CN102496659A - Preparation method for copper zinc tin sulfide thin film material - Google Patents
Preparation method for copper zinc tin sulfide thin film material Download PDFInfo
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- CN102496659A CN102496659A CN2011104533340A CN201110453334A CN102496659A CN 102496659 A CN102496659 A CN 102496659A CN 2011104533340 A CN2011104533340 A CN 2011104533340A CN 201110453334 A CN201110453334 A CN 201110453334A CN 102496659 A CN102496659 A CN 102496659A
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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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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a preparation method for a copper zinc tin sulfide thin film material. The preparation method comprises the following steps of: performing oil removal, electrochemical polishing and activation pretreatment on the surface of a copper foil substrate; depositing metallic zinc and tin by using one of a magnetron sputtering method, an evaporation method, a pulsed laser deposition method and an electrodeposition method to form a metallic preformed layer; annealing the metallic preformed layer in a sulfur-containing protective atmosphere at high temperature; and placing the annealed metallic preformed layer in an alkaline KCN solution for etching. By the preparation method, a copper belt is adopted as a flexible substrate and a back contact conductive material, so that the usage of expensive metallic molybdenum is greatly reduced, and production cost is decreased; and a Cu-S phase formed by excessive copper is favorable for the growth of copper zinc tin sulfide crystal grains, reduces charge carrier recombination centers and improves photoelectric conversion efficiency. The copper zinc tin sulfide thin film material prepared by the method is easy to produce in large scale, and can be popularized and applied in a thin film solar cell industry.
Description
Technical field
The invention discloses a kind of copper-zinc-tin-sulfur (Cu
2ZnSnS
4) preparation method of thin-film material; Belong to the photoelectric material technical field of new energies.
Background technology
Solar energy has become the effectively section of having that solves world energy sources crisis now as a kind of inexhaustible, nexhaustible green energy resource.Photovoltaic generation is the of paramount importance means of economic utilization solar energy, and therefore the research to various solar cells receives increasing attention.
Using at present maximum in the middle of the solar cell photoelectric converting material is Si semiconductor, the problem of its existence, the major obstacle that problem such as too high like cost of material, that the light decay effect is obvious, electricity conversion is low becomes such solar cell development and uses.The compound film semiconductor solar cell becomes the focus of present photovoltaic research and industry with its lower cost, high theoretical electricity conversion and stronger plurality of advantages such as capability of resistance to radiation.Wherein the CIGS based thin film solar cell has moved towards industrial circle from academia gradually through nearly 40 years development; And obtained the highest 20.4% electricity conversion; Yet In in this kind compound and Ga be dissipated metal, cost an arm and a leg and reserves limited, this becomes the obstacle that such solar cell further develops.The copper-zinc-tin-sulfur film material with the direct band gap (good) of its about 1.5eV with the solar radiation matching, the absorption coefficient of light is high, raw material reserves in the earth's crust are big, cost is low, efficient is high, plurality of advantages such as undamped and nontoxic, becomes the optimal candidate material of compound film solar cell photoelectric converting material.
The copper-zinc-tin-sulfur film preparation methods is generally on the plating molybdenum glass and adopts magnetron sputtering or coevaporation method to prepare the metal preformed layer, under the atmosphere of sulfur-bearing, carries out The high temperature anneal then.This kind technological process need adopt expensive metal molybdenum as back of the body contact material, and the adhesion of metal molybdenum and metal preformed layer is relatively poor, in the The high temperature anneal process, can produce the cavity between the two, has a strong impact on the electricity conversion of solar cell.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and provide a kind of copper strips that adopts as flexible substrates and conduction back of the body contact material, preparation cost is low, electricity conversion is high, material contacts with the back of the body the strong copper-zinc-tin-sulfur film preparation methods of adhesion.
