CN112802924B - Preparation method of copper-potassium-zinc-tin-sulfur absorption layer - Google Patents

Preparation method of copper-potassium-zinc-tin-sulfur absorption layer Download PDF

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CN112802924B
CN112802924B CN202110039924.2A CN202110039924A CN112802924B CN 112802924 B CN112802924 B CN 112802924B CN 202110039924 A CN202110039924 A CN 202110039924A CN 112802924 B CN112802924 B CN 112802924B
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copper
zinc tin
absorption layer
potassium
powder
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CN112802924A (en
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庄大明
赵明
任国铵
王晨
李羽娴
董梁正
陶圣叶
仝浩
王汉鹏
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Tsinghua University
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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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1864—Annealing
    • H—ELECTRICITY
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    • 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
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    • 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
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • H—ELECTRICITY
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    • 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
    • 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
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a preparation method of a copper-potassium-zinc-tin-sulfur absorption layer, belonging to the technical field of photoelectric material preparation. The invention directly utilizes the copper potassium zinc tin sulfur target material to prepare the prefabricated layer of the copper potassium zinc tin sulfur absorbing layer through vacuum magnetron sputtering, and then obtains the absorbing layer of the copper potassium zinc tin sulfur absorbing layer through annealing, wherein the potassium element is uniformly distributed, the operation is simple, the process stability is high, and the production cost is low. Specifically, compared with the prior art, the method provided by the invention reduces the step of depositing KF after sputtering, and simultaneously, the K element can be uniformly distributed in the finally obtained absorption layer of the copper-potassium-zinc-tin-sulfur absorption layer, so that the advantages of K element passivation defect and promotion of grain growth can be uniformly embodied in the whole copper-potassium-zinc-tin-sulfur absorption layer.

Description

Preparation method of copper-potassium-zinc-tin-sulfur absorption layer
Technical Field
The invention relates to the technical field of photoelectric material preparation, in particular to a preparation method of a copper-potassium-zinc-tin-sulfur absorption layer.
Background
Copper zinc tin sulfide (Cu) 2 ZnSnS 4 CZTS for short) thin-film solar cells are taken as the representative of third-generation solar cells, and have the advantages of high photoelectric conversion efficiency, stable performance, good radiation resistance, low preparation cost and the like. To obtainThe semiconductor absorption layer with large crystal grains and good crystal quality generally needs a high-temperature process, but the CZTS absorption layer has poor high-temperature stability and is easy to decompose at high temperature, so that a series of problems such as crystal defects, component change, performance deterioration and the like are caused.
Introducing K element into the CZTS absorption layer to obtain a CKZTS (copper potassium zinc tin sulfur) absorption layer, so that the crystal boundary defect of the CZTS absorption layer can be passivated, and the quality of the CZTS absorption layer is improved; meanwhile, the method is favorable for promoting element diffusion and helping grain growth, so that the CKZTS absorbing layer with good crystallization quality can be obtained at a lower temperature of not more than 600 ℃. In the prior art, when a CKZTS absorption layer is prepared, two methods are mainly included, one method is to prepare a CZTS thin film or a CZT alloy prefabricated film by a sputtering method, a KF (potassium fluoride) layer is deposited on the surface of the CZTS thin film or the CZT alloy prefabricated film by means of thermal evaporation, and in the subsequent vulcanization annealing process, the CKZTS absorption layer is obtained through element diffusion; the method has complex process and is not beneficial to industrial production, and the K element is intensively distributed on the surface layer of CZTS, so that the K element cannot be uniformly distributed. The other method is to prepare the CKZTS absorbing layer by a solution method, and concretely, potassium salt is added on the basis of a precursor solution of the CZTS absorbing layer; the method is particularly carried out under non-vacuum conditions, is not suitable for large-area production and continuous production, and has poor operation stability. Therefore, it is an urgent technical problem to be solved to provide a preparation method of CKZTS absorbing layer with simple operation and uniform distribution of K element.
Disclosure of Invention
The invention aims to provide a preparation method of a copper potassium zinc tin sulfur absorption layer, which is simple to operate and uniform in potassium element distribution in the prepared copper potassium zinc tin sulfur absorption layer.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a copper-potassium-zinc-tin-sulfur absorption layer, which comprises the following steps of:
providing a copper potassium zinc tin sulfur target material;
performing vacuum magnetron sputtering on the copper potassium zinc tin sulfur target to obtain a copper potassium zinc tin sulfur prefabricated layer;
annealing the copper potassium zinc tin sulfur prefabricated layer to obtain a copper potassium zinc tin sulfur absorption layer; wherein the copper potassium zinc tin sulfur absorption layer comprises the following components: the atomic percentage of potassium is 0.005-10%, the ratio of the atomic percentage of S to the total atomic percentage of Cu, zn and Sn is (0.8-1.3): 1, the ratio of the atomic percentage of Cu to the total atomic percentage of Zn and Sn is (0.6-1.0): 1, the atomic percentage ratio of Zn to Sn is (0.8-1.4): 1.
preferably, the preparation method of the copper potassium zinc tin sulfur target material comprises the following steps:
ball-milling the CZTS powder and the KF powder to obtain mixed powder; wherein the CZTS powder is Cu 2 S powder, znS powder and SnS 2 A mixture of powders;
and sintering the mixed powder to obtain the copper-potassium-zinc-tin-sulfur target material.
Preferably, the ball milling is wet milling, which further comprises, after the wet milling: drying the obtained wet-milled material to obtain mixed powder;
wherein, the ball milling medium adopted by the wet milling comprises ethanol or water, the mass ratio of the total mass of the CZTS powder and the KF powder to the mass of the milling balls and the ball milling medium is 1: (1-20): (1-20); the rotation speed of the wet grinding is 100-600 rpm, and the time is 0.5-20 h.
Preferably, the sintering mode comprises atmospheric pressure sintering, hot pressing sintering or hot isostatic pressing sintering.
Preferably, the operating conditions of the atmospheric sintering include: the green compact pressure is 50-300 MPa, the sintering temperature is 400-900 ℃, and the sintering time is 1-40 h;
the operating conditions of the hot-pressing sintering comprise: the sintering temperature is 400-900 ℃, the sintering pressure is 30-100 MPa, and the sintering time is 1-40 h;
the operation conditions of the hot isostatic pressing sintering comprise: the sintering temperature is 400-900 ℃, the sintering pressure is 100-300 MPa, and the sintering time is 1-40 h.
Preferably, the operating conditions of the vacuum magnetron sputtering include: background vacuum of 1.0X 10 -4 ～1.0×10 - 2 Pa, argon as working gas, 0.1-10.0 Pa of working pressure and 20-700 ℃ of substrate temperature.
Preferably, the thickness of the copper potassium zinc tin sulfur prefabricated layer is 0.2-5.0 μm.
Preferably, the annealing is performed under vacuum conditions or under a specific gas atmosphere condition, the specific gas including at least one of argon, nitrogen, and hydrogen sulfide.
Preferably, the annealing temperature is 300-600 ℃ and the annealing time is 0.1-3 h.
Preferably, the thickness of the copper potassium zinc tin sulfur absorption layer is 0.2 to 5.0 μm.
The invention provides a preparation method of a copper-potassium-zinc-tin-sulfur absorption layer, which comprises the following steps of: providing a copper potassium zinc tin sulfur target material; performing vacuum magnetron sputtering on the copper potassium zinc tin sulfur target to obtain a copper potassium zinc tin sulfur prefabricated layer; annealing the copper potassium zinc tin sulfur prefabricated layer to obtain a copper potassium zinc tin sulfur absorption layer; wherein the copper potassium zinc tin sulfur absorption layer comprises the following components: the atomic percentage of potassium is 0.005-10%, the ratio of the atomic percentage of S to the total atomic percentage of Cu, zn and Sn is (0.8-1.3): 1, the ratio of the atomic percentage of Cu to the total atomic percentage of Zn and Sn is (0.6-1.0): 1, the atomic percentage ratio of Zn to Sn is (0.8-1.4): 1. according to the invention, the CKZTS prefabricated layer is prepared by directly utilizing the copper-potassium-zinc-tin-sulfur target material through vacuum magnetron sputtering, and then the CKZTS absorption layer can be obtained through annealing, wherein the potassium element is uniformly distributed, the operation is simple, the process stability is high, and the production cost is low. Specifically, compared with the prior art, the method provided by the invention reduces the step of depositing KF after sputtering, and simultaneously, the K element can be uniformly distributed in the finally obtained CKZTS absorption layer, and the advantages of K element passivation defect and grain growth promotion can be uniformly embodied in the whole CKZTS absorption layer.
Furthermore, the CKZTS absorbing layer is prepared by directly utilizing the CKZTS target material, the K element is partially substituted by the Cu element to finally form the CKZTS absorbing layer, the K element is easy to gather at the grain boundary, the grain boundary defect is passivated, and simultaneously the K element is easy to gather at the grain boundary 2 The Se low-temperature liquefied phase is favorable for promoting the diffusion and the help of elementsPromoting the growth of crystal grains, and obtaining the CKZTS absorption layer with good crystallization quality and zinc-stannum ore phase composition under the condition of lower temperature not more than 600 ℃, wherein the forbidden bandwidth of the CKZTS absorption layer is adjustable between 0.95 and 1.55eV, and the mobility is 0.1 to 100cm 2 ·V -1 ·s -1 Carrier concentration of 1X 10 15 ～1×10 18 cm -3 The resistivity is less than 500 omega cm, the micro-morphology is smooth, and the conductive type is p type. The CKZTS absorption layer provided by the invention can be directly used for preparing CKZTS thin film solar cells, and the efficiency of the obtained CKZTS thin film solar cells exceeds 5 percent.
Drawings
FIG. 1 is a SEM photograph of a section of a CZTS absorbing layer prepared in comparative example 1 and a SEM photograph of a section of a CKZTS absorbing layer prepared in example 3;
fig. 2 is a current-voltage characteristic curve of the CZTS thin film solar cell prepared in comparative example 2 and the CKZTS thin film solar cell prepared in example 5.
Detailed Description
The invention provides a preparation method of a copper-potassium-zinc-tin-sulfur absorption layer, which comprises the following steps:
providing a copper potassium zinc tin sulfur target material;
performing vacuum magnetron sputtering on the copper potassium zinc tin sulfur target to obtain a copper potassium zinc tin sulfur prefabricated layer;
annealing the copper potassium zinc tin sulfur prefabricated layer to obtain a copper potassium zinc tin sulfur absorption layer; wherein the copper potassium zinc tin sulfur absorption layer comprises the following components: the atomic percentage of potassium is 0.005-10%, the ratio of the atomic percentage of S to the total atomic percentage of Cu, zn and Sn is (0.8-1.3): 1, the ratio of the atomic percentage of Cu to the total atomic percentage of Zn and Sn is (0.6-1.0): 1; the atomic percentage ratio of Zn to Sn is (0.8-1.4): 1.
first, the composition of the cu-k-zn-sn-s absorption layer provided by the present invention will be described. In the invention, the composition of the copper potassium zinc tin sulfur absorption layer comprises: the atomic percentage of potassium is 0.005-10%, specifically 0.005%, 0.5% or 10%; the atomic percentage of S to the total atomic percentage of Cu, zn and Sn is (0.8-1.3): 1, preferably 1:1; the atomic percentage of Cu to the total atomic percentage of Zn and Sn is (0.6-1.0): 1, specifically, it may be 0.7: 1. 0.8:1 or 0.9:1; the atomic percentage ratio of Zn to Sn is (0.8-1.4): 1, specifically, it may be 0.9: 1. 1.1:1 or 1.3:1.
the following is a description of the method for producing the copper-potassium-zinc-tin-sulfur absorption layer according to the present invention.
The invention provides a copper-potassium-zinc-tin-sulfur target material. In the invention, the composition of the copper potassium zinc tin sulfur target material is consistent with that of the copper potassium zinc tin sulfur absorption layer. In the invention, the preparation method of the copper potassium zinc tin sulfur target preferably comprises the following steps:
ball-milling the CZTS powder and the KF powder to obtain mixed powder; wherein the CZTS powder is Cu 2 S powder, znS powder and SnS 2 A mixture of powders;
and sintering the mixed powder to obtain the copper-potassium-zinc-tin-sulfur target material.
The invention ball-mills CZTS powder and KF powder to obtain mixed powder. In the invention, the CZTS powder is Cu 2 S powder, znS powder and SnS 2 A mixture of powders. In the invention, the ratio of the components in the CZTS powder and the ratio of the CZTS powder to KF powder meet the composition requirements of the copper potassium zinc tin sulfur target. In the invention, the ball milling is preferably wet milling, the ball milling medium adopted by the wet milling preferably comprises ethanol or water, and the mass ratio of the total mass of the CZTS powder and the KF powder to the mass of the milling balls and the ball milling medium is preferably 1: (1-20): (1-20); the rotation speed of the wet grinding is preferably 100-600 rpm, and the time is preferably 0.5-20 h. In the present invention, the wet milling preferably further comprises: and drying the obtained wet-milled material to obtain mixed powder. The drying method is not particularly limited, and the materials can be fully dried. According to the invention, the raw material powders can be fully mixed while being refined through ball milling, and part of the powders can also undergo chemical combination reaction in the ball milling process, so that the high-quality target material with uniformly distributed elements can be finally obtained through ball milling.
After the mixed powder is obtained, the mixed powder is sintered to obtain the copper-potassium-zinc-tin-sulfur target material. In the present invention, the sintering manner preferably includes atmospheric pressure sintering, hot press sintering or hot isostatic pressing sintering. In the present invention, the operating conditions of the atmospheric sintering include: the green compact pressure is preferably 50 to 300MPa, more preferably 100 to 200MPa; the sintering temperature is preferably 400-900 ℃, and more preferably 500-600 ℃; the sintering time is preferably 1 to 40 hours, more preferably 5 to 10 hours. In the present invention, the operating conditions of the hot press sintering include: the sintering temperature is preferably 400-900 ℃, and more preferably 500-600 ℃; the sintering pressure is preferably 30 to 100MPa, more preferably 50 to 70MPa; the sintering time is preferably from 1 to 40 hours, more preferably from 5 to 10 hours. In the present invention, the operating conditions of the hot isostatic pressing sintering include: the sintering temperature is preferably 400-900 ℃, and more preferably 500-600 ℃; the sintering pressure is preferably 100 to 300MPa, more preferably 150 to 250MPa; the sintering time is preferably 1 to 40 hours, more preferably 5 to 10 hours. The invention can obtain the target material with high quality by the sintering method; and the process stability is good, the yield of the target is high, and the method has a good industrial application prospect.
After the copper potassium zinc tin sulfur target is obtained, the copper potassium zinc tin sulfur target is subjected to vacuum magnetron sputtering to obtain a copper potassium zinc tin sulfur prefabricated layer. In the present invention, the operating conditions of the vacuum magnetron sputtering include: the background vacuum is preferably 1.0X 10 -4 ～1.0×10 -2 Pa, specifically 1.0X 10 -4 Pa、2.0×10 -3 Pa、1.0×10 -3 Pa or 2.0X 10 -4 Pa; the working gas is preferably argon, more preferably high-purity argon (the purity is preferably 99.99%); the working air pressure is preferably 0.1-10.0 Pa, and specifically can be 0.5Pa, 0.7Pa or 1.2Pa; the substrate temperature is preferably 20-700 ℃, and specifically can be 20 ℃, 100 ℃ or 500 ℃; the substrate is preferably glass, namely, the copper potassium zinc tin sulfur target is subjected to vacuum magnetron sputtering to form a copper potassium zinc tin sulfur prefabricated layer on the surface of the substrate. In the invention, the thickness of the copper-potassium-zinc-tin-sulfur prefabricated layer is preferably 0.2 to 5.0 mu m.
After the copper potassium zinc tin sulfur prefabricated layer is obtained, the copper potassium zinc tin sulfur prefabricated layer is annealed to obtain the copper potassium zinc tin sulfur absorption layer. In the present invention, the annealing may be performed under a vacuum condition or under a specific gas atmosphere condition, and the specific gas preferably includes at least one of argon, nitrogen, and hydrogen sulfide, and specifically may be argon, nitrogen, or hydrogen sulfide; the specific gas is preferably a high purity gas, and the purity is independently preferably 99.99%, 99.5%, 99.9%.
According to the invention, a proper annealing mode is preferably selected according to the composition of the copper potassium zinc tin sulfur prefabricated layer so as to ensure that the components in the finally prepared copper potassium zinc tin sulfur absorption layer are stable, and the film layer is uniform and has no holes. In the embodiment of the present invention, specifically, the composition of the Cu-k-Zn-Sn-sulfur preform layer is calculated by the composition of the Cu-k-Zn-Sn-sulfur target material, and when S/(Cu + Zn + Sn) =1, cu/(Zn + Sn) =0.7, zn/Sn =0.9, and the k content is 0.005at.%, the annealing is preferably performed under vacuum conditions; when S/(Cu + Zn + Sn) =1, cu/(Zn + Sn) =0.8 to 0.9, zn/Sn =1.1 to 1.3, and the k content is 0.5 to 10at.%, the annealing is preferably performed under a specific gas atmosphere, more preferably a nitrogen atmosphere, and the pressure provided by the nitrogen atmosphere is preferably 50kPa.
In the present invention, the annealing temperature is preferably 300 to 600 ℃, more preferably 500 to 580 ℃; the temperature is preferably increased from room temperature to the temperature required by annealing, and the heating rate is preferably 5-20 ℃/min; the annealing time is preferably 0.1 to 3 hours, more preferably 0.5 to 1.5 hours, and the annealing time is started when the temperature is raised to the temperature required for annealing. In the invention, the annealing can promote element diffusion and combination, help the crystal grains to grow, and is beneficial to obtaining the copper potassium zinc tin sulfur absorption layer with the kesterite phase composition and the micron-sized crystal grains. In the present invention, the thickness of the copper potassium zinc tin sulfur absorption layer is preferably 0.2 to 5.0 μm.
The phase composition of the copper potassium zinc tin sulfur absorption layer prepared by the method provided by the invention is a kesterite phase structure, the forbidden bandwidth is 0.95-1.55 eV, the resistivity is 1-500 omega cm, and the mobility is 0.1-100 cm 2 ·V -1 ·s -1 Concentration of carrier 1X 10 15 ～1×10 18 cm -3 The method can be directly applied to the preparation of CKZTS thin-film solar cells. The invention does not specially limit the structure of the CKZTS thin-film solar cell, and the structure known by the technicians in the field can be adopted, and the structure can be specifically an antireflection layer/a transparent electrode layer/a window layer/a buffer layer/an absorption layer (CKZTS)/a metal back electrode/a substrate, wherein the quality of the CKZTS absorption layer directly determines the conversion efficiency of the thin-film solar cell, and the efficiency of the CKZTS thin-film solar cell prepared by adopting the CKZTS absorption layer provided by the invention exceeds 5%.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The preparation of the CKZTS target material comprises the following steps:
providing CZTS powder, wherein the CZTS powder is Cu 2 S powder, znS powder and SnS 2 A mixture of powders wherein S/(Cu + Zn + Sn) =0.9, cu/(Zn + Sn) =0.6, zn/Sn =1.1 in atomic ratio;
putting 300g of CZTS powder, 30g of KF powder, 1700g of grinding balls and 1700g of absolute ethyl alcohol into a ball milling tank, carrying out ball milling for 8h under the condition that the rotating speed is 300rpm, and drying the obtained ball milling material to obtain mixed powder;
treating the mixed powder by adopting a normal pressure sintering process to obtain a CKZTS target material; the preparation method specifically comprises the steps of placing the mixed powder into a press, maintaining the pressure for 15min under the condition that the pressure is 100MPa, demoulding to obtain a pressed compact, placing the pressed compact into a sintering furnace, sintering for 5h at 600 ℃ in a high-purity argon atmosphere, cooling to room temperature (25 ℃) along with the furnace to obtain the CKZTS target material, wherein the compaction rate of the CKZTS target material is 95.3%, and the CKZTS target material has no defects such as cracks, cracking and the like.
Example 2
CKZTS targets were prepared according to the method of example 1, wherein S/(Cu + Zn + Sn) =1, cu/(Zn + Sn) =0.7, zn/Sn =0.9, k content is 0.005at.%, on an atomic ratio basis;
carrying out vacuum magnetron sputtering on the CKZTS target material by taking glass as a substrate, and depositing on the glass to obtain a CKZTS prefabricated layer with the thickness of 1.5 mu m; wherein the operating conditions of the vacuum magnetron sputtering comprise: the vacuum of the sputtering background is 2.0 multiplied by 10 -3 Pa, the working gas is high-purity argon, the sputtering pressure is 1.2Pa, and the substrate temperature is 500 ℃;
and (3) putting the CKZTS prefabricated layer into an annealing furnace, heating to 580 ℃ from room temperature at the speed of 20 ℃/min, carrying out vacuum annealing for 60min, and then cooling to room temperature along with the furnace to obtain a CKZTS absorption layer with the thickness of 1.5 mu m.
The conductive type of the CKZTS absorbing layer prepared in the example is p type, the resistivity is 270.2 omega cm, and the carrier mobility is 11.25cm 2 ·V -1 ·s -1 The carrier concentration is 9.78X 10 15 cm -3 。
Example 3
The CKZTS target was prepared according to the method of example 1, wherein, in atomic ratio, S/(Cu + Zn + Sn) =1, cu/(Zn + Sn) =0.8, zn/Sn =1.1, k content is 0.5at.%;
carrying out vacuum magnetron sputtering on the CKZTS target material by taking glass as a substrate, and depositing on the glass to obtain a CKZTS prefabricated layer with the thickness of 2.0 mu m; wherein the operating conditions of the vacuum magnetron sputtering comprise: sputtering background vacuum of 1.0 x 10 -3 Pa, the working gas is high-purity argon, the sputtering pressure is 0.7Pa, and the substrate temperature is 20 ℃;
and (3) putting the CKZTS prefabricated layer into an annealing furnace, heating to 550 ℃ from room temperature at the speed of 10 ℃/min, keeping the temperature for 30min for annealing, wherein the annealing atmosphere is 50kPa high-purity nitrogen, and then cooling to room temperature along with the furnace to obtain a CKZTS absorption layer with the thickness of 2.0 mu m.
The CKZTS absorbing layer prepared in the example has p-type conductivity, resistivity of 232.5 omega cm and carrier mobility of 5.65cm 2 ·V -1 ·s -1 A carrier concentration of 1.22X 10 17 cm -3 。
Example 4
The CKZTS target was prepared according to the method of example 1, wherein, in atomic ratio, S/(Cu + Zn + Sn) =1, cu/(Zn + Sn) =0.9, zn/Sn =1.3, and k content is 10at.%;
carrying out vacuum magnetron sputtering on the CKZTS target material by taking glass as a substrate, and depositing on the glass to obtain a CKZTS prefabricated layer with the thickness of 1.0 mu m; wherein the operating conditions of the vacuum magnetron sputtering comprise: the vacuum of the sputtering background is 2.0 multiplied by 10 -4 Pa, the working gas is high-purity argon, the sputtering pressure is 0.5Pa, and the substrate temperature is 100 ℃;
and (3) putting the CKZTS prefabricated layer into an annealing furnace, heating to 500 ℃ from room temperature at the speed of 5 ℃/min, keeping the temperature for 90min for annealing, wherein the annealing atmosphere is 50kPa high-purity nitrogen, and then cooling to room temperature along with the furnace to obtain a CKZTS absorption layer with the thickness of 1.0 mu m.
The CKZTS absorption layer prepared in the embodiment has p-type conductivity, resistivity of 335.0 omega cm and carrier mobility of 16.37cm 2 ·V -1 ·s -1 The carrier concentration is 5.68 x 10 16 cm -3 。
Example 5
The CKZTS target was prepared according to the method of example 1, wherein, in atomic ratio, S/(Cu + Zn + Sn) =1, cu/(Zn + Sn) =0.8, zn/Sn =1.1, k content is 0.5at.%;
preparing a CKZTS absorbing layer by using the Mo-plated soda-lime glass (soda-lime glass/Mo) as a substrate according to the method in the example 2 to obtain the soda-lime glass/Mo/CKZTS absorbing layer;
and depositing CdS on the surface of the CKZTS absorbing layer in the soda-lime glass/Mo/CKZT absorbing layer by using a water bath method to serve as a buffer layer, and depositing ZnO and ZnO on the surface of the CdS buffer layer by using a magnetron sputtering method to serve as a window layer to obtain the CKZTS thin-film solar cell.
Comparative example 1
A CZTS absorbing layer was prepared as in example 3, except that K was not added.
Comparative example 2
A CZTS thin film solar cell was prepared as in example 5, except that K was not added.
Fig. 1 is a cross-sectional SEM photograph of the CZTS absorbing layer prepared in comparative example 1 and a cross-sectional SEM photograph of the CKZTS absorbing layer prepared in example 3, wherein (a) is the cross-sectional SEM photograph of the CZTS absorbing layer prepared in comparative example 1, and (b) is the cross-sectional SEM photograph of the CKZTS absorbing layer prepared in example 3, it can be seen from fig. 1 that the doping of K element in example 3 is beneficial to the growth of crystal grains at low temperature, the crystal grain size is significantly increased compared with the CZTS absorbing layer, the crystal quality is significantly improved, and this is beneficial to improving the photoelectric conversion efficiency of the CZTS-based thin film solar cell.
Fig. 2 is a voltage-current characteristic curve of the CZTS thin film solar cell prepared in comparative example 2 and the CKZTS thin film solar cell prepared in example 5, and it can be seen from fig. 2 that the photoelectric conversion efficiency of the CKZTS thin film solar cell is about 6.8%, which is equivalent to that of the CZTS thin film solar cell.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A preparation method of a copper potassium zinc tin sulfur absorption layer comprises the following steps:
providing a copper potassium zinc tin sulfur target material;
performing vacuum magnetron sputtering on the copper potassium zinc tin sulfur target to obtain a copper potassium zinc tin sulfur prefabricated layer;
annealing the copper potassium zinc tin sulfur prefabricated layer to obtain a copper potassium zinc tin sulfur absorption layer; wherein, the composition of the copper potassium zinc tin sulfur absorption layer comprises: the atomic percentage of the potassium is 0.005-0.5%, the atomic percentage of the S and the total atomic percentage of the Cu, the Zn and the Sn are (0.8-1.3): 1, the ratio of the atomic percentage of Cu to the total atomic percentage of Zn and Sn is (0.6-1.0): 1, the atomic percentage ratio of Zn to Sn is (0.8-1.4): 1; the annealing is carried out in a nitrogen atmosphere, and the pressure provided by the nitrogen atmosphere is 50kPa; the annealing temperature is 300-600 ℃, and the heating rate from room temperature to the temperature required by annealing is 5-20 ℃/min; the annealing time is 0.1-0.5 h, and the annealing time is counted by the temperature rising to the temperature required by annealing;
the preparation method of the copper potassium zinc tin sulfur target comprises the following steps:
ball-milling the CZTS powder and the KF powder to obtain mixed powder; wherein the CZTS powder is Cu 2 S powder, znS powder and SnS 2 A mixture of powders;
sintering the mixed powder under normal pressure to obtain a copper-potassium-zinc-tin-sulfur target material; the operating conditions of the atmospheric sintering comprise: the green compact pressure is 50-300 MPa, the sintering temperature is 400-900 ℃, and the sintering time is 1-40 h.
2. The method of claim 1, wherein the ball milling is wet milling, and further comprising, after the wet milling: drying the obtained wet-milled material to obtain mixed powder;
wherein, the ball milling medium adopted by the wet milling comprises ethanol or water, the mass ratio of the total mass of the CZTS powder and the KF powder to the mass of the milling balls and the ball milling medium is 1: (1-20): (1-20); the rotation speed of the wet grinding is 100-600 rpm, and the time is 0.5-20 h.
3. The method according to claim 1, wherein the operating conditions of the vacuum magnetron sputtering include: background vacuum of 1.0X 10 -4 ～1.0×10 -2 Pa, argon as working gas, 0.1-10.0 Pa as working pressure and 20-700 ℃ of substrate temperature.
4. The production method according to claim 1 or 3, wherein the thickness of the copper potassium zinc tin sulfide preform layer is 0.2 to 5.0 μm.
5. The method of claim 1, wherein the annealing is performed under vacuum conditions or under a specific gas atmosphere conditions, and the specific gas includes at least one of argon, nitrogen, and hydrogen sulfide.
6. The production method according to claim 1, wherein the thickness of the copper potassium zinc tin sulfur absorption layer is 0.2 to 5.0 μm.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104846342A (en) * 2015-05-27 2015-08-19 清华大学 Copper-zinc-tin-sulfur sputtering target and preparation method thereof
CN105304763A (en) * 2015-11-10 2016-02-03 云南师范大学 Method for preparing CZTS thin film solar cell based on full vacuum method
CN108468027A (en) * 2018-03-28 2018-08-31 清华大学 A kind of Sb doped copper zinc tin sulfur selenium target and its preparation method and application

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5888240B2 (en) * 2010-12-06 2016-03-16 株式会社豊田中央研究所 Compound semiconductor
US9153729B2 (en) * 2012-11-26 2015-10-06 International Business Machines Corporation Atomic layer deposition for photovoltaic devices
US9443997B2 (en) * 2013-06-28 2016-09-13 International Business Machines Corporation Hybrid CZTSSe photovoltaic device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104846342A (en) * 2015-05-27 2015-08-19 清华大学 Copper-zinc-tin-sulfur sputtering target and preparation method thereof
CN105304763A (en) * 2015-11-10 2016-02-03 云南师范大学 Method for preparing CZTS thin film solar cell based on full vacuum method
CN108468027A (en) * 2018-03-28 2018-08-31 清华大学 A kind of Sb doped copper zinc tin sulfur selenium target and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
The effect of Rb doping on CZTSSe solar cells;Y Wu，et al;《Solar Energy》;20190715;第187卷;269-273 *

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