CN105127438A - Method for preparing CIGS powder - Google Patents
Method for preparing CIGS powder Download PDFInfo
- Publication number
- CN105127438A CN105127438A CN201510581193.9A CN201510581193A CN105127438A CN 105127438 A CN105127438 A CN 105127438A CN 201510581193 A CN201510581193 A CN 201510581193A CN 105127438 A CN105127438 A CN 105127438A
- Authority
- CN
- China
- Prior art keywords
- powder
- source power
- indium
- gallium
- cigs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention relates to a method for preparing CIGS powder and belongs to the technical field of photovoltaic material preparation. The method includes the steps that a copper source, an indium source, a gallium source and a selenium resource are mixed according to a certain proportion for ball milling, and the obtained mixture of copper, indium, gallium and selenium is placed in a vacuum sintering furnace for solid-phase synthesis under protection gas; the mixture is cooled to room temperature and taken out for grinding and screening, and the CIGS powder is obtained. According to method for preparing the CIGS powder, the copper powder adopted in the raw material powder is nanometer powder, low-temperature short-term synthesis can be achieved, the solid-phase synthesis stage is facilitated, and energy consumption is lowered; the synthesis process is simple, easy to operate and low in cost, and large-scale industrial application is facilitated.
Description
Technical field
The present invention relates to a kind of method preparing CIGS powder; Belong to photovoltaic material preparing technical field.
Background technology:
The many merits such as CIGS thin film solar cell (CIGS is writing a Chinese character in simplified form of CuInxGa (1-x) Se2) is high with its efficiency, stability strong, radiation hardness, consumptive material are few become the study hotspot of area of solar cell in recent years.The performance of this battery determines primarily of the quality of absorbed layer CIGS thin film, its main preparation methods has at present: selenizing method, electrodeposition process and spraying high-temperature decomposition etc. after coevaporation method, metal initialization layer, but due to CIGS thin film complex structure, crystalline film requirement condition is higher, also there is various problem based on the preparation method of selenizing method after coevaporation method and metal preformed layer, hinder the process of its industrialization.And target as sputter film forming is with good stability, the features such as film even compact become the object that each enterprise falls over each other to study.
The preparation of target take powder as raw material, the synthesis of powder stock adopts elementsynthesis preparation, the raw material that present elementsynthesis adopts usually is block or coarse grained powder, undertaken synthesizing (synthesis temperature is generally more than 500 DEG C) by high temperature process heat technique, possess skills route maturation, and preparation process is easy to the feature controlled.But energy consumption is high, generated time is long.
There is the method much prepare nanometer CIGS powder in prior art, but yet there are no employing Nanometer Copper source and/or indium source and/or gallium source and/or selenium source to prepare the report of CIGS powder.
Summary of the invention
The present invention is directed to the weak point that prior art exists, the invention provides a kind of method preparing CIGS powder that energy consumption is low, efficiency is high.
A kind of method preparing CIGS powder of the present invention, comprises the steps:
Chemical formula by CuInxGa (1-x) Se2 is joined after copper source power, indium source power, gallium source power, the selenium source powder got mix, under protective atmosphere, sinter in 350-450 DEG C, preferably 350-420 DEG C, more preferably 350-400 DEG C, obtain CIGS powder; Described copper source power granularity is less than or equal to 100nm, is preferably 10-100nm; The value of more preferably 20-80nm, described x is 0<x<1; X is preferably 0.7.
A kind of method preparing CIGS powder of the present invention, the time of sintering is 2-5 hour.
A kind of method preparing CIGS powder of the present invention, described copper source power is selected from least one in copper powder, Berzeline powder.
A kind of method preparing CIGS powder of the present invention, described indium source power is selected from least one in indium powder, indium selenide powder.
A kind of method preparing CIGS powder of the present invention, described gallium source power is selected from least one in gallium powder, gallium selenide powder.
A kind of method preparing CIGS powder of the present invention, described selenium source powder is selected from least one in selenium powder, Berzeline powder, indium selenide powder, gallium selenide powder.
