CN100580961C - Method for preparing CuInS2 thin film - Google Patents

Method for preparing CuInS2 thin film Download PDF

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CN100580961C
CN100580961C CN200810121188A CN200810121188A CN100580961C CN 100580961 C CN100580961 C CN 100580961C CN 200810121188 A CN200810121188 A CN 200810121188A CN 200810121188 A CN200810121188 A CN 200810121188A CN 100580961 C CN100580961 C CN 100580961C
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film
chemical plating
5mol
cuins
preparation
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CN101378094A (en
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杨德仁
崔方明
汪雷
盛夏
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Zhejiang University ZJU
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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 discloses a method for preparing a CulnS<2> film and the adopted method is chemical plating. The method for preparing the CulnS<2> film comprises the following steps: first, a Cu film is deposited on the substrates of active metal of Mo, Ti, Fe or Pd which are washed up by adopting the method of chemical plating; and then, an In film is deposited by adopting the method of chemical plating so as to obtain a Cu-In precursor; next, under sulfur-containing argon or nitrogen protective atmosphere, the prepared Cu-In precursor is processed for 30-180 minutes at the temperature of 300-700 DEG C, or the prepared Cu-In precursor is processed for 10-50 minutes at the temperature of 50-160 DEG C and then processed for 30-180 minutes at the temperature of 300-700 DEG C, and finally the CulnS<2> film is obtained. The preparation technique is simple. The adoption of the method does not need vacuum equipment, therefore, the cost is much lower than that of sputtering method and coevaporation method; the usage of electricity is not needed, therefore the cost is even lower than that of electrofacing electroplating method; and the prepared film surface has even compactness and few pores, thus completely meeting the demands for being served as the absorbing layer of solar batteries.

