CN103773083A - Optical interference color change pigment and its preparation method and application - Google Patents
Optical interference color change pigment and its preparation method and application Download PDFInfo
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- CN103773083A CN103773083A CN201210396799.1A CN201210396799A CN103773083A CN 103773083 A CN103773083 A CN 103773083A CN 201210396799 A CN201210396799 A CN 201210396799A CN 103773083 A CN103773083 A CN 103773083A
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- 230000003287 optical effect Effects 0.000 title claims abstract description 30
- 239000000049 pigment Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 16
- 239000003973 paint Substances 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 7
- 239000010409 thin film Substances 0.000 claims abstract description 7
- -1 coatings Substances 0.000 claims abstract description 6
- 230000000007 visual effect Effects 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000004033 plastic Substances 0.000 claims abstract description 4
- 229920003023 plastic Polymers 0.000 claims abstract description 4
- 239000002537 cosmetic Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 239000010408 film Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 13
- 239000010445 mica Substances 0.000 claims description 9
- 229910052618 mica group Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000012686 silicon precursor Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract 1
- 229960001296 zinc oxide Drugs 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 6
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- HTCXJNNIWILFQQ-UHFFFAOYSA-M emmi Chemical compound ClC1=C(Cl)C2(Cl)C3C(=O)N([Hg]CC)C(=O)C3C1(Cl)C2(Cl)Cl HTCXJNNIWILFQQ-UHFFFAOYSA-M 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QHTQPPYLUBCTKV-UHFFFAOYSA-N N-methylmethanamine titanium Chemical compound [Ti].CNC QHTQPPYLUBCTKV-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
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- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a preparation method of an optical interference pigment, and characterized in that: by an atomic layer deposition technology, alternately depositing high refractive index and low refractive index multilayer oxide thin films on a sheet substrate, and by accurate adjustment and control of the refractive index and thickness of thin film materials, obtaining the optical interference pigment with the color changed with change of visual angles. The atomic layer deposition technology can guarantee the inherent smoothness of the sheet substrate surface, has excellent covering power, and full realizes the expression of optical interference color. The preparation method of the optical interference color change pigment is used in the industries of paints, coatings, plastics, ceramics, glass and cosmetics.
Description
Technical field
The present invention designs a kind of pigment and its preparation method and application, particularly relates to a kind of optical interference camouflage paint and its preparation method and application.
Background technology
Light interfere pigment is metal oxide or the nonmetal oxide of alternating deposit high refractive index and low-refraction on flat substrates, utilize optical interference to produce color, can be used in paint, coating, plastics, pottery, glass, makeup and printing-ink industry.The interference color of pigment are determined by light refractive index and the thickness of oxide skin.If thin-film refractive index and gauge control are improper, will make coated interference pigment reflect too many light at whole visible light wave range, cause human eye perceives very bright, but do not have coloured phenomenon.Therefore,, for the colour index that controlled film is, the thickness of each layer is fine adjustment each other, thickness error is controlled in the scope of Ethylmercurichlorendimide level.Main application wet-chemical coating method is prepared light interfere pigment on the flat substrates such as mica, glass, tinsel at present.But, wet chemical method, for example sol-gel method, can not accurately be controlled at the thickness of each rete within the scope of Ethylmercurichlorendimide level.In addition, wet chemical method can cause the surperficial intrinsic smoothness of thin slice base material deteriorated, and the dispersity of particle is not enough, causes irregular reflection, can not make full use of the reflected light of slice surfaces, can not fully realize the expression of interference color.Ald (Atomic Layer Deposition, ALD) technology can well solve above-mentioned technical problem.The presoma reacting keeps separating each other, does not directly occur to react between gas phase, and surface chemical reaction only occurs.Deposit film can reach the control of atomic level, film thickness can simply and accurately be controlled by the cycle number of reaction, the multilayer film of heterogeneity also can directly obtain, and has the ability of big area, batch deposition film, and film has excellent model keeping character and repeatability.Atomic layer deposition method also can guarantee the intrinsic smoothness of thin slice substrate surface, has fabulous covering power, fully realizes the expression of optical interference look.
Summary of the invention
Object of the present invention is for the deficiency of current techniques, a kind of preparation method of brand-new optical interference pigment is provided, use technique for atomic layer deposition on flat substrates, alternately to prepare the oxide membranous layer of high refractive index and low-refraction, accurately control the thickness of rete, obtain with the different different colours interference of light pigment that reflects of viewing angle.
