CN101695997A - Preparation method of copper zinc tin selenium photovoltaic material - Google Patents

Preparation method of copper zinc tin selenium photovoltaic material Download PDF

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Publication number
CN101695997A
CN101695997A CN200910309577A CN200910309577A CN101695997A CN 101695997 A CN101695997 A CN 101695997A CN 200910309577 A CN200910309577 A CN 200910309577A CN 200910309577 A CN200910309577 A CN 200910309577A CN 101695997 A CN101695997 A CN 101695997A
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preparation
powder
photovoltaic material
copper
zinc tin
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CN200910309577A
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魏浩
张亚非
郭炜
王雨化
赵刚
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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    • 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
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Abstract

The invention relates to a preparation method of a copper zinc tin selenium photovoltaic material in the technical field of photovoltaic material, comprising the following steps: step 1, treating copper powder, zinc powder and tin powder respectively with sulfuric acid or hydrochloric acid; step 2. carrying out filtration under reduced pressure and vacuum drying; step 3. mixing with selenium powder and ball-milling under the shielding of inert gas; step 4. statically pressing the ball-milled materials to obtain a lump material; step 5, sintering under the shielding of inert gas to obtain the copper zinc tin selenium photovoltaic material. The method of the invention avoids the defects of pulse laser deposition and other methods that equipment is high, deposition in large area can be realized difficultly, high-temperature selenylation is required, and the like; and the method of the invention has simple requirements on equipment and is suitable for industrialization production.

