CN104233433B - A kind of method preparing cuprous oxide film - Google Patents
A kind of method preparing cuprous oxide film Download PDFInfo
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- CN104233433B CN104233433B CN201410522930.3A CN201410522930A CN104233433B CN 104233433 B CN104233433 B CN 104233433B CN 201410522930 A CN201410522930 A CN 201410522930A CN 104233433 B CN104233433 B CN 104233433B
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- copper sheet
- oxide film
- cuprous oxide
- sodium hydrate
- aqueous solution
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 25
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000036647 reaction Effects 0.000 claims abstract description 19
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 230000009514 concussion Effects 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 230000009466 transformation Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 21
- 239000010408 film Substances 0.000 description 14
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 10
- 239000010409 thin film Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 210000002457 barrier cell Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a kind of method preparing cuprous oxide film, its comprise the steps: the copper sheet after first processing with cleaning as anode, platinized platinum as negative electrode, 0.1～the sodium hydrate aqueous solution of 0.5mol/L as electrolyte, DC voltage be 8～10V, DC current be under 0.5～1.0A electrolytic condition, to carry out cell reaction 1～3 minutes；Again with 0.01～0.05mol/L sodium hydrate aqueous solution as electrolyte, DC voltage be 2～5V, DC current be under 0.01～0.05A electrolytic condition, to carry out cell reaction 40～120 minutes；Finally make annealing treatment.The inventive method has the advantages such as simple to operate, easily controllable, applicable large area production, and the controllable growth of cuprous oxide film structure and thickness can be realized, prepared cuprous oxide film has the nanocrystalline structure that crystallite dimension is 100～150nm, is conducive to improving the photoelectric transformation efficiency of solar cell.
Description
Technical field
The present invention relates to a kind of method preparing cuprous oxide film, belongs to electrochemical material preparing technical field.
Background technology
Red copper oxide (Cu2O) being cuprite structure, belong to cubic structure, lattice paprmeter is 0.463nm.It is a kind of direct
Bandgap semiconductor material, its energy gap is about 2.1eV, and acceptor level is positioned at 0.4eV in valence band, and donor level ratio is led
Carry low 1.1～1.3eV, can be by excited by visible light that wavelength is 400～800nm.Let it be to the greatest extent, and photoelectric properties are wayward,
But it has lot of advantages, such as nontoxic, with low cost, higher photoelectricity theoretical yield, the absorption efficiency height to visible ray
Deng.The Cu of polycrystalline state2The stability of O is fine, can hardly be reduced to simple substance Cu or is oxidized to the Cu of bivalence, becoming one
The semi-conducting material that potentiality are the biggest, can be applicable to numerous areas, such as: solaode, efficiency light chemical cell optoelectronic pole,
Magnetic device and photocatalysis etc..Especially on solar cell, the different resistivity according to preparation condition can be 102～104Ω·cm
In the range of change, it is seen that the absorptance of optical range is higher, and its theoretical conversion efficiency is up to 20%, and this makes it to make
For the absorbed layer of thin film heteroj junction battery, but its photoelectric transformation efficiency needs to be improved further up to now.
Red copper oxide (Cu2O) being a kind of typical p-type semiconductor material, the N-shaped doping realizing it at present is the most highly difficult,
Thus be also difficult to prepare Cu2O homojunction battery, but Cu2O can be formed with other material has Schottky potential barrier or hetero-junctions
Cu2O solaode, such as Cu2The Schottky barrier cell of O/Cu, Cu2O/ZnO and Cu2O/CdS's is heterogeneous
Junction battery.Cu2Vacuum thermal evaporation, chemical oxidation, thermal oxide, sputtering, chemistry is had known to the preparation method of O thin-film material
Vapour deposition and electrochemical deposition etc..Cu2The preparation of O thin-film material still suffers from many problems and difficulty, Cu2O thin film
The impact of phase constituent and pattern is also not very clear, the Cu prepared2O particle diameter is relatively big (micron order).Chinese patent CN1556250
Use metallic copper anodes electrolytically generated Red copper oxide, prepared Red copper oxide in the electrolyte containing acetonitrile and oxolane
400～600 DEG C of nitrogen protection calcinings, in the method technique, electrolyte contains toxic substance, needs high-temperature process simultaneously, is not suitable for
The application performance requirement of industrialized production and solar cell.
