CN103232060A - Preparation method of CdS film - Google Patents
Preparation method of CdS film Download PDFInfo
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- CN103232060A CN103232060A CN2013101638301A CN201310163830A CN103232060A CN 103232060 A CN103232060 A CN 103232060A CN 2013101638301 A CN2013101638301 A CN 2013101638301A CN 201310163830 A CN201310163830 A CN 201310163830A CN 103232060 A CN103232060 A CN 103232060A
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- glass substrate
- cadmium
- ito glass
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000011521 glass Substances 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 21
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 12
- 150000001661 cadmium Chemical class 0.000 claims description 9
- 238000006713 insertion reaction Methods 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000000427 thin-film deposition Methods 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 5
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims description 4
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229940075417 cadmium iodide Drugs 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 abstract 1
- 235000019345 sodium thiosulphate Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The invention relates to a preparation method of a CdS film. The preparation method comprises the following steps of: (1) cleaning an indium tin oxide (ITO) glass substrate; (2) preparing reaction liquid; (3) placing the reaction liquid into a reaction tank, vertically inserting the cleaned ITO glass substrate into the reaction liquid and fixing, stirring and heating the reaction liquid, vibrating the reaction tank or knocking the outer wall of the reaction tank, adding thiourea or sodium thiosulfate, stirring the reaction liquid, continuously vibrating the reaction tank or knocking the outer wall of the reaction tank, and depositing a film; and (4) after the film is deposited, taking out the ITO glass substrate, placing the ITO glass substrate into deionized water, performing ultrasonic cleaning, and drying to obtain the CdS film. The surface appearance of the CdS film produced by using the preparation method is improved and the uniformity is obviously improved, and a large area of CdS films growing uniformly and densely can be obtained.
Description
Affiliated field
The present invention relates to technical field of solar batteries, be specifically related to a kind of preparation method of CdS film.
Background technology
The CdS film is typical group material, and its energy gap is about 2.42eV, therefore has very excellent physical properties.The CdS film is mainly used in the solar cell field.The CdS film is as the Window layer of these batteries, and its preparation quality directly has influence on the photoelectric transformation efficiency of final battery.
At present, the preparation method of Chang Yong CdS film is CBD method (chemical bath method).Way of the prior art is: at first reaction solution is placed reactive tank, and also fixing in the vertical insertion reaction liquid of substrate then, use the stirring rod stirred solution, in substrate surface deposition one deck CdS film, supersound process then.
The CBD method has simple, with low cost, the easy growth phase of equipment to the advantages such as CdS film of even compact.Therefore become the first-selection of scale operation CdS film.
But, when existing C dS membrane process prepares large-area CdS film, in the process that in the solution that contains the ammoniacal liquor existence, stirs with stirring rod, stir and very easily in the aqueous solution, produce bubble, and be attached on the ITO conductive glass, in the complex compound stage that generates cadmium, the position of adhering to bubble can not have the complex compound deposition, produce hole in the time of will causing subsequent deposition CdS, these holes can make the degradation of CdS film.
Summary of the invention
The object of the present invention is to provide large-area preparation go out evenly, fine and close, and can reduce the preparation method of CdS film of the generation of hole.
Concrete technical scheme of the present invention is as follows:
A kind of preparation method of CdS film comprises the steps:
(1) cleans the ito glass substrate;
(2) configuration reaction solution;
(3) reaction solution is placed reactive tank, also fixing in the vertical insertion reaction liquid of ito glass substrate after will cleaning then, stirring, temperature reaction liquid also vibrate reactive tank or beat the reactive tank outer wall, add thiocarbamide or Sulfothiorine then, stirring reaction liquid also continues the vibration reactive tank or beats reactive tank outer wall, deposit film;
(4) treat that thin film deposition is good after, the ito glass substrate taken out place deionized water to carry out ultrasonic cleaning, dry then, obtain the CdS film.
The cleaning step of ito glass substrate is as follows in the step (1): used earlier acetone, ethanol, each ultrasonic cleaning ito glass substrate of deionized water successively 15-20 minute; Use HCl and H then
2O
2Mixing solutions ultrasonic cleaning 10-15min; Used the deionized water ultrasonic cleaning again 10-20 minute.
The massfraction of HCl is 7-10% in the described mixing solutions, H
2O
2Massfraction be 4-5%.
The concrete steps of configuration reaction solution are as follows in the step (2): the solubility cadmium salt is dissolved in is configured to the cadmium salt soln that amount concentration is 0.001 ~ 0.02mol/L in the deionized water earlier, add then and the ammonium salt of cadmium salt with acid group, the amount concentration of ammonium salt is 0.01 ~ 0.1 mol/L; Add NH again
3H
2O regulator solution pH value obtains reaction solution to 10-11.
