CN106229362B - Preparation method of copper indium gallium selenide thin film and copper indium gallium selenide thin film - Google Patents
Preparation method of copper indium gallium selenide thin film and copper indium gallium selenide thin film Download PDFInfo
- Publication number
- CN106229362B CN106229362B CN201610841978.XA CN201610841978A CN106229362B CN 106229362 B CN106229362 B CN 106229362B CN 201610841978 A CN201610841978 A CN 201610841978A CN 106229362 B CN106229362 B CN 106229362B
- Authority
- CN
- China
- Prior art keywords
- layer
- cigs
- film
- thin film
- cigs thin
- 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.)
- Active
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title abstract 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 35
- 238000000151 deposition Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 15
- 150000003346 selenoethers Chemical class 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims description 70
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 65
- 229910052708 sodium Inorganic materials 0.000 claims description 65
- 239000011669 selenium Substances 0.000 claims description 37
- 238000004544 sputter deposition Methods 0.000 claims description 32
- 229910052711 selenium Inorganic materials 0.000 claims description 31
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 26
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 23
- 239000010408 film Substances 0.000 claims description 10
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- ZIALXKMBHWELGF-UHFFFAOYSA-N [Na].[Cu] Chemical compound [Na].[Cu] ZIALXKMBHWELGF-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000000427 thin-film deposition Methods 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 27
- 239000010949 copper Substances 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 229940065287 selenium compound Drugs 0.000 description 10
- 230000009466 transformation Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000013077 target material Substances 0.000 description 6
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 4
- NMHFBDQVKIZULJ-UHFFFAOYSA-N selanylideneindium Chemical compound [In]=[Se] NMHFBDQVKIZULJ-UHFFFAOYSA-N 0.000 description 4
- 229910001182 Mo alloy Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 3
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to the technical field of photovoltaic thin film materials, in particular to a preparation method of a copper indium gallium selenide thin film and the copper indium gallium selenide thin film. The preparation method comprises the following steps: forming a first sodium-doped copper indium gallium selenide prefabricated layer containing selenide series compounds on a substrate deposited with a back electrode through magnetron sputtering; performing selenylation heat treatment on the sodium-doped copper indium gallium selenide prefabricated layer to obtain a first copper indium gallium selenide thin film layer; and (3) repeating the steps (1) and (2) periodically and circularly, wherein In each period, Ga/(In + Ga) is different, and Ga/(In + Ga) is increased after being reduced from the first CIGS thin film layer to the last CIGS thin film layer. The copper indium gallium selenide thin film consists of n sodium-doped copper indium gallium selenide thin film layers with different band gaps, the band gaps of the sodium-doped copper indium gallium selenide thin film layers are firstly reduced and then increased along the deposition growth direction of the thin film, and n is larger than or equal to 3. The invention can effectively improve the photoelectric conversion efficiency and increase the open-circuit voltage of the solar cell.
Description
Technical field
The present invention relates to photovoltaic film field of material technology, the preparation method and copper of more particularly to a kind of CIGS thin-film
Indium gallium selenium film.
Background technology
Copper-indium-galliun-selenium film solar cell has the advantages that transformation efficiency is high, cost is relatively low, is adapted to large-scale production.Its
Absorbed layer belongs to I-III-VI race's semi-conducting material, has 1.04~1.65e V adjustable energy gap and up to 105cm-1Suction
Coefficient is received, in numerous thin film solar cells, copper-indium-galliun-selenium film solar cell is considered as most promising one
Kind.Between last decade, have become the focus of vast researcher research.
Research finds, light absorbing layer of the CIGS thin-film as solar cell, energy during the V-shaped distribution of its energy gap
The effective electrical properties for improving photovoltaic cell device, relative to it is flat can band distribution or it is unidirectional can with distribution scenario,
Copper-indium-gallium-selenium semiconductor film with the double gradient-structures of V-type can be lifted in the case where ensureing preferable current collection efficiency to be opened
Road voltage.The present invention optimizes preparation method based on secondary, obtains photoelectric transformation efficiency height, the big CIGS of open-circuit voltage
Film.
