CN101834232A - Method for preparing cadmium-zinc-sulfur membrane under acid condition based on chemical water bath method - Google Patents
Method for preparing cadmium-zinc-sulfur membrane under acid condition based on chemical water bath method Download PDFInfo
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- CN101834232A CN101834232A CN201010177408A CN201010177408A CN101834232A CN 101834232 A CN101834232 A CN 101834232A CN 201010177408 A CN201010177408 A CN 201010177408A CN 201010177408 A CN201010177408 A CN 201010177408A CN 101834232 A CN101834232 A CN 101834232A
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Abstract
The invention discloses a method for preparing a cadmium-zinc-sulfur membrane (Cd1-xZnxS) under an acid condition based on a chemical water bath method. In the method, cadmium ions is supplied by cadmium salt, zinc ions is supplied by zinc salt and sulfur ions is supplied by sodium thiosulfate or thioacetamide to a substrate, such as conductive glass and the like and urea is taken as a buffer, so that the Cd1-xZnxS membrane is deposited on the surface of the substrate. The method comprises the following steps of: weighing reaction chemical substances in a stoichiometric ratio and dissolving the substances in deionized water with a certain volume; adjusting the pH value of solution to between 3.5 and 5.5 with diluted hydrochloric acid; putting reaction solution into sealed glass ware; and slowly heating the reaction solution to a target temperature in a water bath kettle with a magnetic stirrer. The Cd1-xZnxS membrane prepared by the method is dense and uniform, and has excellent surface appearance and optical performance. When cadmium acetate is used as the cadmium salt, a high-quality Cd1-xZnxS membrane can be prepared at normal temperature.
Description
Technical field
The present invention relates to photoelectric component, specifically refer to be equipped with based on the chemical bath legal system under a kind of acid condition the method for cadmium-zinc-sulfur membrane, it is used for the window layer of solar battery material.
Background technology
Along with the fast development of global economy, non-renewable resources such as coal, oil, natural gas reduce day by day, seek contain abundant, can not be exhausted, safety, clean new forms of energy become the pressing issues that current mankind faces.Take up an area of the solar energy of ball gross energy more than 99%, have inexhaustiblely, do not have pollution characteristics, thereby become competitively one of the new forms of energy of development and utilization of various countries scientist.
Research and most widely used solar cell mainly are monocrystalline silicon, polysilicon and amorphous silicon series photovoltaic cell at present.Yet the silion cell cost of electricity-generating is 2 to 3 times of traditional cost of electricity-generating, and it is increasing with the difficulty that reduces cost further to improve the silicon materials photovoltaic device efficiency.On the contrary, though electricity conversion is lower in the hull cell, the life-span is shorter, the low temperature process technology has reduced energy consumption, and is convenient to adopt inexpensive substrate such as glass, stainless steel, relevant electronic gas and glass industry are also full-fledged, and supply and price are more stable.From market prospects, hull cell will be more more wide than traditional crystal silicon cell in the application of aspects such as BIPV, the construction of large-scale low-cost power station.CdTe and CuInGaSe
2Solar cell is typical case's representative of thin-film solar cells.And Cd
1-xZn
xThe S film is to be applied in CdTe and CuInGaSe
2Indispensable Window layer material in the solar cell, Cd
1-xZn
xThe photoelectric properties of S film have directly influenced the conversion efficiency of photovoltaic cell.
Cd
1-xZn
xThe preparation method of S film has a variety of, such as magnetron sputtering, and electro-deposition, spray pyrolysis, chemical bath or the like.Wherein immersion method have that cost is low, film-forming temperature is low, be suitable for preparing large area film, be easy to realize continuous production, pollution-free, superiority such as consumption of materials is few, be subjected to people to pay close attention to greatly, be the focus of present solar cell research.Cadmium source, sulphur source ratio and kind in the deposition process, the buffer metering, annealing temperature and atmosphere, the disposal of substrate has material impact to the film quality of final deposition gained.Traditional chemical bath prepares Cd
1-xZn
xThe method of S film is to provide S by the sulphur source under alkali condition
2-Combine and be deposited on substrate surface with metal ion.We have synthesized the Cd with excellent surface pattern and optical property under acid condition
1-xZn
xThe S film can prepare high-quality Cd at normal temperatures when cadmium salt adopts cadmium acetate
1-xZn
xThe S film.