A kind of method preparing CIGS powder of the present invention, described protective atmosphere is argon gas.
A kind of method preparing CIGS powder of the present invention, is mixed joining copper source power, indium source power, gallium source power, the selenium source powder got by the ball milling under protective atmosphere; During ball milling, control rotating speed is 300-500r/min, and the time is 3-6 hour.
In order to reach better effect, the compound after ball milling is generally placed in vacuum sintering furnace, under protection gas, carry out synthesis in solid state target product.After sintered, take out target product under cool to room temperature and carry out grinding, sieving, the CIGS powder of required particle diameter can be obtained.
Principle and advantage
High-specific surface area, high activity that the present invention utilizes nano raw material to have cleverly, by ball milling, further enhancing the activity of material powder while batch mixing; Make under the synergy of above-mentioned condition the present invention can 350-450 DEG C, even just can prepare superior CIGS powder fast at 350 DEG C.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention,
Fig. 2 is the X-ray diffractogram of products obtained therefrom in embodiment 1-4.
Fig. 3 is the X-ray diffractogram of products obtained therefrom in comparative example 1-4.
As can be seen from Figure 1 technological process of the present invention.
In Fig. 2, No. 1 curve is the XRD figure of embodiment 1 products obtained therefrom; No. 2 curves are the XRD figure of embodiment 2 products obtained therefrom; No. 3 curves are the XRD figure of embodiment 3 products obtained therefrom; No. 4 curves are the XRD figure of embodiment 4 products obtained therefrom.
In Fig. 3, No. 1 curve is the XRD figure of comparative example 1 products obtained therefrom; No. 2 curves are the XRD figure of comparative example 2 products obtained therefrom; No. 3 curves are the XRD figure of comparative example 3 products obtained therefrom; No. 4 curves are the XRD figure of comparative example 1 products obtained therefrom.
Detailed description of the invention
Introduce method of the present invention in detail below, comprise the following steps:
First, needed raw material is mixed rear ball milling according to a certain percentage, the CIGS compound fully mixed after ball milling.In implementation process, according to copper: indium: gallium: the ratio of the amount of substance of selenium is: 1:0.7:0.3:2 carries out proportioning, to ensure the quality of follow-up making target.
Then, the compound obtained after ball milling is placed in vacuum sintering furnace synthesis in solid state, and passes into inert protective gas.In implementation process, protective gas adopts argon gas.The existence of protective gas not only can prevent reactant oxidized, improves the purity of alloy powder, and the volatilization of selenium when being conducive to subsequent reactions.
Finally, during stove cool to room temperature to be sintered, take out compound and carry out crushing grinding, screening obtains the CIGS powder of desired particle size.
Below, the embodiment of the present application is described.
Embodiment 1
In the present embodiment, copper source power is copper powder; Its particle diameter is 100nm;
In the present embodiment, indium source power is indium powder and indium selenide powder; Its average grain diameter is 200nm;
In the present embodiment, gallium source power is gallium powder and gallium selenide powder; Its average grain diameter is 200nm;
In the present embodiment, selenium source powder is indium selenide powder and gallium selenide powder, and its average grain diameter is 200nm;
Be that 1:0.7:0.3:2 prepares quaternary alloy powder CIGS according to the ratio of the amount of substance of copper, indium, gallium, selenium, take material powder according to ratio, wherein the particle diameter of Cu powder used is 100nm.Then by ball milling after raw material mixing, drum's speed of rotation is 500r/min, and ball milling 6 hours makes raw material mix.The compound taken out after ball milling is placed in vacuum sintering furnace synthesis in solid state, and passes into argon shield.Be raised to 450 DEG C with the programming rate of 5 DEG C/min, insulation 2h, then takes out in-furnace temperature cool to room temperature.Powder after synthesis carries out XRD analysis, only there is CIGS quaternary alloy phase, there is not other simple substance or Compound Phase, illustrates that synthesis completes.
