CN102306685B - Low-cost preparation method of CZTS (Cu2ZnSnS4) thin film solar battery absorption layer - Google Patents

Low-cost preparation method of CZTS (Cu2ZnSnS4) thin film solar battery absorption layer Download PDF

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CN102306685B
CN102306685B CN2011102783021A CN201110278302A CN102306685B CN 102306685 B CN102306685 B CN 102306685B CN 2011102783021 A CN2011102783021 A CN 2011102783021A CN 201110278302 A CN201110278302 A CN 201110278302A CN 102306685 B CN102306685 B CN 102306685B
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tin
zinc
copper
thin film
sulfur
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CN102306685A (en
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邵乐喜
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ZHANJIANG NORMAL UNIVERSITY
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ZHANJIANG NORMAL UNIVERSITY
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    • 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
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Abstract

The invention relates to a low-cost preparation method of a CZTS (Cu2ZnSnS4) thin film solar battery absorption layer, belonging to the technical field of semiconductor photoelectric materials and devices. The method is characterized by preparing a metal precursor of Cu, Zn and Sn by adopting a common evaporation method; and vulcanizing the front precursor in sulfur vapor so as to get a polycrystalline CZTS thin film, wherein the prepared polycrystalline CZTS thin film has a similar stannite structure and a direct band gap width adaptive to the solar spectrum, absorption coefficient for visible light, and the characteristics of electrical resistivity, carrier mobility and the like, and the CZTS thin film is suitable for being taken as the thin film solar battery absorption layer. Raw materials for preparing the CZTS thin film solar battery absorption layer by adopting the method have rich sources and are non-toxic, the preparation technology is simple, the performances of a thin film are easy to control, and the method is suitable for scale chemical engineering production.

