CN109581564A - A kind of multi-layer cermet film and preparation method thereof with structure color - Google Patents
A kind of multi-layer cermet film and preparation method thereof with structure color Download PDFInfo
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Abstract
The invention discloses a kind of multi-layer cermet films with structure color, outward successively include metal layer, dielectric layer and metal nanometer line array-ceramic thin film from substrate；In the metal nanometer line array-ceramic thin film, metal nanometer line is uprightly distributed in ceramic phase, the diameter of metal nanometer line is not less than 2nm, highly identical as the thickness of the metal nanometer line array-ceramic thin film, the spacing 1.5-20nm between metal nanometer line.Absorption characteristic of the multi-layer cermet film in visible light wave segment limit is easy to regulate and control, and color-gamut range obtained is big, brightness and saturation degree are preferable.A kind of preparation method of multi-layer cermet film with structure color is also disclosed, the preparation method is simple, and it is at low cost, it is suitble to large area preparation.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to a kind of multi-layer cermet film with structure color and its
Preparation method.
Background technique
Traditional chemical dye and pigment generates different colors by the selective absorbing to visible light, but they are past
Toward poisonous and harmful, environment is unfriendly, fugitive color and is difficult to the disadvantages of recycling under illumination and high temperature.It is contaminated compared to chemistry
Material, the schemochrome material based on artificial micro-structure, have the characteristics that recoverable facilitate, chemical stability it is good, while can be with
Diffraction limit is broken through, imaging resolution is improved.These characteristics pass schemochrome in ultrahigh resolution imaging, FPD, optics
Sense detects and there is important potential application in the anti-fake equal fields of advanced optical.
Illumination causes the collective oscillation of metal free charge, as surface phasmon in metal surface.Metal micro-nano knot
Coupling in structure between photon and free electron gas forms the visible light that plasmon resonance absorbs (or radiation) special frequency channel, from
And generate phasmon schemochrome.By changing the morphology and size of phasmon metal Nano structure, reach regulation light characteristic
Purpose, therefore same material can produce out different colors, and which strongly simplifies the manufacturing processes of different colours unit.
Compared with the periodic dielectric structures such as photonic crystal, semiconductor nanowires, strong confinement is in the equal from sharp of nanometer metal structure surface
First effect can be such that the scale of device is more miniaturized.The anisotropy of noble metal nano cable architecture leads to its surface phasmon
Resonance has a variety of resonance modes such as axially and radially, and the array that nano wire of a large amount of adjacent spacings less than 5nm forms makes altogether
Strong coupling is showed between vibration mode, so that its multiband selective absorbing characteristic to light can be realized.In nano-wire array
In, electric field by strong local between adjacent nanowires, while also have standing wave resonance generation.In addition, metal nanometer line is being handed over
Generated dipole induces image charge in the metal layer in Electromagnetic Field, can also realize between plasmon resonance mode more
For complicated coupling.Due to a variety of mechanism simultaneously generation effect, related micro-nano structure colour developing regulation can it is more flexible and
Diversification.At the same time, while exciting phasmon, the electrode that can also be used as device uses metal structure, realizes outer
The driving of boundary's power supply, to possess huge application prospect in photoelectricity integration field.
The Chinese patent literature of Publication No. CN104914494A discloses a kind of golden using nano impression preparation band chassis
Belong to the method that hole obtains whole chromatogram schemochrome, the nanostructure is a series of Square array hole in different-diameter/periods
System of battle formations shape has the adjustable anomalous transmission peak of (360nm~810nm) peak position in visible light wave range.
The Chinese patent literature of Publication No. CN108059829A discloses a kind of knot that enhanced strength type low angle is interdependent
Structure color material and preparation method thereof, the material is by anti-albumen photonic crystal and is filled in the anti-anti- protein structure of albumen photonic crystal
Elastomer composite in hole is constituted, its color does not change under different viewing angles and different stretch intensity.
