CN116815174A - Chemical oxidizing solution for preparing heat absorption layer, heat absorption layer and preparation method thereof - Google Patents
Chemical oxidizing solution for preparing heat absorption layer, heat absorption layer and preparation method thereof Download PDFInfo
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- CN116815174A CN116815174A CN202311100338.XA CN202311100338A CN116815174A CN 116815174 A CN116815174 A CN 116815174A CN 202311100338 A CN202311100338 A CN 202311100338A CN 116815174 A CN116815174 A CN 116815174A
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- 239000000126 substance Substances 0.000 title claims abstract description 73
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 46
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 53
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 230000003647 oxidation Effects 0.000 claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 47
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 230000017525 heat dissipation Effects 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 150000001879 copper Chemical class 0.000 claims abstract description 18
- 150000002815 nickel Chemical class 0.000 claims abstract description 17
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims description 5
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 claims description 5
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000007800 oxidant agent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000110 cooling liquid Substances 0.000 abstract description 4
- 238000009413 insulation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 57
- 238000012360 testing method Methods 0.000 description 15
- 229940000207 selenious acid Drugs 0.000 description 8
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910001374 Invar Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000537 White brass Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- -1 selenium ion Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
The invention relates to the field of heat dissipation, in particular to a chemical oxidation liquid for preparing a heat absorption layer, the heat absorption layer and a preparation method thereof, and aims to solve the problems that the heat absorption layer arranged on the surface of a current heat dissipation material still has poor heat conduction performance, poor high-temperature stability and the like. The chemical oxidizing liquid for preparing the heat absorbing layer comprises the following components: selenic acid, copper salt, nickel salt, pH regulator and complexing agent. The preparation method comprises the following steps: providing a substrate; activating the matrix to obtain an activated matrix; carrying out chemical oxidation on the activated matrix to obtain a matrix containing the heat dissipation coating; the chemical oxidation liquid for preparing the heat absorption layer is adopted as an oxidation reagent in the chemical oxidation. The chemical oxidizing liquid for preparing the heat absorption layer provided by the invention ensures that the obtained coating has good heat absorption and insulation performance, high temperature resistance and adhesion performance with a matrix, and is beneficial to the improvement of the temperature of fins in heat dissipation equipment, so that the heat exchange between the fins and cooling liquid is improved, and the high-performance heat dissipation equipment is facilitated.
Description
Technical Field
The invention relates to the field of heat dissipation, in particular to a chemical oxidation liquid for preparing a heat absorption layer, the heat absorption layer and a preparation method thereof.
Background
Currently, heat dissipation capability is an important indicator affecting the performance of a power module. The power module can produce a large amount of heat in the course of working, if not dispel the heat effectively, the accumulation of heat can lead to power module high temperature, probably causes equipment trouble, performance decline even damage. The power module is generally configured with a radiator, i.e. a radiating fin is mounted on the radiator, and radiating efficiency is improved through a large surface area of the radiator and a heat exchange design (water cooling), and a common power module radiator is a fin radiator or a fin radiator.
A heat-dissipating coating composition comprising graphene and ceramic particles, wherein the weight ratio of graphene to ceramic particles is 10:1-1:5, is disclosed as CN111269592 a. The heat dissipation coating composition is coated on the surface of a substrate material in a spray coating mode, a doctor blade coating mode, a screen printing mode, an electroplating mode and the like, so that the heat dissipation performance is good, the heat dissipation efficiency is up to 500-2000W/m.K, and the heat dissipation coating composition has a wide tolerance temperature range and can reach-50-500 ℃.
CN107620030a discloses a heat dissipation type tungsten copper coating material for electronic packaging and a preparation method thereof, wherein the heat dissipation type tungsten copper coating material comprises the following components in percentage by mass: 70-90% of tungsten, 10-28% of copper, 0-1% of iron, 0-0.85% of cobalt and 0-0.15% of trace elements; the microelements are palladium, nickel and tin; the preparation method comprises the following steps: mixing the coating powder prepared according to the proportion, and agglomerating and sintering; taking an oxygen-free copper matrix for machining, cleaning the surface and carrying out sand blasting; spraying the sintered coating powder onto the oxygen-free copper matrix after the second step by plasma; carrying out laser remelting on the surface of the oxygen-free copper matrix subjected to plasma spraying; carrying out mechanical processing and grinding polishing on the oxygen-free copper matrix subjected to laser remelting; and plating a Ni/Au layer on the oxygen-free copper substrate after polishing. According to the scheme, the material-adjustable thermal expansion coefficient can be realized, the isolation buffer effect can be realized, the chip is prevented from being damaged, the compactness of the coating is improved, the porosity is reduced, the heat conducting property is enhanced, and the combination between the coating and the matrix is firmer.