The surface albedo of a definite film structure is the function of lambda1-wavelength and input angle.In the time of a given input angle, just can obtain this film structure under this condition by the reflection spectrum curve of Wavelength distribution, each definite film structure has corresponding reflection spectrum, and this reflection spectrum changes the change with input angle.Carry out as required the design of film system, reasonable computation apolegamy film material and thicknesses of layers, change refractive index and film thickness value, just can reach predetermined reflection spectrum index.The optical thin film with interference structure can be obtained to light interfere pigment after a series of processing such as pulverizing, classification, surface treatment.Under certain vacuum condition, utilize technique for atomic layer deposition the oxide material of different refractivity successively alternating deposition on flat substrates, can guarantee homogeneity and the compactness of rete, and the error of thicknesses of layers can be controlled in the scope of Ethylmercurichlorendimide level, this has guaranteed in technique, and optical interference pigment performance is stable, compact structure, can not fade, have strong weathering resistance and shear resistant.
The invention provides a kind of preparation method of optical interference pigment, it is characterized in that, by the multilevel oxide film of technique for atomic layer deposition alternating deposit high refractive index and low-refraction on flat substrates, fine adjustment and specific refractory power and the thickness of controlling thin-film material, obtain the light interfere pigment that color changes with visual angle change.
Described ald at flat substrates deposition high refractive index oxide film is: the reaction chamber of atomic layer deposition apparatus is evacuated to 10～16 hPa, question response cavity temperature reaches 100～300 ℃, start the first reactant zinc, or tin, or the presoma of titanium passes into the high pure nitrogen pulse of 0.1～0.3 second and enters reaction chamber, by chemisorption to flat substrates, pass into again on 3～5 seconds high pure nitrogen pulse cleaning substrates with physics mode absorption, excess zinc in reaction chamber, or tin, or titanium precursor body; Then pass into 0.1～0.3 second water vapor, or other oxygen source presoma pulses, chemisorption is to the first reactive material, then falls unnecessary water vapor with 3～5 seconds high pure nitrogen pulse cleanings, or other oxygen source presomas; Repeat said process and obtain certain thickness high refractive index layer.
Described ald refers at flat substrates deposition low-refraction sull: the reaction chamber of atomic layer deposition apparatus is evacuated to 10～16 hPa, question response cavity temperature reaches 100～300 ℃, start the first reactant aluminium, or the presoma of silicon passes into the high pure nitrogen pulse of 0.1～0.3 second and enters reaction chamber, by chemisorption to flat substrates, pass into again on 3～5 seconds high pure nitrogen pulse cleaning substrates with physics mode absorption, excess of aluminum in reaction chamber, or silicon precursor; Then pass into 0.1～0.3 second water vapor, or other oxygen source presoma pulses, chemisorption is to the first reactive material, then falls unnecessary water vapor with 3～5 seconds high pure nitrogen pulse cleanings, or other oxygen source presomas; Repeat said process and obtain a low-index layer.
Described high-index material is to be not less than 2 oxide material in visible light wave range specific refractory power, is specially zinc oxide or titanium oxide or stannic oxide; Described low-index material be in visible light wave range specific refractory power not higher than 1.8 oxide material, be specially aluminum oxide or silicon oxide.
Described multilevel oxide film has following film structure feature: H/L/ ... / H, H is the oxide membranous layer of high refractive index, L is the oxide membranous layer of low-refraction, high low-index film H and L alternating deposit, and last one deck is high refractive index layer H, total number of plies of whole film structure is an odd number, and is less than or equal to 9.
The thickness of described individual layer high refractive index layer (H) and individual layer low-index film (L) is 20 nanometer to 200 nanometers.
Described flat substrates is mica, or tinsel, or glass.
The flat substrates of deposition oxide film is pulverized, obtained optical interference pigment.
The invention provides a kind of optical interference pigment being prepared by aforesaid method.
