CN106057930A - Method for preparing copper-gallium-selenium photoelectric thin film from copper chloride and gallium chloride - Google Patents
Method for preparing copper-gallium-selenium photoelectric thin film from copper chloride and gallium chloride Download PDFInfo
- Publication number
- CN106057930A CN106057930A CN201610419906.6A CN201610419906A CN106057930A CN 106057930 A CN106057930 A CN 106057930A CN 201610419906 A CN201610419906 A CN 201610419906A CN 106057930 A CN106057930 A CN 106057930A
- Authority
- CN
- China
- Prior art keywords
- gallium
- copper
- chloride
- thin film
- selenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 26
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 14
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 title claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000011669 selenium Substances 0.000 claims description 32
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 claims description 31
- 229910052711 selenium Inorganic materials 0.000 claims description 30
- 239000010408 film Substances 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000005357 flat glass Substances 0.000 claims description 3
- -1 gallium chlorides Chemical class 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000873 masking effect Effects 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- 238000010025 steaming Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a method for preparing a copper-gallium-selenium photoelectric thin film from copper chloride and gallium chloride, and belongs to the technical field of preparation of photoelectric thin films for solar cells. The method comprises the following steps: cleaning a glass substrate first, then putting copper chloride, gallium chloride and selenium dioxide into a solvent, adjusting the pH value to 4.0-7.0, spinning the mixture onto the glass substrate to obtain a precursor thin film, drying, putting the precursor thin film into an airtight container containing diamide hydrate which is not in contact with the precursor thin film sample, charging the airtight container filled with the sample into an oven, heating and preserving the heat, finally taking out and drying the sample to obtain the copper-gallium-selenium photoelectric thin film. The method does not need high temperature or high vacuum, and is low in requirement for instruments, low in production cost, high in production efficiency and easy to operate. The copper-gallium-selenium photoelectric thin film has good continuity and uniformity; the main phase is a copper-gallium-selenium phase, and the new process easily controls the component and the structure of the target product, so that a production cost with low cost and capability of realizing industrialization is provided for preparing a high-performance copper-gallium-selenium photoelectric thin film.
Description
Technical field
The invention belongs to solar cell optoelectronic film preparing technical field, particularly relate to a kind of by copper chloride and gallium chloride
The method preparing copper gallium selenium conductive film.
Background technology
Having entered since 21 century, the energy and environmental problem become the focus that people focus more on, in the face of lack of energy and
The environmental pollution that traditional energy brings, people start progressively to find the novel energy new round that can substitute for traditional fossil energy
Energy revolution the most slowly raises the curtain.Photovoltaic generation have safe and reliable, noiseless, pollution-free, restriction less, failure rate is low,
The advantages such as easy maintenance, it is possible to use this cleaning of solar energy, safety and the regenerative resource of environmental protection, the most too
The research and development in positive electricity pond is increasingly subject to pay attention to.
Copper gallium selenium film solar battery may be considered one of the most promising hull cell at present, its light absorbing zone
Being made up of the copper-based conductors material of low cost, absorbing ability is much stronger than crystalline silicon, in solar spectrum district optical absorption depth micro-
Rice magnitude.The absorption coefficient of light of copper gallium selenium is up to 105cm-1, hence it is evident that higher than solar cell materials such as Si and CdTe, the most very
It is suitable for doing light absorbing material.Additionally, copper gallium selenium also have a series of a little: (1) copper gallium selenium is direct band-gap semicondictor, and this can subtract
Few requirement to minority carrier diffusion；(2) at room temperature copper gallium selenium band gap is adjustable, and along with the change of gallium content, its band gap can
With consecutive variations in the range of 1.04～1.67eV；(3) copper gallium selenium absorptance is very big, and conversion efficiency is high, stable performance, thin film
Thickness is little, about 2 μm, and the price of raw material is relatively low, and time prepared by large area, price is relatively low；(4) at wider composition range internal resistance
Rate is the least；(5) capability of resistance to radiation is strong, does not has photo attenuation effect, thus service life is long；(6) p-type copper gallium selenium material
Lattice structure can be mated with common N-type window material (such as CdS, ZnO) with electron affinity.