Described solubility cadmium salt is selected from a kind of in cadmium acetate, Cadmium chloride fine powder, cadmium iodide, cadmium nitrate, the Cadmium Sulphate.
Be warming up to 80 ℃-90 ℃ in the step (3), vibrate reactive tank or beat the reactive tank outer wall, add thiocarbamide or Sulfothiorine then, the amount concentration of the thiocarbamide of adding or Sulfothiorine is 0.001-0.01 mol/L.
Vibrate reactive tank or beat reactive tank outer wall 30-60s every 3min in the step (3).
Oven dry in the step (4) is to toast 5-10min under halogen tungsten lamp.
Reactive tank is placed on the magnetic stirring apparatus in the step (3).
When the present invention prepares the CdS film to cadmium salt, optimize with the ammonium salt of acid group, the addition sequence of thiocarbamide; In temperature-rise period, earlier at the complex compound of ito glass substrate deposition cadmium, when reaching a certain particular value, temperature adds sulphur source (thiocarbamide or Sulfothiorine) again.Such purpose is in order effectively to promote heterogeneous nucleation, to avoid occurring in the phenomenon of temperature rise period homogeneous nucleation.The present invention is when the complex compound of ito glass substrate deposition cadmium, because NH
3H
2The existence of O, constantly stirring reaction liquid can make and very easily adhere to bubble on the ito glass substrate.If these bubbles are not in time driven away, the complex compound of cadmium is deposited on will be inhomogeneous on the ITO substrate, and then influence homogeneity and the compactness of back CdS film preparation.The present invention vibrates reactive tank or beats the reactive tank outer wall in this process, in time drive away the bubble that is attached on the ITO.After adding thiocarbamide or Sulfothiorine, also will vibrate reactive tank or beat the reactive tank outer wall, its purpose has two, and the one, bubble is driven away, deposit uniform CdS film; The 2nd, the macrobead CdS cluster that homogeneous nucleation is formed diminishes by the method that shakes.Facts have proved that the CdS film surface appearance that adopts the method for the invention to generate is improved, and also obviously raising of homogeneity, even, the fine and close CdS film of large-area growth can be obtained.
Description of drawings
Fig. 1 is the microscope enlarged view of 500 times of the CdS film surfaces of embodiment 1 preparation;
Fig. 2 is the microscope enlarged view of 1000 times of the CdS film surfaces of embodiment 1 preparation;
Fig. 3 is the microscope enlarged view of 500 times of the CdS film surfaces of embodiment 2 preparation;
Fig. 4 is the microscope enlarged view of 1000 times of the CdS film surfaces of embodiment 2 preparation;
Fig. 5 is the microscope enlarged view of 500 times of the CdS film surfaces of embodiment 3 preparation;
Fig. 6 is the microscope enlarged view of 1000 times of the CdS film surfaces of embodiment 3 preparation;
Fig. 7 is the microscope enlarged view of 1000 times of the CdS film surfaces of Comparative Examples 1 preparation.
Embodiment
Among the present invention, pick up counting when adding thiocarbamide or Sulfothiorine, by can the grow CdS film of different thickness of control depositing time, we generally control depositing time about 20-30min, and the thickness of the CdS film that obtains is between 100-130nm.
Embodiment 1
(1) earlier the ito glass substrate is used successively acetone, ethanol, each ultrasonic cleaning of deionized water 20 minutes, removed the dirt on surface; Again with containing HCl and H
2O
2Mixing solutions ultrasonic cleaning 10 minutes, in the mixing solutions massfraction of HCl be 10%, H
2O
2Massfraction be 5%; Used deionized water more ultrasonic 20 minutes.
(2) configuration reaction soln: earlier cadmium acetate is dissolved in the deionized water, the amount concentration of cadmium acetate is 0.02mol/L, adds CH then
3COONH
4, CH
3COONH
4Amount concentration in solution is 0.04mol/L; Add NH again
3H
2O regulator solution pH to 10.5 obtains reaction solution.
(3) reaction solution is placed reactive tank, also fixing in the vertical insertion reaction liquid of the ito glass substrate after will cleaning then, reactive tank is placed on the magnetic stirring apparatus, open switch, beat reactive tank outer wall 30s every 3min in heat temperature raising, the temperature-rise period then; Be warming up to 80 ℃, add thiocarbamide then, the amount concentration of the thiocarbamide of adding is 0.004 mol/L, and stirring reaction liquid also continues to beat reactive tank outer wall 30s every 3min, and deposit film adds fashionable picking up counting with thiocarbamide, and depositing time is 20min.