Summary of the invention
The acid condition that the purpose of this invention is to provide a kind of simple possible prepares Cd down
1-xZn
xThe method of S film, the photovoltaic cell Window layer material that obtains having better surface topography, crystal property and optical property.
Method of the present invention is to utilize hydrogen ion and sulphur source generation chemical reaction under the acid condition to discharge sulphion, and cadmium (zinc) ion that produces with cadmium (zinc) salt hydrolysis (ionization) forms Cd at substrate surface
1-xZn
xThe S film, urea is as the buffer reaction speed in the deposition process.
Preparation Cd of the present invention
1-xZn
xThe method of S film comprises the steps:
1. the cleaning of substrate
FTO electro-conductive glass, quartz plate or silicon chip are adopted acetone successively, alcohol, ultrasonic 20 minutes of deionized water adopts nitrogen to dry up then, places 90 ℃ drying box to preserve then.
2. the configuration of reaction solution
The molar concentration of cadmium salt and zinc salt is controlled at 0.006～0.01M, and the molar concentration in sulphur source is controlled at 0.06～0.1M, and the molar concentration of buffers such as ammonium chloride is controlled at 0.01～0.05M.Take by weighing the cadmium salt of certain mass by stoichiometric proportion, zinc salt and sulphur source, and buffer are dissolved in the deionized water of certain volume, and regulate between pH value to 3.5～5.5 with the acid solution of dilution.
3. chemical bath deposition process
Reaction solution is positioned in the closed container under the normal temperature, the anchor clamps fixed vertical that substrate is made of polytetrafluoroethylene is positioned over that closed container slowly is heated to target temperature in the reaction solution in water-bath, thermometer monitoring reaction solution temperature, in the deposition process reaction solution is made agitation as appropriate, and shake substrate once in a while.
4. the cleaning of deposit film
The film of deposition gained removes the bulky grain of film surface in deionized water for ultrasonic, and nitrogen dries up and is placed in the air drying case and preserves.
The present invention has prepared Cd under acid condition
1-xZn
xS film, film thickness are between 20～1500nm, and the film particle size is between 100～300nm, and energy gap is between 2.2～3.5eV.
Advantage of the present invention is: prepared Cd
1-xZn
xThe S film is evenly fine and close, has surface of good pattern and optical property.When adopting cadmium acetate, cadmium salt can prepare high-quality Cd at normal temperatures
1-xZn
xThe S film.
Description of drawings
Fig. 1: Cd
0.95Zn
0.05The EDX figure of S film.
Fig. 2: Cd
0.95Zn
0.05The SEM figure of S film.
Fig. 3: Cd
0.95Zn
0.05The XRD figure of S film.
Fig. 4: Cd
0.95Zn
0.05The absorption spectrogram of S film.
Embodiment:
Embodiment 1:
1. cleaning substrate: with the ultrasonic cleaning 20 minutes in chloroform of FTO electro-conductive glass, used the acetone ultrasonic cleaning then 20 minutes, continued in absolute ethyl alcohol ultrasonic cleaning 20 minutes, N
2Dry up, standby.
2. reaction solution configuration: press reaction solution 0.2L and calculate, take by weighing caddy (0.019M) 0.8677 gram, zinc nitrate (0.001M) 0.0595 gram, thioacetamide (0.02M) 0.3 gram, urea (0.5M) 6 grams are dissolved in the 0.2L deionized water, regulate pH value to 4.5 with the acid solution of dilution.
3. chemical bath deposition process
Reaction solution is positioned in the closed container under the normal temperature, the anchor clamps fixed vertical that substrate is made of polytetrafluoroethylene is positioned over that closed container slowly is heated to 80 ℃ in the reaction solution in water-bath, thermometer monitoring reaction solution temperature, in the deposition process reaction solution is made agitation as appropriate, and shake substrate once in a while, react and take out sample after 90 minutes.
4. the cleaning of deposit film
The film of deposition gained removes the bulky grain of film surface in deionized water for ultrasonic, and nitrogen dries up and is placed in the air drying case and preserves.
Present embodiment obtains the Cd that thickness is about 400nm
0.95Zn
0.05The S film.
Fig. 1, Fig. 2, Fig. 3, Fig. 4 have provided Cd respectively
0.95Zn
0.05The EDX of S film, SEM, XRD absorbs spectrogram.