Description

The preparation method of copper zinc tin selenium photovoltaic material
Technical field
The present invention relates to a kind of preparation method of photoelectric material technical field, be specifically related to a kind of preparation method of copper zinc tin selenium photovoltaic material.
Background technology
Copper-zinc-tin-selenium (Cu 2ZnSnSe 4, english abbreviation is CZTSe) and energy gap (1.45eV) and the desired best energy gap of semiconductor solar cell (1.5eV) be very approaching, and in addition, this material is to utilize that higher zinc and the tin element of the amount of containing replaced copper-indium-galliun-selenium (Cu on the earth's crust 2InGaSe 2, english abbreviation is CIGS) in indium and gallium element, it is environmentally friendly not contain poisonous composition, is one of candidate material that substitutes copper-indium-galliun-selenium solar cell absorption layer.
Find that through literature search Kim etc. rolled up the 3373rd～3379 page of the 10th phase in 2007 the 204th at " Physica Status Solidi (A) Applicationsand Materials " and delivered Pulsed laser deposition ofquaternary Cu to prior art 2ZnSnSe 4" (pulsed laser deposition prepares Cu to thin films 2ZnSnSe 4Film) since, the professional has developed Cu such as pulsed laser deposition, magnetron sputtering, coevaporation vacuum plating 2ZnSnSe 4The preparation method, but these methods exist apparatus expensive, are not easy to shortcomings such as big area deposition.Therefore, proposed a kind of can the preparation in a large number, Cu with low cost and eco-friendly 2ZnSnSe 4The preparation method, significant for the present technique field.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of copper zinc tin selenium photovoltaic material is provided.Method equipment requirements of the present invention is simple, is fit to suitability for industrialized production.
The present invention is achieved by the following technical solutions, may further comprise the steps:
Step 1, with copper powder, zinc powder and glass putty are respectively with sulfuric acid or salt acid treatment;
Step 2, filtration under diminished pressure, vacuum-drying;
Step 3 is mixed with selenium powder afterwards, ball milling under protection of inert gas;
Step 4, the material static pressure that ball milling is good obtains block;
Step 5, sintering under protection of inert gas obtains copper zinc tin selenium photovoltaic material.
In the step 1, described copper powder, the purity of zinc powder and glass putty is 4N～6N.
In the step 1, described sulfuric acid or hydrochloric acid are treated to, and are 1～5% sulfuric acid or hydrochloric acid stir process 5～60 minutes with massfraction.
In the step 2, described vacuum-drying is, 30～80 ℃ of dryings are 6～24 hours under the vacuum.
In the step 3, the mol ratio of copper powder, zinc powder, glass putty and selenium powder is: (2～2.2): (1～1.2): (1～1.2): (4～4.2).
In the step 3, described ball milling is specially: the quality that adds agate ball is 5～100 times of ball milling material.
In the step 3, described ball milling is that 50～300rpm handled 6～96 hours.
In the step 4, described static pressure is static pressure such as the pressure of 10～60MPa 5～60 minutes.
In the step 5, described being sintered to, 300 ℃～1500 ℃ sintering 1～12 hour.
The present invention passes through to select copper, zinc, tin, four kinds of suitable stoicheiometries of monomer of selenium, the high energy mechanical ball mill mixing, and isostatic pressing, then high temperature sintering under the protection of inert gas obtains a large amount of Cu fast 2ZnSnSe 4Photoelectric material.Principle of the present invention is under the protection of inert gas state and the condition of high temperature; monomeric substance obtains very big energy from the external world; the atom out-shell electron is very active; trend towards between atom toward the minimum stable state development of energy; and four kinds of monomers of copper, zinc, tin, selenium can obtain Cu through the ball milling thorough mixing after the high-temperature heat treatment 2ZnSnSe 4Photoelectric material.
Compared with prior art, the present invention has following beneficial effect: method of the present invention avoided apparatus expensive that methods such as pulsed laser deposition exist, be not easy to the big area deposition and need shortcomings such as high temperature selenizing, it is simple to have equipment requirements, is fit to the advantage of suitability for industrialized production.
Description of drawings
Fig. 1 is the Cu of embodiment 1 preparation 2ZnSnSe 4The X ray diffracting spectrum of photoelectric material;
Fig. 2 is the Cu of embodiment 2 preparations 2ZnSnSe 4The X ray diffracting spectrum of photoelectric material;
Fig. 3 is the Cu of embodiment 4 preparations 2ZnSnSe 4The X ray diffracting spectrum of photoelectric material;
Fig. 4 is the Cu of embodiment 4 preparations 2ZnSnSe 4The X ray diffracting spectrum of photoelectric material;
Fig. 5 is the Cu of embodiment 5 preparations 2ZnSnSe 4The X ray diffracting spectrum of photoelectric material.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
With copper powder (4N), zinc powder (4N) and glass putty (4N) is respectively 5 minutes after-filtration of dilute sulphuric acid stir process of 5% with massfraction, 80 ℃ of vacuum-drying 24 hours; Again with copper, zinc, glass putty and the selenium powder (4N) handled well 2.1: 1.1: 1.1 in molar ratio: 4.1 add in the ball grinders, add the agate ball that is about 100 times of quality of material, vacuumize earlier after the sealing, logical again high pure nitrogen protection.On planetary ball mill with the rotating speed ball mill mixing of 180rpm 96 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 60MPa 5 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high-purity argon gas, high temperature sintering is 4 hours in 700 ℃, obtains Cu 2ZnSnSe 4Photoelectric material, the X-ray diffractogram of material such as Fig. 1.
Embodiment 2
With copper powder (6N), zinc powder (6N) and glass putty (6N) is respectively 60 minutes after-filtration of dilute sulphuric acid stir process of 1% with massfraction, 60 ℃ of vacuum-drying 15 hours; Again with copper, zinc, glass putty and the selenium powder (2N) handled well 2.2: 1.2: 1.2 in molar ratio: 4.2 add in the ball grinders, add the agate ball that is about 40 times of quality of material, vacuumize earlier after the sealing, logical again high-purity argon gas protection.On planetary ball mill with the rotating speed ball mill mixing of 300rpm 6 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 5MPa 60 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high-purity argon gas, high temperature sintering is 1 hour in 1000 ℃, obtains Cu 2ZnSnSe 4Photoelectric material, the X-ray diffractogram of material such as Fig. 2.
Embodiment 3
With copper powder (4N), zinc powder (4N) and glass putty (4N) is respectively 20 minutes after-filtration of dilute sulphuric acid stir process of 5%, 1%, 5% with massfraction, 50 ℃ of vacuum-drying 8 hours; Again with copper, zinc, glass putty and the selenium powder (5N) handled well 2: 1: 1 in molar ratio: 4 add in the ball grinders, add the agate ball that is about 5 times of quality of material, vacuumize earlier after the sealing, logical again high-pure helium gas shiled.On planetary ball mill with the rotating speed ball mill mixing of 50rpm 24 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 30MPa 10 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high-purity argon gas, high temperature sintering is 12 hours in 300 ℃, obtains Cu 2ZnSnSe 4Photoelectric material, the X-ray diffractogram of material such as Fig. 3.
Embodiment 4
With copper powder (5N), zinc powder (5N) and glass putty (5N) is respectively 5 minutes after-filtration of dilute hydrochloric acid stir process of 3% with massfraction, 30 ℃ of vacuum-drying 6 hours; Again with copper, zinc, glass putty and the selenium powder (4N) handled well 2.1: 1.1: 1.1 in molar ratio: 4.1 add in the ball grinders, add the agate ball that is about 100 times of quality of material, vacuumize earlier after the sealing, logical more high-purity CO 2Protection.On planetary ball mill with the rotating speed ball mill mixing of 180rpm 96 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 20MPa 15 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high-purity helium, high temperature sintering is 12 hours in 700 ℃, obtains Cu 2ZnSnSe 4Photoelectric material, the X-ray diffractogram of material such as Fig. 4.
Embodiment 5
With copper powder (5N), zinc powder (5N) and glass putty (5N) is respectively 60 minutes after-filtration of dilute hydrochloric acid stir process of 1% with massfraction, 46 ℃ of vacuum-drying 2 hours; Again with copper, zinc, glass putty and the selenium powder (5N) handled well 2.2: 1.2: 1.2 in molar ratio: 4.2 add in the ball grinders, add the agate ball that is about 40 times of quality of material, vacuumize earlier after the sealing, logical again high pure nitrogen protection.On planetary ball mill with the rotating speed ball mill mixing of 300rpm 6 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 10MPa 60 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high pure nitrogen, high temperature sintering is 4 hours in 1500 ℃, obtains Cu 2ZnSnSe 4Photoelectric material, the X-ray diffractogram of material such as Fig. 5.

