CN103194726A - Preparation process of cuprum-indium-gallium-selenium film - Google Patents
Preparation process of cuprum-indium-gallium-selenium film Download PDFInfo
- Publication number
- CN103194726A CN103194726A CN2013101190278A CN201310119027A CN103194726A CN 103194726 A CN103194726 A CN 103194726A CN 2013101190278 A CN2013101190278 A CN 2013101190278A CN 201310119027 A CN201310119027 A CN 201310119027A CN 103194726 A CN103194726 A CN 103194726A
- Authority
- CN
- China
- Prior art keywords
- film
- cuprum
- indium
- layer
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a preparation process of a cuprum-indium-gallium-selenium film. The preparation process comprises the following three steps: evaporating and plating a first-layer film on a substrate at the current of 30 to 100 mA under the condition of 200 to 400 DEG C, thereby forming an area poor in cuprum and rich in indium and gallium, wherein the first-layer film mainly contains the indium, the gallium and the selenide and a little amount of the cuprum; evaporating and plating a second-layer film at the current of 80 to 150 mA under the condition of 300 to 600 DEG C, thereby forming the area rich in the cuprum, wherein the second-layer film mainly contains the cuprum, the indium, the gallium and the selenide; and evaporating and plating a third-layer film at the current of 20 to 150 mA under the condition of 300 to 600 DEG C, thereby forming the area poor in the cuprum again, wherein the third-layer film mainly contains the indium, the gallium and the selenide and a little amount of the cuprum. Therefore, the whole film structure poor in the cuprum is ensured. According to the method, a cuprum-indium-gallium-selenium solar cell is prepared by utilizing single sources via the evaporating and plating process in the three steps. By utilizing an electric beam vaporimeter with a heating baseboard and Cu2InxGa1-xSe2 powder as the single sources, the efficient film structure poor in the cuprum is realized by changing the current size. Besides the film is poor in the cuprum, the film also has an absorbed layer intraconnection structure, a large-size particle interface and a gradient structure. As a result, based on the structures of the film, the high efficiency of the prepared cell is ensured.
Description
Technical field
The present invention relates to technical field of solar batteries, relate in particular to a kind of manufacturing process of CIGS thin-film.
Background technology
Copper indium gallium selenium solar cell comprises glass film plates or the flexible stainless steel of one deck rigidity usually, contain molybdenum layer simultaneously, p-type CuInGaSe absorbed layer, Cadmium Sulfide or zinc sulphide buffer layer, intrinsic zinc oxide, transparent conductive oxide Window layer (TCO) and surperficial contact layer.CIGS thin-film is the core of CIGS manufacture of solar cells.The manufacture method of copper indium gallium selenium solar cell can be divided into vacuum method and antivacuum method substantially at present.Vacuum method comprises that mainly common vapour deposition method and sputter add back selenizing treatment process.
Be total to vapour deposition method: all be a kind of common deposition method in laboratory and commercial applications.Vapour deposition method uses a plurality of evaporation sources to make CuInGaSe absorbed layer altogether.Vapour deposition method can well be controlled processing parameter and regulate film and form structure and band gap altogether.Yet the uniformity coefficient of vapour deposition method still faces some problems when scale operation altogether.Simultaneously, how accurately controlling each evaporation source also is a great problem that common vapour deposition method need solve.
Sputter and back selenizing facture: be the technology that present CuInGaSe absorbed layer research is in daily use.It comprises technological processs such as sputter and selenizing.This method is raw material with copper indium gallium target or copper/indium/gallium target, uses the method for cosputtering or sputter continuously that alloy deposition is formed amorphous thin film; Again film is carried out selenizing in the environment of Selenium hydride or selenium afterwards, finally form p-type absorption layer.Last selenizing step has certain environment hidden danger, because hydrogen selenide gas has toxicity, this method needs high temperature simultaneously, and this has also increased the technology cost.
Antivacuum method: comprise printing, electrochemical filming method, method of spin coating etc.In antivacuum all methods, the Nanosolar company of the U.S. is higher with the CIGS battery efficiency that antivacuum printing process obtains at present.
Summary of the invention
Goal of the invention: at the deficiencies in the prior art, the purpose of this invention is to provide a kind of manufacturing process of CIGS thin-film, make it have simple environmental protection, advantages such as economic actual effect.