Embodiment 2:
1. cleaning substrate: with the ultrasonic cleaning 20 minutes in chloroform of FTO electro-conductive glass, used the acetone ultrasonic cleaning then 20 minutes, continued in absolute ethyl alcohol ultrasonic cleaning 20 minutes, N
2Dry up standby.
2. reaction solution configuration: press reaction solution 0.2L and calculate, take by weighing cadmium acetate (0.02M) 1.066 grams, thioacetamide (0.02M) 0.3 gram, urea (0.5M) 6 grams are dissolved in the 0.2L deionized water, regulate pH value to 5 with the acid solution of dilution.
3. chemical bath deposition process
Reaction solution is positioned in the closed container under the normal temperature, and the anchor clamps fixed vertical that substrate is made of polytetrafluoroethylene is positioned in the reaction solution, and closed container is placed on the magnetic stirring apparatus table top, and shakes substrate once in a while, reacts and takes out sample after 5 hours.
4. the cleaning of deposit film
The film of deposition gained removes the bulky grain of film surface in deionized water for ultrasonic, and nitrogen dries up and is placed in the air drying case and preserves.
Present embodiment obtains the CdS film that thickness is about 150nm.
Embodiment 3:
1. cleaning substrate: with the ultrasonic cleaning 20 minutes in chloroform of FTO electro-conductive glass, used the acetone ultrasonic cleaning then 20 minutes, continued in absolute ethyl alcohol ultrasonic cleaning 20 minutes, N
2Dry up standby.
2. reaction solution configuration: press reaction solution 0.2L and calculate, take by weighing zinc nitrate (0.02M) 1.19 grams, thioacetamide (0.02M) 0.3 gram, urea (0.5M) 6 grams are dissolved in the 0.2L deionized water, regulate pH value to 4 with the acid solution of dilution.
3. chemical bath deposition process
Reaction solution is positioned in the closed container under the normal temperature, the anchor clamps fixed vertical that substrate is made of polytetrafluoroethylene is positioned over that closed container slowly is heated to 80 ℃ in the reaction solution in water-bath, thermometer monitoring reaction solution temperature, in the deposition process reaction solution is made agitation as appropriate, and shake substrate once in a while, react and take out sample after 180 minutes.
4. the cleaning of deposit film
The film of deposition gained removes the bulky grain of film surface in deionized water for ultrasonic, and nitrogen dries up and is placed in the air drying case and preserves.
Present embodiment obtains the ZnS film that thickness is about 220nm.
Embodiment 4:
1. cleaning substrate: with the ultrasonic cleaning 20 minutes in chloroform of FTO electro-conductive glass, used the acetone ultrasonic cleaning then 20 minutes, continued in absolute ethyl alcohol ultrasonic cleaning 20 minutes, N
2Dry up standby.
2. reaction solution configuration: press reaction solution 0.2L and calculate, take by weighing caddy (0.02M) 0.9134 gram, thioacetamide (0.02M) 0.3 gram, urea (0.5M) 6 grams are dissolved in the 0.2L deionized water, regulate pH value to 5.5 with the acid solution of dilution.
3. chemical bath deposition process
Reaction solution is positioned in the closed container under the normal temperature, the anchor clamps fixed vertical that substrate is made of polytetrafluoroethylene is positioned over that closed container slowly is heated to 80 ℃ in the reaction solution in water-bath, thermometer monitoring reaction solution temperature, in the deposition process reaction solution is made agitation as appropriate, and shake substrate once in a while, reaction solution is stabilized in 80 ℃ of reactions 20 minutes, takes out sample.
4. the cleaning of deposit film
The film of deposition gained removes the bulky grain of film surface in deionized water for ultrasonic, and nitrogen dries up and is placed in the air drying case and preserves.
Present embodiment obtains the CdS film that thickness is about 130nm.