However, the current heat dissipation device still has the problem of poor heat exchange effect between the fins and the cooling medium.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a chemical oxidizing solution for preparing a heat absorption layer, the heat absorption layer and a preparation method thereof, so as to solve the problem of poor heat exchange effect between fins and cooling media in the current heat dissipation material.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a chemical oxidizing solution for preparing a heat absorbing layer, the chemical oxidizing solution for preparing a heat absorbing layer comprising: selenic acid, copper salt, nickel salt, pH regulator and complexing agent.
According to the chemical oxidizing solution for preparing the heat absorption layer, through the design of the oxidizing solution for preparing the coating, the obtained coating has good heat absorption and heat preservation, high temperature resistance and adhesion performance with a substrate, the temperature at the fin is improved, the heat exchange efficiency of the fin and the cooling liquid is improved, the heat dissipation efficiency of the heat dissipation device is improved, and the high-performance heat dissipation device is obtained.
As a preferred technical scheme of the present invention, the chemical oxidizing solution for preparing the heat absorbing layer includes:
2.5-3.5g/L selenic acid, 2-4g/L copper salt, 2.5-3.2g/L nickel salt and 3-4g/L complexing agent, and the pH value is 1.5-3.8.
As a preferred embodiment of the present invention, the copper salt comprises copper sulfate and/or copper nitrate.
Preferably, the nickel salt comprises nickel sulphate and/or nickel nitrate.
Preferably, the pH adjustor comprises 1 or a combination of at least 2 of sodium dihydrogen phosphate, nitric acid, sulfuric acid, phosphoric acid, or hydrochloric acid.
Preferably, the complexing agent comprises an aminocarboxylic acid and/or aminocarboxylate.
In a second aspect, the present invention provides a method for preparing a heat absorbing layer, the method comprising:
providing a substrate;
activating the matrix to obtain an activated matrix;
carrying out chemical oxidation on the activated matrix to obtain a matrix containing the heat dissipation coating;
the chemical oxidation adopts the chemical oxidation liquid for preparing the heat absorption layer as the oxidation reagent.
As a preferred embodiment of the present invention, the substrate includes 1 of iron, iron alloy, copper or copper alloy.
As a preferable technical scheme of the invention, the activation is to adopt mixed acid to carry out acid washing treatment on the substrate.
Preferably, the mixed acid used in the activation comprises: 290-310g/L of hydrochloric acid and 190-210g/L of sulfuric acid.
As a preferred technical scheme of the invention, the activation temperature is 25-40 ℃.
Preferably, the activation time is 3-5min.
As a preferable technical scheme of the invention, the chemical oxidation time is 15-20min.
In a third aspect, the present invention provides a heat-absorbing layer prepared by the preparation method according to the second aspect;
the film layer of the heat absorption layer comprises copper selenide and nickel selenide.
Compared with the prior art, the invention has the following beneficial effects:
(1) The heat absorption coating provided by the invention can obviously improve the heat absorption performance of the radiator fin, has very high emissivity of more than or equal to 0.91W/(mK) and can effectively conduct heat through radiation; meanwhile, the coating can reduce the contact thermal resistance between the heat radiating material and the heat radiating source, and improves the heat absorbing effect of the heat radiating fins, so that the temperature of the heat radiating fins is improved, the temperature difference between the heat radiating fins and the cooling liquid is improved, and the heat transfer efficiency is effectively improved.
(2) The heat absorption layer can realize the weight reduction of the radiator, the thickness of the coating can be controlled in the range of a few micrometers to tens of micrometers, and the volume and the weight of the radiator can be reduced.