Summary of the invention
The problems referred to above existed for prior art, it is an object of the invention to provide a kind of without high-temperature process, applicable industrialization
Produce the method preparing cuprous oxide film that the application performance with solar cell requires.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of method preparing cuprous oxide film, comprises the steps:
A) it is cleaned copper sheet processing；
B) with cleaning process after copper sheet as anode, platinized platinum as negative electrode, 0.1～0.5mol/L sodium hydrate aqueous solution be electrolysis
Matter, DC voltage be 8～10V, DC current be under 0.5～1.0A electrolytic condition, to carry out cell reaction 1～3 minutes；
C) copper sheet obtained with step b) again as anode, platinized platinum as negative electrode, 0.01～the sodium hydrate aqueous solution of 0.05mol/L be
Electrolyte, DC voltage be 2～5V, DC current be under 0.01～0.05A electrolytic condition, to carry out cell reaction 40～120
Minute；
D) copper sheet that step c) obtains is made annealing treatment, obtain cuprous oxide film.
Preferably, the cleaning of copper sheet is processed and includes operating as follows by step a): copper sheet is placed sequentially in sodium hydroxide
Aqueous solution and aqueous hydrochloric acid solution carry out ultrasonic immersion until copper sheet surface cleaning, then clean with dehydrated alcohol concussion, finally use
Deionized water cleans.
As further preferred scheme, described sodium hydrate aqueous solution and the concentration of aqueous hydrochloric acid solution be 0.01～
0.1mol/L。
Preferably, step b), when being electrolysed, stirs electrolyte solution with the rotating speed of 200～400 revs/min simultaneously.
Preferably, step c), when being electrolysed, stirs electrolyte solution with the rotating speed of 50～100 revs/min simultaneously.
Preferably, step b) and step c) all carries out cell reaction at 5～40 DEG C.
Preferably, the annealing of step d) be under vacuum with the ramp of 5～15 DEG C/min to 175～
185 DEG C, after being incubated 2～4 hours, naturally cool to room temperature.
Compared with prior art, there is advantages that
1, the present invention uses constant potential mode to make anodic oxidation, simple to operate, easily controllable, is suitable for large area and produces；
2, the present invention can be by controlling concentration and the cell reaction time of electrolyte solution, it is achieved cuprous oxide film structure and thickness
The controllable growth of degree；
3 it is demonstrated experimentally that the Red copper oxide (Cu for preparing of the present invention2O) thin film has nanocrystalline structure, crystallite dimension be 100～
150nm, is conducive to improving the photoelectric transformation efficiency of solar cell.
Accompanying drawing explanation
Fig. 1 has the cross section SEM photograph of Red copper oxide film sample by copper sheet one superficial growth that the present invention is obtained；
Fig. 2 has the surface topography map of Red copper oxide film sample by copper sheet one superficial growth that the present invention is obtained, and (SEM shines
Sheet)；
Fig. 3 has the XRD diffracting spectrum of Red copper oxide film sample by copper sheet one superficial growth that the present invention is obtained.
Detailed description of the invention
Below in conjunction with specific embodiments and the drawings, the present invention is expanded on further.
Embodiment 1
One, take the metal copper sheet of an a size of 40mm × 50mm × 1mm, first clean the greasy dirt on surface with detergent, connect
Under ultrasound condition successively with sodium hydrate aqueous solution and the aqueous hydrochloric acid solution ultrasonic leaching respectively of 0.05mol/L of 0.05mol/L
Bubble is to copper sheet surface cleaning (about 5～10min), then uses dehydrated alcohol ultrasonic cleaning, finally uses deionized water rinsing；
Two, at room temperature, with step one cleaning process after copper sheet as anode, platinized platinum as negative electrode, the hydroxide of 0.3mol/L
Sodium water solution is electrolyte, DC voltage be 9V, DC current be 0.7A electrolytic condition under carry out cell reaction 2min,
Cell reaction stirs electrolyte solution with the speed of 300rpm simultaneously；
Three, at room temperature, with step 2 obtain copper sheet as anode, platinized platinum as negative electrode, the sodium hydroxide water of 0.03mol/L
Solution is electrolyte, DC voltage be 3V, DC current be 0.03A electrolytic condition under carry out cell reaction 80min,
Cell reaction stirs electrolyte solution with the speed of 70rpm simultaneously；
Four, copper sheet step 3 obtained, rinses rear natural air drying well with deionized water；It is then placed in crucible in vacuum
Make annealing treatment in stove: with the speed of 10 DEG C/min, furnace temperature is risen to 180 DEG C, after being incubated 3 hours, naturally cool to room temperature,
I.e. obtain copper sheet one superficial growth and have the sample of cuprous oxide film.
The cross section SEM photograph of obtained sample is as it is shown in figure 1, as seen from Figure 1: use the inventive method, can be at copper base
The cuprous oxide film of Surface Creation about 2～3 μ m-thick.
The surface topography map (SEM photograph) of obtained sample is as in figure 2 it is shown, as seen from Figure 2: use the inventive method institute
Red copper oxide (the Cu obtained2O) thin film has nanocrystalline structure, and crystallite dimension is 100～150nm.