Claims (5)
1. be equipped with the method for cadmium-zinc-sulfur membrane under the acid condition based on the chemical bath legal system, it is characterized in that: it comprises the steps:
1). the cleaning of substrate
Substrate is successively at acetone, alcohol, and deionized water for ultrasonic 20 minutes, nitrogen dries up, and places 90 ℃ drying box to preserve then;
2). the configuration of reaction solution
Take by weighing the cadmium salt of certain mass by stoichiometric proportion, zinc salt, sulphur source and buffer are dissolved in the certain volume deionized water, and regulate pH value with the acid solution of dilution;
3). the chemical bath deposition process
Reaction solution is positioned over closed container, slowly is heated to target temperature in water-bath, and the deposition certain hour is made agitation as appropriate to reaction solution in the deposition process, and shaken substrate once in a while;
4). the cleaning of deposit film
The film of deposition gained removes the bulky grain of film surface in deionized water for ultrasonic, and nitrogen dries up standby;
2. be equipped with the method for cadmium-zinc-sulfur membrane under the acid condition according to claim 1 based on the chemical bath legal system, it is characterized in that: the cadmium salt described in the step 2 adopts caddy, cadmium sulfate, cadmium acetate, cadmium nitrate or cadmium iodide; Described zinc salt adopts zinc chloride, zinc sulfate, zinc acetate or zinc nitrate; Sodium thiosulfate or thioacetamide are adopted in described sulphur source; Described buffer adopts urea.
3. the method that is equipped with cadmium-zinc-sulfur membrane under the acid condition according to claim 1 based on the chemical bath legal system, it is characterized in that: the acid solution of the dilution of the conditioned reaction solution pH value described in the step 2 adopts watery hydrochloric acid, dilute sulfuric acid or rare nitric acid, and solution pH value scope is between 3.5～5.5.
4. the method that is equipped with cadmium-zinc-sulfur membrane under the acid condition according to claim 1 based on the chemical bath legal system, it is characterized in that: the target temperature described in the step 3 is 20～90 ℃ when cadmium salt adopts cadmium acetate, is 60～90 ℃ when cadmium salt adopts all the other materials.
5. be equipped with the method for cadmium-zinc-sulfur membrane under the acid condition according to claim 1 based on the chemical bath legal system, it is characterized in that: the substrate described in the step 1 can adopt wave carrier piece, frosted glass, electro-conductive glass, silicon chip and titanium sheet.
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|---|---|---|---|
| CN201010177408A CN101834232A (en) | 2010-05-14 | 2010-05-14 | Method for preparing cadmium-zinc-sulfur membrane under acid condition based on chemical water bath method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010177408A CN101834232A (en) | 2010-05-14 | 2010-05-14 | Method for preparing cadmium-zinc-sulfur membrane under acid condition based on chemical water bath method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275980A (en) * | 2011-06-14 | 2011-12-14 | 上海大学 | Water-bath preparation method of Cu2ZnSnS4 or Cu2CdSnS4 nanocrystalline film |
| CN102766900A (en) * | 2012-08-20 | 2012-11-07 | 北京四方继保自动化股份有限公司 | Method for preparing cadmium sulfide film by using chemical bath deposition method |
| CN103320774A (en) * | 2013-07-15 | 2013-09-25 | 北京四方继保自动化股份有限公司 | Chemical bath deposition method of cadmium sulfide film and device thereof |
-
2010
- 2010-05-14 CN CN201010177408A patent/CN101834232A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275980A (en) * | 2011-06-14 | 2011-12-14 | 上海大学 | Water-bath preparation method of Cu2ZnSnS4 or Cu2CdSnS4 nanocrystalline film |
| CN102275980B (en) * | 2011-06-14 | 2013-01-09 | 上海大学 | Water-bath preparation method of Cu2ZnSnS4 or Cu2CdSnS4 nanocrystalline film |
| CN102766900A (en) * | 2012-08-20 | 2012-11-07 | 北京四方继保自动化股份有限公司 | Method for preparing cadmium sulfide film by using chemical bath deposition method |
| CN102766900B (en) * | 2012-08-20 | 2016-03-30 | 北京四方继保自动化股份有限公司 | A kind of chemical bath legal system that adopts is for the method for cadmium sulphide membrane |
| CN103320774A (en) * | 2013-07-15 | 2013-09-25 | 北京四方继保自动化股份有限公司 | Chemical bath deposition method of cadmium sulfide film and device thereof |
| CN103320774B (en) * | 2013-07-15 | 2015-09-02 | 北京四方继保自动化股份有限公司 | A kind of method of depositing cadmium sulfide film by chemical water bath and device |
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Open date: 20100915 |