A kind of copper-zinc-tin-sulfur film preparation methods of the present invention comprises following steps:
The first step: copper foil base material surface preparation
With copper foil base material surface degreasing, electrochemical polish, activation;
Second step: copper foil base material surface deposition metallic zinc and tin form the metal preformed layer
Handle copper foil base material surface deposition metallic zinc and the tin obtain in the first step, said deposition adopts a kind of in magnetron sputtering method, evaporation, pulsed laser deposition method, the electrodeposition process;
The 3rd step: the metal preformed layer carries out The high temperature anneal under sulfur-bearing atmosphere
There is the copper foil base material of metallic zinc and tin to place protective atmosphere the surface deposition of the second step gained, is heated to 200～600 ℃,, zinc and tin metal preformed layer are carried out The high temperature anneal through carrier gas input sulphur source;
The 4th step: etching processing
Place alkaline KCN solution to carry out etching processing the Copper Foil after the processing of the 3rd step, adopt deionized water that film surface is cleaned, dries after the etching processing and promptly obtain the copper-zinc-tin-sulfur film material.
In a kind of copper-zinc-tin-sulfur film preparation methods of the present invention, said degreasing fluid adopts the sodium hydroxide solution of 0.1M/L; Said electrochemical polish adopts the mixed liquor of sulfuric acid, phosphoric acid, deionized water and polyethylene glycol to carry out, and each constituent mass percentage of said mixed liquor is: the polyethylene glycol 1-10g/L of sulfuric acid 10-30%, phosphatase 11 0-30%, deionized water 40-80%, molecular weight 6000; Polishing used current density is 10～100mA/cm
2, solution temperature is 20 ℃～80 ℃; It is that 10%～50% sulfuric acid solution carries out that said activating solution adopts mass fraction.
In a kind of copper-zinc-tin-sulfur film preparation methods of the present invention, the process of said plated metal zinc and tin is selected from a kind of in plated metal zinc behind plated metal tin behind the first plated metal zinc, the first plated metal tin, alternating deposit metal zinc-tin or codeposition metallic zinc and the metallic tin; In the sedimentary deposit, the mol ratio of said metallic zinc and metallic tin is 0.2～5.
In a kind of copper-zinc-tin-sulfur film preparation methods of the present invention, said metal preformed layer carries out the The high temperature anneal technological parameter and is under sulfur-bearing atmosphere: annealing temperature is that 200～600 ℃, programming rate are that 5～100 ℃/s, temperature retention time are 1～120 minute; The annealing furnace internal gas pressure is 0.01～1atm, and gas flow is 10～1000sccm.
In a kind of copper-zinc-tin-sulfur film preparation methods of the present invention, said sulphur source is selected from least a in sulfur vapor, artificial gold steam, the hydrogen sulfide.
In a kind of copper-zinc-tin-sulfur film preparation methods of the present invention, said etching processing technological parameter is: the mass percent concentration of alkaline KCN solution is 1%～50%, and the time is 1～20 minute, and temperature is 25 ℃～80 ℃.
The present invention contact electric conducting material as flexible substrates with the back of the body with copper strips, and deposition zinc and tin formation metal preformed layer on copper strips places the metal preformed layer and carries out The high temperature anneal under the sulfur-bearing atmosphere and prepare the copper-zinc-tin-sulfur film material.This material is smooth through surface compact after the etching processing, and composition meets desirable stoichiometric proportion, and crystallite dimension is 1～2 μ m, and electricity and optical property all meet the requirement of thin-film solar cell photoelectric converting material.The preparation method compares with the conventional solar cell absorbing layer film, and the present invention adopts copper strips to contact electric conducting material as flexible substrates with the back of the body, has practiced thrift the use of expensive metal molybdenum greatly, has reduced production cost; Wherein the Cu-S of excess copper formation helps growing up of copper-zinc-tin-sulfur crystal grain mutually, has reduced the charge carrier complex centre, has increased electricity conversion; Utilize the inventive method to prepare the copper-zinc-tin-sulfur film material, be easy to large-scale production, help popularization and the application of this material in thin-film solar cells industry.
