CN104716227A - Method for manufacturing CZTS thin film solar cell absorbing layer - Google Patents

Method for manufacturing CZTS thin film solar cell absorbing layer Download PDF

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Publication number
CN104716227A
CN104716227A CN201310714978.XA CN201310714978A CN104716227A CN 104716227 A CN104716227 A CN 104716227A CN 201310714978 A CN201310714978 A CN 201310714978A CN 104716227 A CN104716227 A CN 104716227A
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evaporation source
substrate
evaporation
thin film
solar cell
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王胜利
杨亦桐
杨立
李微
赵彦民
乔在祥
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CETC 18 Research Institute
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    • 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
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • 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
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • H01L31/0327—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4 characterised by the doping material
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention relates to a method for manufacturing a CZTS thin film solar cell absorbing layer. The method includes the steps that Cu, Zn, Sn, Se and NaF are co-evaporated on the lower face of a flexible substrate, so that a copper-rich CZTS thin film is formed; a substrate baffle is closed, after Cu and NaF are cooled, the substrate baffle is opened, Zn, Sn and Se are co-evaporated on the lower face of the flexible substrate, and the substrate baffle is closed; after Zn is cooled, the substrate baffle is opened and the substrate is cooled in the atmosphere of Sn and Se; the CZTS thin film solar cell absorbing layer is formed on the flexible substrate. By the adoption of the method, flexible PI serves as the substrate, a co-evaporation method is adopted, the evaporation temperature, the evaporation time, and the evaporation sequence and the like of the evaporation sources of Cu, Zn, Sn and Se are controlled, so that a reaction route and composition are controlled, the post-selenylation and annealing processes are avoided, the manufactured CZTS thin film solar cell absorbing layer is high in crystallization quality and good in evenness, the manufacturing process is simple, repeatability is high, and the industrialization of CZTS thin film solar cells is facilitated.

