CN102943238A - Preparation method of thin-film solar cell - Google Patents

Preparation method of thin-film solar cell Download PDF

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Publication number
CN102943238A
CN102943238A CN2012104654443A CN201210465444A CN102943238A CN 102943238 A CN102943238 A CN 102943238A CN 2012104654443 A CN2012104654443 A CN 2012104654443A CN 201210465444 A CN201210465444 A CN 201210465444A CN 102943238 A CN102943238 A CN 102943238A
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layer
preparation
cuin
bottom electrode
substrate
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李微
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CETC 18 Research Institute
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CETC 18 Research Institute
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a preparation method of a thin-film solar cell. The preparation method comprises the steps: preparing a bottom electrode on a substrate, an absorbing layer, a buffer layer, a window layer and an upper electrode sequentially. The preparation method is characterized in that the absorbing layer is prepared on the bottom electrode by utilizing CuIn1-XGaxSe2 target material according to a radio frequency magnetron sputtering method and an annealing treatment method. A CuIn1-XGaxSe2 layer is prepared on the bottom electrode by utilizing CuIn1-XGaxSe2 compound target material according to a radio frequency magnetron sputtering method, and a CuIn1-XGaxSe2 phase is formed in the sputtering process, so that the crystallinity of the absorbing layer is improved only by virtue of a simple heat treatment process, Grains reach the micron level, the performance of the absorbing layer is improved, the performance of the thin-film solar cell is effectively improved; and compared with a traditional coevaporation process and a metal precast layer sputtering and selenizing process, the preparation method has the advantages that the technological process is greatly simplified, the process repetitiveness is good and the process is controllable.