Embodiment
Below in conjunction with embodiment, the present invention is done further explain, but must not these embodiment be interpreted as the restriction to protection range of the present invention.
Embodiment 1
(1) will carry out preliminary treatment with the copper strips that the back of the body contacts electric conducting material as flexible substrates
The preliminary treatment of copper strips is oil removing, electrochemical polish and activation.Wherein degreasing fluid adopts the sodium hydroxide solution of 0.1M/L; Electrochemical polish liquid adopts the mixed liquor of the polyethylene glycol 10g/L of sulfuric acid 30%, phosphoric acid 30%, deionized water 40%, molecular weight 6000, and polishing used current density is 10mA/cm
2, solution temperature is 80 ℃; What activating solution adopted is that mass fraction is 10% sulfuric acid solution.
(2) forming the metal preformed layer through deposition zinc on the pretreated copper strips and tin
Deposition process is a magnetron sputtering method, and depositional mode is a plated metal tin behind the first plated metal zinc, and the metallic zinc of deposition and the mol ratio of metallic tin are 0.2.
(3) the metal preformed layer is placed carry out The high temperature anneal under the sulfur-bearing atmosphere
Metal preformed layer annealing temperature is that 200 ℃, programming rate are that 5 ℃/s, temperature retention time are 10 minutes, and the annealing furnace internal gas pressure is that 0.01atm, gas flow are 10sccm, and the reactant gas of employing is a sulfur vapor.
(4) the said film of step (3) is carried out etching processing, obtain finished product
Said lithographic method is the solution etching.Etching processing employing mass percent concentration is 1% alkaline KCN solution, and the time is 20 minutes, and temperature is 50 ℃.
Obtaining thickness is the copper-zinc-tin-sulfur photovoltaic film of 1 μ m, does not have the cavity with the copper substrate interface, and crystallite dimension Scherrer formula as a result is calculated as 0.859 μ m, and conduction type is the p type, and band gap width is 1.50eV.
Embodiment 2
(1) will carry out preliminary treatment with the copper strips that the back of the body contacts electric conducting material as flexible substrates
The preliminary treatment of copper strips is oil removing, electrochemical polish and activation.Wherein degreasing fluid adopts the sodium hydroxide solution of 0.1M/L; Electrochemical polish liquid adopts the mixed liquor of the polyethylene glycol 1g/L of sulfuric acid 30%, phosphatase 11 0%, deionized water 60%, molecular weight 6000, and polishing used current density is 50mA/cm
2, solution temperature is 50 ℃; What activating solution adopted is that mass fraction is 30% sulfuric acid solution.
(2) forming the metal preformed layer through deposition zinc on the pretreated copper strips and tin
Deposition process is an evaporation, and depositional mode is a plated metal zinc behind the first plated metal tin, and the metallic zinc of deposition and the mol ratio of metallic tin are 3.
(3) the metal preformed layer is placed carry out The high temperature anneal under the sulfur-bearing atmosphere
Metal preformed layer annealing temperature is that 500 ℃, programming rate are that 50 ℃/s, temperature retention time are 60 minutes, and the annealing furnace internal gas pressure is that 0.1atm, gas flow are 100sccm, and the reactant gas of employing is the artificial gold steam.
(4) the said film of step (3) is carried out etching processing, obtain finished product
Said lithographic method is the solution etching.Etching processing employing mass percent concentration is 10% alkaline KCN solution, and the time is 15 minutes, and temperature is 40 ℃.
Obtaining thickness is the copper-zinc-tin-sulfur photovoltaic film of 1.5 μ m, does not have the cavity with the copper substrate interface, and crystallite dimension Scherrer formula as a result is calculated as 0.968 μ m, and conduction type is the p type, and band gap width is 1.49eV.