The preparation method of copper gallium selenium mainly has solvent-thermal method, spray pyrolysis method (Spray Prolysis), electrojet at present
Method, electro-deposition, chemical deposition, the chemical vapor transportation method of closing, chemical gaseous phase deposition, molecular beam epitaxy, reactive sputtering,
Vacuum vapor deposition method, Metalorganic chemical vapor deposition method, etc..Owing to copper gallium selenium cost of material is low, and its band gap can be along with gallium
Content and change, thus improve photoelectric transformation efficiency, be therefore the most rising a kind of solar cell material, but existing
There are process route complexity, preparation cost high, thus need also exist for exploring the preparation technology of low cost.
Method is the same as before, and other method also has different defects.Related to the present invention also has such as Publication about Document:
[1] Zheng Ping ping, Ding Tie zhu, Kang Zhen feng, Liu Wen de, Prearation
of Intermediate Band Semiconductor Materials CuGaSe2:Ge. Journal of Synthetic
Crystals Vol.43 No.8 (2014)1921-1925.
Essentially describe employing pulsed laser deposition on calcium soda-lime glass substrate, prepare CuGaSe2: Ge thin film, and penetrate with X
Line diffractometer, thin film is tested characterizing by scanning electron microscope.
[2] Li Zhang, Qing He, Jianping Xiao,Chuanming Xu, yuming Xue,
YunSun, Study of Polycrystalline CuGaSe2 and CuGa3Se5 Thin Films Deposited by
PVD. 15th International Photovoltaic Science and Engineering Conference (2005)
1176-1177.
Essentially describe and utilize PVD method, prepare copper gallium selenium thin film in Mo back end, and the copper gallium selenium thin film of preparation is become mutually and
Pattern test characterizes.
[3] Zhao Yan min, Xiao Wen, Li Wei, Yang Li, Qiao Zai xiang,
Influence of Substrates on the Wide Band Gap CGS Thin Films. Journal of
Synthetic Crystals.Vol.42 No.12 (2013) 2572-2575.
Essentially describe use " three-step approach " coevaporation technique, prepare copper gallium selenium thin film on different substrates, and by thin
The analysis of the composition of film, pattern, structure and electric property, obtains the substrate impact on preparing copper gallium selenium thin film.
[4] Zhang Li, He Qing, Xu Chuan Ming, Xue Yu Ming, LI Chang Jian, The
effect of composition on structural and electronic properties in
polycrystalline CuGaSe2 thin film. Chinese Physics B. Vol. 17, No. 8 (2008)
3138-3142.
Essentially describe coevaporation method and prepare copper gallium Se solar cell thin film, and analyze the thing phase of the thin film of copper gallium selenium
And pattern, and the electrical property of copper gallium selenium thin film is characterized.
Summary of the invention
The present invention is to solve the deficiencies in the prior art, and invented a kind of entirely different with the preparation method of prior art
, the preparation technology of copper gallium selenium solar cell thin-film material.
The present invention uses spin coating-chemistry co-reducing process to prepare copper gallium selenium thin-film material, and employing soda-lime glass is substrate, with chlorine
Change copper, gallium chloride, selenium dioxide are raw material, with two kinds of deionized water, ethylene glycol, ethanolamine, ammonia or these four raw material with
On mixture be solvent, adjust the pH value of solution with ammonia for assist medium, amount is than first preparing with spin-coating method by elements
The precursor thin-film of certain thickness cupric gallium selenium, with hydrazine hydrate as reducing agent, adds in hermetic container at a lower temperature
Heat, makes precursor thin-film reduction concurrent GCMS computer reaction obtain target product.
The concrete preparation method of the present invention includes following steps in sequence:
A. carry out the cleaning of glass substrate, be that sulphuric acid by volume put into by 20mm × 20mm sheet glass: distilled water=2:1 by size
Solution in, ultrasonic waves for cleaning 30min；Sheet glass is put into volume ratio acetone again: in the solution of distilled water=5:1, ultrasound wave is clear
Wash 30min；In distilled water, glass substrate is used sonic oscillation 30min again；Glass substrate obtained above is emitted on glass
Ware is sent in baking oven, dry for masking at 100 DEG C.