(3) The heat dissipation coating prepared by the chemical oxidation solution for preparing the heat absorption layer has good high temperature resistance, and the copper selenide in the film layer can be kept stable in a high temperature environment and is not easy to melt or decompose, so that the coating is suitable for high temperature heat dissipation application, and further, the coating provides a protective layer for metal to prevent oxidation, corrosion and abrasion.
Drawings
FIG. 1 is an XRD spectrum of the coating obtained in example 1 of the present invention;
FIG. 2 is an SEM photograph of the coating obtained in example 1 of the present invention;
FIG. 3 is an AFM photograph of the coating obtained in example 1 of the present invention.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
the embodiment provides a chemical oxidizing solution for preparing a heat absorbing layer, the chemical oxidizing solution for preparing a heat absorbing layer comprising: selenic acid, copper salt, nickel salt, pH regulator and complexing agent.
Specifically, the chemical oxidizing solution for preparing the heat absorbing layer comprises:
2.5-3.5g/L selenic acid, 2-4g/L copper salt, 2.5-3.2g/L nickel salt and 3-4g/L complexing agent, and the pH value is 1.5-3.8.
In the invention, the density of the film layer is firstly increased and then decreased along with the increase of the copper salt content (the density is too low to lead to sparse coating, the surface of the substrate can not be completely covered, and the heat absorption capacity is affected). This is because, when the Cu ion content is too high, further reduction of copper cannot be prevented due to the fixation of the selenium ion concentration, and a metal lattice is generated. When the concentration is more than 2g/L, the film layer is bluish and mixed with red, so that the absorptivity is affected; when the concentration is too low, the surface of the matrix does not have enough Cu atoms to be formed.
After the concentration of the nickel salt is more than 3g/L, the density of the film layer is reduced. This is because when the concentration is too high, nickel selenide (NiSe) precipitates are formed by the reaction and deposited on the surface of the substrate.
In summary, the ratio of selenious acid to copper salt should be proper, otherwise, the film forming quality is directly affected. The experiment also shows that the content of the copper sulfate cannot be more than that of selenious acid, otherwise, the film forming speed is high, the film layer is loose, the film layer is easy to fall off after being dried, and the adhesive force is poor. Comprehensively considering, the optimal formula of the copper sulfate is determined to be 2.5-3.5g/L of selenious acid, 2-4g/L of copper salt, 2.5-3.2g/L of nickel salt and 3-4g/L of complexing agent, and the pH value is 1.5-3.8.
The concentration of selenious acid in the chemical oxidizing solution for preparing the heat absorbing layer is 2.5-3.5g/L, for example, 2.5g/L, 2.6g/L, 2.7g/L, 2.8g/L, 2.9g/L, 3g/L, 3.1g/L, 3.2g/L, 3.3g/L, 3.4g/L, or 3.5g/L, etc., but the concentration is not limited to the recited values, and other values not recited in the range are equally applicable.
The concentration of copper salt in the chemical oxidizing solution for preparing the heat absorbing layer is 2-4g/L, for example, 2g/L, 2.2g/L, 2.4g/L, 2.6g/L, 2.8g/L, 3g/L, 3.2g/L, 3.4g/L, 3.6g/L, 3.8g/L or 4g/L, etc., but not limited to the recited values, and other values not recited in the range are equally applicable.
The concentration of the nickel salt in the chemical oxidizing solution for preparing the heat absorbing layer is 2.5-3.2g/L, for example, 2.5g/L, 2.6g/L, 2.7g/L, 2.8g/L, 2.9g/L, 3g/L, 3.1g/L, or 3.2g/L, etc., but not limited to the recited values, and other values not recited in the range are equally applicable.
The concentration of the complexing agent in the chemical oxidizing solution for preparing the heat absorbing layer is 3-4g/L, for example, 3g/L, 3.1g/L, 3.2g/L, 3.3g/L, 3.4g/L, 3.5g/L, 3.6g/L, 3.7g/L, 3.8g/L, 3.9g/L or 4g/L, etc., but not limited to the listed values, and other values not listed in the range are equally applicable.
In particular, the copper salt comprises copper sulphate and/or copper nitrate.
In particular, the nickel salt comprises nickel sulphate and/or nickel nitrate.