Embodiment 3
(1) will carry out preliminary treatment with the copper strips that the back of the body contacts electric conducting material as flexible substrates
The preliminary treatment of copper strips is oil removing, electrochemical polish and activation.Wherein degreasing fluid adopts the sodium hydroxide solution of 0.1M/L; Electrochemical polish liquid adopts the mixed liquor of the polyethylene glycol 5g/L of sulfuric acid 10%, phosphatase 11 0%, deionized water 80%, molecular weight 6000, and polishing used current density is 100mA/cm
2, solution temperature is 20 ℃; What activating solution adopted is that mass fraction is 50% sulfuric acid solution.
(2) forming the metal preformed layer through deposition zinc on the pretreated copper strips and tin
Deposition process can be selected the pulsed laser deposition method for use, and depositional mode is an alternating deposit metal zinc-tin, and the metallic zinc of deposition and the mol ratio of metallic tin are 5.
(3) the metal preformed layer is placed carry out The high temperature anneal under the sulfur-bearing atmosphere
Metal preformed layer annealing temperature is that 600 ℃, programming rate are that 100 ℃/s, temperature retention time are 120 minutes, and the annealing furnace internal gas pressure is that 1atm, gas flow are 1000sccm, and the reactant gas of employing is a hydrogen sulfide.
(4) the said film of step (3) is carried out etching processing, obtain finished product
Said lithographic method is the solution etching.Etching processing employing mass percent concentration is 50% alkaline KCN solution, and the time is 5 minutes, and temperature is 80 ℃.
Obtaining thickness is the copper-zinc-tin-sulfur photovoltaic film of 0.7 μ m, does not have the cavity with the copper substrate interface, and crystallite dimension Scherrer formula as a result is calculated as 0.549 μ m, and conduction type is the p type, and band gap width is 1.57eV.
Embodiment 4
(1) will carry out preliminary treatment with the copper strips that the back of the body contacts electric conducting material as flexible substrates
The preliminary treatment of copper strips is one or more in oil removing, electrochemical polish and the activation.Wherein degreasing fluid adopts the sodium hydroxide solution of 0.1M/L; Electrochemical polish liquid adopts the mixed liquor of the polyethylene glycol 3g/L of sulfuric acid 20%, phosphoric acid 20%, deionized water 60%, molecular weight 6000, and polishing used current density is 70mA/cm
2, solution temperature is 40 ℃; What activating solution adopted is that mass fraction is 25% sulfuric acid solution.
(2) forming the metal preformed layer through deposition zinc on the pretreated copper strips and tin
Deposition process is an electrodeposition process, and depositional mode is codeposition zinc and tin, and the metallic zinc of deposition and the mol ratio of metallic tin are 1.
(3) the metal preformed layer is placed carry out The high temperature anneal under the sulfur-bearing atmosphere
Metal preformed layer annealing temperature is that 300 ℃, programming rate are that 40 ℃/s, temperature retention time are 60 minutes; The annealing furnace internal gas pressure is 0.5atm, and gas flow is 300sccm; The reactant gas that adopts is a hydrogen sulfide.
(4) the said film of step (3) is carried out etching processing, obtain finished product
Said lithographic method is the solution etching.Etching processing employing mass percent concentration is 10% alkaline KCN solution, and the time is 10 minutes, and temperature is 60 ℃.
Obtaining thickness is the copper-zinc-tin-sulfur photovoltaic film of 1.2 μ m, does not have the cavity with the copper substrate interface, and crystallite dimension Scherrer formula as a result is calculated as 0.903 μ m, and conduction type is the p type, and band gap width is 1.49eV.