B. copper chloride, gallium chloride, selenium dioxide are put in solvent, make the material in solution uniformly mix, and regulate pH
Value.Specifically, 1.0～3.0 parts of copper chlorides, 1.5～4.5 parts of gallium chlorides, 1.3～3.9 parts of selenium dioxide can be put into 110
～in the solvent of 450 parts, make the material in solution uniformly mix, can add 100～250 parts of ammonia to adjust the pH value of solution is
4.0～7.0, the mixed solution of at least one during wherein solvent is deionized water, ethylene glycol, ethanolamine, ammonia.
C. make the substrate of solution described in outside uniform application step b, and dry, obtain precursor thin-film sample.Permissible
Above-mentioned solution is dripped on the glass substrate that is placed on sol evenning machine, restart sol evenning machine and rotate with 300～3500 revs/min certain
Time, after making the solution on dripping be coated with uniformly, after substrate being dried at 100 DEG C, again repeat to drip upper previous solu and rotation
Dry again after coating, so repeat 5～15 times, obtained certain thickness precursor thin-film sample the most on a glass substrate.
D. step c gained precursor thin-film sample is placed on support, be placed with hydrazine hydrate can hermetic container, before making
Drive body thin film sample not contact with hydrazine.Put into 35～40 parts of hydrazine hydrates.The hermetic container that will be equipped with precursor thin film sample is put
Enter in baking oven, be heated between 160～220 DEG C, temperature retention time 5～20 hours, then it is cooled to room temperature and takes out.
E. by step d gains so that it is after room temperature natural drying, copper gallium selenium conductive film is i.e. obtained.
The present invention need not high temperature high vacuum condition, requires low to instrument and equipment, and production cost is low, and production efficiency is high, easily
In operation.Gained copper gallium selenium conductive film has preferable seriality and uniformity, and principal phase is copper gallium selenium phase, and this new technology is easy
Control composition and the structure of target product, provide a kind of low cost for preparing high performance copper gallium selenium conductive film, can realize
Large-scale industrial production.
Detailed description of the invention
Embodiment 1
A. the cleaning of glass substrate: be carried out glass substrate as previously mentioned, substrate size is 20mm × 20mm.
B. 1.5 parts of copper chlorides, 1.5 parts of gallium chlorides and 2.0 parts of selenium dioxide are put in 378.07 parts of deionized waters uniform
Mixing, adding ammonia to pH is 4.5, utilizes more than ultrasonic activation 30min, makes the material in solution uniformly mix.
C. dripping to above-mentioned solution, on the glass substrate that is placed on sol evenning machine, restart sol evenning machine, sol evenning machine is with 300
Rev/min rotate 5 seconds, rotate 15 seconds with 3000 revs/min, after making the solution on dripping be coated with uniformly, at 100 DEG C, substrate is dried
After, dry again after again repeating to drip upper previous solu and rotary coating, be so repeated 10 times, obtain the most on a glass substrate
Certain thickness precursor thin-film sample.
D. the precursor thin-film sample of above-mentioned technique gained is put into sealable container, and puts into 37.807 parts of hydration connection
Ammonia, precursor thin film sample is placed on support and makes it not contact with hydrazine.Baking put into by the hermetic container that will be equipped with precursor thin film sample
In case, it is heated to 200 DEG C, temperature retention time 10 hours, then it is cooled to room temperature and takes out.
E. by step d gains, carry out room temperature natural drying, obtain copper gallium selenium conductive film.
Claims (5)
1. the method being prepared copper gallium selenium conductive film by copper chloride and gallium chloride, including following steps in sequence:
A. the cleaning of glass substrate；
B. 1.0～3.0 parts of copper chlorides, 1.0～3.0 parts of gallium chlorides, 1.3～3.9 parts of selenium dioxide are put into 110～450 parts
In solvent, make the material in solution uniformly mix, and adjust pH value to 4.0～7.0；
C. make the substrate of solution described in outside uniform application step b, and dry, obtain precursor thin-film sample；
D. step c gained precursor thin-film sample is placed on support, be placed with hydrazine hydrate can hermetic container, make presoma
Film sample does not contacts with hydrazine；The hermetic container that will be equipped with precursor thin film sample is put in baking oven, is heated to 160～220 DEG C
Between, temperature retention time 5～20 hours, then it is cooled to room temperature and takes out；