Description

A kind of preparation CuInS 2The method of film
Technical field
The present invention relates to be used for the CuInS of solar cell absorbed layer 2The preparation method of film.
Background technology
The mankind enter 21 century, and the demand of the energy is constantly increased.The current energy that supports development of world economy mainly is non-renewable fossil energy, i.e. coal, oil and natural gas.Estimate that according to brainstrust in world's conventional energy resource, present explored oil or gas reserves will though coal resources are abundanter relatively, face the crisis of shortage equally approximately having exploited in the 50-100 in future.In addition, these energy in use pollute environment easily, and cause acid rain thus, serious ecological problem such as depletion of the ozone layer, greenhouse effect.
Along with the development of human economy, energy problem has become the matter of utmost importance that countries in the world face.Therefore, the research and development of the regenerative resource of cleaning is the emphasis that international academic community is paid close attention to.Solar energy is a kind of inexhaustible pollution-free clear energy sources.As solar energy environmental protection, regenerative resource, since the 1950's just research, its application is extensive gradually.The oil crisis of the seventies allows the application of solar cell put on the research schedule.At present, solar cell mainly contains: single crystalline Si, polysilicon, amorphous Si, GaAs, CdS, CdTe, CuInS 2Etc. type.
CuInS 2Thin-film solar cells has lot of advantages.At first, CuInS 2Absorption coefficient is very big, and energy gap is near the best energy gap (1.45eV) of solar cell.Secondly, it is a direct gap semiconductor, the luminous efficiency height.The 3rd, CuInS 2Can make very thin film, save cost.And CuInS 2Can present the semiconductor property of p type or n type owing to different defect types, this makes it be easy to make homojunction.And, CuInS 2The theoretical transformation rate of homojunction solar cell reaches as high as 32%, and this numerical value is the highest in similar photovoltaic device, further, and CuInS 2Battery has good anti-radiation performance.Based on above advantage, CuInS 2It is present rising a kind of solar cell semiconductor material.
Prepare CuInS at present 2The method of film mainly contains sputtering method, coevaporation method, galvanoplastic, spraying process, chemical bath method etc.The film quality of sputtering method and coevaporation method preparation is better, but because present apparatus expensive and the vacuum technology that adopts, thereby make CuInS 2Hull cell does not have too big advantage yet on cost; The equipment that galvanoplastic, spraying process and chemical bath method adopt is simple, and cost is lower, but the film quality of preparation is also very low, can't prepare high-quality battery.So, preparation quality CuInS higher, with low cost how 2Film becomes a technical barrier of solar energy circle.
Summary of the invention
The objective of the invention is in order to obtain quality CuInS preferably 2Film reduces CuInS simultaneously 2The thin film solar cell production cost, and a kind of preparation CuInS is provided 2The method of film.
The present invention prepares CuInS 2The method of film, employing be the method for chemical plating, concrete steps are as follows:
1) adopt chemical plating method on the Mo that cleans up, Ti, Fe or Pd reactive metal substrate, to deposit the Cu film, the solution formula of Electroless Cu Plating is: mantoquita 0.001-5mol/l, complexing agent 0.001-5mol/l, reducing agent 0.001-5mol/l, and the pH value of regulator solution is to alkalescence;
2) adopt chemical plating method deposition In film on the film of step 1) preparation, obtain the Cu-In presoma, the solution formula of chemical plating In is: In salt 0.001-5mol/l; Complexing agent 0.001-5mol/l; Reducing agent 0.001-5mol/l, and the pH value of regulator solution is to alkalescence;
3) with the Cu-In presoma for preparing, under protective atmospheres such as argon gas that contains sulphur or nitrogen,, perhaps handled 10-50 minute at 50-160 ℃ earlier in 300-700 ℃ of processing 30-180 minute, handled 30-180 minute at 300-700 ℃ again, obtain CuInS 2Film.
The used complexing agent of above-mentioned electroless copper and chemical plating In is one or more in EDTA, disodium ethylene diamine tetraacetate, sodium potassium tartrate tetrahydrate, natrium citricum, triethanolamine, ammonium salt, glycerine and the malic acid.
Above-mentioned electroless copper and the used reducing agent of chemical plating In are formaldehyde, sodium dihydric hypophosphite or sodium borohydride.
Said mantoquita can be copper chloride, copper nitrate or copper sulphate among the present invention.Said In salt can be inidum chloride, indium nitrate or indium sulfate.
CuInS 2The thickness of film was determined by the electroless deposition time.
Beneficial effect of the present invention is:
The present invention proposes to adopt chemical plating (also crying electroless plating) preparation CuInS first 2Film, this method deposits Cu at first respectively on Mo, Ti, Fe or Pd reactive metal substrate, the In film obtains the Cu-In presoma, and heat treatment obtains CuInS then 2Film, preparation technology is simple.Adopt this method needing no vacuum equipment, cost is much cheaper than sputtering method and coevaporation method; Also need not electricity consumption, cost even also lower than galvanoplastic; And the film surface of preparation is evenly fine and close, and hole seldom satisfies the requirement as the absorbed layer of solar cell fully.
Description of drawings
Fig. 1 is CuInS 2The XRD figure of film;
Fig. 2 is CuInS 2The SEM figure of film;
Fig. 3 is CuInS 2The energy spectrogram of film.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
At first adopt the method for chemical plating, deposition Cu film is 15 minutes on the Mo substrate that cleans up, and the solution formula of electroless copper is as follows: copper sulphate 0.02mol/l; Natrium citricum 0.02mol/l; Formaldehyde 0.1mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 11.
Adopt the method for chemical plating, on the substrate that deposits the Cu film, deposition In film, the time is 5 minutes, obtains the Cu-In presoma.The prescription of chemical plating In solution is as follows: inidum chloride 0.01mol/l; EDTA0.01mol/l; Sodium borohydride 0.05mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 11.
With the Cu-In presoma for preparing, under the nitrogen atmosphere protection that contains sulphur, earlier 150 ℃ of heat treatments 20 minutes.500 ℃ of heat treatments 60 minutes, obtain the CuInS of thickness 1.27 μ m then 2Film.The XRD figure of film, as shown in Figure 1, SEM figure as shown in Figure 2, Zhi Bei thin film crystallization degree height as seen from the figure, surperficial even compact is more than the average grain size 1 μ m, measure (see figure 3) through power spectrum, Cu, In, S atomic ratio are 1.03: 1: 2.02, satisfy the requirement as the absorbed layer of solar cell fully.
Embodiment 2