Made metal micro-nanostructure is gone at present, and common micro-nano technology technology includes electron beam lithography skill
The technologies such as art, nanometer embossing, focused-ion-beam lithography and laser direct-writing.These method and processes are complicated, cost and to equipment
Requirement it is high, while being difficult to realize large area preparation.In addition, typical schemochrome includes metal grating nanostructure, metal foil
The nano aperture structure of film, metal-dielectric-metal resonance structure etc., these structures often do not have good in atmospheric environment
Stability and mechanical performance, further limit their practical application.
Summary of the invention
The multi-layer cermet film and preparation method thereof with structure color that the present invention provides a kind of, in visible light
Absorption characteristic in wavelength band is easy to regulate and control, and color-gamut range obtained is big, brightness and saturation degree are preferable.
The technical solution of the present invention is as follows:
A kind of multi-layer cermet film with structure color successively includes metal layer, dielectric layer from substrate outward
With metal nanometer line array-ceramic thin film；
In the metal nanometer line array-ceramic thin film, metal nanometer line is uprightly distributed in ceramic phase, metal nano
The diameter of line be not less than 2nm, it is highly identical as the thickness of the metal nanometer line array-ceramic thin film, metal nanometer line it
Between spacing be 1.5~20nm.
In the multi-layer cermet film, metal nanometer line array is orderly and is densely distributed in ceramic phase, passes through control
The distribution of metal nanometer line array processed can obtain different nano wire micro-structures, the different nano wire micro-structure is special
Sign counter sample shows different color, and metal layer mainly plays a part of to transmit and reflect to incident light, and dielectric layer is in
Between metal layer and metal nanometer line array-ceramic thin film, mainly regulate and control metal nanometer line and metal interlevel Charged Couple
Effect, convenient for accurately controlling the absorption peak position of laminated film, to regulate and control the color of device.
When the metal nanometer line in metal nanometer line array-ceramic thin film diameter be not less than 2nm, metal nanometer line it
Between spacing be 1.5~20nm, metal nanometer line reaches in the percentage by volume of the metal nanometer line array-ceramic thin film
5%~60%.
The multi-layer cermet film receives the response characteristic of incident light and the microstructure features of metal nanometer line, i.e. metal
The size and arrangement situation of rice noodles and the dielectric constant of nano wire surrounding medium are closely related.Nanowire diameter and it is adjacent between
Away from appropriateness change and can significantly regulate and control the resonant frequency of surface phasmon, cause the movement for absorbing peak position and absorption intensity
Significant change.Therefore, in order to obtain color-gamut range big, brightness and the preferable multi-layer cermet film of saturation degree, metal
Nanowire diameter is 3~7nm, and the spacing between metal nanometer line is 2.5~10nm.In this way, metal nanometer line is in the metal
Nano-wire array-ceramic thin film percentage by volume reaches 10%~40%.
Preferably, metal nanometer line array-the ceramic thin film with a thickness of 50~300nm.
Dielectric layer and metal layer part are smaller to the regulation amplitude of absorption characteristic, can finely be adjusted to gained color
It is whole.For the power of accuracy controlling metal nanometer line and the effect of metal interlevel Charged Couple, accurately to control the suction of laminated film
Receive peak position, to regulate and control the color of device, the dielectric layer with a thickness of 0.5~30nm.In order to meet reflection or through mould
Formula colour developing dual requirements, the metal layer with a thickness of 3~200nm.
Wherein, the metal layer material is identical with metal nano wire material, the dielectric layer material and ceramic phase material
It is identical.In this way while guaranteeing that absorption characteristic of the multi-layer cermet film in visible light wave segment limit is easy to regulate and control, letter
Preparation method is changed.
Preferably, metal material is gold, platinum, silver, copper, one in aluminium, or both any alloy formed, that is to say, that
Metal nanometer line can be gold, platinum, silver, copper or aluminium nano wire, and metal layer, which can be gold, silver, aluminium or platinum layer, to be gold
Silver, golden platinum or aerdentalloy layer；Dielectric layer material is oxide, nitride, carbide, boride or silica；Ceramics
It is mutually oxide, nitride, carbide, boride or silica.