Description

A kind of preparation method of thin film solar cell
Technical field
The invention belongs to the solar cell device preparing technical field, particularly relate to a kind of preparation method of thin film solar cell.
Background technology
Compound semiconductor copper indium diselenide (CuInSe with yellow copper structure 2, being abbreviated as CIS) and serial miscible crystal is the direct band gap material, with its thin film solar cell as absorption layer, is considered to one of the most promising third generation compound photovoltaic cell, its composition comprises: CuInSe 2, CuIn 1-XGa xSe 2, CuInS 2, CuIn 1-XGa xS 2, CuIn 1-XGa xSe 2-yS yDeng.Existing copper-indium-galliun-selenium (sulphur) thin film solar cell, at the later development eighties in 20th century novel solar cell out, be the photovoltaic device that consists of at soda-lime glass, tinsel (stainless steel foil, titanium foil, molybdenum foil, aluminium foil etc.) or polyimide film substrate difference deposit multilayer film, typical structure is following multi-layer film structure: substrate/bottom electrode/absorption layer/buffer layer/Window layer/antireflective coating/top electrode.
Studies show that absorption layer copper-indium-galliun-selenium (sulphur) film plays conclusive effect to battery performance.Because many, the complex structure of elemental composition, mainly by Cu, In, Ga, Se or/and four kinds or five kinds elements of S are synthetic, be that compound by multiple mutual solid solution consists of, the stoicheiometry of each element and distribution thereof are the important factors that determines battery performance in the optical absorbing layer.
In CIGS thin-film solar cell, absorption layer copper-indium-galliun-selenium/sulphur thin film technology method mainly is divided into two classes: first kind method is polynary coevaporation method, namely in vacuum chamber, react coevaporation as the source take Cu, In, Ga and Se, or with bivariate distribution coevaporations such as Cu+Se, In+Se, Ga+Se.Coevaporation method requires vaporator rate and the deposition on substrate of every kind of element all to require accurate control, just can obtain uniform film, has improved the cost of manufacture of battery; The Equations of The Second Kind method is selenizing method behind the metal preformed layer, namely deposits Cu, In, Ga layer at substrate by proportioning first, and Seization in Se atmosphere forms the CuIn that satisfies ratio requirement again 1-XGa xSe 2Polycrystal film, or substitute selenium with sulphur carries out the thermo-chemical treatment of sulphur content footwork behind vulcanization reaction or the first selenium, forms CuIn 1-XGa xS 2Or CuIn 1-XGa xSe 2-XS 2Film.The Equations of The Second Kind method is beneficial to the advantages such as industrialization and is subject to extensive concern owing to it, wherein especially most widely used general with the sputtering and selenization technique method, its technical characterstic is for adopting simple substance or alloy target material splash-proofing sputtering metal prefabricated membrane Cu-In-Ga, then adopt Selenium hydride or solid-state selenium source selenizing, owing to Selenium hydride severe toxicity adopts the composition of the absorption layer film that solid-state selenium source then prepares wayward, so that the performance of the absorption layer film of preparation is low, cause the thin film solar cell performance of preparation low.
Summary of the invention
The present invention provides the absorption layer performance high for solving the technical problem that exists in the background technology, be conducive to improve the thin film solar cell performance, and preparation process is easy, process is controlled, the preparation method of a kind of thin film solar cell of good process repeatability.
The technical scheme that the present invention takes is:
A kind of preparation method of thin film solar cell, with glass, flexible metal or polyimide film as substrate, be included in and prepare successively bottom electrode, absorption layer, buffer layer, Window layer and top electrode on the substrate, be characterized in: described absorption layer comprises that following preparation process: ⑴ adopts CuIn 1-XGa xSe 2The compound target by radio-frequency magnetron sputter method, prepares CuIn at the bottom electrode of substrate 1-XGa xSe 2Layer, ⑵ is to being shaped with CuIn among the ⑴ 1-XGa xSe 2The substrate of layer carries out anneal, obtains CuIn on the bottom electrode 1-XGa XSe 2Compound semiconductor film is as absorption layer.
The present invention can also adopt following technical scheme:
Described radio-frequency magnetron sputter method comprises: the substrate that will be shaped with bottom electrode is inserted vacuum sputtering equipment, equipment is vacuumized be＜3 * 10 -3When Pa, temperature reach 200-500 ° of C, pass into Ar gas, with the CuIn of chalcopyrite phase 1-XGa XSe 2(X=0.2-0.4) the compound target is at 1.0-5.0W/cm 2Target power output density under bottom electrode is carried out rf magnetron sputtering, obtain the CuIn that thickness is the 0.7-2.5 micron on the bottom electrode 1-XGa xSe 2Layer; Described anneal comprises: will be shaped with CuIn 1-XGa XSe 2The substrate of layer is inserted in the vacuum annealing furnace, and substrate speed with 20-50 ° of C/min in vacuum or Ar atmosphere is warming up to 350-590 ° of C, keeps temperature 5-30min, naturally be cooled to room temperature after, the small extremely micron-sized CuIn of the crystal grain that makes 1-XGa xSe 2Absorption layer.
Before preparation CdS buffer layer, adopt first direct current magnetron sputtering process at the In of absorption layer preparation thickness 10-30 micron 2S 3Then film adopts the chemical bath method at transition layer preparation CdS buffer layer as transition layer; Position near buffer layer obtains CuIn 1-XGa xSe 2-yS yFilm (wherein: X=0.2-0.4, y=0-2).
Described flexible metal is titanium foil or stainless steel foil.
Advantage and positively effect that the present invention has are:
1, the present invention is owing to adopted CuIn 1-XGa xSe 2Compound target radio-frequency magnetron sputter method prepares CuIn at bottom electrode 1-XGa xSe 2Layer has namely formed CuIn in sputter procedure 1-XGa xSe 2Phase, only need namely to have improved by the brief heat treating process degree of crystallinity of absorption layer, crystal grain reaches micron order, improved the performance of absorption layer, Effective Raise the performance of thin film solar cell, and compare traditional coevaporation technique and metal preformed layer sputtering and selenization technique technique, and greatly simplified technological process, good process repeatability, process is controlled.