Technical scheme: in order to realize the foregoing invention purpose, the technical solution used in the present invention is as follows:
A kind of manufacturing process of CIGS thin-film is three-step approach, may further comprise the steps:
(1) under 200 ~ 400 ℃ of conditions, with electric current the first layer film on evaporation in the substrate of 30 ~ 100mA, forms the rich indium gallium zone (main component is indium gallium selenium and a spot of copper) of poor copper;
(2) under 300 ~ 600 ℃ condition, with second layer film on the electric current evaporation of 80 ~ 150mA, form copper rich region territory (main component is copper-indium-galliun-selenium);
(3) under 300 ~ 600 ℃ condition, with three-layer thin-film on the evaporation of 20 ~ 150mA electric current, form the poor copper of one deck zone (main component is gallium indium selenium and a spot of copper) again, to guarantee the poor steel structure of film integral;
Wherein, used single source is Cu
2In
xGa
1-xSe
2Powder, equipment are the electron beam evaporation instrument that heated substrates is housed, and constant voltage is 7KV.
Plate the metal molybdenum of a layer thickness 200 nanometers to 1.5 micron in described substrate in advance with method of evaporating or sputtering method, the resistivity of molybdenum layer is 0.2 to 5 ohmcm.
Plating a layer thickness with chemical basin sedimentation or atomic deposition method at CuInGaSe absorbed layer is that 40 nanometers are to Cadmium Sulfide or the zinc sulphide transition layer of 250 nanometers, at 150 ~ 250 ℃ of annealing of temperature, 1 ~ 5min; Then, plate intrinsic zinc oxide and aluminum zinc oxide transparency electrode with sputtering instrument or ald machine, afterwards, the evaporation plated electrode.
CIGS thin-film is deposited on 2 ~ 6 millimeters the soda-lime glass or on the stainless steel thin slice or on the aluminium foil or on the plastic sheet.
In the present invention, (1) whole CuInGaSe absorbed layer is made of the nanometer p-n junction, so electronics and the hole recombination probability that forms photon diminishes and battery efficiency will be improved.(2) three-step approach forms gradient-structure, produces the back field, reduces electronics and hole recombination probability, thereby improves the efficient of solar cell.(3) owing to the content of selenium in the powder of single source is abundant, in whole steps, the film that plates is in the atmosphere of selenizing from the beginning to the end.Do not need to carry out the back selenizing and handle, saved heat energy, shortened the production time, protected environment.
Beneficial effect: compared with prior art, the present invention prepares copper indium gallium selenium solar cell for single three step of source vapour deposition method.Electron beam evaporation instrument and the Cu of heated substrates are housed by use
2In
xGa
1-xSe
2Powder by changing size of current, is realized the high-level efficiency membrane structure of poor copper as single source.Except poor copper, this film also has the absorption layer interconnect structure, large-size particle interface and gradient-structure.This structure has guaranteed the prepared cell high-level efficiency.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explanation.
Embodiment 1
What the present invention adopted is a kind of brand-new CIGS thin-film manufacturing process.Dan Yuansan step vapour deposition method has formed gradient-structure and absorption layer intraconnection structure.Realize the deposition of high-level efficiency battery core layer by change size of current, base reservoir temperature.CIGS thin-film is deposited on 2 millimeters to 6 millimeters the soda-lime glass or the stainless steel thin slice, or on the aluminium foil, or on the plastic sheet (polyimide, poly terephthalic acid class plastics etc.).All plate in advance the metal molybdenum of a layer thickness 200 nanometers to 1.5 micron in all substrates with method of evaporating or sputtering method, the resistivity of molybdenum layer is 0.2 ~ 5 ohmcm.Plating a layer thickness with chemical basin sedimentation (CBD) or atomic deposition method (ALD) at CuInGaSe absorbed layer is that 40 nanometers are to Cadmium Sulfide or the zinc sulphide transition layer of 250 nanometers, at 150 ~ 250 ℃ of annealing of temperature, 1 ~ 5min.Then, plate intrinsic zinc oxide and aluminum zinc oxide transparency electrode with sputtering instrument or ald machine, afterwards, the evaporation plated electrode.
CIGS thin-film manufacturing process of the present invention, used single source is Cu
2In
xGa
1-xSe
2Powder, major equipment are the electron beam evaporation instrument that heated substrates is housed, and constant voltage is 7KV.Specifically be divided into three steps:
Step 1: under 200 ~ 400 ℃ of conditions, with electric current the first layer film on evaporation in the substrate of 30 ~ 100mA, its main component is indium gallium selenium and a spot of copper, forms the rich indium gallium of poor copper zone;
Step 2: under 300 ~ 600 ℃ condition, with second layer film on the electric current evaporation of 80 ~ 150mA, its main component is copper-indium-galliun-selenium, forms the copper rich region territory;
Step 3: under 300 ~ 600 ℃ condition, with three-layer thin-film on the evaporation of 20 ~ 150mA electric current, its main component is gallium indium selenium and a spot of copper, forms the poor copper of one deck zone again, to guarantee the poor steel structure of film integral.