At first adopt the method for chemical plating, deposition Cu film is 10 minutes on the Mo substrate that cleans up,, the solution formula of electroless copper is as follows: copper chloride 0.02mol/l; EDTA 0.02mol/l; Sodium dihydric hypophosphite 0.1mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 11.
Adopt the method for chemical plating then, on the substrate that deposits the Cu film, deposition In film, the time is 5 minutes, obtains the Cu-In presoma, the solution formula of chemical plating In is as follows: indium sulfate 0.01mol/l; Natrium citricum 0.01mol/l; Sodium dihydric hypophosphite 0.05mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 12.
The Cu-In presoma for preparing under the argon gas atmosphere protection that contains sulphur, 450 ℃ of heat treatments of temperature 90 minutes, is obtained the CuInS of thickness 1.25 μ m 2Film.Observe through XRD test and SEM, find the thin film crystallization degree height of preparation, the film surface even compact, more than the average grain size 1 μ m, measure Cu, In through power spectrum, the S atomic ratio is 1.01: 1: 2.06, satisfies the requirement as the absorbed layer of solar cell fully.
Embodiment 3
At first adopt the method for chemical plating, deposition Cu film is 20 minutes on the Ti substrate that cleans up, and the solution formula of electroless copper is as follows: copper sulphate 0.001mol/l; EDTA, glycerine, each 0.001mol/l of malic acid; Formaldehyde 0.001mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 11.
Adopt the method for chemical plating, on the substrate that deposits the Cu film, deposition In film, the time is 15 minutes, obtains the Cu-In presoma.The prescription of chemical plating In solution is as follows: indium nitrate 0.001mol/l; Disodium ethylene diamine tetraacetate, sodium potassium tartrate tetrahydrate, each 0.001mol/l of natrium citricum; Sodium borohydride 0.001mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 11.
With the Cu-In presoma for preparing, under the nitrogen atmosphere protection that contains sulphur, earlier 50 ℃ of heat treatments 30 minutes.300 ℃ of heat treatments 90 minutes, obtain the CuInS of thickness 1.01 μ m then 2Film.Observe through XRD test and SEM, find the thin film crystallization degree height of preparation, the film surface even compact, more than the average grain size 1 μ m, measure Cu, In through power spectrum, the S atomic ratio is 1.05: 1: 2.08, satisfies the requirement as the absorbed layer of solar cell fully.
Embodiment 4
At first adopt the method for chemical plating, deposition Cu film is 2 minutes on the steel substrate that cleans up, and the solution formula of electroless copper is as follows: copper sulphate 5mol/l; Disodium ethylene diamine tetraacetate 5mol/l; Formaldehyde 5mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 11.
Adopt the method for chemical plating, on the substrate that deposits the Cu film, deposition In film, the time is 4 minutes, obtains the Cu-In presoma.The prescription of chemical plating In solution is as follows: inidum chloride 5mol/l; Disodium ethylene diamine tetraacetate 5mol/l; Sodium borohydride 5mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 10.
With the Cu-In presoma for preparing, under the argon gas atmosphere protection that contains sulphur, earlier 160 ℃ of heat treatments 15 minutes.700 ℃ of heat treatments 60 minutes, obtain the CuInS of thickness 2.48 μ m then 2Film.Observe through XRD test and SEM, find the thin film crystallization degree height of preparation, the film surface even compact, more than the average grain size 1 μ m, measure Cu, In through power spectrum, the S atomic ratio is 1.07: 1: 2.02, satisfies the requirement as the absorbed layer of solar cell fully.
Embodiment 5
At first adopt the method for chemical plating, deposition Cu film is 10 minutes on the Pd substrate that cleans up, and the solution formula of electroless copper is as follows: copper nitrate 0.001mol/l; Each 0.001mol/l of triethanolamine and ammonium chloride; Formaldehyde 0.001mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 11.
Adopt the method for chemical plating, on the substrate that deposits the Cu film, deposition In film, the time is 4 minutes, obtains the Cu-In presoma.The prescription of chemical plating In solution is as follows: inidum chloride 5mol/l; Disodium ethylene diamine tetraacetate 5mol/l; Sodium borohydride 5mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 10.
With the Cu-In presoma for preparing, under the nitrogen atmosphere protection that contains sulphur,, obtain the CuInS of thickness 2.34 μ m 300 ℃ of heat treatments 180 minutes 2Film.Observe through XRD test and SEM, find the thin film crystallization degree height of preparation, the film surface even compact, more than the average grain size 1 μ m, measure Cu, In through power spectrum, the S atomic ratio is 1.02: 1: 2.06, satisfies the requirement as the absorbed layer of solar cell fully.
Embodiment 6
At first adopt the method for chemical plating, deposition Cu film is 2 minutes on the Mo substrate that cleans up, and the solution formula of electroless copper is as follows: copper sulphate 5mol/l; Disodium ethylene diamine tetraacetate 5mol/l; Formaldehyde 5mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 11.
Adopt the method for chemical plating, on the substrate that deposits the Cu film, deposition In film, the time is 15 minutes, obtains the Cu-In presoma.The prescription of chemical plating In solution is as follows: indium nitrate 0.001mol/l; Each 0.001mol/l of triethanolamine and ammonium chloride; Sodium borohydride 0.001mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 10.
With the Cu-In presoma for preparing, under the argon gas atmosphere protection that contains sulphur, earlier 120 ℃ of heat treatments 10 minutes.500 ℃ of heat treatments 60 minutes, obtain the CuInS of thickness 2.36 μ m then 2Film.Observe through XRD test and SEM, find the thin film crystallization degree height of preparation, the film surface even compact, more than the average grain size 1 μ m, measure Cu, In through power spectrum, the S atomic ratio is 1.02: 1: 2.05, satisfies the requirement as the absorbed layer of solar cell fully.
Embodiment 7
At first adopt the method for chemical plating, deposition Cu film is 8 minutes on the Ti substrate that cleans up, and the solution formula of electroless copper is as follows: copper sulphate 0.05mol/l; Each 0.025mol/l of disodium ethylene diamine tetraacetate and natrium citricum; Formaldehyde 0.05mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 11.
Adopt the method for chemical plating, on the substrate that deposits the Cu film, deposition In film, the time is 7 minutes, obtains the Cu-In presoma.The prescription of chemical plating In solution is as follows: indium sulfate 0.04mol/l; Each 0.02mol/l of triethanolamine and ammonium chloride; Sodium borohydride 0.04mol/l adopts alkaline reagent that the pH value of solution value is adjusted to 10.
With the Cu-In presoma for preparing, under the nitrogen atmosphere protection that contains sulphur,, obtain the CuInS of thickness 1.78 μ m 700 ℃ of heat treatments 30 minutes 2Film.Observe through XRD test and SEM, find the thin film crystallization degree height of preparation, the film surface even compact, more than the average grain size 1 μ m, measure Cu, In through power spectrum, the S atomic ratio is 1.07: 1: 2.08, satisfies the requirement as the absorbed layer of solar cell fully.

