CN102447009B - Preparation method of solar battery absorption layer thin film material - Google Patents
Preparation method of solar battery absorption layer thin film material Download PDFInfo
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- CN102447009B CN102447009B CN201110409449XA CN201110409449A CN102447009B CN 102447009 B CN102447009 B CN 102447009B CN 201110409449X A CN201110409449X A CN 201110409449XA CN 201110409449 A CN201110409449 A CN 201110409449A CN 102447009 B CN102447009 B CN 102447009B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a preparation method of a solar battery absorption layer thin film material, which comprises the following steps of: firstly, magnetron-sputtering molybdenum metal as a precursor on a substrate; then, depositing a Cu3Bi alloy layer thin film as a prefabricated film by adopting a three-electrode electrochemical system; and finally, vulcanizing and annealing the metal prefabricated film Cu3Bi to obtain a Cu3BiS3 (CBS) thin film. The invention has the beneficial effects that the absorption layer thin film material adopts a direct band gap material; the forbidden band width of the absorption layer thin film material is close to 1.24eV and is close to the optimal band gap of a solar battery, and the light absorption coefficient of the absorption layer thin film material in a visible light region is larger than 105 cm-1.
Description
Technical field:
The present invention relates to a kind of preparation method of solar cell absorbed layer thin-film material, belong to the photovoltaic cell technical field of material.
Background technology:
At present, the absorbing layer of thin film solar cell semi-conducting material of two kinds of main flows, Copper Indium Gallium Selenide (CIGS) material and cadmium telluride (CdTe) material, be subjected to towards large-scale production the time that raw material are rare, expensive, the constraint of the toxicity of component, very expensive as In metal among the CIGS, Te output among the CdTe is limited, all the raw material bottleneck can occur when the cell power generation amount reaches the GW magnitude.Cd is toxic in addition, has further increased the difficulty of producing, and therefore, needs to seek more excellent absorbed layer semiconductor.
In recent years, for seeking cheapness, environmental protection, the needs of solar battery obsorbing layer semi-conducting material efficiently, the ternary chalcogen semiconductor has attracted people more and more to pay close attention to. copper bismuth sulphur (Cu wherein
3BiS
3, being called for short CBS) and semiconductor receives maximum concerns, and this ternary semiconductor material only comprises that the nature reserves are abundant, cheap, the element of environmental sound.In addition, experiment measuring finds that its energy gap crack is 1.4eV, and near the optimum band gap of unijunction solar cell, and its absorption coefficient of light is very high by (＞10
5Cm
-1), have high photoelectric conversion efficiency.
Cu
3BiS
3(CBS) preparation method of thin-film material is known a thermal evaporation, solid-state response chemical bath method and physical evaporation sedimentation etc., the research of this type of material is faced with many problems and difficulty, successful preparation patent and application as the absorbed layer material do not appear in the newspapers yet in thin film solar cell at present, most studies rests on and changes synthetic method or composition, conditions such as temperature are carried out the level of synthetic material-making device-measurement performance parameter, although observe the variation of device performance, but lack the deep understanding to microphysics mechanism, to the optimization of device performance based on experience.
Summary of the invention:
Problem at background technology proposes the object of the present invention is to provide a kind of solar cell photovoltaic absorbing material Cu
3BiS
3(CBS) preparation method of film.The magnetron sputtering molybdenum adopts three-electrode electro Chemical system sedimentation Cu again as presoma in substrate earlier
3Bi alloy-layer film is as prefabricated membrane, at last with metal prefabricated membrane Cu
3Bi sulfuration and annealing in process obtain Cu
3BiS
3(CBS) film.
Concrete implementation step of the present invention is:
Adopt radio frequency (RF) magnetically controlled sputter method, magnetron sputtering molybdenum (Mo) metal level in the soda-lime glass substrate adopts an one-step electrochemistry system to deposit Cu at molybdenum (Mo) metal level then earlier
3The Bi alloy-layer is at last with Cu
3The Bi alloy-layer vulcanizes and annealing in process, obtains Cu
3BiS
3(CBS) absorbed layer finished product.
The present invention compares advantage and the good effect that has with known technology:
1. the preparation of absorbed layer does not need vacuum condition, and electrochemical deposition adopts a step sedimentation, adopts the constant potential mode in the deposition process, at room temperature need not to stir, and the deposition of alloy can be controlled by monitoring deposited charge amount, and is simple to operate; 2. the absorbed layer material is the direct band gap material, and its energy gap is near 1.24eV, near the optimum band gap of unijunction solar cell, at the visible region absorption coefficient of light big (＞10
5Cm-1).
Description of drawings:
Fig. 1 is process chart of the present invention.Fig. 2 is the device schematic diagram of electrochemical deposition film.1 is work electrode among the figure, and 2 is the molybdenum presoma, and 3 is electrolyte, and 4 is the electrochemical deposition case, and 5 is the Hg|HgO reference electrode, and 6 is electrochemical workstation, and 7 for electrode connects lead, and 8 is that platinum is to electrode.Fig. 3 is the thin film deposition structural representation.