Comparative example 1
Other conditions are completely consistent with embodiment 1, adopt the particle diameter of copper powder, indium powder, gallium powder, indium selenide powder, gallium selenide powder to be 25 microns;
The XRD figure of gained finished product is shown in No. 1 curve in Fig. 3; Can find out, 450 DEG C, adopt that particle diameter is copper powder, indium powder, gallium powder, the indium selenide powder of 25 microns, in sample prepared by gallium selenide powder, peak shape is mixed and disorderly, and this does not obtain the target product of setting.
Embodiment 2
By the method identical with embodiment 1, change the particle diameter of Cu powder.That is, in the present embodiment 2, the particle diameter of raw material Cu powder is 80nm.
Be that 1:0.7:0.3:2 prepares quaternary alloy powder CIGS according to the ratio of the amount of substance of copper, indium, gallium, selenium, take material powder according to ratio.Then by ball milling after raw material mixing, drum's speed of rotation is 400r/min, and ball milling 5 hours makes raw material mix.The compound taken out after ball milling is placed in vacuum sintering furnace synthesis in solid state, and passes into argon shield.Be raised to 420 DEG C with the programming rate of 5 DEG C/min, insulation 2h, then takes out in-furnace temperature cool to room temperature.Powder after synthesis carries out XRD analysis, only there is CIGS quaternary alloy phase, there is not other simple substance or Compound Phase, illustrates that synthesis completes.
Comparative example 2
Other conditions are completely consistent with embodiment 1, adopt the particle diameter of copper powder, indium powder, gallium powder, indium selenide powder, gallium selenide powder to be 15 microns;
The XRD figure of gained finished product is shown in No. 2 curves in Fig. 3; Can find out, 420 DEG C, adopt that particle diameter is copper powder, indium powder, gallium powder, the indium selenide powder of 15 microns, in sample prepared by gallium selenide powder, peak shape is mixed and disorderly, and this does not obtain the target product of setting.
Embodiment 3
By the method identical with embodiment 1, change the particle diameter of Cu powder.That is, in the present embodiment 3, the particle diameter of raw material Cu powder is 50nm.
Be that 1:0.7:0.3:2 prepares quaternary alloy powder CIGS according to the ratio of the amount of substance of copper, indium, gallium, selenium, take material powder according to ratio.Then by ball milling after raw material mixing, drum's speed of rotation is 400r/min, and ball milling 4 hours makes raw material mix.The compound taken out after ball milling is placed in vacuum sintering furnace synthesis in solid state, and passes into argon shield.Be raised to 400 DEG C with the programming rate of 5 DEG C/min, insulation 2h, then takes out in-furnace temperature cool to room temperature.Powder after synthesis carries out XRD analysis, only there is CIGS quaternary alloy phase, there is not other simple substance or Compound Phase, illustrates that synthesis completes.
Comparative example 3
Other conditions are completely consistent with embodiment 1, adopt the particle diameter of copper powder, indium powder, gallium powder, indium selenide powder, gallium selenide powder to be 10 microns;
The XRD figure of gained finished product is shown in No. 3 curves in Fig. 3; Can find out, 400 DEG C, adopt that particle diameter is copper powder, indium powder, gallium powder, the indium selenide powder of 10 microns, in sample prepared by gallium selenide powder, peak shape is mixed and disorderly, and this does not obtain the target product of setting.
Embodiment 4
By the method identical with embodiment 1, change the particle diameter of Cu powder.That is, in the present embodiment 4, the particle diameter of raw material Cu powder is 20nm.
Be that 1:0.7:0.3:2 prepares quaternary alloy powder CIGS according to the ratio of the amount of substance of copper, indium, gallium, selenium, take material powder according to ratio.Then by ball milling after raw material mixing, drum's speed of rotation is 300r/min, and ball milling 3 hours makes raw material mix.The compound taken out after ball milling is placed in vacuum sintering furnace synthesis in solid state, and passes into argon shield.Be raised to 350 DEG C with the programming rate of 5 DEG C/min, insulation 2h, then takes out in-furnace temperature cool to room temperature.Powder after synthesis carries out XRD analysis, only there is CIGS quaternary alloy phase, there is not other simple substance or Compound Phase, illustrates that synthesis completes.
