CN106229362B - A kind of CIGS thin-film preparation method and CIGS thin-film - Google Patents

A kind of CIGS thin-film preparation method and CIGS thin-film Download PDF

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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
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CN106229362A (en
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王文庆
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Huzhou Qiqi Electromechanical Technology Co., Ltd
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Dongguan Lianzhou Intellectual Property Operation and Management Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/0248Semiconductor devices sensitive to infra-red 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
    • H01L31/0256Semiconductor devices sensitive to infra-red 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
    • H01L31/0264Inorganic materials
    • H01L31/032Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322Inorganic 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
    • 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
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/541CuInSe2 material PV cells

Abstract

The present invention relates to photovoltaic film field of material technology, the preparation method and CIGS thin-film of more particularly to a kind of CIGS thin-film.The preparation method of the present invention comprises the following steps:First layer of the magnetron sputtering formation comprising selenides series compound mixes sodium CIGS preformed layer on the substrate of deposition back electrode;Sodium CIGS preformed layer is mixed in selenizing heat treatment, obtains first layer CIGS thin-film layer;Loop cycle repeat step (1), (2), Ga/ (In+Ga) is different in each cycle, and from first layer CIGS thin-film layer into last one layer of CIGS thin-film layer, Ga/ (In+Ga) first reduces to be increased afterwards.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 CIGS thin-film layer band gap and prolongs the thin film deposition direction of growth and first reduce to be increased afterwards, and n is more than or equal to 3.The present invention can effectively improve photoelectric transformation efficiency, while add the open-circuit voltage of solar cell.

Description

A kind of CIGS thin-film preparation method and CIGS thin-film
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。
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