Specifically, the pH adjustor comprises 1 or a combination of at least 2 of sodium dihydrogen phosphate, nitric acid, sulfuric acid, phosphoric acid, or hydrochloric acid.
In the coating preparation process, the matrix is dissolved in acid and interacts with dihydrogen phosphate ions in the solution to form an amorphous mixed phosphate film or a crystalline sodium phosphate insoluble film. Among them, the matching of the phosphating rate with the film formation rate is a key to forming a high quality coating. When the phosphating speed is too slow, the phosphating film is thin, floating ash is generated on the film layer, and the adhesive force is poor; when the phosphating speed is too high, the phosphating film is thick, the film is poor in density and is colored and matt.
Wherein, the addition amount of the pH value regulator is selected according to the limiting pH value of the chemical oxidation liquid.
In particular, the complexing agent comprises an aminocarboxylic acid and/or an aminocarboxylate. For example, EDTA, disodium EDTA, tetrasodium EDTA, etc. may be used.
Further, the invention provides an application of the chemical oxidizing solution for preparing the heat absorption layer, in particular to a preparation method of the heat absorption layer, which comprises the following steps:
providing a substrate;
activating the matrix to obtain an activated matrix;
carrying out chemical oxidation on the activated matrix to obtain a matrix containing the heat dissipation coating;
the chemical oxidation adopts the chemical oxidation liquid for preparing the heat absorption layer as the oxidation reagent.
Specifically, the matrix includes 1 of iron, iron alloy, copper, or copper alloy.
In the invention, the iron alloy comprises invar, ferrosilicon, ferromanganese and the like.
In the invention, the copper alloy comprises red copper, bronze, white copper, brass and the like, wherein the red copper is as follows: t2, T3, TP1, TP2; red copper: TAg, TSn, TBe; bronze: QSi3-1, QSi-1, QSn4-0.3; brass: h62, H63, H65, H68, H70, etc.
Specifically, the activation is to carry out acid washing treatment on the substrate by adopting mixed acid.
Preferably, the mixed acid used in the activation comprises: 290-310g/L of hydrochloric acid and 190-210g/L of sulfuric acid.
In the present invention, the concentration of hydrochloric acid in the mixed acid used is 290 to 310g/L, and for example, 290g/L, 292g/L, 294g/L, 296g/L, 298g/L, 300g/L, 302g/L, 304g/L, 306g/L, 308g/L or 310g/L and the like may be used, but not limited to the values mentioned above, and other values not mentioned in the range are equally applicable.
In the present invention, the concentration of sulfuric acid in the mixed acid used is 190 to 210g/L, and for example, 190g/L, 192g/L, 194g/L, 196g/L, 198g/L, 200g/L, 202g/L, 204g/L, 206g/L, 208g/L, 210g/L, etc., but the sulfuric acid concentration is not limited to the values mentioned above, and other values not mentioned in the range are equally applicable.
Specifically, the activation temperature may be 25 to 40 ℃, for example, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, or the like, but not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the activation time is 3-5min, for example, 3min, 3.5min, 4min, 4.5min, 5min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Specifically, the chemical oxidation time is 15-20min, for example, 15min, 16min, 17min, 18min, 19min or 20min, etc., but the chemical oxidation time is not limited to the listed values, and other values not listed in the range are equally applicable.
In the invention, the chemical oxidizing solution used in the chemical oxidizing process can be used for controlling the concentration of each substance in the solution to accord with a limited range through dynamic adjustment, or can be treated all the time by adopting a batch of solution and then treated again.
Further, the invention also provides a heat absorption layer, which is prepared by adopting the preparation method;
the film layer of the heat absorption layer comprises copper selenide and nickel selenide.
In order to clarify the excellent properties of the chemical oxidizing solution for preparing the heat absorbing layer provided in the present invention, the following examples are specifically provided:
example 1
The embodiment provides a chemical oxidation solution for preparing a heat absorption layer and application thereof, which is a preparation method of the heat absorption layer, and specifically comprises the following steps:
the chemical oxidizing liquid for preparing the heat absorbing layer comprises the following components:
selenic acid 3.8g/L, copper salt (copper sulfate) 2.8g/L, nickel salt (nickel sulfate) 2.8g/L, complexing agent (EDTA) 3.3g/L, and pH 2.2.
