CN104404456A - Preparation method of CZTS (copper-zinc-tin-sulfur) quaternary target - Google Patents

Preparation method of CZTS (copper-zinc-tin-sulfur) quaternary target Download PDF

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Publication number
CN104404456A
CN104404456A CN201410659317.6A CN201410659317A CN104404456A CN 104404456 A CN104404456 A CN 104404456A CN 201410659317 A CN201410659317 A CN 201410659317A CN 104404456 A CN104404456 A CN 104404456A
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powder
tin
czts
zinc
target
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张宁
余新平
容构华
刘鹏
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Beijing Sifang Automation Co Ltd
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Beijing Sifang Automation Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/3407Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy

Abstract

The invention relates to a preparation method of a CZTS (copper-zinc-tin-sulfur) quaternary target. According to the preparation method, high-purity Cu2S powder, ZnS powder and SnS2 powder are taken as raw materials and subjected to sufficient ball milling and uniform mixing in the stoichiometric ratio, the mixed powder is placed in a mold and subjected to hot pressed sintering forming, and the CZTS quaternary target is prepared. The preparation method is simple in process, the prepared CZTS quaternary target has uniform ingredients, the relative density is higher than 90%, the sputtering performance is excellent, and the method is mainly used for preparation and large-scale production of high-efficiency and low-cost CZTS thin-film solar cells.