Description

The preparation method of CZTS absorption layer of thin film solar cell
Technical field
The invention belongs to thin film solar cell manufacture technology field, particularly relate to a kind of preparation method of CZTS absorption layer of thin film solar cell.
Background technology
Thin film solar cell in recent years, especially the development of CIGS thin film solar cell rapidly.At present, the Laboratory Conversion efficiency of CIGS thin film solar cell reaches 20.4%, and its industrialization process is also constantly accelerated.But key element In, Ga reserves are limited in CIGS thin film solar cell absorbed layer, and price is relatively high, limit the extensive industrialized development of CIGS thin film solar cell.CZTS(copper-zinc-tin-sulfur (selenium), i.e. Cu2ZnSn(S, Se) 4) film has similar photoelectric characteristic to CIGS thin film, and CZTS film is with In, Ga in lower Zn, Sn element substitution CIGS thin film of rich reserves, price, reduce further the cost of film preparation, is suitable for large-scale industrialization and produces.Therefore, the thin film solar cell being absorbed layer with CZTS film research becomes focus, and the Laboratory Conversion efficiency of CZTS thin film solar cell is more than 11%.
The method of the current known CZTS of preparation absorption layer of thin film solar cell mainly comprises: on soda-lime glass substrate, first prepare the predecessor of one deck containing Cu, Zn, Sn, and then carry out rear selenizing, annealing in process obtains CZTS absorption layer of thin film solar cell, the method due to the difficulty of rear selenizing, annealing in process larger, course of reaction is wayward, complex manufacturing process, repeatability are poor, the thin film solar cell quality made is lower than power, owing to bending, reduce the scope of application of battery, and the industrialization being difficult to be formed CZTS thin film solar cell is produced.
Summary of the invention
The present invention provides a kind of manufacturing process simple, repeatable high for solving in known technology the technical problem that exists, the thin film solar cell quality made is light, crystalline quality is high, uniformity good, quality is higher than power, battery can bend, the scope of application is wide, is beneficial to the preparation method realizing the CZTS absorption layer of thin film solar cell that industrialization is produced.
The present invention includes following technical scheme:
The preparation method of CZTS absorption layer of thin film solar cell, is characterized in: comprise following preparation process:
Step 1: flexible substrate is coated with below one of film faces down and be fixed on vacuum evaporation chamber roof below rotating shaft specimen holder, is equipped with moveable substrate baffle plate below flexible substrate; Fix a thermocouple above specimen holder, the rotating shaft of the top of thermocouple has substrate heater; Cu evaporation source, Zn evaporation source, NaF evaporation source, Sn evaporation source and Se evaporation source are placed in angle and highly all adjustable five evaporation source bases in vacuum evaporation chamber respectively, wherein the top of Cu evaporation source, Zn evaporation source, NaF evaporation, Sn evaporation source is to the top of distance≤30cm, the Se evaporation source of substrate bottom centre to the distance < 10cm of substrate bottom centre;
Step 2: 5 × 10 are evacuated to vacuum evaporation chamber by pumped vacuum systems -4pa, by described thermocouple control temperature, heated substrate is to 450-550 DEG C; The temperature of each evaporation source heater is controlled by the PID controller outside vacuum evaporation chamber, heating Cu evaporation source to 1200-1300 DEG C, Zn evaporation source is to 420-500 DEG C, Sn evaporation source is to 230-300 DEG C, Se evaporation source to 220-300 DEG C, NaF evaporation source to 500-600 DEG C; Open the substrate baffle plate below flexible substrate, coevaporation Cu, Zn, Sn, Se, NaF below flexible substrate, coevaporation time 20-30min, form rich copper CZTS film;
Step 3: close the substrate baffle plate below flexible substrate, keeps underlayer temperature, Zn, Sn, Se evaporation source evaporating temperature constant; Cu and NaF evaporation source is lowered the temperature with the speed of 10-30 DEG C/min; Open substrate baffle plate after 20min, coevaporation Zn, Sn and Se below flexible substrate, 5-10min closes substrate baffle plate; Sn, Se evaporation source evaporating temperature is constant, and Zn evaporation source is lowered the temperature with the speed of 10-30 DEG C/min; Open substrate baffle plate after 20min, substrate is lowered the temperature with the speed of 10-30 DEG C/min in Sn, Se atmosphere; When flexible substrate temperature is lower than 250 DEG C, close substrate heater and each evaporation source heater, flexible substrate is formed the Cu as CZTS absorption layer of thin film solar cell 2znSnSe 4film manufacturing process.