Claims (9)

1. the preparation method of a copper zinc tin selenium photovoltaic material is characterized in that, may further comprise the steps:
Step 1, with copper powder, zinc powder and glass putty are respectively with sulfuric acid or salt acid treatment;
Step 2, filtration under diminished pressure, vacuum-drying;
Step 3 is mixed with selenium powder afterwards, ball milling under protection of inert gas;
Step 4, the material static pressure that ball milling is good obtains block;
Step 5, sintering under protection of inert gas obtains copper zinc tin selenium photovoltaic material.
2. the preparation method of copper zinc tin selenium photovoltaic material according to claim 1 is characterized in that, in the step 1, and described copper powder, the purity of zinc powder and glass putty is 4N～6N.
3. the preparation method of copper zinc tin selenium photovoltaic material according to claim 1 is characterized in that, in the step 1, described sulfuric acid or hydrochloric acid are treated to, and is 1～5% sulfuric acid or hydrochloric acid stir process 5～60 minutes with massfraction.
4. the preparation method of copper zinc tin selenium photovoltaic material according to claim 1 is characterized in that, in the step 2, described vacuum-drying is, 30～80 ℃ of dryings are 6～24 hours under the vacuum.
5. the preparation method of copper zinc tin selenium photovoltaic material according to claim 1 is characterized in that, in the step 3, the mol ratio of copper powder, zinc powder, glass putty and selenium powder is: (2～2.2): (1～1.2): (1～1.2): (4～4.2).
6. the preparation method of copper zinc tin selenium photovoltaic material according to claim 1 is characterized in that, in the step 3, described ball milling is specially: the quality that adds agate ball is 5～100 times of ball milling material.
7. the preparation method of copper zinc tin selenium photovoltaic material according to claim 1 is characterized in that, in the step 3, described ball milling is: 50～300rpm handled 6～96 hours.
8. the preparation method of copper zinc tin selenium photovoltaic material according to claim 1 is characterized in that, in the step 4, described static pressure is: static pressure such as the pressure of 10～60MPa 5～60 minutes.
9. the preparation method of copper zinc tin selenium photovoltaic material according to claim 1 is characterized in that, in the step 5, and described being sintered to: 300 ℃～1500 ℃ sintering 1～12 hour.
CN200910309577A 2009-11-12 2009-11-12 Preparation method of copper zinc tin selenium photovoltaic material Pending CN101695997A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102372302A (en) * 2010-08-20 2012-03-14 华东师范大学 Copper-zinc-tin-sulfur or copper-zinc-tin-selenium target for absorbed layer of thin-film solar battery, preparation method for target and application of target
CN102627315A (en) * 2012-04-25 2012-08-08 桂林理工大学 Preparation method of wurtzite structure CZTS (Se) system powder
CN102674267A (en) * 2012-05-14 2012-09-19 山东建筑大学 Method for preparing copper, zinc, tin and selenium nanometer powder
CN103681934A (en) * 2013-12-07 2014-03-26 兰州大学 Preparation method for copper-zinc-stannum-sulfur powder, or copper-zinc-stannum-selenium powder or copper-zinc-stannum-sulfur-selenium powder
CN107935060A (en) * 2017-11-24 2018-04-20 上海材料研究所 Stratiform sulfur family photoelectric material and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102372302A (en) * 2010-08-20 2012-03-14 华东师范大学 Copper-zinc-tin-sulfur or copper-zinc-tin-selenium target for absorbed layer of thin-film solar battery, preparation method for target and application of target
CN102627315A (en) * 2012-04-25 2012-08-08 桂林理工大学 Preparation method of wurtzite structure CZTS (Se) system powder
CN102627315B (en) * 2012-04-25 2014-03-12 桂林理工大学 Preparation method of wurtzite structure CZTS (Se) system powder
CN102674267A (en) * 2012-05-14 2012-09-19 山东建筑大学 Method for preparing copper, zinc, tin and selenium nanometer powder
CN103681934A (en) * 2013-12-07 2014-03-26 兰州大学 Preparation method for copper-zinc-stannum-sulfur powder, or copper-zinc-stannum-selenium powder or copper-zinc-stannum-sulfur-selenium powder
CN103681934B (en) * 2013-12-07 2017-04-26 兰州大学 Preparation method for copper-zinc-stannum-sulfur powder, or copper-zinc-stannum-selenium powder or copper-zinc-stannum-sulfur-selenium powder
CN107935060A (en) * 2017-11-24 2018-04-20 上海材料研究所 Stratiform sulfur family photoelectric material and preparation method thereof
CN107935060B (en) * 2017-11-24 2019-11-05 上海材料研究所 Stratiform sulfur family photoelectric material and preparation method thereof

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Open date: 20100421