A kind of preparation method of the multi-layer cermet film with structure color, comprising the following steps:
(1) pre-processed substrate；
(2) choose metal and ceramics be used as target, control metallic target work, step (1) processed substrate surface into
Row magnetron sputtering deposition, obtains metal layer；Then, control ceramic target work carries out magnetron sputtering deposition electricity on the metal layer and is situated between
Matter layer；Finally, control metallic target and ceramic target work at the same time, magnetron sputtering deposited metal nano-wire array-on the dielectric layer
Ceramic thin film obtains multi-layer cermet film；
When magnetron sputtering, metallic target is driven using pulse, radio frequency or DC power supply driving, ceramic target using radio-frequency power supply.
Compared with common micro-nano technology means, the preparation process of magnetron sputtering is simple, and parameter regulation is convenient, compound pottery
The range of choice of porcelain and metal is also bigger.By the regulation to compound ceramic target and metal target power output in sputtering process, and
In conjunction with the adjusting of the low-energy ion bombardment with selective etch effect, realize arrangement to metal nanometer line in laminated film and
Size is adjusted on a large scale.
Wherein substrate can be metal material (copper, aluminium, stainless steel etc.) or inorganic non-metallic material (glass, ceramics, oxygen
Compound, nitride etc.) or flexible material (PET, PI, PVA etc.).For the ease of carrying out optic test, the substrate is quartz
The transparent materials such as piece, sapphire, glass slide and PET, organic glass.
In step (1), the preprocessing process to substrate includes: successively with acetone, ethyl alcohol and deionized water to transparent substrates
It is cleaned by ultrasonic, then carries out heating desorption and echo plasma sputtering cleaning, optimize substrate surface cleannes；For having
Machine object or flexible substrate are cleaned by ultrasonic only with detergent and deionized water, and carry out surface activation process.Substrate is by above-mentioned
After pretreatment, the more conducively high-quality growth of metallic cermet films.
In step (2), magnetron sputtering carries out under an argon atmosphere.By to magnetron sputtering metallic target and compound ceramic target
The adjusting of power, in conjunction with the substrate bias plasma progress selective etch of different capacity and changing for sedimentation time length
Become, the change of the largely microstructure features such as size and spacing of metal nanometer line may be implemented.Different micro-structures are answered
Close film and different-thickness dielectric layer collective effect, may be implemented absorb peak position in visible waveband it is anticipated that regulation,
To obtain the schemochrome of full color covering.
Preferably, when sputtering sedimentation metal nanometer line array-ceramic thin film, power density model used in splash-proofing sputtering metal target
It encloses for 0.3~1.5W/cm2；Sputtering power density range used in ceramic target is 2.5~15W/cm2, sputtering pressure range is 0.1
~1Pa, target-substrate distance are higher than 70mm.
When substrate is insulation transparent substrate, the type of substrate bias is rf bias；When substrate is exhausted conductive, transparent lining
When bottom, the type of substrate bias is rf bias or pulsed bias；Substrate bias power density range is 0.5~3W/cm2, from
Bias is higher than -50V.When substrate bias power density is lower than 0.5W/cm2When, metal is difficult to realize selective growth, can not obtain reality
The self-organizing growth of existing nanowire array structure causes the selective absorbing performance of multilayer film and color to present undesirable.
Further, when sputtering sedimentation metal nanometer line array-ceramic thin film, power density used in splash-proofing sputtering metal target
Range is 0.5~1.2W/cm2；Sputtering power density range used in ceramic target is 5~12W/cm2, sputtering pressure range is
0.15~0.6Pa, target-substrate distance are higher than 90mm, and substrate bias power density range is 1~2.5W/cm2, automatic bias is higher than -70V.