The content of the invention
It is an object of the invention to provide a kind of CIGS thin-film preparation method and CIGS thin-film, the CIGS are thin
Film is good as solar cell light absorption layer quality.
To achieve the above object, the technological means that uses of the present invention for：
A kind of preparation method of CIGS thin-film, comprises the following steps：
(1) first layer of the magnetron sputtering formation comprising selenides series compound mixes sodium copper on the substrate of deposition back electrode
Indium gallium selenium preformed layer；
(2) sodium CIGS preformed layer is mixed in selenizing heat treatment, obtains first layer CIGS thin-film layer；
(3) loop cycle repeat step (1), (2), Ga/ (In+Ga) is different in each cycle, from first layer CIGS
Into last one layer of CIGS thin-film layer, Ga/ (In+Ga) first reduces to be increased film layer afterwards.
Preferably, the back electrode forms for Cu-Mo alloys.
Preferably, the selenides series compound includes one kind or several in Cu-Se, In-Se, Ga-Se, Cu-In-Se
Kind.
Preferably, it is described mix sodium CIGS preformed layer by the target target comprising selenides series compound with
Na2Se targets sputter to be formed jointly.
Preferably, before each selenizing heat treatment, hydatogenesis selenium on sodium CIGS preformed layer is mixed at every layer and forms one layer
Selenium layer.
Preferably, selenizing heat treatment heating process is that first 20 DEG C/min is warming up to 200 DEG C, then 100 DEG C/min is warming up to
510 DEG C~560 DEG C, maintain 2 minutes, then 10 DEG C/min is cooled to 500 DEG C~550 DEG C, maintains 10min~60min.
Preferably, before magnetron sputtering, 10min pre-sputterings are carried out to target used.
A kind of CIGS thin-film, it is made up of the sodium CIGS thin-film layer of mixing of n-layer difference band gap, each layer mixes sodium copper and indium gallium
Selenium film layer band gap first reduces along the thin film deposition direction of growth and increased afterwards, and n is more than or equal to 3.
Preferably, natrium doping amount 0.1%~0.3% in every layer of CIGS layer.
Preferably, Ga/ (In+Ga)=X in n-th layer CIGS thin-film layern, 0.4≤Xn≤0.3。
Relative to prior art, the present invention has advantages below：
CIGS thin-film of the present invention is made up of the sodium CIGS thin-film layer of mixing of n-layer difference band gap, by including selenizing
The sodium CIGS preformed layer annealing selenizing of mixing of thing series compound is formed.
Possess the Ga translational speeds in the selenides of covalent structure than possessing in the metal or alloy of metal combining structure
Ga translational speeds are slow, and selenides series compound can suppress Ga segregations to a certain degree, make every layer to mix sodium CIGS thin-film layer
Middle Ga changes in distribution is small；
Every layer is mixed in sodium CIGS thin-film layer in the case of Ga distributions minor variations, and every layer is mixed sodium CIGS thin-film layer
Internal band gap minor variations, it is combined into plus the horizontal sodium CIGS thin-film layer of mixing of n-layer difference band gap with wider range band
The light absorbing layer of gap distribution, the photon of various energy can be absorbed, improve absorption efficiency, and then improve electricity conversion；Two
Boundary layer band gap is big, and intermediate band gap layer is small so that from first layer CIGS thin-film layer to last one layer of CIGS thin-film layer, prohibits
The variation tendency that bandwidth integrally rises afterwards in first dropping, reduction photo-generated carrier is compound, adds the open-circuit voltage of solar cell；
The doping of sodium can be passivated crystal boundary, reduce the defects of polycrystalline in every layer of CIGS preformed layer, lack every layer film
Sunken all less, overall crystalline quality is good, also, is all doped into sodium element in every tunic, the CIGS acceptor being effectively increased
Concentration, contribute to the conversion efficiency of further increase solar cell.
Therefore, the CIGS thin-film light absorbing layer that prepared by the present invention effectively improves photoelectric transformation efficiency, adds simultaneously
The open-circuit voltage of solar cell.