The XRD diffracting spectrum of obtained sample is as it is shown on figure 3, as seen from Figure 3: occur in that in collection of illustrative plates that at 2 θ angles be 29.75
°, 36.64 °, 61.35 °, 73.99 ° respectively corresponding for Cu2(110), (111), (220) of O, (311) crystal face
Diffraction maximum and 2 θ angles be 43.30 °, (111), (200), (311) of 50.43 °, 89.94 ° Cu substrates the most corresponding
The diffraction maximum of crystal face, further illustrates employing the inventive method, can be at copper base Surface Creation cuprous oxide film.
Embodiment 2
One, take the metal copper sheet of an a size of 40mm × 50mm × 1mm, first clean the greasy dirt on surface with detergent, connect
Under ultrasound condition successively with sodium hydrate aqueous solution and the aqueous hydrochloric acid solution ultrasonic leaching respectively of 0.05mol/L of 0.05mol/L
Bubble is to copper sheet surface cleaning (about 5～10min), then uses dehydrated alcohol ultrasonic cleaning, finally uses deionized water rinsing；
Two, at room temperature, with step one cleaning process after copper sheet as anode, platinized platinum as negative electrode, the hydroxide of 0.1mol/L
Sodium water solution is electrolyte, DC voltage be 8V, DC current be 0.5A electrolytic condition under carry out cell reaction 3min,
Cell reaction stirs electrolyte solution with the speed of 200rpm simultaneously；
Three, at room temperature, with step 2 obtain copper sheet as anode, platinized platinum as negative electrode, the sodium hydroxide water of 0.05mol/L
Solution is electrolyte, DC voltage be 5V, DC current be 0.05A electrolytic condition under carry out cell reaction 40min,
Cell reaction stirs electrolyte solution with the speed of 100rpm simultaneously；
Four, copper sheet step 3 obtained, rinses rear natural air drying well with deionized water；It is then placed in crucible in vacuum
Make annealing treatment in stove: with the speed of 5 DEG C/min, furnace temperature is risen to 175 DEG C, after being incubated 4 hours, naturally cool to room temperature,
I.e. obtain copper sheet one superficial growth and have the sample of cuprous oxide film.
The sample obtained has the XRD diffracting spectrum feature shown in the surface topography shown in Fig. 2 and Fig. 3.
Embodiment 3
One, take the metal copper sheet of an a size of 40mm × 50mm × 1mm, first clean the greasy dirt on surface with detergent,
Then the most ultrasonic with the sodium hydrate aqueous solution of 0.05mol/L and the aqueous hydrochloric acid solution of 0.05mol/L successively under ultrasound condition
It is dipped to copper sheet surface cleaning (about 5～10min), then uses dehydrated alcohol ultrasonic cleaning, finally use deionized water rinsing；
Two, at room temperature, with step one cleaning process after copper sheet as anode, platinized platinum as negative electrode, the hydroxide of 0.5mol/L
Sodium water solution is electrolyte, DC voltage be 10V, DC current be 1.0A electrolytic condition under carry out cell reaction 1min,
Cell reaction stirs electrolyte solution with the speed of 400rpm simultaneously；
Three, at room temperature, with step 2 obtain copper sheet as anode, platinized platinum as negative electrode, the sodium hydroxide water of 0.01mol/L
Solution is electrolyte, DC voltage be 2V, DC current be 0.01A electrolytic condition under carry out cell reaction 120min,
Cell reaction stirs electrolyte solution with the speed of 50rpm simultaneously；
Four, copper sheet step 3 obtained, rinses rear natural air drying well with deionized water；It is then placed in crucible in vacuum
Make annealing treatment in stove: with the speed of 15 DEG C/min, furnace temperature is risen to 185 DEG C, after being incubated 2 hours, naturally cool to room temperature,
I.e. obtain copper sheet one superficial growth and have the sample of cuprous oxide film.
The sample obtained has the XRD diffracting spectrum feature shown in the surface topography shown in Fig. 2 and Fig. 3.
Finally it is necessary described herein: above example is served only for saying technical scheme in further detail
Bright, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art makes according to the foregoing of the present invention
Some nonessential improvement and adjustment belong to protection scope of the present invention.
Claims (6)
1. the method preparing cuprous oxide film, it is characterised in that comprise the steps:
A) it is cleaned copper sheet processing；
B) with cleaning process after copper sheet as anode, platinized platinum as negative electrode, 0.1～0.5mol/L sodium hydrate aqueous solution be electrolysis
Matter, DC voltage be 8～10V, DC current be under 0.5～1.0A electrolytic condition, to carry out cell reaction 1～3 minutes；
C) copper sheet obtained with step b) again as anode, platinized platinum as negative electrode, 0.01～the sodium hydrate aqueous solution of 0.05mol/L be
Electrolyte, DC voltage be 2～5V, DC current be under 0.01～0.05A electrolytic condition, to carry out cell reaction 40～120
Minute；
D) copper sheet that step c) obtains is made annealing treatment: under vacuum with the ramp of 5～15 DEG C/min extremely
175～185 DEG C, after being incubated 2～4 hours, naturally cool to room temperature, obtain cuprous oxide film.