E. by step d gains, carry out natural drying, obtain copper gallium selenium conductive film.
A kind of method being prepared copper gallium selenium conductive film by copper chloride and gallium chloride, its feature exists
In, clean described in step a, be to be 20mm × 20mm by glass substrate size, put into volume ratio sulphuric acid: the solution of distilled water=2:1
In, ultrasonic waves for cleaning；Sheet glass is put into acetone by volume again: in the solution of distilled water=5:1, ultrasonic waves for cleaning；Steaming again
By glass substrate sonic oscillation in distilled water；It is emitted on glass substrate obtained above in glass dish in feeding baking oven to dry and supplies
Masking is used.
A kind of method being prepared copper gallium selenium conductive film by copper chloride and gallium chloride, its feature exists
In, the solvent described in step b is at least one in deionized water, ethanol, ethylene glycol, ethanolamine, ammonia.
A kind of method being prepared copper gallium selenium conductive film by copper chloride and gallium chloride, its feature exists
In, the substrate of uniform application described in step c, is to be smeared by sol evenning machine, and sol evenning machine is with 300～3500 revs/min of rotations, the most right
After substrate is dried, the most so repeat 5～15 times, obtained certain thickness precursor thin-film sample.
A kind of method being prepared copper gallium selenium conductive film by copper chloride and gallium chloride, its feature exists
In, put into 35～40 parts of hydrazine hydrates in hermetic container described in step d.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610419906.6A CN106057930A (en) | 2016-06-15 | 2016-06-15 | Method for preparing copper-gallium-selenium photoelectric thin film from copper chloride and gallium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610419906.6A CN106057930A (en) | 2016-06-15 | 2016-06-15 | Method for preparing copper-gallium-selenium photoelectric thin film from copper chloride and gallium chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106057930A true CN106057930A (en) | 2016-10-26 |
Family
ID=57168515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610419906.6A Pending CN106057930A (en) | 2016-06-15 | 2016-06-15 | Method for preparing copper-gallium-selenium photoelectric thin film from copper chloride and gallium chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106057930A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108520900A (en) * | 2018-05-28 | 2018-09-11 | 山东建筑大学 | A kind of method that nitric acid salt system prepares copper aluminium tellurium thin films |
| CN108682618A (en) * | 2018-05-28 | 2018-10-19 | 山东建筑大学 | A kind of method that chloride system prepares copper gallium tellurium thin films |
| CN108682619A (en) * | 2018-05-28 | 2018-10-19 | 山东建筑大学 | A kind of method that nitric acid salt system prepares copper gallium tellurium thin films |
| CN108711584A (en) * | 2018-05-28 | 2018-10-26 | 山东建筑大学 | A method of preparing copper and indium aluminium tellurium thin films |
| CN108767059A (en) * | 2018-05-28 | 2018-11-06 | 山东建筑大学 | A method of preparing copper and indium gallium tellurium thin films |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101630701A (en) * | 2008-12-03 | 2010-01-20 | 山东建筑大学 | Method for preparing copper-indium-selenium optoelectronic thin film material of solar cell |
| CN102034898A (en) * | 2010-10-20 | 2011-04-27 | 山东建筑大学 | Preparation method of Cu-In-S photoelectric film material for solar cells |
| US20120055612A1 (en) * | 2010-09-02 | 2012-03-08 | International Business Machines Corporation | Electrodeposition methods of gallium and gallium alloy films and related photovoltaic structures |
| CN103526159A (en) * | 2012-07-04 | 2014-01-22 | 甘国工 | Equipment and method for depositing copper-indium-gallium-selenium absorption layer on glass or metal substrate |
-
2016
- 2016-06-15 CN CN201610419906.6A patent/CN106057930A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101630701A (en) * | 2008-12-03 | 2010-01-20 | 山东建筑大学 | Method for preparing copper-indium-selenium optoelectronic thin film material of solar cell |