The preparation method comprises the following steps:
providing a substrate;
activating the matrix to obtain an activated matrix;
carrying out chemical oxidation on the activated matrix to obtain a matrix containing the heat dissipation coating;
wherein the matrix is an invar matrix;
the chemical oxidation liquid for preparing the heat absorption layer is adopted as an oxidation reagent in the chemical oxidation;
the activation is that mixed acid is adopted to carry out acid washing treatment on the matrix; the mixed acid used in the activation includes: 295g/L hydrochloric acid and 200g/L sulfuric acid; the activation temperature is 30 ℃; the activation time is 3min;
the time of the chemical oxidation is 17min.
The XRD spectrum of the obtained coating is shown in figure 1 in detail, and it can be seen that the blackening film layer is mainly composed of amorphous CuSe and a small amount of crystalline components. The blackening film contains selenium, copper elements, nickel, phosphorus, oxygen and other elements. From the blackening liquid composition, it can be inferred that a small amount of unknown substances which are not analyzed by X-ray diffraction may be phosphate. Because the blackening matrix invar mainly comprises iron and nickel, the iron content is higher. In summary, it can be determined that the main film forming material is copper selenide and nickel selenide; the auxiliary film forming material is iron phosphate. The SEM photograph and AFM photograph of the obtained coating are shown in figures 2 and 3, and as can be seen from figure 2, the pore diameter of the coating in the figure is loose, the distribution is uniform, the surface is rough, and no substrate is exposed; as can be seen from FIG. 3, the roughness is 244nm, the roughness is significantly improved, and the light trap structure is increased.
Example 2
The embodiment provides a chemical oxidation solution for preparing a heat absorption layer and application thereof, which is a preparation method of the heat absorption layer, and specifically comprises the following steps:
the chemical oxidizing liquid for preparing the heat absorbing layer comprises the following components:
3.2g/L of selenious acid, 3.6g/L of copper salt (copper nitrate), 3g/L of nickel salt (nickel nitrate) and 3.7g/L of complexing agent (disodium EDTA), and the pH value is 3.
The preparation method comprises the following steps:
providing a substrate;
activating the matrix to obtain an activated matrix;
carrying out chemical oxidation on the activated matrix to obtain a matrix containing the heat dissipation coating;
wherein the matrix is a pure iron matrix;
the chemical oxidation liquid for preparing the heat absorption layer is adopted as an oxidation reagent in the chemical oxidation;
the activation is that mixed acid is adopted to carry out acid washing treatment on the matrix; the mixed acid used in the activation includes: 305g/L of hydrochloric acid and 205g/L of sulfuric acid; the activation temperature is 35 ℃; the activation time is 4min;
the time of the chemical oxidation is 18min.
Example 3
The embodiment provides a chemical oxidation solution for preparing a heat absorption layer and application thereof, which is a preparation method of the heat absorption layer, and specifically comprises the following steps:
the chemical oxidizing liquid for preparing the heat absorbing layer comprises the following components:
3.5g/L of selenious acid, 2g/L of copper salt (copper sulfate), 2.5g/L of nickel salt (nickel nitrate) and 4g/L of complexing agent (EDTA), and the pH value is 1.5.
The preparation method comprises the following steps:
providing a substrate;
activating the matrix to obtain an activated matrix;
carrying out chemical oxidation on the activated matrix to obtain a matrix containing the heat dissipation coating;
the chemical oxidation liquid for preparing the heat absorption layer is adopted as an oxidation reagent in the chemical oxidation;
wherein the matrix is a pure copper matrix;
the activation is that mixed acid is adopted to carry out acid washing treatment on the matrix; the mixed acid used in the activation includes: 310g/L hydrochloric acid and 190g/L sulfuric acid; the activation temperature is 40 ℃; the activation time is 3min;
the time of the chemical oxidation is 20min.
Example 4
The embodiment provides a chemical oxidation solution for preparing a heat absorption layer and application thereof, which is a preparation method of the heat absorption layer, and specifically comprises the following steps:
the chemical oxidizing liquid for preparing the heat absorbing layer comprises the following components:
selenious acid 2.5g/L, copper salt 4g/L, nickel salt 3.2g/L and complexing agent 3g/L, and the pH value is 3.8.