2. the method for claim 1, it is characterised in that the cleaning of copper sheet is processed and includes operating as follows by step a):
Copper sheet is placed sequentially in sodium hydrate aqueous solution and aqueous hydrochloric acid solution and carries out ultrasonic immersion until copper sheet surface cleaning, then use
Dehydrated alcohol concussion is cleaned, and finally cleans with deionized water.
3. method as claimed in claim 2, it is characterised in that: described sodium hydrate aqueous solution and aqueous hydrochloric acid solution dense
Degree is 0.01～0.1mol/L.
4. the method for claim 1, it is characterised in that: step b) is when being electrolysed, simultaneously with 200～400
Rev/min rotating speed stirring electrolyte solution.
5. the method for claim 1, it is characterised in that: step c) is when being electrolysed, simultaneously with 50～100 turns
/ point rotating speed stirring electrolyte solution.
6. the method for claim 1, it is characterised in that: step b) and step c) is all electrolysed at 5～40 DEG C
Reaction.
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| CN201410522930.3A CN104233433B (en) | 2014-10-03 | 2014-10-03 | A kind of method preparing cuprous oxide film |
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| CN106835242B (en) * | 2017-02-05 | 2018-12-21 | 桂林理工大学 | A kind of Cu2The preparation method of O nano-array |
| CN106591922B (en) * | 2017-02-05 | 2018-05-08 | 桂林理工大学 | Cu2Preparation method of O nano film |
| CN107227476B (en) * | 2017-05-27 | 2019-03-01 | 浙江大学 | A kind of core-shell structure cuprous nano pn homojunction material and preparation method thereof |
| CN111394771B (en) * | 2020-04-22 | 2021-05-04 | 哈尔滨工业大学 | Method for preparing coating on surface of copper and copper alloy and copper product |
| CN111610240B (en) * | 2020-06-04 | 2022-11-15 | 南京邮电大学 | Photoelectric biosensor constructed based on cathode photoelectrode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD131044A1 (en) * | 1977-02-21 | 1978-05-24 | Heinz Fink | METHOD FOR THE ELECTROLYTIC PRODUCTION OF AN OXIDIC STAINLESS ON COPPER FOILS |
| US5078844A (en) * | 1990-02-19 | 1992-01-07 | Kunio Katsuma | Method for forming tough, electrical insulating layer on surface of copper material |
| US5401382A (en) * | 1993-03-09 | 1995-03-28 | Usui Kokusai Sangyo Kabushiki Kaisha, Ltd. | Method for forming tough, electrical insulating layer on surface of copper material |
| CN1380914A (en) * | 1999-09-29 | 2002-11-20 | 欧罗巴金属公开有限公司 | Electrochemical method for forming inorganic covering layer on surface of copper material |
| CN1556250A (en) * | 2003-12-31 | 2004-12-22 | �Ϻ���ͨ��ѧ | Electrolysis preparation method of nano cuprous oxide |
| CN101429680A (en) * | 2008-08-01 | 2009-05-13 | 华中师范大学 | Production method for direct growth of one-dimensional nano cuprous oxide array on metallic copper substrate |
-
2014
- 2014-10-03 CN CN201410522930.3A patent/CN104233433B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD131044A1 (en) * | 1977-02-21 | 1978-05-24 | Heinz Fink | METHOD FOR THE ELECTROLYTIC PRODUCTION OF AN OXIDIC STAINLESS ON COPPER FOILS |
| US5078844A (en) * | 1990-02-19 | 1992-01-07 | Kunio Katsuma | Method for forming tough, electrical insulating layer on surface of copper material |
| US5401382A (en) * | 1993-03-09 | 1995-03-28 | Usui Kokusai Sangyo Kabushiki Kaisha, Ltd. | Method for forming tough, electrical insulating layer on surface of copper material |
| CN1380914A (en) * | 1999-09-29 | 2002-11-20 | 欧罗巴金属公开有限公司 | Electrochemical method for forming inorganic covering layer on surface of copper material |
| CN1556250A (en) * | 2003-12-31 | 2004-12-22 | �Ϻ���ͨ��ѧ | Electrolysis preparation method of nano cuprous oxide |
| CN101429680A (en) * | 2008-08-01 | 2009-05-13 | 华中师范大学 | Production method for direct growth of one-dimensional nano cuprous oxide array on metallic copper substrate |
Non-Patent Citations (1)
| Title |
|---|
| Evidence and analysis of parallel growth mechanisms in Cu2O films prepared by Cu anodization;F. Caballero-Briones;《Electrochimica Acta》;20091020;第55卷;第4353–4358页 * |
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