Product is detected, formed gradient-structure, illustrate that also this technology is the key factor that common vapour deposition method can obtain the high-level efficiency copper indium gallium selenium solar cell.
In the present invention, (1) whole CuInGaSe absorbed layer is made of the nanometer p-n junction, so electronics and the hole recombination probability that forms photon diminishes and battery efficiency will be improved.(2) three-step approach forms gradient-structure, produces the back field, reduces electronics and hole recombination probability, thereby improves the efficient of solar cell.(3) owing to the content of selenium in the powder of single source is abundant, in whole steps, the film that plates is in the atmosphere of selenizing from the beginning to the end.Do not need to carry out the back selenizing and handle, saved heat energy, shortened the production time, protected environment.
The present invention prepares copper indium gallium selenium solar cell for single three step of source vapour deposition method.Electron beam evaporation instrument and the Cu of heated substrates are housed by use
2In
xGa
1-xSe
2Powder by changing size of current, is realized the high-level efficiency membrane structure of poor copper as single source.Except poor copper, this film also has the absorption layer interconnect structure, large-size particle interface and gradient-structure.This structure has guaranteed the prepared cell high-level efficiency.
Claims (4)
1. the manufacturing process of a CIGS thin-film is characterized in that, is three-step approach, may further comprise the steps:
(1) under 200 ~ 400 ℃ of conditions, with electric current the first layer film on evaporation in the substrate of 30 ~ 100mA, forms the rich indium gallium of poor copper zone;
(2) under 300 ~ 600 ℃ condition, with second layer film on the electric current evaporation of 80 ~ 150mA, form the copper rich region territory;
(3) under 300 ~ 600 ℃ condition, with three-layer thin-film on the evaporation of 20 ~ 150mA electric current, form the poor copper of one deck zone again, to guarantee the poor steel structure of film integral;
Wherein, used single source is Cu
2In
xGa
1-xSe
2Powder, equipment are the electron beam evaporation instrument that heated substrates is housed, and constant voltage is 7KV.
2. the method for preparing the copper-indium-galliun-selenium ink according to claim 1 is characterized in that: plate the metal molybdenum of a layer thickness 200 nanometers to 1.5 micron in described substrate in advance with method of evaporating or sputtering method, the resistivity of molybdenum layer is 0.2 to 5 ohmcm.
3. the method for preparing the copper-indium-galliun-selenium ink according to claim 1, it is characterized in that: plating a layer thickness with chemical basin sedimentation or atomic deposition method at copper-indium-galliun-selenium/copper-zinc-tin-selenium absorption layer is that 40 nanometers are to Cadmium Sulfide or the zinc sulphide transition layer of 250 nanometers, at 150 ~ 250 ℃ of annealing of temperature, 1 ~ 5min; Then, plate intrinsic zinc oxide and aluminum zinc oxide transparency electrode with sputtering instrument or ald machine, afterwards, the evaporation plated electrode.
