hr to form a black precursor slurry; coating the slurry on a molybdenum foil substrate or a titanium foil substrate to form a precursor thin-film, and drying at low temperature; densifying the precursor thin-film by exerting 10-300 MPa pressure, and subjecting the precursor thin-film to heat treatment under H2 atmosphere, N2 atmosphere or vacuum. The method can accurately control the chemical composition in the precursor thin-film, can ensure the preparation of the In-enriched CuInSe2 semiconductor thin-film solar battery, and is more suitable for forming the absorption layer with uniform composition, compact structure, and flat surface. And, the sintering process is performed under innoxious atmosphere, so as to be safe and practice in operation.

Description

A kind of method for preparing the rich indium light absorbing zone of copper, indium and selenium film solar cell

Technical field

The invention belongs to the photovoltaic material technical field of new energies, relate to semiconductor CuInSe 2The preparation of film, the particularly CuInSe of rich In 2The preparation technology of semiconductor thin-film solar cell light absorbing zone.

Background technology

CuInSe 2Be a kind of direct gap semiconductor compound with yellow copper structure, have suitable energy gap (1.04eV), stable performance under the room temperature does not have light radiation to cause performance degradation effect (S-W effect).CuInSe 2The photoelectric conversion efficiency of thin-film solar cells has surpassed 20%, makes CuInSe 2Become very promising photovoltaic material.

Because CuInSe 2The intrinsic defect autodoping ability of material uniqueness makes it have stronger component tolerance, the CuInSe of the rich In of poor Cu 2(In content is greater than the CuInSe of Cu content for film 2Film) the hole carrier density is higher in, and electric property is better.For the battery of high conversion efficiency, except requiring CuInSe 2Outside the absorbent layer structure densification, its chemical composition In content should be slightly larger than Cu content, and the In content on top layer needs more some more (D Schmid, M Ruckh, FGrunwald, H W Schock. " Chalcopyrite/defect chalcopyrite heterojunctions on the basis ofCuInSe 2", Journal of Applied Physics, 1993,73 (6): 2902-2909).

Solar cell light absorption layer CuInSe 2The preparation method of film is a lot, utilize coating-sintering technology that the presoma slip is coated in and form precursor layer on the matrix, and then selenizing becomes CuInSe 2Film.This group technical matters is simple, and preparation cost is cheap.But in the Cu-In alloy when In content the time greater than Cu content, inclusion compound Cu in the alloy 11In 9With two kinds of things of simple substance In mutually, and In is the metal of dead-soft, and the Cu-In alloy that grinds this rich In can make simple substance In wherein stick on the abrasive media, can't obtain the precursor slip of rich In, so utilize Cu-In alloy and Se powder as raw material at present merely, the final CuInSe that is difficult to obtain rich In 2Film.And be raw material with copper selenide and indium selenide, utilize coating-sintering technology to prepare CuInSe 2Film not only needs very high sintering temperature (1050-1100 ℃), and contain second phase (Naoki Suyama in the film, Noriyuki Ueno, Kuniyoshi Omura, Yuutaro kita, Mikio Murozono. " Methodfor production of Copper Indium Diselenide ", US 4,940,604.1990-6-10).

Summary of the invention

The object of the present invention is to provide a kind of CuInSe 2The preparation method of the rich In light absorbing zone of semiconductor thin-film solar cell adopts coating-sintering process, solves CuInSe 2The problem of the raising of In content and accurate control makes the CuInSe that obtains in the semiconductive thin film 2Film has content, the thing mutually pure and microstructure fine and close characteristics of In content a little more than Cu, to meet the efficient CuInSe of preparation 2The requirement of thin-film solar cells.

Formation of the present invention: select for use Cu-In alloy, indium selenide and Se powder as raw material, according to Cu: In: Se=1: 1.1~1.25: 2~2.2 mixed in molar ratio Cu-In alloy, indium selenide and Se powder, the ball milling mixture is 36~72 hours then, forms the precursor pulp of black; Slurry coating is formed precursor thin-film on metal molybdenum foil or metal titanium foil matrix, 20~50 ℃ of dryings; The pressure that dried precursor thin-film is applied 10~300Mpa makes its densification; Last precursor thin-film is at H 2Atmosphere or N 2Heat treatment in atmosphere or the vacuum.

The Cu of described Cu-In alloy and the mol ratio of In are 1: 0.6~0.8; Indium selenide contains In 4Se 3, InSe, In 6Se 7And In 2Se 3In one or more, the In of indium selenide and the mol ratio of Se are 1: 0.75~1.5.