Brief description of the drawings
Fig. 1 is that the sodium CIGS thin-film layer of mixing by 5 layers of different band gap prepared by the present invention forms CIGS optical thin film
It is preferable can band schematic diagram.
Embodiment
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be formed to the present invention.
Back electrode used in the embodiment of the present invention forms for Cu-Mo alloys, and Cu-Mo alloys and CIGS thin-film adhesiveness are more
It is good.
Embodiment 1
A kind of preparation method of CIGS thin-film, comprises the following steps：
(1) magnetron sputtering forms the first layer for including selenides series compound on the substrate of deposition Cu-Mo back electrodes
Mix sodium CIGS preformed layer；
The substrate for depositing Cu-Mo back electrodes is put into magnetron sputtering chamber, is evacuated to 5 × 10-4Pa, and open argon gas
Control valve, to be passed through the argon gas needed for magnetron sputtering in magnetron sputtering chamber, under Ar Pressure 1.0Pa, target used is entered
Row 10min pre-sputterings, to remove the impurity particle of target material surface absorption.Under Ar Pressure 1.0Pa, sputtering power is adjusted, by copper gold
Belong to target, indium metal target and gallium selenium compound target (Ga2Se3) and Na2Se targets magnetron sputtering on the substrate of deposition Cu-Mo back electrodes
Form 400nm first layers and mix sodium CIGS preformed layer, make Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.4, natrium doping amount
0.1%.
(2) sodium CIGS preformed layer is mixed in selenizing heat treatment, obtains first layer CIGS thin-film layer；
First layer is mixed into sodium CIGS preformed layer to be sent into linear evaporator, 5 × 10-3Under Pa vacuum, heat is steamed
Hair weight is 3g granules of selenium, the SEDIMENTARY SELENIUM on the preformed layer of CIGS second, obtains the selenium layer that a layer thickness is 500nm；Afterwards
Sample is put into annealing furnace, 5 × 10-4In the atmosphere of Pa nitrogen, first 20 DEG C/min is warming up to 200 DEG C, then 100 DEG C/min heatings
To 550 DEG C, 2 minutes are maintained, then 10 DEG C/min is cooled to 540 DEG C, maintains 40min.
(3) repeat step (1), sputtering power, Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.3, natrium doping amount are adjusted
0.15%, form the second layer and mix sodium CIGS preformed layer, repeat step (2) forms second layer CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.36, natrium doping amount
0.1%, form third layer and mix sodium CIGS preformed layer, repeat step (2) forms third layer CIGS thin-film layer.
CIGS thin-film manufactured in the present embodiment is made up of the sodium CIGS thin-film layer of mixing of 3 layers of different band gap, will
It is prepared into solar cell, under conditions of 25 DEG C, AM1.5 to battery device carry out I-V tests, measure battery open circuit electricity
Press 500mv, photoelectric transformation efficiency 11.8%.
Embodiment 2
A kind of preparation method of CIGS thin-film, comprises the following steps：
(1) magnetron sputtering forms the first layer for including selenides series compound on the substrate of deposition Cu-Mo back electrodes
Mix sodium CIGS preformed layer；
The substrate for depositing Cu-Mo back electrodes is put into magnetron sputtering chamber, is evacuated to 5 × 10-4Pa, and open argon gas
Control valve, to be passed through the argon gas needed for magnetron sputtering in magnetron sputtering chamber, under Ar Pressure 1.0Pa, target used is entered
Row 10min pre-sputterings, to remove the impurity particle of target material surface absorption.Under Ar Pressure 1.0Pa, sputtering power is adjusted, by copper gold
Belong to target, indium metal target and gallium selenium compound target (Ga2Se3) and Na2Se targets magnetron sputtering on the substrate of deposition Cu-Mo back electrodes
Form 250nm first layers and mix sodium CIGS preformed layer, make Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=0.4, natrium doping amount
0.1%.