2, the present invention prepares before the CdS buffer layer, adopts at the In of magnetron sputtering method in absorption layer preparation very thin thickness 2S 3Film prepares In as transition layer at magnetron sputtering method 2S 3In the process, can be with part In and S and absorption layer generation chemical reaction, not only so that In content raising in the close absorption layer of buffer layer part can be mixed the S of part simultaneously in absorption layer, so that obtain CuIn in the part of close buffer layer 1-XGa xSe 2-yS yFilm is conducive to further improve the open circuit voltage of battery and improves battery performance.
Embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby exemplify following examples, be described in detail as follows:
A kind of preparation method of thin film solar cell prepares bottom electrode, absorption layer, buffer layer, Window layer and top electrode successively on substrate; Namely with glass, titanium foil, stainless steel foil or polyimide film as substrate; The method for preparing duplicature with magnetron sputtering method or increase the metal/metal oxide transition layer on substrate prepares bottom electrode Mo;
The preparation absorption layer:
Step ⑴: adopt CuIn 1-XGa xSe 2The compound target by radio-frequency magnetron sputter method, prepares CuIn at the bottom electrode Mo of substrate 1-XGa xSe 2Layer; Wherein radio-frequency magnetron sputter method is: the substrate that will be shaped with bottom electrode is inserted vacuum sputtering equipment, equipment is vacuumized be＜3 * 10 -3When Pa, temperature reach 200-500 ° of C, pass into Ar gas, with the CuIn of chalcopyrite phase 1-XGa xSe 2(X=0.2-0.4) the compound target is at 1.0-5.0W/cm 2Target power output density under bottom electrode is carried out rf magnetron sputtering, obtain the CuIn that thickness is the 0.7-2.5 micron on the bottom electrode 1-XGa XSe 2Layer;
Step ⑵: to being shaped with CuIn among the step ⑴ 1-XGa xSe 2The substrate of layer carries out anneal, obtains CuIn on the bottom electrode 1-XGa xSe 2Compound semiconductor film is as absorption layer; Wherein anneal is: will be shaped with CuIn 1-XGa xSe 2The substrate of layer is inserted in the vacuum annealing furnace, and substrate speed with 20-50 ° of C/min in vacuum or Ar atmosphere is warming up to 350-590 ° of C, keeps temperature 5-30min, naturally be cooled to room temperature after, the small extremely micron-sized CuIn of the crystal grain that makes 1-XGa xSe 2Absorption layer is finished the preparation of absorption layer;
The preparation buffer layer:
Before preparation CdS, adopt first direct current magnetron sputtering process at the In of absorption layer preparation thickness 10-30 micron 2S 3Then film adopts the chemical bath method at transition layer preparation CdS buffer layer as transition layer; Position near buffer layer obtains one deck CuIn 1-XGa xSe 2-yS yFilm (wherein: X=0-1, y=0-2);
Adopt radio-frequency magnetron sputter method to prepare the intrinsic ZnO film as Window layer at buffer layer; Adopt direct current magnetron sputtering process at Window layer preparation electrode A l, finish the preparation process of thin film solar cell of the present invention.
Embodiment 1
On 80 μ m titanium foil substrates, prepare thickness as 1 μ m duplicature bottom electrode Mo take direct current magnetron sputtering process; The substrate that is shaped with bottom electrode is inserted vacuum sputtering equipment, equipment is vacuumized when reaching 350 ° of C for 1Pa, temperature, pass into Ar gas, with Cu (In, Ga) Se 2The compound target is at 2W/cm 2Target power output density under bottom electrode is carried out rf magnetron sputtering, obtain thickness on the bottom electrode and be 1.5 microns Cu (In, Ga) Se 2Layer; Then will deposit bottom electrode Mo and Cu (In, Ga) Se 2The substrate of layer is put into vacuum annealing furnace, heats up with the speed of 30 ° of C/min, and underlayer temperature reaches 400 ° of C, keeps temperature 15min, naturally be cooled to room temperature after, the crystal grain that makes is small in micron order Cu (In, Ga) Se 2Absorption layer; Adopt the chemical bath method at transition layer preparation CdS buffer layer; Adopt radio-frequency magnetron sputter method in buffer layer preparation intrinsic ZnO film Window layer; Adopt direct current magnetron sputtering process at Window layer preparation electrode A l, finish the preparation process of thin film solar cell of the present invention.
Embodiment 2
Change the titanium foil substrate into stainless steel foil, other condition is identical with embodiment 1.
Embodiment 3
Change substrate material into glass, other condition is identical with embodiment 1.
Embodiment 4: change substrate material into Kapton, other condition is identical with embodiment 1, and difference is that also underlayer temperature reaches 350 ° of C, keeps temperature 15min.
Embodiment 5: such as the process of embodiment 1, before preparation CdS, adopt direct current magnetron sputtering process at the In of 20 microns of absorption layer preparation thickness 2S 3Then film adopts the chemical bath method at transition layer preparation CdS buffer layer as transition layer, and the position of close buffer layer obtains one deck Cu (In, Ga) (S, Se) 2Film.
Embodiment 6: change substrate material into glass, other condition is identical with embodiment 5.
Embodiment 7: change substrate material into Kapton, other condition is identical with embodiment 5, and difference is that also underlayer temperature reaches 350 ° of C, keeps temperature 15min.
Technological principle of the present invention:
That the present invention adopts is the CuIn that forms the chalcopyrite phase 1-XGa xSe 2The compound target, rather than traditional Cu-Ga or Cu-In target not only simplified preparation process, and reduced the cost of target, improved utilization rate of raw materials.In subsequent anneal is processed, only be an annealing process, make CuIn 1-XGa xSe 2The crystal grain of film absorption layer is small in micron order, needing in the traditional selenizing process to have avoided strictly controlling intensification or the cooling rate of the temperature in Se source and substrate etc.; The present invention not only Effective Raise the performance of absorption layer, in the hope of improving battery performance, and greatly simplified technological process, good process repeatability, process is controlled.
Although the above is described the preferred embodiments of the present invention; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away from the scope situation that aim of the present invention and claim protect, can also make a lot of forms, these all belong within protection scope of the present invention.