Described heat treatment period is 0.5~3 hour, and heat treatment temperature is 400~550 ℃.

Advantage of the present invention and high-lighting effect are: will finally form CuInSe 2The needed element of semiconductor is blended directly in one and reacts, and can accurately control the chemical composition of final film, has guaranteed the CuInSe of rich In 2The formation of semiconductive thin film.The Cu-In alloy and the indium selenide particle of fragility are fully mixed the Se powder in mechanical milling process, form uniform mixture, thereby contain the Se of optimal dose in the precursor film after the coating, than other selenizing methods, be easier to form the uniform absorbed layer of composition, and sintering is at nontoxic H 2Atmosphere or N 2Carry out in atmosphere or the vacuum, safe and practical in the operation.Before heat treatment precursor thin-film is applied pressure and make its densification, can increase the contact area of solid particle in the presoma, the reaction when helping heat treatment between each thing phase is carried out, thereby has reduced the sintering temperature of film, and the CuInSe for preparing 2The semiconductive thin film surfacing, compact structure.

Description of drawings

Fig. 1 is that the precursor pulp that embodiment 1 makes is coated on the metal molybdenum matrix at H 2The following 400 ℃ of CuInSe that heat treatment obtained after 1 hour of atmosphere 2The electron micrograph of film, its precursor film is applied in 200Mpa pressure.

Fig. 2 is that the precursor pulp that embodiment 1 makes is coated on the metal molybdenum matrix at H 2The following 400 ℃ of CuInSe that heat treatment obtained after 1 hour of atmosphere 2The energy spectrum analysis collection of illustrative plates of film, its precursor film is applied in 200Mpa pressure.

Fig. 3 is that the precursor pulp that embodiment 7 makes is coated on the metal molybdenum matrix at H 2The following 400 ℃ of CuInSe that heat treatment obtained after 1 hour of atmosphere 2The X ray diffracting spectrum of film, its precursor film is applied in 200Mpa pressure.Abscissa is an angle of diffraction, and ordinate is a relative intensity.

Fig. 4 is that the precursor pulp that embodiment 7 makes is coated on the metallic titanium matrix at N 2The following 550 ℃ of CuInSe that heat treatment obtained after 0.5 hour of atmosphere 2The X ray diffracting spectrum of film, its precursor film is applied in 10Mpa pressure.Abscissa is an angle of diffraction, and ordinate is a relative intensity.

Embodiment

(1) the Cu-In alloy block is placed Al 2O 3Broken in the mortar, then according to Cu: In: Se=1: 1.2: 2.1 mixed in molar ratio Cu-In alloy, indium selenide and Se powder, and after the mixed with 10 gram mixed powders, 25 gram absolute ethyl alcohols, placed the planetary ball mill ball milling 60 hours, make precursor pulp.Ball-milling medium is ZrO 2Ball.

(2) precursor pulp is coated on metal molybdenum foil or the metal titanium foil matrix, forms precursor thin-film, treat further processing 40 ℃ of dry backs.

Embodiment 1: the CuInSe of rich In 2Absorbed layer is at H 2Low temperature in the atmosphere (400 ℃) preparation

(1) precursor thin-film that forms is applied 200Mpa pressure and make its densification on the metal molybdenum matrix, remove pressure then, obtain fine and close precursor thin-film.

(2) above-mentioned precursor thin-film is placed resistance furnace, logical H 2Deaeration, test pure 3 times after, furnace temperature is risen to 50 ℃, 50 ℃ of preheatings 10 minutes.

(3) be warming up to 230 ℃ according to 5 ℃/minute speed by 50 ℃, be incubated 1 hour.

(4) be warming up to 400 ℃ according to 5 ℃/minute speed by 230 ℃, be incubated and cool to room temperature after 1 hour with the furnace and take out, finally obtain blue-black rich In solar cell CuInSe 2Absorbed layer.

Embodiment 2: the CuInSe of rich In 2Absorbed layer is at N 2Low temperature in the atmosphere (400 ℃) preparation

Operating procedure will feed H with embodiment 1 2Step replace with and feed N 2Logical N 2Behind the deaeration 15 minutes, begin resistance furnace is heated up.Heat treatment finally obtains blue-black rich In solar cell CuInSe after finishing 2Absorbed layer.