Claims (5)

1. one kind prepares CuInS 2The method of film, its step is as follows:
1) adopt chemical plating method on the Mo that cleans up, Ti, Fe or Pd reactive metal substrate, to deposit the Cu film, the solution formula of Electroless Cu Plating is: mantoquita 0.001-5mol/l, complexing agent 0.001-5mol/l, reducing agent 0.001-5mol/l, and the pH value of regulator solution is to alkalescence;
2) adopt chemical plating method deposition In film on the film of step 1) preparation, obtain the Cu-In presoma, the solution formula of chemical plating In is: In salt 0.001-5mol/l; Complexing agent 0.001-5mol/l; Reducing agent 0.001-5mol/l, and the pH value of regulator solution is to alkalescence;
3) with the Cu-In presoma for preparing, under argon gas that contains sulphur or nitrogen protection atmosphere,, perhaps handled 10-50 minute at 50-160 ℃ earlier in 300-700 ℃ of processing 30-180 minute, handled 30-180 minute at 300-700 ℃ again, obtain CuInS 2Film.
2. preparation CuInS according to claim 1 2The method of film is characterized in that the used complexing agent of electroless copper and chemical plating In is one or more in EDTA, disodium ethylene diamine tetraacetate, sodium potassium tartrate tetrahydrate, natrium citricum, triethanolamine, ammonium salt, glycerine and the malic acid.
3. preparation CuInS according to claim 1 2The method of film is characterized in that electroless copper and the used reducing agent of chemical plating In are formaldehyde, sodium dihydric hypophosphite or sodium borohydride.
4. preparation CuInS according to claim 1 2The method of film is characterized in that said mantoquita is copper chloride, copper nitrate or copper sulphate.
5. preparation CuInS according to claim 1 2The method of film is characterized in that said In salt is inidum chloride, indium nitrate or indium sulfate.
CN200810121188A 2008-10-10 2008-10-10 Method for preparing CuInS2 thin film Expired - Fee Related CN100580961C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101982567A (en) * 2010-09-10 2011-03-02 上海太阳能电池研究与发展中心 Preparation method of copper indium selenium sulphur (CuInSe2-xSx) film for solar battery
CN102336928B (en) * 2011-07-08 2012-11-28 北京理工大学 Flexible, environmentally-friendly, transparent and adjustable-illuminant-color film material and preparation method thereof
CN108069393A (en) * 2016-11-14 2018-05-25 中国科学院上海硅酸盐研究所 A kind of hydrogenation Copper thin film and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Characterization of CuInS2 thin films prepared bysulfurizationof Cu-In precursor. YAN You-hua, et al.Transactions of Nonferrous Metals Society of China,No.5. 2008
Characterization of CuInS2 thin films prepared bysulfurizationof Cu-In precursor. YAN You-hua, et al.Transactions of Nonferrous Metals Society of China,No.5. 2008 *
化学镀技术. 伍学高,李铭华,黄渭成，40-45，四川科学技术出版社. 1985
化学镀技术. 伍学高,李铭华,黄渭成，40-45，四川科学技术出版社. 1985 *

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