Embodiment:
(1) is that the sodium alkali glass of 10mm * 10mm adopts washing agent, distilled water, isopropyl acetone and ethanol to carry out ultrasonic cleaning 10 minutes successively with size of foundation base, and is 0.1m3/h nitrogen drying 10 minutes with flow;
(2) adopt the thick molybdenum layer presoma of radio frequency (RF) magnetron sputtering deposition 1 μ m in substrate;
(3) be 99.99% slaine preparation electrolyte with deionized water and purity, electrolyte is for containing 9 mM bismuth nitrates (Bi (NO3)), 30 mM copper sulphate, two hydrates (CuSO4.2H2O), the mixed solution of 2 molar sodium hydroxides (NaOH) and 0.2 mole of sorbierite;
(4) adopt the three-electrode electro Chemical system, with the molybdenum layer presoma for preparing as work electrode, adopt the platinum sheet as to electrode, adopt Ag|AgCl as reference electrode, in the electrolyte for preparing, deposit the Cu3Bi alloy-layer.Deposition process does not at room temperature have stirring and carries out, adopt constant potential (Autolab 20 pressurizers) mode, the chemical potential of Cu3Bi alloy deposition is-0.75V (with respect to the .Ag|AgCl reference electrode), deposition is controlled by monitoring deposited charge amount, time 50-60 minute, obtain Cu3Bi alloy prefabricated membrane;
(5) with washed with de-ionized water alloy prefabricated membrane, and be the nitrogen drying 30 minutes of 0.1m3/h with flow;
(6) Cu3Bi alloy prefabricated membrane is put into crystal vessel, and it is inserted in the Quartz stove tube;
(7) nitrogen that charges into 1 bar pressure in the quartzy stove is as carrier gas, charged pressure 1Pa in the quartzy stove again, and purity is 99.999wt%, flow is the sulfur vapor of 0.1m3/h, at 450-500C
0Heating is 30 minutes under the furnace temperature, naturally cools to room temperature, obtains thick Cu3BiS3 (CBS) finished film of 2 μ m.
Claims (1)
1. the preparation method of a solar cell absorbed layer thin-film material, it is characterized in that: adopt radio frequency magnetron sputtering method, elder generation's sputter molybdenum layer in the soda-lime glass substrate, adopt an one-step electrochemistry system at molybdenum layer deposition Cu3Bi alloy-layer then, at last the Cu3Bi alloy-layer is vulcanized and annealing in process, obtain the Cu3BiS3 absorbed layer
Described preparation method implements according to the following steps
(1) is that the soda-lime glass of 10mm * 10mm adopts washing agent, distilled water, isopropyl acetone and ethanol to carry out ultrasonic cleaning 10 minutes successively with size of foundation base, and is 0.1m3/h nitrogen drying 10 minutes with flow;
(2) adopt the thick molybdenum layer presoma of radio frequency (RF) magnetron sputtering deposition 1 μ m as back electrode in substrate;
(3) deionized water and purity are 99.99% slaine preparation electrolyte, and this electrolyte is for containing 9 mM bismuth nitrates, 30 mM copper sulphate, two hydrates, the mixed solution of 2 molar sodium hydroxides and 0.2 mole of sorbierite;
(4) adopt the three-electrode electro Chemical system, with with the molybdenum layer presoma for preparing as work electrode, adopt the platinum sheet as to electrode, employing Ag|AgCl as reference electrode, deposition Cu3Bi alloy-layer in the electrolyte for preparing, deposition process does not at room temperature have stirring and carries out, adopt Autolab20 pressurizer constant potential mode, the chemical potential of Cu3Bi alloy deposition is-0.75V for the Ag|AgCl reference electrode, deposition is controlled by monitoring deposited charge amount, time 50-60 minute, obtain Cu3Bi alloy prefabricated membrane;
(5) with washed with de-ionized water alloy prefabricated membrane, and be the nitrogen drying 30 minutes of 0.1m3/h with flow;
(6) Cu3Bi alloy prefabricated membrane is put into crystal vessel, and it is inserted in the Quartz stove tube, in quartzy stove, charge into the nitrogen of 1 bar pressure as carrier gas, again toward the interior charged pressure 1Pa of quartzy stove, purity is 99.99wt%, and flow is the sulfur vapor of 0.1m3/h, and heating is 30 minutes under 450-500 ℃ of furnace temperature, naturally cool to room temperature, obtain the thick Cu3BiS3 finished film of 2 μ m.
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| CN201110409449XA CN102447009B (en) | 2011-12-12 | 2011-12-12 | Preparation method of solar battery absorption layer thin film material |
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| CN201110409449XA CN102447009B (en) | 2011-12-12 | 2011-12-12 | Preparation method of solar battery absorption layer thin film material |
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| CN102447009B true CN102447009B (en) | 2013-09-11 |
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| JP5808716B2 (en) * | 2012-07-18 | 2015-11-10 | 株式会社神戸製鋼所 | Method for manufacturing photoelectric conversion element |
| CN106086788B (en) * | 2016-08-10 | 2018-04-10 | 北京理工大学 | A kind of method for preparing copper bismuth sulphur film |
| CN107403853B (en) * | 2017-06-16 | 2018-10-23 | 河南大学 | A kind of ZTO-ZnO/CBS-GSs flexible thin-film solar cells and preparation method thereof |
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Non-Patent Citations (4)
| Title |
|---|
| Effect of preparation conditions on the properties of Cu3BiS3 thin films grown by a two–step process;F.Mesa et al;《 Journal of Physics: Conference Series 167》;20091231;第1-5页 * |
| F.Mesa et al.Effect of preparation conditions on the properties of Cu3BiS3 thin films grown by a two–step process.《 Journal of Physics: Conference Series 167》.2009, |
| N.J.Gerein et al.One-Step Synthesis and Optical and Electrical Properties of Thin Film Cu3BiS3 for Use as a Solar Absorber in Photovoltaic Devices.《Chem. Mater.》.2006,第18卷第6297-6302页. |
| One-Step Synthesis and Optical and Electrical Properties of Thin Film Cu3BiS3 for Use as a Solar Absorber in Photovoltaic Devices;N.J.Gerein et al;《Chem. Mater.》;20061219;第18卷;第6297-6302页 * |
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