Embodiment 3: the CuInSe of rich In 2Absorbed layer is at H 2High temperature in the atmosphere (550 ℃) preparation

(1) precursor thin-film that forms is applied 10Mpa pressure and make its densification on the metal molybdenum matrix, remove pressure then, obtain fine and close precursor thin-film.

(2) above-mentioned precursor thin-film is placed resistance furnace, logical H 2Deaeration, test pure 3 times after, furnace temperature is risen to 50 ℃, 50 ℃ of preheatings 10 minutes.

(3) be warming up to 550 ℃ according to 10 ℃/minute speed by 50 ℃, be incubated and cool to room temperature after 0.5 hour with the furnace and take out, finally obtain blue-black rich In solar cell CuInSe 2Absorbed layer.

Embodiment 4: the CuInSe of rich In 2Absorbed layer is at H 2Atmosphere and N 2Prepare in the atmosphere

After 230 ℃ of insulations of embodiment 1 finish, in resistance furnace, feed N 2, stop to feed H simultaneously 2Later stage makes CuInSe according to the operating procedure of embodiment 2 or embodiment 3 2Precursor thin-film generation sintering finally obtains blue-black rich In solar cell CuInSe 2Absorbed layer.

Embodiment 5: the CuInSe of rich In 2Absorbed layer high temperature (550 ℃) preparation in a vacuum

(1) precursor thin-film that forms is applied 200Mpa pressure and make its densification on the metal molybdenum matrix, remove pressure then, obtain fine and close precursor thin-film.

(2) above-mentioned precursor thin-film is placed vacuum sintering furnace, use mechanical pump to vacuumize and begin when reaching 5pa to heat up.

(3) be warming up to 550 ℃ according to 10 ℃/minute speed by room temperature, be incubated and cool to room temperature after 0.5 hour with the furnace and take out, finally obtain blue-black rich In solar cell CuInSe 2Absorbed layer.

Embodiment 6: CuInSe on metallic titanium matrix 2The preparation of absorbed layer

Utilize embodiment 1 or execute example 2 or execute example 3 or execute example 4 or execute in the example 5 operating procedure constant, the precursor thin-film on the metal molybdenum matrix is replaced with precursor thin-film on the metallic titanium matrix, finally obtain black-and-blue rich In solar cell CuInSe on the metallic titanium matrix 2Absorbed layer.

Embodiment 7: the XRD of sample detects after the heat treatment

The film that obtains among embodiment 1 or embodiment 2 or embodiment 3 or embodiment 4 or embodiment 5 or the embodiment 6 is XRD detects, the result shows that the precursor thin-film that is coated on metal molybdenum matrix or the metallic titanium matrix is at N 2Atmosphere or H 2In atmosphere or the vacuum after 400 ℃ or 550 ℃ of heat treatment, CuInSe 2(101), (112), (211), (200/204) and (116/312) crystal face diffraction maximum fairly obvious, film is grown with (112) crystal face preferred orientation.At N 2Atmosphere or H 2After 400 ℃ and 550 ℃ of heat treatments, obtained very pure CuInSe in atmosphere or the vacuum 2Single-phase.

Claims (3)