(4) treat that thin film deposition is good after, the ito glass substrate taken out places deionized water ultrasonic cleaning 3 times repeatedly, under halogen tungsten lamp, toast 10min then, obtain the CdS film.
Embodiment 2
(1) earlier the ito glass substrate is used successively acetone, ethanol, each ultrasonic cleaning of deionized water 15 minutes, removed the dirt on surface; Again with containing HCl and H
2O
2Mixing solutions ultrasonic cleaning 10 minutes, in the mixing solutions massfraction of HCl be 7%, H
2O
2Massfraction be 4%; Used deionized water more ultrasonic 15 minutes.
(2) configuration reaction soln: earlier with CdCl
2Be dissolved in the deionized water, wherein CdCl in the deionized water
2Amount concentration is 0.008mol/L, adds NH then
4Cl, NH
4The amount concentration of Cl in solution is 0.01mol/L; Add NH again
3H
2O regulator solution pH to 10-11 obtains reaction solution.
(3) reaction solution is placed reactive tank, also fixing in the vertical insertion reaction liquid of the ito glass substrate after will cleaning then, reactive tank is placed on the magnetic stirring apparatus, open switch, beat reactive tank outer wall 45s every 3min in heat temperature raising, the temperature-rise period then; Be warming up to 90 ℃, add Sulfothiorine then, the amount concentration of the Sulfothiorine of adding is 0.01mol/L, stirring reaction liquid also continues to beat reactive tank outer wall 45s every 3min, deposit film adds fashionable picking up counting with Sulfothiorine, and depositing time is 20min.
(4) treat that thin film deposition is good after, the ito glass substrate taken out places deionized water ultrasonic cleaning 3 times repeatedly, under halogen tungsten lamp, toast 5min then, obtain the CdS film.
Embodiment 3
(1) earlier the ito glass substrate is used successively acetone, ethanol, each ultrasonic cleaning of deionized water 18 minutes, removed the dirt on surface; Again with containing HCl and H
2O
2Mixing solutions ultrasonic cleaning 10 minutes, in the mixing solutions massfraction of HCl be 9%, H
2O
2Massfraction be 5%; Used deionized water more ultrasonic 10 minutes.
(2) configuration reaction soln: earlier Cadmium Sulphate is dissolved in the deionized water, wherein the amount concentration of Cadmium Sulphate is 0.008mol/L in the deionized water, adds (NH then
4)
2SO
4, (NH
4)
2SO
4Amount concentration in solution is 0.01mol/L; Add NH again
3H
2O regulator solution pH to 10.5 obtains reaction solution.
(3) reaction solution is placed reactive tank, also fixing in the vertical insertion reaction liquid of the ito glass substrate after will cleaning then, reactive tank is placed on the magnetic stirring apparatus, open switch, beat reactive tank outer wall 60s every 3min in heat temperature raising, the temperature-rise period then; Be warming up to 90 ℃, add thiocarbamide then, the amount concentration of the thiocarbamide of adding is 0.001 mol/L, and stirring reaction liquid also continues to beat reactive tank outer wall 60s every 3min, and deposit film adds fashionable picking up counting with thiocarbamide, and depositing time is 20min.
(4) treat that thin film deposition is good after, the ito glass substrate taken out places deionized water ultrasonic cleaning 3 times repeatedly, under halogen tungsten lamp, toast 8min then, obtain the CdS film.
Comparative Examples 1
(1) earlier the ito glass substrate is used successively acetone, ethanol, each ultrasonic cleaning of deionized water 20 minutes, removed the dirt on surface; Again with containing HCl and H
2O
2Mixing solutions ultrasonic cleaning 10 minutes, in the mixing solutions massfraction of HCl be 10%, H
2O
2Massfraction be 5%; Used deionized water more ultrasonic 20 minutes.
(2) configuration reaction soln: earlier cadmium acetate is dissolved in the deionized water, wherein the amount concentration of cadmium ion is 0.02mol/L in the deionized water, adds CH then
3COONH
4, CH
3COONH
4Amount concentration in solution is 0.04mol/L; Add NH again
3H
2O regulator solution pH to 10-11 obtains reaction solution.
(3) reaction solution is placed reactive tank, also fixing in the vertical insertion reaction liquid of ito glass substrate after will cleaning then, reactive tank is placed on the magnetic stirring apparatus, open switch, be warming up to 80 ℃, add thiocarbamide then, the amount concentration of the thiocarbamide of adding is 0.004 mol/L, stirring reaction liquid, deposit film.