Description

A kind of preparation method of copper-zinc-tin-sulfur quaternary target
Technical field
The invention belongs to photoelectric material technical field, particularly a kind of preparation method of copper-zinc-tin-sulfur quaternary target.
Background technology
Copper-zinc-tin-sulfur has abundance, and low price and the feature such as nontoxic, its energy gap is 1.4 ~ 1.5eV, and its uptake factor is greater than 10 4cm -1, can be used as desirable solar battery obsorbing layer material.Relative CIGS solar film battery, the advantage of CZTS is its cheapness and nontoxic, and the content of its component in the earth's crust comparatively horn of plenty, therefore CZTS becomes the novel thin film solar battery obsorbing layer material of the alternative CIGS of most potentiality.
In recent years, each research institution has started copper-zinc-tin-sulfur series film solar battery exploitation upsurge.The preparation method of copper zinc tin sulfur absorption layer material is of all kinds, and wherein magnetron sputtering method and electrochemical plating are two kinds of preparation methods most with industrial applications prospect.2012, Chawla and Clemens by cosputtering legal system for Cu 2znSnS 4absorbing layer of thin film solar cell, its battery device transformation efficiency reaches 9.3%.
Target is the important raw and processed materials in sputter coating process, and the composition proportion of target and physicals directly affect the photoelectric properties of film.Current, there is correlative study unit and puted forth effort development quaternary compound target one step sputtering method, it is simple that the method has technical process, prepares the features such as thin film composition is even.Application number be 201110432162.9 patent discloses a kind of copper-zinc-tin-sulfur ceramic target and vacuum hot-pressing preparation method thereof thereof, it is characterized in that adopt cupric sulfide, zinc sulphide, sulfuration glass putty according to mol ratio 2:1:1 batching, vacuum to 10 -1~ 10 -2pa, is then warmed up to 800 ~ 1400 DEG C, continuous axial pressure in temperature-rise period, when being pressurized to 10 ~ 30Mpa, starting insulation, pressurize, carries out sintering and obtain copper-zinc-tin-sulfur target.
Summary of the invention
The object of the invention is the preparation method providing a kind of copper-zinc-tin-sulfur target, realize low-firing copper-zinc-tin-sulfur quaternary target, for big area production high-level efficiency device provides starting material support, simplify sputter coating process simultaneously, be specially adapted to the suitability for industrialized production of CZTS thin-film solar cells of high-level efficiency, low cost.
The present invention is concrete by the following technical solutions.
A preparation method for copper-zinc-tin-sulfur quaternary target, is characterized in that: according to the high-purity cuprous sulfide Cu of stoichiometric ratio by purity>=4N 2s, zinc sulphide ZnS, tin disulfide SnS 2powder mixes; Then mixed powder is dried, sieved; Then the powder mixed is placed in mould and prepares CZTS quaternary target by hot pressed sintering.
A kind of preparation method of copper-zinc-tin-sulfur (CZTS) quaternary target, it is characterized in that, described preparation method comprises following steps:
(1) according to stoichiometric ratio Cu 2xzn ysnS (x+y+2)by high-purity cuprous sulfide Cu of purity>=4N 2s, zinc sulphide ZnS, tin disulfide SnS 2powder fully mixes through ball milling;
(2) mixed powder is dried, sieved;
(3) powder mixed is placed in mould, in protective atmosphere, makes CZTS quaternary target by hot-pressing sintering technique.
The application also preferably includes following technical scheme further:
Described in step (1), stoichiometric ratio is: 0.5≤2x/ (1+y)≤1.2,0.7≤y≤1.8.
In step (1), described ball-milling medium is the one in dehydrated alcohol, deionized water or air, and Ball-milling Time is 1 ~ 24h.
In step (3), base vacuum≤3 × 10 of stove interior (whether referring to the background vacuum in grinding tool) during hot pressed sintering -2pa, sintering temperature is 300 ~ 800 DEG C, temperature rise rate 3-30 DEG C/min, and hot pressing pressure is 10 ~ 80MPa, and soaking time is 0.5 ~ 12h, and insulation terminates rear release, cools to less than 200 DEG C taking-ups with the furnace.
In step (3), described protective atmosphere is vacuum or is filled with protective gas, and when for vacuum, described vacuum pressure is below 20Pa; When for protective gas, described protective gas is hydrogen, nitrogen or argon gas, and protective gas atmos is 1atm.
Function main points of the present invention have two aspects, and the first realizes low temperature and pressure and fires copper-zinc-tin-sulfur target, and it two is that the copper-zinc-tin-sulfur target realizing heterogeneity proportioning is fired.
The present invention has following Advantageous Effects:
For realize high-level efficiency, low cost and environmental protection thin-film solar cells needed for target, for the absorption layer material of the required composition of high-level efficiency device preparation, it is low that a kind of preparation method of copper-zinc-tin-sulfur quaternary target that the present invention proposes has hot pressing temperature, good moldability, density high.Present invention process is simple, and obtained CZTS target material composition is even, and relative density reaches more than 90%, and sputtering performance is good, is mainly used in high-level efficiency, the preparation of CZTS thin-film solar cells of low cost and large-scale production.
Embodiment
Below in conjunction with your embodiment concrete, technical scheme of the present invention is described in further detail.