(2) sodium CIGS preformed layer is mixed in selenizing heat treatment, obtains first layer CIGS thin-film layer；
First layer is mixed into sodium CIGS preformed layer to be sent into linear evaporator, 5 × 10-3Under Pa vacuum, heat is steamed
Hair weight is 3g granules of selenium, the SEDIMENTARY SELENIUM on the preformed layer of CIGS second, obtains the selenium layer that a layer thickness is 300nm；Afterwards
Sample is put into annealing furnace, 5 × 10-4In the atmosphere of Pa nitrogen, first 20 DEG C/min is warming up to 200 DEG C, then 100 DEG C/min heatings
To 550 DEG C, 2 minutes are maintained, then 10 DEG C/min is cooled to 540 DEG C, maintains 20min.
(3) repeat step (1), sputtering power, Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.37, natrium doping amount are adjusted
0.1%, form the second layer and mix sodium CIGS preformed layer, repeat step (2) forms second layer CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.82, Ga/ (In+Ga)=0.32, natrium doping amount
0.15%, form third layer and mix sodium CIGS preformed layer, repeat step (2) forms third layer CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.34, natrium doping amount
0.1%, form the 4th layer and mix sodium CIGS preformed layer, repeat step (2) forms the 4th layer of CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=0.38, natrium doping amount
0.1%, form layer 5 and mix sodium CIGS preformed layer, repeat step (2) forms layer 5 CIGS thin-film layer；
CIGS thin-film manufactured in the present embodiment is made up of the sodium CIGS thin-film layer of mixing of 5 layers of different band gap, will
It is prepared into solar cell, under conditions of 25 DEG C, AM1.5 to battery device carry out I-V tests, measure battery open circuit electricity
Press 520mv, photoelectric transformation efficiency 12.5%.
Embodiment 3
A kind of preparation method of CIGS thin-film, comprises the following steps：
(1) magnetron sputtering forms the first layer for including selenides series compound on the substrate of deposition Cu-Mo back electrodes
Mix sodium CIGS preformed layer；
The substrate for depositing Cu-Mo back electrodes is put into magnetron sputtering chamber, is evacuated to 5 × 10-4Pa, and open argon gas
Control valve, to be passed through the argon gas needed for magnetron sputtering in magnetron sputtering chamber, under Ar Pressure 1.0Pa, target used is entered
Row 10min pre-sputterings, to remove the impurity particle of target material surface absorption.Under Ar Pressure 1.0Pa, sputtering power is adjusted, by copper gold
Belong to target, indium selenium compound target (In2Se3) and gallium selenium compound target (Ga2Se3) and Na2Substrate of the Se targets in deposition Cu-Mo back electrodes
Upper magnetron sputtering forms 450nm first layers and mixes sodium CIGS preformed layer, make Cu/ (In+Ga)=0.9, Ga/ (In+Ga)=
0.39, natrium doping amount 0.15%.
(2) sodium CIGS preformed layer is mixed in selenizing heat treatment, obtains first layer CIGS thin-film layer；
First layer is mixed into sodium CIGS preformed layer to be sent into linear evaporator, 5 × 10-3Under Pa vacuum, heat is steamed
Hair weight is 3g granules of selenium, the SEDIMENTARY SELENIUM on the preformed layer of CIGS second, obtains the selenium layer that a layer thickness is 500nm；Afterwards
Sample is put into annealing furnace, 5 × 10-4In the atmosphere of Pa nitrogen, first 20 DEG C/min is warming up to 200 DEG C, then 100 DEG C/min heatings
To 520 DEG C, 2 minutes are maintained, then 10 DEG C/min is cooled to 510 DEG C, maintains 40min.
(3) repeat step (1), sputtering power, Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=0.33, natrium doping are adjusted
Amount 0.21%, form the second layer and mix sodium CIGS preformed layer, repeat step (2) forms second layer CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.9, Ga/ (In+Ga)=0.36, natrium doping amount
0.15%, form third layer and mix sodium CIGS preformed layer, repeat step (2) forms third layer CIGS thin-film layer.