(4) treat that thin film deposition is good after, the ito glass substrate taken out places deionized water ultrasonic cleaning 3 times repeatedly, under halogen tungsten lamp, toast 10min then, obtain the CdS film.
The size of the CdS film that the embodiment of the invention 1 to embodiment 3 prepares is 2.5cm*2.5cm; The size of the CdS film that Comparative Examples 1 prepares is 2cm*2cm.The microscope enlarged view of each CdS film surface is seen Fig. 1 to Fig. 7.
Claims (9)
1. the preparation method of a CdS film is characterized in that comprising the steps:
(1) cleans the ito glass substrate;
(2) configuration reaction solution;
(3) reaction solution is placed reactive tank, also fixing in the vertical insertion reaction liquid of ito glass substrate after will cleaning then, stirring, temperature reaction liquid also vibrate reactive tank or beat the reactive tank outer wall, add thiocarbamide or Sulfothiorine then, stirring reaction liquid also continues the vibration reactive tank or beats reactive tank outer wall, deposit film;
(4) treat that thin film deposition is good after, the ito glass substrate taken out place deionized water to carry out ultrasonic cleaning, dry then, obtain the CdS film.
2. preparation method according to claim 1 is characterized in that the cleaning step of ito glass substrate in the step (1) is as follows: used earlier acetone, ethanol, each ultrasonic cleaning ito glass substrate of deionized water successively 15-20 minute; Use HCl and H then
2O
2Mixing solutions ultrasonic cleaning 10-15min; Used the deionized water ultrasonic cleaning again 10-20 minute.
3. preparation method according to claim 2, the massfraction that it is characterized in that HCl in the described mixing solutions is 7-10%, H
2O
2Massfraction be 4-5%.
4. preparation method according to claim 1, the concrete steps that it is characterized in that configuration reaction solution in the step (2) are as follows: the solubility cadmium salt is dissolved in is configured to the cadmium salt soln that amount concentration is 0.001 ~ 0.02mol/L in the deionized water earlier, add then and the ammonium salt of cadmium salt with acid group, the amount concentration of ammonium salt is 0.01 ~ 0.1 mol/L; Add NH again
3H
2O regulator solution pH value obtains reaction solution to 10-11.
5. preparation method according to claim 4 is characterized in that described solubility cadmium salt is selected from a kind of in cadmium acetate, Cadmium chloride fine powder, cadmium iodide, cadmium nitrate, the Cadmium Sulphate.
6. preparation method according to claim 1, it is characterized in that being warming up in the step (3) 80 ℃-90 ℃, vibrate reactive tank or beat the reactive tank outer wall, add thiocarbamide or Sulfothiorine then, the amount concentration of the thiocarbamide of adding or Sulfothiorine is 0.001-0.01 mol/L.
7. according to the described preparation method of above-mentioned arbitrary claim, it is characterized in that vibrating reactive tank or beaing reactive tank outer wall 30-60s every 3min in the step (3).
8. preparation method according to claim 1 is characterized in that the oven dry in the step (4) is to toast 5-10min under halogen tungsten lamp.
9. preparation method according to claim 1 is characterized in that reactive tank is placed on the magnetic stirring apparatus in the step (3).
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103922612A (en) * | 2014-04-23 | 2014-07-16 | 桂林理工大学 | Method for preparing CdSe film by adopting cold-heat alternating chemical bath method |
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CN1608742A (en) * | 2003-10-21 | 2005-04-27 | 财团法人工业技术研究院 | Microfluid film forming apparatus and method |
CN102351429A (en) * | 2011-07-06 | 2012-02-15 | 南京大学 | Method for preparing wide bandgap nanometer cadmium sulfide thin film |
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2013
- 2013-05-03 CN CN2013101638301A patent/CN103232060A/en active Pending
Patent Citations (2)
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CN1608742A (en) * | 2003-10-21 | 2005-04-27 | 财团法人工业技术研究院 | Microfluid film forming apparatus and method |
CN102351429A (en) * | 2011-07-06 | 2012-02-15 | 南京大学 | Method for preparing wide bandgap nanometer cadmium sulfide thin film |
Non-Patent Citations (3)
Title |
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X.B.XU ET AL.: "INFLUENCE OF CADMIUM SALTS ON A MODIFIED CHEMICAL BATH DEPOSITION OF CADMIUM SULFIDE THIN FILMS", 《SURFACE REVIEW AND LETTERS》, vol. 15, no. 3, 31 December 2008 (2008-12-31), pages 265 - 270 * |
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CN103922612A (en) * | 2014-04-23 | 2014-07-16 | 桂林理工大学 | Method for preparing CdSe film by adopting cold-heat alternating chemical bath method |
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