Example 1: according to stoichiometric ratio Cu 1.68zn 1.1snS 3.94(wherein 2x/ (1+y)=0.8, y=1.1) is by high-purity cuprous sulfide (Cu of purity>=4N 2s), zinc sulphide (ZnS), tin disulfide (SnS 2) powder fully mixes through ball milling, ball-milling medium is dehydrated alcohol, and Ball-milling Time is 12h; Then mixed powder is dried, sieve; The powder mixed is placed in mould, base vacuum≤3 × 10 of hot pressed sintering -2pa, in vacuum be below 20Pa environment in carry out hot pressed sintering, sintering temperature is 600 DEG C, temperature rise rate 10 DEG C/min, and hot pressing pressure is 40MPa, and soaking time is 4h, and insulation terminates rear release, cools to 200 DEG C below taking-ups with the furnace, prepares CZTS quaternary target.This target relative density reaches more than 90%.
Example 2: according to stoichiometric ratio Cu 1.4zn 1.8snS 4.5(wherein 2x/ (1+y)=0.5, y=1.8) is by high-purity cuprous sulfide (Cu of purity>=4N 2s), zinc sulphide (ZnS), tin disulfide (SnS 2) powder fully mixes through ball milling, ball-milling medium is deionized water, and Ball-milling Time is 18h; Then mixed powder is dried, sieve; The powder mixed is placed in mould, base vacuum≤3 × 10 -2pa, is filled with protectiveness nitrogen, and air pressure is carry out hot pressed sintering under 1atm environment, and sintering temperature is 800 DEG C; temperature rise rate 30 DEG C/min, hot pressing pressure is 10MPa, and soaking time is 0.5h; insulation terminates rear release, cools to less than 200 DEG C taking-ups with the furnace, preparation CZTS quaternary target.This target relative density reaches more than 90%.
Example 3: according to stoichiometric ratio Cu 2.04zn 0.7snS 3.72(wherein 2x/ (1+y)=1.2, y=0.7) is by high-purity cuprous sulfide (Cu of purity>=4N 2s), zinc sulphide (ZnS), tin disulfide (SnS 2) powder fully mixes through ball milling, ball-milling medium is deionized water, and Ball-milling Time is 6h; Then mixed powder is dried, sieve; The powder mixed is placed in mould, base vacuum≤3 × 10 -2pa, is filled with protectiveness hydrogen, and air pressure is carry out hot pressed sintering under 1atm environment, and sintering temperature is 300 DEG C; temperature rise rate 3 DEG C/min, hot pressing pressure is 80MPa, and soaking time is 12h; insulation terminates rear release, cools to less than 200 DEG C taking-ups with the furnace, preparation CZTS quaternary target.This target relative density reaches more than 90%.
Example 4: according to stoichiometric ratio Cu 2.86zn 1.6snS 5.03(wherein 2x/ (1+y)=1.1, y=1.6) is by high-purity cuprous sulfide (Cu of purity>=4N 2s), zinc sulphide (ZnS), tin disulfide (SnS 2) powder fully mixes through ball milling, ball-milling medium is air, and Ball-milling Time is 24h; Then mixed powder is directly sieved; The powder mixed is placed in mould, base vacuum≤3 × 10 -2pa, is filled with protectiveness argon gas, and air pressure is carry out hot pressed sintering under 1atm environment, and sintering temperature is 500 DEG C; temperature rise rate 10 DEG C/min, hot pressing pressure is 60MPa, and soaking time is 6h; insulation terminates rear release, cools to less than 200 DEG C taking-ups with the furnace, preparation CZTS quaternary target.This target relative density reaches more than 90%.
Example 5: according to stoichiometric ratio Cu 1.68zn 1.4snS 3.24(wherein 2x/ (1+y)=0.7, y=1.4) is by high-purity cuprous sulfide (Cu of purity>=4N 2s), zinc sulphide (ZnS), tin disulfide (SnS 2) powder fully mixes through ball milling, ball-milling medium is dehydrated alcohol, and Ball-milling Time is 2h; Then mixed powder is dried, sieve; The powder mixed is placed in mould, base vacuum≤3 × 10 -2pa, is filled with protectiveness nitrogen, and air pressure is carry out hot pressed sintering under 1atm environment, and sintering temperature is 700 DEG C; temperature rise rate 20 DEG C/min, hot pressing pressure is 20MPa, and soaking time is 1h; insulation terminates rear release, cools to less than 200 DEG C taking-ups with the furnace, preparation CZTS quaternary target.This target relative density reaches more than 90%.
Example 6: according to stoichiometric ratio Cu 1.71zn 0.9snS 3.755(wherein 2x/ (1+y)=0.9, y=0.9) is by high-purity cuprous sulfide (Cu of purity>=4N 2s), zinc sulphide (ZnS), tin disulfide (SnS 2) powder fully mixes through ball milling, ball-milling medium is dehydrated alcohol, and Ball-milling Time is 1h; Then mixed powder is dried, sieve; The powder mixed is placed in mould, base vacuum≤3 × 10 -2pa, is filled with protectiveness nitrogen, and air pressure is carry out hot pressed sintering under 1atm environment, and sintering temperature is 450 DEG C; temperature rise rate 5 DEG C/min, hot pressing pressure is 30MPa, and soaking time is 8h; insulation terminates rear release, cools to less than 200 DEG C taking-ups with the furnace, preparation CZTS quaternary target.This target relative density reaches more than 90%.
Example 7: according to stoichiometric ratio Cu 1.76zn 1.2snS 4.08(wherein 2x/ (1+y)=0.8, y=1.2) is by high-purity cuprous sulfide (Cu of purity>=4N 2s), zinc sulphide (ZnS), tin disulfide (SnS 2) powder fully mixes through ball milling, ball-milling medium is dehydrated alcohol, and Ball-milling Time is 10h; Then mixed powder is dried, sieve; The powder mixed is placed in mould, base vacuum≤3 × 10 -2pa, is filled with protectiveness nitrogen, and air pressure is carry out hot pressed sintering under 1atm environment, and sintering temperature is 550 DEG C; temperature rise rate 15 DEG C/min, hot pressing pressure is 40MPa, and soaking time is 10h; insulation terminates rear release, cools to less than 200 DEG C taking-ups with the furnace, preparation CZTS quaternary target.This target relative density reaches more than 90%.
Applicant has done detailed description and description to technical scheme of the present invention in conjunction with the embodiments; but those skilled in the art should understand that; above embodiment is only the preferred embodiments of the invention; detailed explanation is just in order to help reader to understand spirit of the present invention better; and be not limiting the scope of the invention; on the contrary, any any improvement of doing based on invention of the present invention spirit or modify all should drop within protection scope of the present invention.