CIGS thin-film manufactured in the present embodiment is made up of the sodium CIGS thin-film layer of mixing of 3 layers of different band gap, will
It is prepared into solar cell, under conditions of 25 DEG C, AM1.5 to battery device carry out I-V tests, measure battery open circuit electricity
Press 512mv, photoelectric transformation efficiency 12.1%.
Embodiment 4
A kind of preparation method of CIGS thin-film, comprises the following steps：
(1) magnetron sputtering forms the first layer for including selenides series compound on the substrate of deposition Cu-Mo back electrodes
Mix sodium CIGS preformed layer；
The substrate for depositing Cu-Mo back electrodes is put into magnetron sputtering chamber, is evacuated to 5 × 10-4Pa, and open argon gas
Control valve, to be passed through the argon gas needed for magnetron sputtering in magnetron sputtering chamber, under Ar Pressure 1.0Pa, target used is entered
Row 10min pre-sputterings, to remove the impurity particle of target material surface absorption.Under Ar Pressure 1.0Pa, sputtering power is adjusted, by copper gold
Belong to target, indium selenium compound target (In2Se3) and gallium selenium compound target (Ga2Se3) and Na2Substrate of the Se targets in deposition Cu-Mo back electrodes
Upper magnetron sputtering forms 250nm first layers and mixes sodium CIGS preformed layer, make Cu/ (In+Ga)=0.75, Ga/ (In+Ga)=
0.39, natrium doping amount 0.25%.
(2) sodium CIGS preformed layer is mixed in selenizing heat treatment, obtains first layer CIGS thin-film layer；
First layer is mixed into sodium CIGS preformed layer to be sent into linear evaporator, 5 × 10-3Under Pa vacuum, heat is steamed
Hair weight is 3g granules of selenium, the SEDIMENTARY SELENIUM on the preformed layer of CIGS second, obtains the selenium layer that a layer thickness is 300nm；Afterwards
Sample is put into annealing furnace, 5 × 10-4In the atmosphere of Pa nitrogen, first 20 DEG C/min is warming up to 200 DEG C, then 100 DEG C/min heatings
To 550 DEG C, 2 minutes are maintained, then 10 DEG C/min is cooled to 540 DEG C, maintains 20min.
(3) repeat step (1), sputtering power, Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.36, natrium doping amount are adjusted
0.19%, form the second layer and mix sodium CIGS preformed layer, repeat step (2) forms second layer CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.32, natrium doping amount
0.1%, form third layer and mix sodium CIGS preformed layer, repeat step (2) forms third layer CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.34, natrium doping amount
0.19%, form the 4th layer and mix sodium CIGS preformed layer, repeat step (2) forms the 4th layer of CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.75, Ga/ (In+Ga)=0.38, natrium doping amount
0.25%, form layer 5 and mix sodium CIGS preformed layer, repeat step (2) forms layer 5 CIGS thin-film layer；
CIGS thin-film manufactured in the present embodiment is made up of the sodium CIGS thin-film layer of mixing of 5 layers of different band gap, will
It is prepared into solar cell, under conditions of 25 DEG C, AM1.5 to battery device carry out I-V tests, measure battery open circuit electricity
Press 530mv, photoelectric transformation efficiency 12.9%.
Embodiment 5
A kind of preparation method of CIGS thin-film, comprises the following steps：
(1) magnetron sputtering forms the first layer for including selenides series compound on the substrate of deposition Cu-Mo back electrodes
Mix sodium CIGS preformed layer；
The substrate for depositing Cu-Mo back electrodes is put into magnetron sputtering chamber, is evacuated to 5 × 10-4Pa, and open argon gas
Control valve, to be passed through the argon gas needed for magnetron sputtering in magnetron sputtering chamber, under Ar Pressure 1.0Pa, target used is entered
Row 10min pre-sputterings, to remove the impurity particle of target material surface absorption.Under Ar Pressure 1.0Pa, sputtering power is adjusted, by copper gallium
Close target, indium selenium compound target (In2Se3) and gallium selenium compound target (Ga2Se3) and Na2Substrate of the Se targets in deposition Cu-Mo back electrodes
Upper magnetron sputtering forms 450nm first layers and mixes sodium CIGS preformed layer, make Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=
0.4, natrium doping amount 0.25%.