The present invention can also adopt following technical measures:
Described specimen holder is made up of many vertically and horizontally arranged dismantled and assembled stainless steel strip right-angled intersections.
Described substrate heater is the snakelike stove silk be coiled into.
The advantage that the present invention has and good effect:
1. the present invention with flexible PI for substrate, adopt coevaporation method, by controlling copper Cu, zinc Zn, tin Sn, the evaporating temperature, time, order etc. of selenium Se evaporation source and then control response path and becoming to be grouped into, avoid rear selenizing, annealing process, the CZTS film absorption layer crystalline quality made is high, uniformity good, manufacturing process is simple, repeatable high, is beneficial to the industrialization of CZTS thin film solar cell;
2. the present invention by evaporating NaF in deposition process, and Na atom in CZTS film, improves the electric property of absorbed layer by diffusion profile, contributes to the raising of CZTS thin film solar cell conversion efficiency;
3. present invention employs the wedge shape stainless steel base of angle, highly all changeable fixing each evaporation source, ensure that uniformity sizes substrate making CZTS film absorption layer.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares CZTS absorption layer of thin film solar cell vaporising device schematic side view.
In figure, 1-vacuum evaporation chamber, 2-substrate heater, 3-flexible substrate, 4-specimen holder, 5-Cu evaporation source, 6-Zn evaporation source, 7-NaF evaporation source, 8-Sn evaporation source, 9-Se evaporation source, 10-substrate baffle plate, 11-thermocouple, 12-evaporation source base, 13-rotating shaft.
Embodiment
For summary of the invention of the present invention, Characteristic can be disclosed further, be also described in detail as follows by reference to the accompanying drawings especially exemplified by following instance:
The preparation method of CZTS absorption layer of thin film solar cell, is characterized in: comprise following preparation process:
Step 1: flexible substrate is coated with below one of film faces down and be fixed on vacuum evaporation chamber roof below rotating shaft specimen holder, is equipped with moveable substrate baffle plate below flexible substrate; Fix a thermocouple above specimen holder, the rotating shaft of the top of thermocouple has substrate heater; Cu evaporation source, Zn evaporation source, NaF evaporation source, Sn evaporation source and Se evaporation source are placed in angle and highly all adjustable five wedge type evaporation source bases in vacuum evaporation chamber respectively, wherein the top of Cu evaporation source, Zn evaporation source, NaF evaporation, Sn evaporation source is to the top of distance≤30cm, the Se evaporation source of substrate bottom centre to the distance < 10cm of substrate bottom centre;
Step 2: 5 × 10 are evacuated to vacuum evaporation chamber by pumped vacuum systems -4pa, by described thermocouple control temperature, heated substrate is to 450-550 DEG C; The temperature of each evaporation source heater is controlled by the PID controller outside vacuum evaporation chamber, heating Cu evaporation source to 1200-1300 DEG C, Zn evaporation source is to 420-500 DEG C, Sn evaporation source is to 230-300 DEG C, Se evaporation source to 220-300 DEG C, NaF evaporation source to 500-600 DEG C; Open the substrate baffle plate below flexible substrate, coevaporation Cu, Zn, Sn, Se, NaF below flexible substrate, coevaporation time 20-30min, form rich copper CZTS film;
Step 3: close the substrate baffle plate below flexible substrate, keeps underlayer temperature, Zn, Sn, Se evaporation source evaporating temperature constant; Cu and NaF evaporation source is lowered the temperature with the speed of 10-30 DEG C/min; Open substrate baffle plate after 20min, coevaporation Zn, Sn and Se below flexible substrate, 5-10min closes substrate baffle plate; Sn, Se evaporation source evaporating temperature is constant, and Zn evaporation source is lowered the temperature with the speed of 10-30 DEG C/min; Open substrate baffle plate after 20min, substrate is lowered the temperature with the speed of 10-30 DEG C/min in Sn, Se atmosphere; When flexible substrate temperature is lower than 250 DEG C, close substrate heater and each evaporation source heater, flexible substrate is formed poor copper Cu 2znSnSe 4film is as CZTS absorption layer of thin film solar cell.
Described specimen holder is made up of many vertically and horizontally arranged dismantled and assembled stainless steel strip right-angled intersections.
Described substrate heater is the snakelike stove silk be coiled into.
Embodiment:
Step 1: as shown in Figure 1, is arranged on a roof by the outside vacuum evaporation chamber 1 driving rotating shaft 13 to rotate; By 10 × 10cm 2pI flexible substrate 3 one side be coated with 500-800nm Mo back electrode, in flexible substrate, Mo back electrode one faces down below the specimen holder 4 that is fixed on and is made up of many vertically and horizontally arranged dismantled and assembled stainless steel strip right-angled intersections below rotating shaft, is equipped with to be installed on below specimen holder and can the substrate baffle plate 10 of opening and closing in vacuum evaporation chamber below flexible substrate; Fix a thermocouple 11 above specimen holder, on the rotating shaft above thermocouple, fixing horizontal direction is that the stove silk of snakelike coiling is as substrate heater 2; Vacuum evaporation chamber inner bottom part has annular array and angle and highly all adjustable five evaporation source bases 12, respectively carries the Cu evaporation source 5 of heater, Zn evaporation source 6, NaF evaporation source 7, Sn evaporation source 8 and Se evaporation source 9 and is placed in five evaporation source bases respectively; Adjust each evaporation source angle, make the upper port elongated central line of each evaporation source be intersected in substrate center; Adjust each evaporation source height, make Cu source, Zn source, Sn source, NaF source mouth be less than or equal to 30cm to substrate center distance, Se source mouth is less than 10cm to substrate center distance;
Step 2: vacuumize vacuum evaporation chamber by pumped vacuum systems, treats that vacuum degree is better than 5 × 10 -4during Pa, controlled the temperature of substrate heater by thermocouple, underlayer temperature is added to 450-550 DEG C; The heater that each evaporation source carries is controlled by the PID controller outside vacuum evaporation chamber, heating Cu evaporation source to 1200-1300 DEG C, Zn evaporation source is to 420-500 DEG C, Sn evaporation source is to 230-300 DEG C, Se evaporation source is to 220-300 DEG C, NaF evaporation source is to 500-600 DEG C, and met by each source temperature of adjustment: Cu evaporation rate is a bit larger tham Zn evaporation rate, and Sn, Se evaporation rate is all greater than its stoichiometric proportion; After each evaporation source evaporation rate is stablized, open the substrate baffle plate below flexible substrate, coevaporation Cu, Zn, Sn, Se, NaF on the Mo back electrode face of PI flexible substrate, coevaporation time 20-30min, Mo back electrode face is formed rich copper CZTS film;
Step 3: close the substrate baffle plate below flexible substrate, keep underlayer temperature, Zn, Sn, Se evaporation source evaporating temperature constant, Cu evaporation source, NaF evaporation source are lowered the temperature with the speed of 10-30 DEG C/min, substrate baffle plate is opened after 20min, coevaporation Zn, Sn and Se below flexible substrate, 5-10min closes substrate baffle plate; Sn, Se evaporation source evaporating temperature is constant, and Zn evaporation source is with the cooling of the speed of 10-30 DEG C/min, and open substrate baffle plate after 20min, substrate is lowered the temperature with the speed of 10-30 DEG C/min in Sn, Se atmosphere; When underlayer temperature is lower than 250 DEG C, close substrate heater and each evaporation source heater, flexible substrate preparing thickness is 1.0-1.5um, 0.8≤Cu/ (Zn+Sn)≤1.0, band gap is 1.0-1.4eV, and tack is good, component is even, crystal grain is large, and Na uniform doping, close to the poor copper Cu of stoichiometric proportion 2znSnSe 4film, as CZTS absorption layer of thin film solar cell, completes the manufacturing process of CZTS absorption layer of thin film solar cell.
Operation principle:
Adopt coevaporation method, by controlling copper Cu, zinc Zn, tin Sn, the evaporating temperature, time, order etc. of selenium Se evaporation source and then control response path and becoming to be grouped into, control Cu evaporation rate is slightly larger than Zn evaporation rate, and Sn, Se keep excessive evaporation; 1) Cu, Zn, Sn, Se are combined to CZTS film; 2) unnecessary Cu and Se is at Surface Creation Cu xse y, the Cu when underlayer temperature is more than 520 DEG C xse ybecome liquid phase, and liquid Cu xse yexistence by the CZTS of inductive formation large grain size, this is favourable to thin film solar cell; 3) Cu of reaction generation 2znSnSe 4go out SnSe and Se of gaseous state at underlayer temperature higher than easy decomposition evaporation when 400 DEG C, and Sn, Se keep excessive evaporation effectively to suppress it to decompose; Continue evaporation a small amount of Zn, Sn, Se, Cu more than needed continues reaction to generating poor copper Cu 2znSnSe 4film is as CZTS absorption layer of thin film solar cell.
Although be described the preferred embodiments of the present invention by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing under the ambit that present inventive concept and claim protect, a lot of form can also be made.These all belong within protection scope of the present invention.