1. one kind prepares CuInSe 2The method of the rich In light absorbing zone of thin-film solar cells, it is characterized in that: select for use Cu-In alloy, indium selenide and Se powder as raw material, according to Cu: In: Se=1: 1.1~1.25: 2~2.2 mixed in molar ratio Cu-In alloy, indium selenide and Se powder, the ball milling mixture is 36~72 hours then, forms the precursor pulp of black; Slurry coating is formed precursor thin-film on metal molybdenum foil or metal titanium foil matrix, 20~50 ℃ of dryings; The pressure that dried precursor thin-film is applied 10~300Mpa makes its densification; Last precursor thin-film is at H 2Atmosphere or N 2Heat treatment in atmosphere or the vacuum.
2. it is characterized in that in accordance with the method for claim 1: the Cu of described Cu-In alloy and the mol ratio of In are 1: 0.6~0.8; Indium selenide contains In 4Se 3, InSe, In 6Se 7And In 2Se 3In one or more, the In of indium selenide and the mol ratio of Se are 1: 0.75~1.5.
3. in accordance with the method for claim 1, it is characterized in that: described heat treatment period is 0.5~3 hour, and heat treatment temperature is 400~550 ℃.
CNB2007101779145A 2007-11-22 2007-11-22 Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer CN100466305C (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101820031A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Manufacturing method of copper indium gallium selenium and/or sulfur light absorption preformed layer without adhesive and active agent
CN101820024A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Production method of multiple copper indium gallium selenide (sulfur) light-absorbing precursor layers
CN101820030A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Non-vacuum manufacturing method of CIGS and/or CIGSS (copper-indium-gallium-selenium and/or sulphur) light absorbing layer
CN101818375A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Method for preparing copper-indium-gallium-selenium(sulfur) light absorption layer by adopting non-vacuum process
CN101820026A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Non-vacuum manufacturing method of CIGS (copper-indium-gallium-selenium) slurry
CN101826574A (en) * 2010-02-10 2010-09-08 昆山正富机械工业有限公司 Method for making copper-indium-gallium-selenium light-absorbing layer under non-vacuum condition
CN101840959A (en) * 2010-02-11 2010-09-22 昆山正富机械工业有限公司 Method for manufacturing slurry of solar absorbing layer, solar absorbing layer and slurry thereof
CN101840958A (en) * 2010-02-11 2010-09-22 昆山正富机械工业有限公司 Antivacuum method for manufacturing copper indium gallium selenide sizing agent
CN101840957A (en) * 2010-02-11 2010-09-22 昆山正富机械工业有限公司 Preparation method for anti-vacuum manufacture of copper-indium-gallium-selenium slurry
CN101901852A (en) * 2010-02-11 2010-12-01 昆山正富机械工业有限公司 Manufacturing method and application of surfactant-free solar absorbing layer slurry
CN101913575A (en) * 2010-08-31 2010-12-15 武汉理工大学 Method for preparing In4Se3 thermoelectric compound powder
CN101525126B (en) * 2009-03-16 2011-04-20 大连交通大学 Preparation process of CuInSe2 solar battery material
CN102145385A (en) * 2010-02-10 2011-08-10 昆山正富机械工业有限公司 Method for mixing copper indium gallium selenide slurry without interfacial active agent or solvent
CN101694854B (en) * 2009-05-22 2012-10-17 中国科学技术大学 Synthesizing method for preparing CIS film and device by non-vacuum liquid phase chemical method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
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JPS6464369A (en) * 1987-09-04 1989-03-10 Matsushita Electric Ind Co Ltd Manufacture of indium copper selenide

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101525126B (en) * 2009-03-16 2011-04-20 大连交通大学 Preparation process of CuInSe2 solar battery material
CN101694854B (en) * 2009-05-22 2012-10-17 中国科学技术大学 Synthesizing method for preparing CIS film and device by non-vacuum liquid phase chemical method
CN101826574A (en) * 2010-02-10 2010-09-08 昆山正富机械工业有限公司 Method for making copper-indium-gallium-selenium light-absorbing layer under non-vacuum condition
CN102145385A (en) * 2010-02-10 2011-08-10 昆山正富机械工业有限公司 Method for mixing copper indium gallium selenide slurry without interfacial active agent or solvent
CN101840958A (en) * 2010-02-11 2010-09-22 昆山正富机械工业有限公司 Antivacuum method for manufacturing copper indium gallium selenide sizing agent
CN101820026A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Non-vacuum manufacturing method of CIGS (copper-indium-gallium-selenium) slurry
CN101840959A (en) * 2010-02-11 2010-09-22 昆山正富机械工业有限公司 Method for manufacturing slurry of solar absorbing layer, solar absorbing layer and slurry thereof
CN101818375A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Method for preparing copper-indium-gallium-selenium(sulfur) light absorption layer by adopting non-vacuum process
CN101840957A (en) * 2010-02-11 2010-09-22 昆山正富机械工业有限公司 Preparation method for anti-vacuum manufacture of copper-indium-gallium-selenium slurry
CN101901852A (en) * 2010-02-11 2010-12-01 昆山正富机械工业有限公司 Manufacturing method and application of surfactant-free solar absorbing layer slurry
CN101820030A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Non-vacuum manufacturing method of CIGS and/or CIGSS (copper-indium-gallium-selenium and/or sulphur) light absorbing layer
CN101820024A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Production method of multiple copper indium gallium selenide (sulfur) light-absorbing precursor layers
CN101820031A (en) * 2010-02-11 2010-09-01 昆山正富机械工业有限公司 Manufacturing method of copper indium gallium selenium and/or sulfur light absorption preformed layer without adhesive and active agent
CN101913575A (en) * 2010-08-31 2010-12-15 武汉理工大学 Method for preparing In4Se3 thermoelectric compound powder
CN101913575B (en) * 2010-08-31 2012-05-30 武汉理工大学 Method for preparing In4Se3 thermoelectric compound powder

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