(2) sodium CIGS preformed layer is mixed in selenizing heat treatment, obtains first layer CIGS thin-film layer；
First layer is mixed into sodium CIGS preformed layer to be sent into linear evaporator, 5 × 10-3Under Pa vacuum, heat is steamed
Hair weight is 3g granules of selenium, the SEDIMENTARY SELENIUM on the preformed layer of CIGS second, obtains the selenium layer that a layer thickness is 600nm；Afterwards
Sample is put into annealing furnace, 5 × 10-4In the atmosphere of Pa nitrogen, first 20 DEG C/min is warming up to 200 DEG C, then 100 DEG C/min heatings
To 540 DEG C, 2 minutes are maintained, then 10 DEG C/min is cooled to 530 DEG C, maintains 45min.
(3) repeat step (1), sputtering power, Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=0.33, natrium doping are adjusted
Amount 0.2%, form the second layer and mix sodium CIGS preformed layer, repeat step (2) forms second layer CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=0.37, natrium doping amount
0.25%, form third layer and mix sodium CIGS preformed layer, repeat step (2) forms third layer CIGS thin-film layer.
CIGS thin-film manufactured in the present embodiment is made up of the sodium CIGS thin-film layer of mixing of 3 layers of different band gap, will
It is prepared into solar cell, under conditions of 25 DEG C, AM1.5 to battery device carry out I-V tests, measure battery open circuit electricity
Press 520mv, photoelectric transformation efficiency 11.4%.
Embodiment 6
A kind of preparation method of CIGS thin-film, comprises the following steps：
(1) magnetron sputtering forms the first layer for including selenides series compound on the substrate of deposition Cu-Mo back electrodes
Mix sodium CIGS preformed layer；
The substrate for depositing Cu-Mo back electrodes is put into magnetron sputtering chamber, is evacuated to 5 × 10-4Pa, and open argon gas
Control valve, to be passed through the argon gas needed for magnetron sputtering in magnetron sputtering chamber, under Ar Pressure 1.0Pa, target used is entered
Row 10min pre-sputterings, to remove the impurity particle of target material surface absorption.Under Ar Pressure 1.0Pa, sputtering power is adjusted, by copper gallium
Close target, indium selenium compound target (In2Se3) and gallium selenium compound target (Ga2Se3) and Na2Substrate of the Se targets in deposition Cu-Mo back electrodes
Upper magnetron sputtering forms 250nm first layers and mixes sodium CIGS preformed layer, make Cu/ (In+Ga)=0.72, Ga/ (In+Ga)=
0.39, natrium doping amount 0.15%.
(2) sodium CIGS preformed layer is mixed in selenizing heat treatment, obtains first layer CIGS thin-film layer；
First layer is mixed into sodium CIGS preformed layer to be sent into linear evaporator, 5 × 10-3Under Pa vacuum, heat is steamed
Hair weight is 3g granules of selenium, the SEDIMENTARY SELENIUM on the preformed layer of CIGS second, obtains the selenium layer that a layer thickness is 350nm；Afterwards
Sample is put into annealing furnace, 5 × 10-4In the atmosphere of Pa nitrogen, first 20 DEG C/min is warming up to 200 DEG C, then 100 DEG C/min heatings
To 540 DEG C, 2 minutes are maintained, then 10 DEG C/min is cooled to 530 DEG C, maintains 15min.