Comparative example 4
Other conditions are completely consistent with embodiment 1, adopt the particle diameter of copper powder, indium powder, gallium powder, indium selenide powder, gallium selenide powder to be 10 microns;
The XRD figure of gained finished product is shown in No. 4 curves in Fig. 3; Can find out, 350 DEG C, adopt that particle diameter is copper powder, indium powder, gallium powder, the indium selenide powder of 10 microns, in sample prepared by gallium selenide powder, peak shape is mixed and disorderly, and this does not obtain the target product of setting.
Claims (10)
1. prepare the method for CIGS powder for one kind, it is characterized in that: the chemical formula by CuInxGa (1-x) Se2 is joined after copper source power, indium source power, gallium source power, the selenium source powder got mix, under protective atmosphere, sinter in 350-450 DEG C, obtain CIGS powder; The granularity of described copper source power, indium source power, gallium source power, selenium source powder is all less than or equal to 100nm; The value of described x is 0<x<1.
2. a kind of method preparing CIGS powder according to claim 1; it is characterized in that: the chemical formula by CuInxGa (1-x) Se2 is joined after copper source power, indium source power, gallium source power, the selenium source powder got mix; under protective atmosphere; sinter in 350-420 DEG C, obtain CIGS powder.
3. a kind of method preparing CIGS powder according to claim 1, is characterized in that: described x equals 0.7.
4. a kind of method preparing CIGS powder according to claim 1 and 2, is characterized in that: the time of sintering is 2-5 hour.
5. a kind of method preparing CIGS powder according to claim 1 and 2, is characterized in that: described copper source power is selected from least one in copper powder, Berzeline powder.
6. a kind of method preparing CIGS powder according to claim 1 and 2, is characterized in that: described indium source power is selected from least one in indium powder, indium selenide powder.
7. a kind of method preparing CIGS powder according to claim 1 and 2, is characterized in that: described gallium source power is selected from least one in gallium powder, gallium selenide powder.
8. a kind of method preparing CIGS powder according to claim 1 and 2, is characterized in that: described selenium source powder is selected from selenium powder.
9. a kind of method preparing CIGS powder according to claim 1 and 2, is characterized in that: described protective atmosphere is argon gas.
10. a kind of method preparing CIGS powder according to claim 1 and 2, is characterized in that: mixed joining copper source power, indium source power, gallium source power, the selenium source powder got by the ball milling under protective atmosphere; During ball milling, control rotating speed is 300-500r/min, and the time is 3-6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510581193.9A CN105127438A (en) | 2015-09-14 | 2015-09-14 | Method for preparing CIGS powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510581193.9A CN105127438A (en) | 2015-09-14 | 2015-09-14 | Method for preparing CIGS powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105127438A true CN105127438A (en) | 2015-12-09 |
Family
ID=54713190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510581193.9A Pending CN105127438A (en) | 2015-09-14 | 2015-09-14 | Method for preparing CIGS powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105127438A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260513A (en) * | 2008-04-23 | 2008-09-10 | 王东生 | Solar energy battery copper-indium-gallium-selenium film key target material and preparation method thereof |
| CN101613091A (en) * | 2009-07-27 | 2009-12-30 | 中南大学 | A kind of CIGS powder, target, film and preparation method thereof |
| US20110073688A1 (en) * | 2009-09-25 | 2011-03-31 | Jenn Feng New Energy Co., Ltd. | Method for fabricating cigs nanoparticles |