The present invention also provides the application of the optical interference camouflage paint being prepared by aforesaid method in paint, coating, plastics, pottery, glass, cosmetic industry.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1:
By flat substrates mica (size is 20～60 microns) put into atomic layer deposition apparatus carry powdered sample annex after be placed in again reaction chamber, be evacuated between 10～16hPa.Question response cavity temperature reaches 150 ℃, start the process of ald zinc oxide film (H layer): zinc ethyl presoma passes into the high pure nitrogen pulse of 0.1 second and enters reaction chamber, by chemisorption to mica, then pass on 3 seconds high pure nitrogen pulse cleaning substrates with physics mode absorption, excessive zinc ethyl in reaction chamber; Then pass into water vapor pulse in 0.1 second, chemisorption is to the first reactive material, then falls unnecessary water vapor with 4 seconds high pure nitrogen pulse cleanings.Said process completes the deposition of the zinc-oxide film of a circulation, and repetition said process obtains the zinc oxide film (H layer) of thickness approximately 54 nanometers for 271 times.After H layer has deposited, deposit again L layer alumina layer: continue to pass into the trimethyl aluminium presoma pulse of 0.1 second to reaction chamber, make its with chemical mode saturated adsorption on the surface of zinc oxide film, then fall unnecessary trimethyl aluminium presoma with 3 seconds high pure nitrogen pulse cleanings; Then pass into water vapor pulse 0.1 second, then fall unnecessary water vapor with the high pure nitrogen pulse cleaning of 4 seconds.Said process completes the deposition of the aluminum oxide of a circulation, repeats said process and obtains the alumina layer (L layer) that thickness is about 64 nanometers for 638 times.Finally, continue as previously described the zinc oxide film of deposition 54 nanometers, complete the optical interference pigment of H/L/H trilamellar membrane architecture.Observation visual angle color of coated interference pigment when vertically changing to level is changed to redness through purple by hyacinthine.
Embodiment 2:
By flat substrates mica (size is 20～60 microns) put into atomic layer deposition apparatus carry powdered sample annex after be placed in again reaction chamber, be evacuated between 10～16hPa.Question response cavity temperature reaches 150 ℃, start the process of ald zinc oxide film (H layer): zinc ethyl presoma passes into the high pure nitrogen pulse of 0.1 second and enters reaction chamber, by chemisorption to mica, then pass on 3 seconds high pure nitrogen pulse cleaning substrates with physics mode absorption, excessive zinc ethyl in reaction chamber; Then pass into water vapor pulse in 0.1 second, chemisorption is to the first reactive material, then falls unnecessary water vapor with 4 seconds high pure nitrogen pulse cleanings.Said process completes the deposition of the zinc-oxide film of a circulation, and repetition said process obtains the zinc oxide film (H layer) of thickness approximately 54 nanometers for 271 times.After H layer has deposited, deposit again L layer alumina layer: continue to pass into the trimethyl aluminium presoma pulse of 0.1 second to reaction chamber, make its with chemical mode saturated adsorption on the surface of zinc oxide film, then fall unnecessary trimethyl aluminium presoma with 3 seconds high pure nitrogen pulse cleanings; Then pass into water vapor pulse 0.1 second, then fall unnecessary water vapor with the high pure nitrogen pulse cleaning of 4 seconds.Said process completes the deposition of the aluminum oxide of a circulation, repeats said process and obtains the alumina layer (L layer) that thickness is about 64 nanometers for 638 times.Continue the zinc oxide film of repeated deposition 54 nanometers and the alumina layer of 64 nanometers successively.Finally, continue as previously described the zinc oxide film of deposition 54 nanometers, complete the optical interference pigment of H/L/H/lH five tunic architecture.Observation visual angle color of coated interference pigment when vertically changing to level is changed with similar described in embodiment 1 to redness through purple by hyacinthine, but the saturation ratio of color is higher.
Embodiment 3:
By flat substrates mica (size is 20～60 microns) put into atomic layer deposition apparatus carry powdered sample annex after be placed in again reaction chamber, be evacuated between 10～16hPa.Question response cavity temperature reaches 150 ℃, start the process of ald titanium oxide layer (H layer): four (dimethylamine) titanium precursor body passes into the high pure nitrogen pulse of 1 second and enters reaction chamber, by chemisorption to mica, then pass on 3 seconds high pure nitrogen pulse cleaning substrates with physics mode absorption, excessive four (dimethylamine) titanium in reaction chamber; Then pass into water vapor pulse in 0.1 second, chemisorption is to the first reactive material, then falls unnecessary water vapor with 4 seconds high pure nitrogen pulse cleanings.Said process completes the deposition of the thin film of titanium oxide of a circulation, and repetition said process obtains the titanium oxide layer (H layer) of thickness approximately 51 nanometers for 729 times.After H layer has deposited, deposit again L layer alumina layer: continue to pass into the trimethyl aluminium presoma pulse of 0.1 second to reaction chamber, make its with chemical mode saturated adsorption on the surface of titanium oxide layer, then fall unnecessary trimethyl aluminium presoma with 3 seconds high pure nitrogen pulse cleanings; Then pass into water vapor pulse 0.1 second, then fall unnecessary water vapor with the high pure nitrogen pulse cleaning of 4 seconds.Said process completes the deposition of the aluminum oxide of a circulation, repeats said process and obtains the alumina layer (L layer) that thickness is about 72 nanometers for 716 times.Finally, continue as previously described the titanium oxide layer of deposition 51 nanometers, complete the optical interference pigment of H/L/H trilamellar membrane architecture.Observation visual angle color of coated interference pigment when vertically changing to level is changed to purple through bluish-green, blueness by green.