The preparation method comprises the following steps:
providing a substrate;
activating the matrix to obtain an activated matrix;
carrying out chemical oxidation on the activated matrix to obtain a matrix containing the heat dissipation coating;
the chemical oxidation liquid for preparing the heat absorption layer is adopted as an oxidation reagent in the chemical oxidation;
wherein the substrate is a copper alloy substrate (the copper alloy is T2 red copper);
the activation is that mixed acid is adopted to carry out acid washing treatment on the matrix; the mixed acid used in the activation includes: 290g/L of hydrochloric acid and 210g/L of sulfuric acid; the activation temperature is 25 ℃; the activation time is 5min;
the time of the chemical oxidation is 15min.
Example 5
The difference from example 1 is only that selenious acid is not contained.
Example 6
The only difference from example 1 is that copper sulphate is exchanged for copper chloride of equal concentration.
Example 7
The only difference from example 1 is the substitution of nickel sulphate for nickel chloride of equal concentration.
Example 8
The only difference from example 1 is that EDTA is replaced with an equal concentration of citric acid.
Example 9
The only difference from example 1 is that EDTA was replaced with hydroquinone at an equal concentration.
The coating materials obtained in examples 1 to 9 were subjected to heat absorption performance test, adhesion test, salt spray resistance test, and the test procedure was as follows:
heat absorption properties
The coating has high emissivity and high blackness (the sunlight absorptivity is more than 90 percent), can improve the radiation heat exchange between the radiating fins and the cooling liquid, and obviously improves the heat exchange efficiency. The heat absorption capacity of the coating is characterized by infrared heat emissivity in the test, and the specific process is as follows: the proportion of the total heat amount of the heat emitted in the specified wavelength range (generally 4-50 μm) is measured by a thermal imager, a thermocouple or the like, and the result is calculated as the mass concentration of the heat emitted.
Adhesion test
The test adopts a scratch test to evaluate the adhesive force between the coating and the matrix, and in the test process, a scriber is used for pulling 3-4cm in parallel, six cuts are formed, and a paint film is cut through to a substrate; then the cutting mark is vertical to the former by the same method, and the cutting mark is six times; this forms a number of small squares. For a soft substrate, forming each diagonal line along the grid pattern by using a soft brush, and lightly sweeping forward and backward for several times to grade; for a hard substrate, cleaning is firstly carried out, then an adhesive tape (generally a 3M adhesive tape is used), the adhesive tape is required to be in full contact with an experimental area, the adhesive tape can be rubbed back and forth by fingers to ensure that the adhesive tape is in good contact, then the adhesive tape is pulled out rapidly, and a visual or magnifying glass comparison standard is used for comparing and grading with an explanatory drawing. The criteria for its classification are described as:
0-the cut edge is completely smooth, and no lattice falls off.
Some coating at the 1-intersection is dropped off, and the affected area cannot be obviously larger than 5%.
2-coating is dropped off at the intersection of the incisions or along the edges of the incisions, the affected area is 5% -15%.
The 3-coat falls off in large areas along the cut edge portion or all at 15% -35% of the affected cross-cut area.
4-the whole strip is fallen off along the edge, some grids are partially or completely fallen off, and the affected area is 35% -65%.
The degree of 5-exfoliation exceeded grade 4.
When the adhesion is measured by the cross-cut method, a coating film having a thickness of 250 μm can be measured at the maximum. Different cross-cut spacing can be selected according to the thickness of the coating, generally the coating is smaller than 60 mu m, the spacing between hard substrates is 1mm, and the spacing between soft substrates is 2mm; the thickness of the coating is 60-120 mu m, and the spacing between the soft substrate and the hard substrate is 2mm; the thickness of the coating is more than 120 mu m, and the distance between the soft substrate and the hard substrate is 3mm. In ISO12944, it is stated that adhesion needs to be of class 1 to be acceptable.
Salt spray resistance test
Experiment salt spray resistance tests were performed on the coatings according to the GB/T2423.17 standard. The test procedure was as follows:
first, a sample to be tested is mounted in a test box.