Claims (6)
1. copper-zinc-tin-sulfur film preparation methods comprises following steps:
The first step: copper foil base material surface preparation
With copper foil base material surface degreasing, electrochemical polish, activation;
Second step: copper foil base material surface deposition metallic zinc and tin form the metal preformed layer
Handle copper foil base material surface deposition metallic zinc and the tin obtain in the first step, said deposition adopts a kind of in magnetron sputtering method, evaporation, pulsed laser deposition method, the electrodeposition process;
The 3rd step: the metal preformed layer carries out The high temperature anneal under sulfur-bearing atmosphere
There is the copper foil base material of metallic zinc and tin to place protective atmosphere the surface deposition of the second step gained, is heated to 200～600 ℃,, zinc and tin metal preformed layer are carried out The high temperature anneal through carrier gas input sulphur source;
The 4th step: etching processing
Place alkaline KCN solution to carry out etching processing the Copper Foil after the processing of the 3rd step, adopt deionized water that film surface is cleaned, dries after the etching processing and promptly obtain the copper-zinc-tin-sulfur film material.
2. a kind of copper-zinc-tin-sulfur film preparation methods according to claim 1 is characterized in that said oil removing
Adopt the sodium hydroxide solution of 0.1M/L; Said electrochemical polish adopts the mixed liquor of sulfuric acid, phosphoric acid, deionized water and polyethylene glycol to carry out, and each constituent mass percentage of said mixed liquor is: the polyethylene glycol 1-10g/L of sulfuric acid 10-30%, phosphatase 11 0-30%, deionized water 40-80%, molecular weight 6000; Polishing used current density is 10～100mA/cm
2, solution temperature is 20 ℃～80 ℃; It is that 10%～50% sulfuric acid solution carries out that said activating solution adopts mass fraction.
3. a kind of copper-zinc-tin-sulfur film preparation methods according to claim 2; It is characterized in that the process of said plated metal zinc and tin is selected from a kind of in plated metal zinc behind plated metal tin behind the first plated metal zinc, the first plated metal tin, alternating deposit metal zinc-tin or codeposition metallic zinc and the metallic tin; In the sedimentary deposit, the mol ratio of said metallic zinc and metallic tin is 0.2～5.
4. a kind of copper-zinc-tin-sulfur film preparation methods according to claim 3; It is characterized in that said metal preformed layer carries out the The high temperature anneal technological parameter and is under sulfur-bearing atmosphere: annealing temperature is that 200～600 ℃, programming rate are that 5～100 ℃/s, temperature retention time are 1～120 minute; The annealing furnace internal gas pressure is 0.01～1atm, and gas flow is 10～1000sccm.
5. a kind of copper-zinc-tin-sulfur film preparation methods according to claim 4 is characterized in that, said sulphur source is selected from least a in sulfur vapor, artificial gold steam, the hydrogen sulfide.
6. according to any described a kind of copper-zinc-tin-sulfur film preparation methods of claim 1-4; It is characterized in that; Said etching processing technological parameter is: the mass percent concentration of alkaline KCN solution is 1%～50%, and the time is 1～20 minute, and temperature is 25 ℃～80 ℃.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985783A (en) * | 2014-04-15 | 2014-08-13 | 广东工业大学 | Method for preparing copper zinc tin sulfide thin film on flexible substrate through magnetron sputtering method |
| CN104201236A (en) * | 2014-08-11 | 2014-12-10 | 深圳清华大学研究院 | Copper-zinc-tin sulfide thin film preparation method |