| US20120055612A1 (en) * | 2010-09-02 | 2012-03-08 | International Business Machines Corporation | Electrodeposition methods of gallium and gallium alloy films and related photovoltaic structures |
| CN102034898A (en) * | 2010-10-20 | 2011-04-27 | 山东建筑大学 | Preparation method of Cu-In-S photoelectric film material for solar cells |
| CN103526159A (en) * | 2012-07-04 | 2014-01-22 | 甘国工 | Equipment and method for depositing copper-indium-gallium-selenium absorption layer on glass or metal substrate |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108520900A (en) * | 2018-05-28 | 2018-09-11 | 山东建筑大学 | A kind of method that nitric acid salt system prepares copper aluminium tellurium thin films |
| CN108682618A (en) * | 2018-05-28 | 2018-10-19 | 山东建筑大学 | A kind of method that chloride system prepares copper gallium tellurium thin films |
| CN108682619A (en) * | 2018-05-28 | 2018-10-19 | 山东建筑大学 | A kind of method that nitric acid salt system prepares copper gallium tellurium thin films |
| CN108711584A (en) * | 2018-05-28 | 2018-10-26 | 山东建筑大学 | A method of preparing copper and indium aluminium tellurium thin films |
| CN108767059A (en) * | 2018-05-28 | 2018-11-06 | 山东建筑大学 | A method of preparing copper and indium gallium tellurium thin films |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102034898B (en) | Preparation method of Cu-In-S photoelectric film material for solar cells | |
| CN106057930A (en) | Method for preparing copper-gallium-selenium photoelectric thin film from copper chloride and gallium chloride | |
| CN104795456B (en) | Electrodeposition process prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials | |
| CN102603202A (en) | Method for preparing tin selenide photoelectric thin film | |
| CN108539026B (en) | Preparation method of perovskite thin film with micron tube array structure | |
| CN102153288A (en) | Method for preparing copper disulfide thin film with preferred orientation | |
| You et al. | Reactive Ion etching activating TiO2 substrate for planar heterojunction Sb2S3 solar cells with 6.06% efficiency | |
| CN103400894B (en) | A kind of method preparing zinc sulfide optoelectronic film | |
| CN103390692B (en) | A kind of method preparing copper indium tellurium thin films | |
| CN106067489A (en) | A kind of method being prepared copper gallium selenium conductive film by copper chloride and Ganite (Fujisawa). | |
| CN110165020A (en) | One kind being based on CdS/SnO2Mix the efficient Sb of N-type layer2Se3Hull cell and preparation method thereof | |
| CN105552166A (en) | Method for preparing copper-indium-diselenide photoelectric film by two-step method of nitrate system | |
| CN105914246A (en) | Method for using copper sulphate and gallium nitrate to prepare copper gallium selenide photoelectric film | |
| CN109616550A (en) | A kind of raising Sb2Se3The method of film crystal grain columnar growth trend | |
| CN106082690A (en) | A kind of method being prepared copper and indium sulfur optoelectronic film by copper sulfate | |
| CN105895717A (en) | Method for preparing copper indium gallium selenide photoelectric film from copper chloride and gallium nitrate | |
| CN105932081A (en) | Method for preparing copper indium sulfide photoelectric thin film from copper chloride | |
| CN106024976A (en) | Method for preparing copper gallium sulfide photoelectric thin film from copper chloride | |
| CN106098813A (en) | A kind of method being prepared copper gallium selenium conductive film by copper nitrate and gallium chloride | |
| CN105932111A (en) | Method for preparing copper-indium-gallium-selenide photoelectric thin film from copper chloride and gallium chloride | |
| CN105679856A (en) | Preparation method for Mg-doped ZnO thin film window layer through low-temperature solution method and application therefor | |
| CN105895744A (en) | Method for preparing copper gallium selenide photoelectric film from copper nitrate and gallium nitrate | |
| CN106024928A (en) | Method for preparing copper-gallium-selenide photoelectric thin film from copper sulfate and gallium chloride | |
| CN105655447A (en) | Large-area preparation method of perovskite films suitable for various substrate shapes | |
| CN105529243A (en) | Method for copper indium diselenide optoelectronic film by sulphate system in two-step process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161026 |