Then, the sodium chloride solution with a certain concentration is atomized to form salt mist, and the salt mist is dispersed in a test chamber.
The sample is exposed to the environment for a period of time during which the sample is inspected and recorded for corrosion.
Finally, the samples were removed from the test chamber, cleaned, and dried, and then subjected to detailed corrosion evaluations, such as bare metal area, corrosion rate, corrosion depth, and the like.
The standard stipulates that the test period is 16h, 24h, 48h, 96h and the like, and from the practical use environment, the corrosion-free coating surface after 48h corrosion is stipulated to be qualified in the test, and the corrosion resistance of the coating is reliable.
The results obtained by the test are shown in Table 1.
TABLE 1
As can be seen from the results of the above embodiments, the coating prepared from the chemical oxidizing solution for preparing the heat absorption layer provided by the invention has good heat absorption performance, high temperature resistance and adhesion performance with the substrate, and is beneficial to improving the heat dissipation performance of the heat dissipation device, thereby being beneficial to obtaining the high-performance heat dissipation device.
It is stated that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e., it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A chemical oxidizing liquid for preparing a heat absorbing layer, the chemical oxidizing liquid for preparing a heat absorbing layer comprising: selenic acid, copper salt, nickel salt, pH regulator and complexing agent.
2. The chemical oxidizing solution for preparing a heat sink of claim 1, wherein the chemical oxidizing solution for preparing a heat sink comprises:
2.5-3.5g/L selenic acid, 2-4g/L copper salt, 2.5-3.2g/L nickel salt and 3-4g/L complexing agent, and the pH value is 1.5-3.8.
3. The chemical oxidizing solution for producing a heat absorbing layer according to claim 1 or 2, wherein the copper salt comprises copper sulfate and/or copper nitrate;
the nickel salt comprises nickel sulfate and/or nickel nitrate;
the complexing agent comprises an aminocarboxylic acid and/or aminocarboxylate.
4. A chemical oxidizing solution for producing a heat sink of claim 3, wherein said pH adjustor comprises 1 or a combination of at least 2 of sodium dihydrogen phosphate, nitric acid, sulfuric acid, phosphoric acid, or hydrochloric acid.
5. A method of producing a heat sink, the method comprising:
providing a substrate;
activating the matrix to obtain an activated matrix;
carrying out chemical oxidation on the activated matrix to obtain a matrix containing the heat dissipation coating;
the chemical oxidation uses the chemical oxidizing liquid for preparing the heat absorbing layer according to any one of claims 1 to 3 as an oxidizing agent.
6. The method of manufacturing according to claim 5, wherein the substrate comprises 1 of iron, iron alloy, copper, or copper alloy.
7. The method according to claim 5, wherein the activation is an acid washing treatment of the substrate with a mixed acid;
the mixed acid used in the activation includes: 290-310g/L of hydrochloric acid and 190-210g/L of sulfuric acid.
8. The method of claim 5, wherein the activation temperature is 25-40 ℃;
the activation time is 3-5min.
9. The method of claim 5, wherein the chemical oxidation is carried out for a period of 15 to 20 minutes.
10. A heat sink layer, characterized in that it is produced by the production method according to any one of claims 5 to 9;
the film layer of the heat absorption layer comprises copper selenide and nickel selenide.
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| JPS61288339A (en) * | 1985-06-17 | 1986-12-18 | Matsushita Electronics Corp | Indirectly-heated cathode for cathode-ray tube |
| CN110565082A (en) * | 2019-10-15 | 2019-12-13 | 攀枝花学院 | Steel normal-temperature blackening agent, preparation method thereof and blackening method |
| CN115613020A (en) * | 2022-09-22 | 2023-01-17 | 上海应用技术大学 | Metal blackening treatment method |
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| JPS61288339A (en) * | 1985-06-17 | 1986-12-18 | Matsushita Electronics Corp | Indirectly-heated cathode for cathode-ray tube |
| CN110565082A (en) * | 2019-10-15 | 2019-12-13 | 攀枝花学院 | Steel normal-temperature blackening agent, preparation method thereof and blackening method |
| CN115613020A (en) * | 2022-09-22 | 2023-01-17 | 上海应用技术大学 | Metal blackening treatment method |
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