Claims (10)
1. the preparation method of an optical interference pigment, it is characterized in that, by the multilevel oxide film of technique for atomic layer deposition alternating deposit high refractive index and low-refraction on flat substrates, fine adjustment and specific refractory power and the thickness of controlling thin-film material, obtain the light interfere pigment that color changes with visual angle change.
2. the preparation method of a kind of optical interference camouflage paint according to claim 1, it is characterized in that, described ald at flat substrates deposition high refractive index oxide film is: the reaction chamber of atomic layer deposition apparatus is evacuated to 10～16 hPa, question response cavity temperature reaches 100～300 ℃, start the first reactant zinc, or tin, or the presoma of titanium passes into the high pure nitrogen pulse of 0.1～0.3 second and enters reaction chamber, by chemisorption to flat substrates, pass into again on 3～5 seconds high pure nitrogen pulse cleaning substrates with physics mode absorption, excess zinc in reaction chamber, or tin, or titanium precursor body, then pass into 0.1～0.3 second water vapor, or other oxygen source presoma pulses, chemisorption is to the first reactive material, then falls unnecessary water vapor with 3～5 seconds high pure nitrogen pulse cleanings, or other oxygen source presomas, repeat said process and obtain certain thickness high refractive index layer.
3. the preparation method of a kind of optical interference camouflage paint according to claim 1, it is characterized in that, described ald refers at flat substrates deposition low-refraction sull: the reaction chamber of atomic layer deposition apparatus is evacuated to 10～16 hPa, question response cavity temperature reaches 100～300 ℃, start the first reactant aluminium, or the presoma of silicon passes into the high pure nitrogen pulse of 0.1～0.3 second and enters reaction chamber, by chemisorption to flat substrates, pass into again on 3～5 seconds high pure nitrogen pulse cleaning substrates with physics mode absorption, excess of aluminum in reaction chamber, or silicon precursor, then pass into 0.1～0.3 second water vapor, or other oxygen source presoma pulses, chemisorption is to the first reactive material, then falls unnecessary water vapor with 3～5 seconds high pure nitrogen pulse cleanings, or other oxygen source presomas, repeat said process and obtain a low-index layer.
4. the preparation method of a kind of optical interference camouflage paint according to claim 1, is characterized in that, described high-index material is to be not less than 2 oxide material in visible light wave range specific refractory power, is specially zinc oxide or titanium oxide or stannic oxide; Described low-index material be in visible light wave range specific refractory power not higher than 1.8 oxide material, be specially aluminum oxide or silicon oxide.
5. the preparation method of a kind of optical interference camouflage paint according to claim 1, it is characterized in that, described multilevel oxide film has following film structure feature: H/L/ ... / H, H is the oxide membranous layer of high refractive index, L is the oxide membranous layer of low-refraction, high low-index film H and L alternating deposit, and last one deck is high refractive index layer H, total number of plies of whole film structure is an odd number, and is less than or equal to 9.
6. the preparation method of a kind of optical interference camouflage paint according to claim 1, is characterized in that, the thickness of described individual layer high refractive index layer (H) and individual layer low-index film (L) is 20 nanometer to 200 nanometers.
7. the preparation method of a kind of optical interference camouflage paint according to claim 1, is characterized in that, described flat substrates is mica, or tinsel, or glass.
8. the preparation method of a kind of optical interference camouflage paint according to claim 1, is characterized in that, the flat substrates of deposition oxide film is pulverized, and obtains optical interference pigment.
9. the optical interference pigment being prepared by the method described in claim 1～7 any one.
10. by the application of the optical interference camouflage paint described in 8 in paint, coating, plastics, pottery, glass, cosmetic industry described in claim.
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| CN201210396799.1A CN103773083B (en) | 2012-10-18 | 2012-10-18 | Optical interference color change pigment and its preparation method and application |
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| CN201210396799.1A CN103773083B (en) | 2012-10-18 | 2012-10-18 | Optical interference color change pigment and its preparation method and application |
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| CN110885972A (en) * | 2019-10-30 | 2020-03-17 | 杭州美迪凯光电科技股份有限公司 | ALD preparation method for eliminating dot defects of camera module and product thereof |
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