Claims (8)

1. a preparation method for copper-zinc-tin-sulfur quaternary target, is characterized in that: according to the high-purity cuprous sulfide Cu of stoichiometric ratio by purity>=4N 2s, zinc sulphide ZnS, tin disulfide SnS 2powder mixes; Then mixed powder is dried, sieved; Then the powder mixed is placed in mould and prepares CZTS quaternary target by hot pressed sintering.
2. a preparation method for copper-zinc-tin-sulfur quaternary target, is characterized in that, described preparation method comprises following steps:
(1) according to stoichiometric ratio Cu 2xzn ysnS (x+y+2)by high-purity cuprous sulfide Cu of purity>=4N 2s, zinc sulphide ZnS, tin disulfide SnS 2powder fully mixes through ball milling;
(2) mixed powder is dried, sieved;
(3) powder mixed is placed in mould, in protective atmosphere, makes CZTS quaternary target by hot-pressing sintering technique.
3. preparation method according to claim 2, is characterized in that: described in step (1), stoichiometric ratio is: 0.5≤2x/ (1+y)≤1.2,0.7≤y≤1.8.
4. preparation method according to claim 2, is characterized in that: in step (1), and described ball-milling medium is the one in dehydrated alcohol, deionized water or air, and Ball-milling Time is 1 ~ 24h.
5. preparation method according to claim 2, is characterized in that: in step (3), base vacuum≤3 × 10 of stove interior (whether referring to the background vacuum in grinding tool) during hot pressed sintering -2pa, sintering temperature is 300 ~ 800 DEG C, temperature rise rate 3-30 DEG C/min, and hot pressing pressure is 10 ~ 80MPa, and soaking time is 0.5 ~ 12h, and insulation terminates rear release, cools to less than 200 DEG C taking-ups with the furnace.
6. preparation method according to claim 2, is characterized in that: in step (3), and described protective atmosphere is vacuum or is filled with protective gas.
7. preparation method according to claim 2, is characterized in that: when protective atmosphere is vacuum, and described vacuum pressure is below 20Pa.
8. preparation method according to claim 2, is characterized in that: when protective atmosphere is for being protective gas, described protective gas is hydrogen, nitrogen or argon gas, and protective gas atmos is 1atm.
CN201410659317.6A 2014-11-19 2014-11-19 Preparation method of CZTS (copper-zinc-tin-sulfur) quaternary target Pending CN104404456A (en)

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Cited By (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
CN105821376A (en) * 2015-12-24 2016-08-03 云南师范大学 Preparation method for copper-zinc-tin sulfide target
CN105821384A (en) * 2015-09-24 2016-08-03 云南师范大学 Method for preparing copper-zinc-tin sulfide film through multi-component dual-target co-sputtering

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JP2010245238A (en) * 2009-04-03 2010-10-28 Promatic Kk Photoelectric conversion device and method of manufacturing the same, as well as method of manufacturing sulfide sintered compact target
CN102610673A (en) * 2012-03-23 2012-07-25 华东师范大学 Copper zinc tin sulfur compound thin-film solar cell and preparation method thereof
CN103172378A (en) * 2011-12-21 2013-06-26 北京有色金属研究总院 Copper/zinc/tin/sulfur ceramic target material and vacuum hot pressing preparation method thereof

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Publication number Priority date Publication date Assignee Title
JP2010245238A (en) * 2009-04-03 2010-10-28 Promatic Kk Photoelectric conversion device and method of manufacturing the same, as well as method of manufacturing sulfide sintered compact target
CN103172378A (en) * 2011-12-21 2013-06-26 北京有色金属研究总院 Copper/zinc/tin/sulfur ceramic target material and vacuum hot pressing preparation method thereof
CN102610673A (en) * 2012-03-23 2012-07-25 华东师范大学 Copper zinc tin sulfur compound thin-film solar cell and preparation method thereof

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Cited By (4)

* 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
CN105821384A (en) * 2015-09-24 2016-08-03 云南师范大学 Method for preparing copper-zinc-tin sulfide film through multi-component dual-target co-sputtering
CN105821384B (en) * 2015-09-24 2018-08-28 云南师范大学 The method that polynary target double target co-sputtering prepares copper-zinc-tin-sulfur film
CN105821376A (en) * 2015-12-24 2016-08-03 云南师范大学 Preparation method for copper-zinc-tin sulfide target

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Application publication date: 20150311