Description

A kind of low-cost preparation method of absorbing layer of copper-zinc-tin-sulfur film solar cell
Technical field
The present invention relates to a kind of low-cost preparation method of absorbing layer of copper-zinc-tin-sulfur film solar cell, espespecially copper-zinc-tin-sulfur (Cu 2ZnSnS 4, be called for short CZTS) and the preparation method of absorbing layer of thin film solar cell, belong to photoelectric semiconductor material and device technology field.
Background technology
In recent years, along with exhausting gradually of the non-renewable resources such as oil limited on the earth and coal, the utilization and exploitation of regenerative resource seems more and more urgent, wherein, solar energy power generating is radiated ground solar energy and is transformed into continuously electric energy by the opto-electronic conversion of the photovoltaic devices such as solar cell inexhaustible, has become the competitor of the safest in the regenerative resource, environmental protection and tool potentiality.The bottleneck of at present restriction solar energy power generating industry development is that cost is higher and conversion efficiency is on the low side, selects and manufactures originally from material, and thin film solar cell is unique selection.Selected battery material and optimization component design and fabrication technology, conversion efficiency is expected to get a promotion; Enhance production capacities and enhance productivity, cost also can be reduced thereupon.
The direct band gap that quaternary compound semiconductor copper-zinc-tin-sulfur owing to have mates with solar spectrum very much (1.4 ~ 1.5eV), and to the high absorption coefficient (10 of visible light 4Cm -1) and become the novel thin film solar cell absorbed layer material of tool potentiality.Zinc and the tin abundance in the earth's crust is respectively 75 and 2.2 ppm in the copper-zinc-tin-sulfur, aboundresources and environmentally friendly because not containing the toxicity composition.1967, Nitsche and Sargent utilized the vapor transportation method successfully to prepare the monocrystalline copper-zinc-tin-sulfur, and the copper-zinc-tin-sulfur crystal that obtains has the stannite structure that is similar to copper iron tin sulphur; The class stannite structure of copper-zinc-tin-sulfur can be regarded as by zinc and tin atom and replaces respectively the copper tin sulphur (CuInS with yellow copper structure 2) in half phosphide atom and consist of; 1988, Ito and Nakazawa successfully prepared copper-zinc-tin-sulfur film first with the atomic beam sputtering technology, and had reported that the open circuit voltage of copper-zinc-tin-sulfur/transparent conducting glass (CZTS/TCO) heterojunction diode is 165 mV; 1997, the Friedlmeier report has the open circuit voltage of 570mV and 2.3% conversion efficiency by the copper-zinc-tin-sulfur film of the method preparation of vacuum evaporation metal simple-substance and binary sulfide and zinc oxide/cadmium sulfide that cadmium sulfide/zinc oxide consists of/copper-zinc-tin-sulfur heterojunction; 2003, the research group of Katagiri adopted the battery structure of Al-Doped ZnO/cadmium sulfide/copper-zinc-tin-sulfur/molybdenum at the soda-lime glass substrate, obtain 5.45% conversion efficiency.Copper-zinc-tin-sulfur film is multi-element compounds, and its photoelectric properties are improper to atom ratio and Lattice Matching and fault of construction that produce is very responsive, causes the conversion efficiency of the thin film solar cell take copper-zinc-tin-sulfur as absorbed layer well below copper indium diselenide (CuInSe 2) 19.2% conversion efficiency.Obviously, the technology of preparing of development and improvement high-quality, high evenness copper-zinc-tin-sulfur film, on the basis of its architectural characteristic of further investigation and photoelectricity performance, grasp the key factor and the mechanism of action that affect photoelectric properties, and then explore the effective way that promotes copper-zinc-tin-sulfur film solar cell conversion efficiency, become the key subjects of current this field face.
The standby copper-zinc-tin-sulfur film of sulfuration legal system commonly used, because intermediate product (zinc sulphide, artificial gold) volatile performance is different, very large change can occur in comparing in the end product in the atomic ratio of three kinds of metal components and the presoma, causes the desirable stoichiometric proportion that is difficult to realize each component of end product.In order to overcome this difficult point, thereby each composition stoicheiometry in the end product is effectively controlled in the volatilization that the present invention adopts two step temperature-raising methods can effectively reduce intermediate product in sulfuration process.
Summary of the invention
Main purpose of the present invention provides the preparation method of a kind of low cost, high-quality copper-zinc-tin-sulfur film.
In order to address the above problem, the technical solution adopted in the present invention is:
Utilize first the common evaporation of vacuum to prepare the metal precursor film of copper, zinc and tin, more described presoma is vulcanized in the sulfur vapor under the nitrogen protection.
The preparation method of this copper-zinc-tin-sulfur film solar cell absorbed layer vulcanizes behind the common evaporation metal presoma of employing vacuum, is suitable as the polycrystalline copper zinc-tin-sulfur film that absorption layer of thin film solar cell is used at glass or the preparation of plating molybdenum glass substrate.Evaporation source is purity 99.99% and above high purity zinc, copper and tin, and different according to each congruent melting point and vapour pressure are by regulating the mass ratio of metal in the evaporation source, the stoichiometric proportion of each composition of control presoma.
Concrete grammar is as follows:
(1) metal precursor thin film technology
Substrate is selected simple glass or plating molybdenum glass, with alcohol, acetone and other organic solvent immersion, Ultrasonic Cleaning, dry for standby; Carry out the evaporation of presoma at the conventional vacuum coating machine, substrate does not heat, the distance of evaporation source and substrate is 25 ~ 35cm, with evaporation source: purity be 99.99% and above high purity zinc, copper and tin be placed in the same molybdenum boat, be 2 * 10 at the base vacuum of vacuum evaporation cavity -3Under the condition more than the Pa evaporation source is evaporated fully, the metal precursor film of preparation copper, zinc and tin, wherein three kinds of metallic zinc, copper and tin are a kind of of particle, sheet or powder, and mass ratio is respectively at copper: (zinc+tin)=0.9 ~ 1.0 and zinc: between tin=1.1 ~ 1.0; Base vacuum at least will be 2 * 10 -3Pa;
(2) sulfuration of metal precursor film
In the conventional vacuum high temperature furnace, carry out the sulfuration of metal precursor film, put into an amount of solid-state elemental sulfur in the quartz boat, deposit the substrate of presoma placed on it and put into the center of stove, flow is that the nitrogen of 25 ~ 35 sccm passes into vacuum furnace, sulfuration is carried out under nitrogen protection, furnace temperature is warming up to 250 ~ 350 ℃ with the speed of 5 ~ 15 ℃/min, kept 30 ~ 40 minutes, and then be warming up to 450 ~ 550 ℃ of curing temperatures with the speed of 40 ~ 55 ℃/min, make presoma in the mixed airflow of sulfur vapor and nitrogen, keep 2.5 ~ 3.0h to vulcanize under the different conditions of vulcanizations; Flow is that the nitrogen of 30 sccm passes into vacuum furnace, sulfuration is carried out under nitrogen protection, furnace temperature is warming up to 300 ℃ with the speed of 10 ℃/min, kept 30 minutes, and then be warming up to 450 ~ 550 ℃ of curing temperatures with the speed of 50 ℃/min, make presoma in the mixed airflow of sulfur vapor and nitrogen, keep 2.0 ~ 3.0h to vulcanize under the different conditions of vulcanizations; Naturally cool to room temperature, the copper-zinc-tin-sulfur film preparation is finished.
The present invention with respect to the beneficial effect of prior art is:
The preparation method of copper-zinc-tin-sulfur film solar cell absorbed layer of the present invention; owing to using the hydrogen sulfide gas of sulphur steam rather than severe toxicity in the sulfuration; improved the fail safe of producing; both can guarantee the raising of production efficiency and avoid the discharging of toxic materials; fundamentally workout cost and problem of environmental pollution make the real large-scale industrial production of copper-zinc-tin-sulfur base thin film solar battery become possibility.
Embodiment
Below by embodiment the present invention is described in further details, these embodiment only are used for illustrating the present invention, do not limit the scope of the invention.
In conjunction with example explanation execution mode, concrete preparation technology is as follows:
The metal precursor deposition:
1. substrate is selected simple glass, through alcohol or acetone organic solvent soak, Ultrasonic Cleaning, oven dry;
2. carry out the evaporation of presoma on the conventional vacuum coating machine, substrate does not heat.The system vacuum degree is higher than 2 * 10 -3Pa; Evaporating temperature is controlled by current source;
3. put into metallic zinc, tin and copper in the molybdenum boat, copper/zinc+tin atom ratio is that 0.9, Zn/Sn is 1.1, regulates evaporation time evaporation source is all evaporated.The distance of evaporation source and substrate is 25 ~ 35cm, for the uniformity substrate that increases film can uniform rotation;
The presoma sulfuration:
1. sulfidation is carried out in the vacuum high-temperature tube furnace, puts into an amount of solid-state elemental sulfur in the quartz boat, deposits the substrate of presoma placed on it and put into the center of stove, and flow is that the nitrogen of 30 sccm passes into vacuum furnace;
2. furnace temperature is warming up to 300 ℃ with the speed of 10 ℃/min, keeps 30 minutes, and then rises to 500 ℃ with the speed of 50 ℃/min, makes presoma keep 3h to vulcanize in the mixed airflow of sulfur vapor and nitrogen under this temperature;
3. naturally cool to room temperature, the copper-zinc-tin-sulfur film preparation is finished.
The sample of preparation utilizes X-ray diffractometer to carry out the XRD test, and chemical composition is by the energy dispersive X ray spectrum analysis, and optical absorption characteristics is by ultraviolet-visible light (UV-VIS) spectrophotometer measurement, and electrical properties is measured by the Hall effect tester.
The result shows: more near the stoichiometric proportion of copper-zinc-tin-sulfur, its crystalline quality is better for the stoicheiometry of film, has single-phase class stannite structure.Resistivity, carrier mobility and carrier concentration are respectively 1.46 Ω cm, 4.2 cm 2/ VS and 2.37 * 10 18Cm -3, optical bandwidth is about 1.51eV.

Claims (1)

1. the low-cost preparation method of an absorbing layer of copper-zinc-tin-sulfur film solar cell adopts the common evaporation metal of vacuum
The method of presoma after cure prepares the polycrystalline that is suitable as absorption layer of thin film solar cell at glass or plating molybdenum glass substrate
Copper-zinc-tin-sulfur film; It is characterized in that: comprise the steps:
(1) metal precursor thin film technology
Substrate is selected simple glass or plating molybdenum glass, with alcohol, the immersion of acetone organic solvent, Ultrasonic Cleaning, dry for standby; Carry out the evaporation of presoma at the conventional vacuum coating machine, substrate does not heat, the distance of evaporation source and substrate is 25 ~ 35cm, with evaporation source: purity be 99.99% and above high purity zinc, copper and tin be placed in the same molybdenum boat, be 2 * 10 at the base vacuum of vacuum evaporation cavity -3Under the condition more than the Pa evaporation source is evaporated fully, the metal precursor film of preparation copper, zinc and tin, wherein three kinds of metallic zinc, copper and tin are a kind of of particle, sheet or powder, and its mass ratio is respectively at copper: (zinc+tin)=0.9 ~ 1.0 and zinc: between tin=1.1 ~ 1.0;
(2) sulfuration of metal precursor film
In the conventional vacuum high temperature furnace, carry out the sulfuration of metal precursor film; put into an amount of solid-state elemental sulfur in the quartz boat; deposit the substrate of presoma placed on it and put into the center of stove; flow is that the nitrogen of 25 ~ 35 sccm passes into vacuum furnace; sulfuration is carried out under nitrogen protection; furnace temperature is warming up to 250 ~ 350 ℃ with the speed of 5 ~ 15 ℃/min; kept 30 ~ 40 minutes; and then be warming up to 450 ~ 550 ℃ of curing temperatures with the speed of 40 ~ 55 ℃/min, presoma is kept in the mixed airflow of sulfur vapor and nitrogen 2.5 ~ 3.0h vulcanizes; Naturally cool to room temperature, the copper-zinc-tin-sulfur film preparation is finished.
CN2011102783021A 2011-09-20 2011-09-20 Low-cost preparation method of CZTS (Cu2ZnSnS4) thin film solar battery absorption layer Expired - Fee Related CN102306685B (en)

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CN102730751A (en) * 2012-06-13 2012-10-17 成都先锋材料有限公司 Cu-Zn-Sn-S photovoltaic material, and preparation method and preparation device thereof
CN103094422A (en) * 2013-01-29 2013-05-08 电子科技大学 Doping craft in copper-zinc oxide tin sulphur selenium film preparation
CN103107243A (en) * 2013-02-03 2013-05-15 电子科技大学 Copper zinc tin sulfur thin film preparation method with doping process adopted
CN103165748B (en) * 2013-02-28 2016-06-15 宁波大学 A kind of method preparing copper-zinc-tin-sulfur solar battery obsorbing layer thin film
CN103400903A (en) * 2013-08-15 2013-11-20 吉林大学 Preparation method for improving grain size and density of CZTS film
CN105648492A (en) * 2016-01-13 2016-06-08 中国科学院上海技术物理研究所 Preparation method of copper-zinc-tin-sulfur film

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