Claims (3)

  1. The preparation method of 1.CZTS absorption layer of thin film solar cell, is characterized in that: comprise following preparation process:
    Step 1: flexible substrate is coated with below one of film faces down and be fixed on vacuum evaporation chamber roof below rotating shaft specimen holder, is equipped with moveable substrate baffle plate below flexible substrate; Fix a thermocouple above specimen holder, the rotating shaft of the top of thermocouple has substrate heater; Cu evaporation source, Zn evaporation source, NaF evaporation source, Sn evaporation source and Se evaporation source are placed in angle and highly all adjustable five evaporation source bases in vacuum evaporation chamber respectively, wherein the top of Cu evaporation source, Zn evaporation source, NaF evaporation, Sn evaporation source is to the top of distance≤30cm, the Se evaporation source of substrate bottom centre to the distance < 10cm of substrate bottom centre;
    Step 2: 5 × 10 are evacuated to vacuum evaporation chamber by pumped vacuum systems -4pa, by described thermocouple control temperature, heated substrate is to 450-550 DEG C; The temperature of each evaporation source heater is controlled by the PID controller outside vacuum evaporation chamber, heating Cu evaporation source to 1200-1300 DEG C, Zn evaporation source is to 420-500 DEG C, Sn evaporation source is to 230-300 DEG C, Se evaporation source to 220-300 DEG C, NaF evaporation source to 500-600 DEG C; Open the substrate baffle plate below flexible substrate, coevaporation Cu, Zn, Sn, Se, NaF below flexible substrate, coevaporation time 20-30min, form rich copper CZTS film;
    Step 3: close the substrate baffle plate below flexible substrate, keeps underlayer temperature, Zn, Sn, Se evaporation source evaporating temperature constant; Cu and NaF evaporation source is lowered the temperature with the speed of 10-30 DEG C/min; Open substrate baffle plate after 20min, coevaporation Zn, Sn and Se below flexible substrate, 5-10min closes substrate baffle plate; Sn, Se evaporation source evaporating temperature is constant, and Zn evaporation source is lowered the temperature with the speed of 10-30 DEG C/min; Open substrate baffle plate after 20min, substrate is lowered the temperature with the speed of 10-30 DEG C/min in Sn, Se atmosphere; When flexible substrate temperature is lower than 250 DEG C, close substrate heater and each evaporation source heater, flexible substrate is formed the Cu as CZTS absorption layer of thin film solar cell 2znSnSe 4film manufacturing process.
  2. 2. the preparation method of CZTS absorption layer of thin film solar cell according to claim 1, is characterized in that: described specimen holder is made up of many vertically and horizontally arranged dismantled and assembled stainless steel strip right-angled intersections.
  3. 3. the preparation method of CZTS absorption layer of thin film solar cell according to claim 1, is characterized in that: described substrate heater is the snakelike stove silk be coiled into.
CN201310714978.XA 2013-12-16 2013-12-16 Method for manufacturing CZTS thin film solar cell absorbing layer Pending CN104716227A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105633212A (en) * 2015-12-29 2016-06-01 中国电子科技集团公司第十八研究所 Method and device for preparing gradient band gap light absorption layer based on one-step co-evaporation technology
CN105679884A (en) * 2016-04-14 2016-06-15 董友强 Preparation method of CZTS photovoltaic cell
CN112281119A (en) * 2020-09-28 2021-01-29 深圳先进技术研究院 Copper-cadmium-zinc-tin-selenium light absorption layer, preparation method thereof and short-wave infrared detector

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102652368A (en) * 2009-12-15 2012-08-29 韩国能源技术研究院 Cu-In-Zn-Sn-(Se,S)-based thin film for solar cell and preparation method thereof
US20130071966A1 (en) * 2011-09-19 2013-03-21 Intermolecular, Inc. Combinatorial methods for developing superstrate thin film solar cells

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102652368A (en) * 2009-12-15 2012-08-29 韩国能源技术研究院 Cu-In-Zn-Sn-(Se,S)-based thin film for solar cell and preparation method thereof
US20130071966A1 (en) * 2011-09-19 2013-03-21 Intermolecular, Inc. Combinatorial methods for developing superstrate thin film solar cells

Non-Patent Citations (1)

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Title
INGRID REPINS,ETC: "Co-evaporated Cu2ZnSnSe4 films and devices", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105633212A (en) * 2015-12-29 2016-06-01 中国电子科技集团公司第十八研究所 Method and device for preparing gradient band gap light absorption layer based on one-step co-evaporation technology
CN105679884A (en) * 2016-04-14 2016-06-15 董友强 Preparation method of CZTS photovoltaic cell
CN112281119A (en) * 2020-09-28 2021-01-29 深圳先进技术研究院 Copper-cadmium-zinc-tin-selenium light absorption layer, preparation method thereof and short-wave infrared detector

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