Claims (5)

1. the preparation method of a thin film solar cell, with glass, flexible metal or polyimide film as substrate, be included in and prepare successively bottom electrode, absorption layer, buffer layer, Window layer and top electrode on the substrate, it is characterized in that: described absorption layer comprises that following preparation process: ⑴ adopts CuIn 1-XGa xSe 2The compound target by radio-frequency magnetron sputter method, prepares CuIn at the bottom electrode of substrate 1-XGa xSe 2Layer, ⑵ is to being shaped with CuIn among the ⑴ 1-XGa xSe 2The substrate of layer carries out anneal, obtains CuIn on the bottom electrode 1-XGa xSe 2Compound semiconductor film is as absorption layer.
2. the preparation method of described thin film solar cell according to claim 1, it is characterized in that: described radio-frequency magnetron sputter method comprises: the substrate that will be shaped with bottom electrode is inserted vacuum sputtering equipment, equipment is vacuumized be＜3 * 10 -3When Pa, temperature reach 200-500 ° of C, pass into Ar gas, with the CuIn of chalcopyrite phase 1-XGa xSe 2(X=0.2-0.4) the compound target is at 1.0-5.0W/cm 2Target power output density under bottom electrode is carried out rf magnetron sputtering, obtain the CuIn that thickness is the 0.7-2.5 micron on the bottom electrode 1-XGa xSe 2Layer; Described anneal comprises: will be shaped with CuIn 1-XGa XSe 2The substrate of layer is inserted in the vacuum annealing furnace, and substrate speed with 20-50 ° of C/min in vacuum or Ar atmosphere is warming up to 350-590 ° of C, keeps temperature 5-30min, naturally be cooled to room temperature after, the small extremely micron-sized CuIn of the crystal grain that makes 1-XGa xSe 2Absorption layer.
3. the preparation method of described thin film solar cell according to claim 1 and 2 is characterized in that: buffer layer before preparation CdS, adopt first direct current magnetron sputtering process at the In of absorption layer preparation thickness 10-30 micron 2S 3Then film adopts the chemical bath method at transition layer preparation CdS buffer layer as transition layer; Position near buffer layer obtains CuIn 1-XGa XSe 2-yS yFilm (wherein: X=0.2-0.4, y=0-2).
4. the preparation method of described thin film solar cell according to claim 1 and 2, it is characterized in that: described flexible metal is titanium foil or stainless steel foil.
5. the preparation method of described thin film solar cell according to claim 3, it is characterized in that: described flexible metal is titanium foil or stainless steel foil.
CN2012104654443A 2012-11-16 2012-11-16 Preparation method of thin-film solar cell Pending CN102943238A (en)

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CN103346213A (en) * 2013-07-01 2013-10-09 上海中科高等研究院 Preparation method for solar cell absorbing layer
CN105009304A (en) * 2013-03-12 2015-10-28 韩国能源研究技术研究所 Solar cell having rear buffer layer and production method therefor
CN112259639A (en) * 2020-10-20 2021-01-22 北京圣阳科技发展有限公司 Low-cost preparation method applied to CIGS thin-film solar cell with glass substrate

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105009304A (en) * 2013-03-12 2015-10-28 韩国能源研究技术研究所 Solar cell having rear buffer layer and production method therefor
CN103346213A (en) * 2013-07-01 2013-10-09 上海中科高等研究院 Preparation method for solar cell absorbing layer
CN112259639A (en) * 2020-10-20 2021-01-22 北京圣阳科技发展有限公司 Low-cost preparation method applied to CIGS thin-film solar cell with glass substrate

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Application publication date: 20130227