(3) repeat step (1), sputtering power, Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.36, natrium doping amount are adjusted
0.15%, form the second layer and mix sodium CIGS preformed layer, repeat step (2) forms second layer CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=0.32, natrium doping amount
0.1%, form third layer and mix sodium CIGS preformed layer, repeat step (2) forms third layer CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.8, Ga/ (In+Ga)=0.34, natrium doping amount
0.15%, form the 4th layer and mix sodium CIGS preformed layer, repeat step (2) forms the 4th layer of CIGS thin-film layer；
Repeat step (1), adjust sputtering power, Cu/ (In+Ga)=0.72, Ga/ (In+Ga)=0.37, natrium doping amount
0.15%, form layer 5 and mix sodium CIGS preformed layer, repeat step (2) forms layer 5 CIGS thin-film layer；
CIGS thin-film manufactured in the present embodiment is made up of the sodium CIGS thin-film layer of mixing of 5 layers of different band gap, will
It is prepared into solar cell, under conditions of 25 DEG C, AM1.5 to battery device carry out I-V tests, measure battery open circuit electricity
Press 515mv, photoelectric transformation efficiency 12.8%.
Claims (6)
1. a kind of preparation method of CIGS thin-film, it is characterised in that comprise the following steps：
(1) first layer of the magnetron sputtering formation comprising selenides series compound mixes sodium copper and indium gallium on the substrate of deposition back electrode
Selenium preformed layer；
(2) sodium CIGS preformed layer is mixed in selenizing heat treatment, obtains first layer CIGS thin-film layer；Each selenizing heat treatment
Before, hydatogenesis selenium on sodium CIGS preformed layer is mixed at every layer and forms one layer of selenium layer；Selenizing heat treatment heating process is first 20
DEG C/min is warming up to 200 DEG C, then 100 DEG C/min is warming up to 510 DEG C~560 DEG C, maintains 2 minutes, and then 10 DEG C/min is cooled to
500 DEG C~550 DEG C, maintain 10min~60min；Natrium doping amount 0.1%~0.3% in every layer of CIGS layer；
(3) loop cycle repeat step (1), (2), Ga/ (In+Ga) is different in each cycle, from first layer CIGS thin-film
Into last one layer of CIGS thin-film layer, Ga/ (In+Ga) first reduces to be increased layer afterwards；
CIGS thin-film obtained above is made up of the sodium CIGS thin-film layer of mixing of n-layer difference band gap, and each layer mixes sodium copper and indium
Gallium selenium film layer band gap first reduces along the thin film deposition direction of growth to be increased afterwards, and n is more than or equal to 3.
2. the preparation method of CIGS thin-film according to claim 1, it is characterised in that：The back electrode is Cu-Mo
Alloy forms.
3. the preparation method of CIGS thin-film according to claim 1, it is characterised in that：The selenides series chemical combination
Thing includes the one or more in Cu-Se, In-Se, Ga-Se, Cu-In-Se.
4. the preparation method of CIGS thin-film according to claim 1, it is characterised in that：It is described that to mix sodium CIGS pre-
Preparative layer passes through target target and Na comprising selenides series compound2Se targets sputter to be formed jointly.
5. the preparation method of CIGS thin-film according to claim 1, it is characterised in that：Before magnetron sputtering, to used
Target carries out 10min pre-sputterings.
6. the preparation method of CIGS thin-film according to claim 1, it is characterised in that：N-th layer CIGS thin-film
Ga/ (In+Ga)=X in layern, 0.4≤Xn≤0.3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610841978.XA CN106229362B (en) | 2016-09-22 | 2016-09-22 | Preparation method of copper indium gallium selenide thin film and copper indium gallium selenide thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610841978.XA CN106229362B (en) | 2016-09-22 | 2016-09-22 | Preparation method of copper indium gallium selenide thin film and copper indium gallium selenide thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106229362A CN106229362A (en) | 2016-12-14 |
| CN106229362B true CN106229362B (en) | 2018-03-16 |
Family
ID=58076589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610841978.XA Active CN106229362B (en) | 2016-09-22 | 2016-09-22 | Preparation method of copper indium gallium selenide thin film and copper indium gallium selenide thin film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106229362B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112086538A (en) * | 2019-06-12 | 2020-12-15 | 领凡新能源科技(北京)有限公司 | Method for producing light absorption layer of solar cell and solar cell |