| CN103658671A (en) * | 2013-12-27 | 2014-03-26 | 柳州百韧特先进材料有限公司 | Method for preparing nanometer CIGS powder |
| CN103695850A (en) * | 2013-12-27 | 2014-04-02 | 柳州百韧特先进材料有限公司 | Preparation method of solar battery CIGS (copper indium gallium selenium) target material |
| CN103706799A (en) * | 2013-12-27 | 2014-04-09 | 柳州百韧特先进材料有限公司 | Method for preparing CIGS powder through dry method |
-
2015
- 2015-09-14 CN CN201510581193.9A patent/CN105127438A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260513A (en) * | 2008-04-23 | 2008-09-10 | 王东生 | Solar energy battery copper-indium-gallium-selenium film key target material and preparation method thereof |
| CN101613091A (en) * | 2009-07-27 | 2009-12-30 | 中南大学 | A kind of CIGS powder, target, film and preparation method thereof |
| US20110073688A1 (en) * | 2009-09-25 | 2011-03-31 | Jenn Feng New Energy Co., Ltd. | Method for fabricating cigs nanoparticles |
| CN103658671A (en) * | 2013-12-27 | 2014-03-26 | 柳州百韧特先进材料有限公司 | Method for preparing nanometer CIGS powder |
| CN103695850A (en) * | 2013-12-27 | 2014-04-02 | 柳州百韧特先进材料有限公司 | Preparation method of solar battery CIGS (copper indium gallium selenium) target material |
| CN103706799A (en) * | 2013-12-27 | 2014-04-09 | 柳州百韧特先进材料有限公司 | Method for preparing CIGS powder through dry method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100590891C (en) | Process for preparation of absorption layer of solar cell | |
| CN101958369B (en) | Method for preparing copper-indium-gallium-selenium film material | |
| CN101531529A (en) | Preparation method of CuInxGa1-xSe2 powder | |
| Wang et al. | Preparation and properties of Cu2FeSnS4 nanocrystals by ultrasound-assisted microwave irradiation | |
| EP2589571A1 (en) | Powder, sintered body and sputtering target, each containing elements cu, in, ga and se, and method for producing the powder | |
| CN101885071B (en) | Method for preparing copper-zinc-tin-selenium nano powder material | |
| CN110722171A (en) | Method for preparing rare earth oxide doped tungsten and molybdenum spherical powder for 3D printing | |
| JP2017511784A (en) | Method for doping Cu (In, Ga) (S, Se) 2 nanoparticles with sodium or antimony | |
| CN104701138A (en) | Preparation method for CZTS (Se) nano-crystalline thin film | |
| CN105705674B (en) | Cu-Ga alloy sputtering target and method for producing same | |
| CN109706525B (en) | Bismuth-based topological insulator material and preparation method thereof | |
| CN103633165B (en) | Yellow copper structure Intermediate Gray solar battery obsorbing layer material and preparation method thereof | |
| KR101509332B1 (en) | Preparation of copper selenide compound controlling particle size and composition | |
| TW200832727A (en) | Target and thin film fabricated by the target | |
| CN103706799A (en) | Method for preparing CIGS powder through dry method | |
| CN105127438A (en) | Method for preparing CIGS powder | |
| CN103626495B (en) | Preparation method for CIGS target material through pressureless sintering | |
| CN105821376A (en) | Preparation method for copper-zinc-tin sulfide target | |
| KR20110055138A (en) | Manufacturing method of photoelectric conversion film | |
| CN105742385B (en) | A kind of copper and iron zinc-tin sulfur micron single crystal grain and preparation method thereof and the application in terms of preparing solaode | |
| CN101383384A (en) | Silver copper composite oxide film material for photoelectric semiconductor | |
| CN111924874A (en) | Preparation method of copper-zinc-tin-based powder | |
| Kim et al. | Preparation of precursor particles by cryogenic mechanical milling for the deposition of CuInS2 thin films | |
| KR101418831B1 (en) | Target for light absorption layer of thin film solar cell, method for the same and the thin film solar cell | |
| CN103658671B (en) | A kind of method preparing nanometer CIGS powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151209 |