| CN104591265A (en) * | 2014-12-26 | 2015-05-06 | 中南大学 | Method for preparing copper-zinc-tin-sulfur nano particles |
| CN105633202A (en) * | 2014-11-06 | 2016-06-01 | 中物院成都科学技术发展中心 | Surface treatment method of solar cell flexible substrate |
| CN105633198A (en) * | 2014-11-06 | 2016-06-01 | 中物院成都科学技术发展中心 | Electrochemical treatment method for surface etching of absorption layer of copper zinc tin sulfide thin film solar cell |
| CN107086251A (en) * | 2017-04-19 | 2017-08-22 | 河北大学 | A kind of method for etching copper-zinc-tin-sulfur film surface second phase |
| CN109830571A (en) * | 2019-02-27 | 2019-05-31 | 湘潭大学 | A kind of method of acid copper after annealing preparation copper and tin sulphur solar battery film material |
| CN109872944A (en) * | 2019-02-28 | 2019-06-11 | 西北有色金属研究院 | A kind of preparation method of indium sulphur solar battery obsorbing layer |
| CN110267189A (en) * | 2019-07-16 | 2019-09-20 | 大族激光科技产业集团股份有限公司 | A kind of processing method being bonded functional die surface |
| WO2020000599A1 (en) * | 2018-06-27 | 2020-01-02 | 北京铂阳顶荣光伏科技有限公司 | Cigs solar cell and preparation method thereof |
| CN113380924A (en) * | 2021-06-04 | 2021-09-10 | 南开大学 | Method for regulating and controlling components of absorption layer of copper-based thin film solar cell and solar cell prepared by method |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985783B (en) * | 2014-04-15 | 2016-06-22 | 广东工业大学 | Utilize the method that magnetron sputtering method prepares copper-zinc-tin-sulfur film on flexible substrates |
| CN103985783A (en) * | 2014-04-15 | 2014-08-13 | 广东工业大学 | Method for preparing copper zinc tin sulfide thin film on flexible substrate through magnetron sputtering method |
| CN104201236A (en) * | 2014-08-11 | 2014-12-10 | 深圳清华大学研究院 | Copper-zinc-tin sulfide thin film preparation method |
| CN105633202B (en) * | 2014-11-06 | 2017-05-10 | 中物院成都科学技术发展中心 | Surface treatment method of solar cell flexible substrate |
| CN105633198A (en) * | 2014-11-06 | 2016-06-01 | 中物院成都科学技术发展中心 | Electrochemical treatment method for surface etching of absorption layer of copper zinc tin sulfide thin film solar cell |
| CN105633202A (en) * | 2014-11-06 | 2016-06-01 | 中物院成都科学技术发展中心 | Surface treatment method of solar cell flexible substrate |
| CN105633198B (en) * | 2014-11-06 | 2017-05-10 | 中物院成都科学技术发展中心 | Electrochemical treatment method for surface etching of absorption layer of copper zinc tin sulfide thin film solar cell |
| CN104591265B (en) * | 2014-12-26 | 2016-12-07 | 中南大学 | The method preparing copper-zinc-tin-sulfur nano particles |
| CN104591265A (en) * | 2014-12-26 | 2015-05-06 | 中南大学 | Method for preparing copper-zinc-tin-sulfur nano particles |
| CN107086251A (en) * | 2017-04-19 | 2017-08-22 | 河北大学 | A kind of method for etching copper-zinc-tin-sulfur film surface second phase |
| CN107086251B (en) * | 2017-04-19 | 2019-02-15 | 河北大学 | A method of etching copper-zinc-tin-sulfur film surface second phase |
| WO2020000599A1 (en) * | 2018-06-27 | 2020-01-02 | 北京铂阳顶荣光伏科技有限公司 | Cigs solar cell and preparation method thereof |
| CN109830571A (en) * | 2019-02-27 | 2019-05-31 | 湘潭大学 | A kind of method of acid copper after annealing preparation copper and tin sulphur solar battery film material |
| CN109872944A (en) * | 2019-02-28 | 2019-06-11 | 西北有色金属研究院 | A kind of preparation method of indium sulphur solar battery obsorbing layer |
| CN110267189A (en) * | 2019-07-16 | 2019-09-20 | 大族激光科技产业集团股份有限公司 | A kind of processing method being bonded functional die surface |
| CN113380924A (en) * | 2021-06-04 | 2021-09-10 | 南开大学 | Method for regulating and controlling components of absorption layer of copper-based thin film solar cell and solar cell prepared by method |
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Application publication date: 20120613 |