4. the method for preparing the copper-indium-galliun-selenium ink according to claim 1 is characterized in that: CIGS thin-film is deposited on 2 ~ 6 millimeters the soda-lime glass or on the stainless steel thin slice or on the aluminium foil or on the plastic sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101190278A CN103194726A (en) | 2013-04-08 | 2013-04-08 | Preparation process of cuprum-indium-gallium-selenium film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101190278A CN103194726A (en) | 2013-04-08 | 2013-04-08 | Preparation process of cuprum-indium-gallium-selenium film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103194726A true CN103194726A (en) | 2013-07-10 |
Family
ID=48717539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101190278A Pending CN103194726A (en) | 2013-04-08 | 2013-04-08 | Preparation process of cuprum-indium-gallium-selenium film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103194726A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103515482A (en) * | 2013-09-10 | 2014-01-15 | 华中科技大学 | Copper-indium-gallium-selenium thin film solar cell absorption layer and preparation method and application thereof |
| CN104716229A (en) * | 2013-12-16 | 2015-06-17 | 中国电子科技集团公司第十八研究所 | Cu-Zn-Sn-Se thin film solar cell preparation method |
| CN104851941A (en) * | 2014-03-06 | 2015-08-19 | 陈庆丰 | Method for manufacturing absorption layer in thin film solar cell and method for manufacturing thin film solar cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851742A (en) * | 2009-03-31 | 2010-10-06 | 比亚迪股份有限公司 | Preparation method of compound semiconductor film |
-
2013
- 2013-04-08 CN CN2013101190278A patent/CN103194726A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851742A (en) * | 2009-03-31 | 2010-10-06 | 比亚迪股份有限公司 | Preparation method of compound semiconductor film |
Non-Patent Citations (2)
| Title |
|---|
| ZHAO-HUI LI, ER AL.: "Properties of the Cu(In,Ga)Se2 absorbers deposited by electron-beam evaporation method for solar cells", 《CURRENT APPLIED PHYSICS》, no. 11, 31 December 2011 (2011-12-31), pages 28 - 33, XP027332205 * |
| 谈晓辉: "铜铟镓硒薄膜太阳电池吸收层的研究", 《中国博士学位论文全文数据库 工程科技2辑》, no. 7, 15 July 2012 (2012-07-15) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103515482A (en) * | 2013-09-10 | 2014-01-15 | 华中科技大学 | Copper-indium-gallium-selenium thin film solar cell absorption layer and preparation method and application thereof |
| CN104716229A (en) * | 2013-12-16 | 2015-06-17 | 中国电子科技集团公司第十八研究所 | Cu-Zn-Sn-Se thin film solar cell preparation method |
| CN104716229B (en) * | 2013-12-16 | 2017-06-27 | 中国电子科技集团公司第十八研究所 | The preparation method of copper-zinc-tin-selefilm film solar cell |
| CN104851941A (en) * | 2014-03-06 | 2015-08-19 | 陈庆丰 | Method for manufacturing absorption layer in thin film solar cell and method for manufacturing thin film solar cell |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107871795B (en) | A kind of regulation method of the band gap gradient of the cadmium doping copper zinc tin sulfur selenium film based on flexible molybdenum substrate | |
| CN102652368B (en) | Cu-In-Zn-Sn-(Se,S)-based thin film for solar cell and preparation method thereof | |
| CN102254998B (en) | Cadmium-free CuInGaSe thin film solar cell assembly and preparing method of zinc sulfide buffer layer thin film thereof | |
| CN101789469B (en) | Method for preparing light absorption layer of Cu-In-Ga-Se-S thin film solar cell | |
| CN103866236A (en) | Arrangement method of copper-indium-gallium-selenium thin-film battery co-evaporation linear sources | |
| CN102694066B (en) | Method for improving photoelectric conversion efficiency of solar cell panel | |
| CN103915516A (en) | Sodium doping method for CIGS-based thin film photovoltaic material | |
| CN103762257B (en) | The preparation method of copper-zinc-tin-sulfur absorbed layer film and copper-zinc-tin-sulfur solar cell | |
| CN103060861A (en) | Method for preparing copper-zinc-tin-sulfur film through co-electrodeposition | |
| CN102694077B (en) | Preparation method of CIGS (copper indium gallium diselenide) thin-film solar cell | |
| CN102437237A (en) | Chalcopyrite type thin film solar cell and manufacturing method thereof | |
| CN103194726A (en) | Preparation process of cuprum-indium-gallium-selenium film | |
| CN105551936A (en) | Method for preparing copper-indium-sulfide photoelectric film by two-step method of nitrate system | |
| JP2014045000A (en) | Compound solar cell and method for manufacturing the same | |
| CN102214737A (en) | Preparation method of compound thin film for solar battery | |
| CN102956722B (en) | Thin-film solar cell | |
| CN105474371B (en) | Layer system for the thin-layer solar cell with sodium indium sulfide cushion | |
| US8119513B1 (en) | Method for making cadmium sulfide layer | |
| CN104051577A (en) | Manufacturing method capable of improving crystallization property of copper zinc tin sulfur film of solar cell absorption layer | |
| CN103413842A (en) | Al doped ZnO transparent conducting micrometer/nanometer wire array film and preparation method thereof | |
| CN104716229A (en) | Cu-Zn-Sn-Se thin film solar cell preparation method | |
| CN102163652A (en) | Preparation method of thin-film solar cell | |
| CN103225060B (en) | Method for preparing copper-zinc-tin-sulfur thin film | |
| CN108807572B (en) | Silver indium gallium selenide thin film and preparation method and application thereof | |
| CN105428458A (en) | Method for preparing copper-indium sulfide optoelectronic thin film by adopting sulfate system two-step method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130710 |