| CN110257770B (en) * | 2019-06-21 | 2022-02-18 | 铜仁梵晖新能源有限公司 | Method for preparing V-type doped copper indium gallium selenide absorption layer by PVD (physical vapor deposition) method |
| CN113571594B (en) * | 2021-07-16 | 2023-06-16 | 北京交通大学 | Copper indium gallium selenium battery and manufacturing method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130164916A1 (en) * | 2011-12-21 | 2013-06-27 | Intermolecular, Inc. | Absorbers for high efficiency thin-film pv |
| CN102544132B (en) * | 2012-01-17 | 2014-12-03 | 上海联孚新能源科技集团有限公司 | Copper indium gallium selenide cell and preparation method thereof |
| CN103077980B (en) * | 2013-01-25 | 2016-04-20 | 中国农业大学 | A kind of copper-indium-galliun-selenium film solar cell and preparation method thereof |
-
2016
- 2016-09-22 CN CN201610841978.XA patent/CN106229362B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106229362A (en) | 2016-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3249408B2 (en) | Method and apparatus for manufacturing thin film light absorbing layer of thin film solar cell | |
| Dimmler et al. | Scaling‐up of CIS technology for thin‐film solar modules | |
| CN105655235B (en) | A kind of method and apparatus that gradient band gap light absorbing layer is prepared based on continuous evaporation technique | |
| US20140124011A1 (en) | Heat Treatment Process and Photovoltaic Device Based on Said Process | |
| US8044477B1 (en) | Photovoltaic device and method for making | |
| CN104143579A (en) | Antimony-base compound thin film solar cell and manufacturing method thereof | |
| CN106229362B (en) | Preparation method of copper indium gallium selenide thin film and copper indium gallium selenide thin film | |
| CN105336800A (en) | Preparation method of light absorption layer of CIGS-base thin film solar cell | |
| CN106449816B (en) | A kind of preparation method of CIGS thin-film | |
| WO2013185506A1 (en) | Method for preparing copper indium gallium diselenide thin-film solar cell | |
| CN102214737B (en) | Preparation method of compound thin film for solar battery | |
| US20120180858A1 (en) | Method for making semiconducting film and photovoltaic device | |
| CN103469170B (en) | A kind of sputtering target for thin-film solar cells | |
| CN111128747A (en) | Preparation method of laminated absorption layer of double-gradient band gap CIGS solar cell | |
| JPH0955378A (en) | Precursor for forming semiconductor thin film and manufacture of semiconductor thin film | |
| CN106653946A (en) | Method for depositing cadmium telluride film solar cell absorption layer | |
| CN106409934A (en) | Preparation method of CIGS solar cell absorption layer | |
| CN103474514B (en) | The preparation method of copper indium gallium selenium solar cell | |
| CN114203842A (en) | Wide-bandgap copper-gallium-selenium light absorption layer, preparation method thereof and solar cell | |
| Yang et al. | Photoluminescence study of the defect-induced recombination in Cu (In, Ga) Se2 solar cell | |
| KR102015985B1 (en) | Method for manufacturing CIGS thin film for solar cell | |
| US20120080306A1 (en) | Photovoltaic device and method for making | |
| CN102943237A (en) | Preparation method of copper indium gallium diselenide thin film solar cell absorbing layer | |
| CN110323293B (en) | Copper indium gallium selenium thin film solar cell | |
| TWI443840B (en) | Quaternary compound thin-film and method for preparing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191118 Address after: 313000 1-B, building 1, No. 656, Qixing Road, high tech Zone, Wuxing District, Huzhou City, Zhejiang Province Patentee after: Huzhou Qiqi Electromechanical Technology Co., Ltd Address before: 523000 Guangdong province Dongguan City Songshan Lake high tech Industrial Zone Building 406 industrial development productivity Patentee before: Dongguan Lianzhou Intellectual Property Operation Management Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220513 Address after: No.8, Qingxia Road, Chengyang District, Qingdao City, Shandong Province Patentee after: QINGDAO JUSTO PACKAGING Co.,Ltd. Address before: 313000 1-B, building 1, No. 656 Qixing Road, high tech Zone, Wuxing District, Huzhou City, Zhejiang Province Patentee before: Huzhou Qiqi Electromechanical Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |