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Preparation method for Cu2ZnSn(S1-xSex)4 film with continuously adjustable Se/S ratio

A thin film, cu2 technology, applied in the field of Cu2ZnSn4 thin film preparation, can solve the problems of strong pollution, high film production cost, low raw material utilization rate and production efficiency, achieve high efficiency, overcome poor controllability, optimize Se/S than the effect

Inactive Publication Date: 2017-05-10
GENERAL RESEARCH INSTITUTE FOR NONFERROUS METALS BEIJNG
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The liquid phase method is usually highly polluting, which is not conducive to sustainable development; the vacuum evaporation method prepares small-area films with good quality, but it is difficult to ensure the controllability of film uniformity and element ratio when preparing large-area films, and the utilization rate of raw materials and The production efficiency is low, resulting in high cost of film production; the utilization rate of sputtering raw materials is high, the chemical ratio of each element can be better adjusted, the preparation repeatability is improved, and it is suitable for the manufacture of large-area thin film batteries

Method used

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  • Preparation method for Cu2ZnSn(S1-xSex)4 film with continuously adjustable Se/S ratio

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preparation example Construction

[0019] Such as figure 1 As shown, the Cu with continuously adjustable Se / S ratio of the present invention 2 ZnSn(S 1-x Se x )4 The preparation method of the thin film mainly includes three steps: 1) the substrate is cleaned; 2) with Cu 2 (S 1-x Se x ), Zn(S 1-x Se x ) and Sn(S 1-x Se x ) 2 is the target material (0≤x≤1), using magnetron sputtering to prepare Cu 2 ZnSn(S 1-x Se x ) 4 film; 3) performing heat treatment on the film, and the heat treatment atmosphere is selected from a sulfide atmosphere, a selenization atmosphere or a mixed atmosphere of a sulfide atmosphere and a selenization atmosphere.

[0020] The present invention can prepare Cu with consistent ratio of metal elements and continuously adjustable Se / S ratio 2 ZnSn(S 1-x Se x ) 4 film.

Embodiment 1

[0022] Using magnetron sputtering technology, Cu 2 S, ZnS and SnS 2 As the target material, the as-deposited film was prepared by co-sputtering, and then the crystallized Cu 2 ZnSnS 4 (x=0) film, specifically:

[0023] Step 1: Substrate Cleaning

[0024] The soda-lime glass substrate was ultrasonically cleaned with deionized water, acetone and absolute ethanol in sequence for 10 min, and the remaining ethanol on the substrate surface was blown off with a nitrogen gun.

[0025] Step 2: Thin Film Deposition

[0026] The target is Cu 2 S, ZnS and SnS 2 , the sputtering gas is Ar gas, the sputtering pressure is 0.25Pa, and the film is deposited by co-sputtering, in which Cu 2 S, ZnS and SnS 2 The targets are all radio frequency sputtering, Cu 2 S, ZnS and SnS 2 The sputtering power of the target is 65W, 85W and 27W in turn, and the sputtering time is 20min.

[0027] Step 3: Thin film heat treatment

[0028] After the film deposition is completed, the film is vulcanized...

Embodiment 2

[0030] Using magnetron sputtering technology, Cu 2 Se, ZnSe, and SnSe 2 As the target material, the deposited film was prepared by layered sputtering, and then crystallized Cu was prepared by selenization heat treatment. 2 ZnSnSe 4 (x=1) film, specifically:

[0031] Step 1: Substrate Cleaning

[0032] The soda-lime glass substrate was ultrasonically cleaned with deionized water, acetone and absolute ethanol in sequence for 10 min, and the remaining ethanol on the substrate surface was blown off with a nitrogen gun.

[0033] Step 2: Thin Film Deposition

[0034] The target is Cu 2 Se, ZnSe, and SnSe 2 , the sputtering gas is Ar gas, the sputtering pressure is 0.5Pa, and the thin film is deposited by layered sputtering. Among them, Cu 2 Se, ZnSe, and SnSe 2 The targets are all radio frequency sputtering, and the deposition sequence is ZnSe, SnSe 2 and Cu 2 Se, ZnSe, SnSe 2 and Cu 2 The sputtering power of the Se target was 80W, 30W and 50W in turn, and the sputtering...

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Abstract

The invention discloses a preparation method for a Cu2ZnSn(S1-xSex)4 film with a continuously adjustable Se / S ratio, wherein x is not less than 0 and not greater than 1. The method comprises the following steps: 1) cleaning a substrate; 2) taking Cu2(S1-xSex), Zn(S1-xSex) and Sn(S1-xSex)2 as target materials, and preparing an as-deposited film through a magnetron sputtering technology; and 3) carrying out heat treatment on the film to obtain a crystallized Cu2ZnSn(S1-xSex)4 film. The Cu2ZnSn(S1-xSex)4 film with the same metal element ratio and the continuously adjustable Se / S ratio can be obtained through the preparation method disclosed by the invention.

Description

technical field [0001] The invention relates to a Cu with continuously adjustable Se / S ratio 2 ZnSn(S 1-x Se x ) 4 The invention relates to a thin film preparation method, which belongs to the technical field of optical thin film preparation. Background technique [0002] Cu 2 ZnSnS 4 (CZTS) is a direct band gap semiconductor with a wide absorption band in the ultraviolet-visible band, a band gap of ~1.5eV, and an absorption coefficient as high as 10 4 cm -1 , the theoretical photoelectric conversion efficiency of the cell is as high as 32.2% [Guo Q.J. et al., J.Am.Chem.Soc., 131(2009), 11672]. In addition, as Cu(In, Ga)(S, Se) 2 An alternative to thin-film batteries, CZTS replaces Cu(In,Ga)(S,Se) with Zn and Sn, which are abundant in the earth's crust 2 The rare and precious metals In and Ga in CZTS greatly reduce the preparation cost of solar cells. Therefore, CZTS is a sustainable thin-film solar cell absorber material. However, the current laboratory maximum ef...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C23C14/35C23C14/58
CPCC23C14/352C23C14/5806
Inventor 王吉宁韩皓刘晓鹏蒋利军王树茂
Owner GENERAL RESEARCH INSTITUTE FOR NONFERROUS METALS BEIJNG
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