Above-mentioned multi-layer cermet film can also be that from substrate successively include metal nanometer line array-Ceramic Composite outward
Layer, dielectric layer and metal layer, specific structural parameters limitation and above-mentioned identical.
Above-mentioned multi-layer cermet film has multiple absorption peaks simultaneously, and incident angle is insensitive, and absorption peak is can
Light-exposed and near infrared band variation range is in 350~1000nm.
Compared with prior art, the invention has the following advantages that
(1) the micro-nano technologies means such as common photoetching are compared, magnetically controlled sputter method of the present invention is not necessarily to template, work
Skill is simple, and cost is relatively low, is suitble to large area preparation, and adjustment parameter is convenient.It is different from the existing generation mode of schemochrome, tightly
The superfine metal nanometer line array and metal-layer structure of solid matter column are more diversified with the mechanism of action between incident light, thus regulate and control
Means are more flexible, and it is richer to obtain color.
(2) wider to the selection face of metal material and ceramic matrix in the present invention, it can select in layers as needed not
With metal or ceramic material construct laminated film, to meet the needs of different practical applications.
(3) in the present invention to substrate material used without particular/special requirement, rigidity or flexible, insulation or conductive, organic or nothing
Machine material can be used as substrate use, be greatly enlarged the application range of related device.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to do simply to introduce, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art, can be with root under the premise of not making the creative labor
Other accompanying drawings are obtained according to these attached drawings.
Fig. 1 is the low power TEM pattern in cermet multi-layer compound film section prepared by embodiment 1；
Fig. 2 is the high power TEM pattern in cermet multi-layer compound film section prepared by embodiment 1；
Fig. 3 is the optical photograph and corresponding absorption spectrum of cermet multi-layer compound film prepared by embodiment 1；
Fig. 4 is the high power TEM pattern in cermet multi-layer compound film section prepared by embodiment 2；
Fig. 5 is the optical photograph and corresponding absorption spectrum of cermet multi-layer compound film prepared by embodiment 2；
The optics of the large-area metal ceramic multilayer laminated film deposited on the flexible PET substrate that Fig. 6 is prepared for embodiment 3
Photo.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, with reference to the accompanying drawings and embodiments to this
Invention is described in further detail.It should be appreciated that the specific embodiments described herein are only used to explain the present invention,
And the scope of protection of the present invention is not limited.
For following embodiment using silicon wafer, quartz plate and PET as substrate, metal material selects Jin Heyin, ceramic material selection two
Silica and aluminium oxide, dielectric substance select silica and aluminium oxide, and metal layer material selects gold thin film.It is splashed by correlation
The adjustment of parameter is penetrated, the size and distribution of nanowires of gold in cermet film layer are changed, dielectric layer thickness is adjusted, prepares not
With the laminated film of color.Its reflecting properties is tested using spectroscopic ellipsometer, characterizes its response characteristic to incident light.
Embodiment 1
It successively uses acetone, ethyl alcohol and deionized water to be cleaned by ultrasonic 15min respectively silicon wafer and quartz plate, removes surface contamination
Object；Silicon wafer after cleaning is fixed on substrate pallet with being dried with nitrogen；Tray loading is entered in magnetron sputtering apparatus settling chamber,
Forvacuum simultaneously is to 10-4Pa or less；Being passed through argon stream makes settling chamber's air pressure be maintained at 0.4Pa, cleans gold with radio-frequency sputtering
Target and silica target 10min, and it is biased cleaning substrate 5min；After etch cleaner, settling chamber's air pressure is adjusted
To 0.3Pa, silica target power supply is closed, the baffle before opening gold target starts to sputter, the Sputtering power density for adjusting gold target is
3.5W/cm2, deposited metal layer, sedimentation time 25min.Gold target driving power is closed, while starting titanium dioxide silicon target driving electricity
Source, power density are set as 5W/cm2, while applying substrate bias power density is 1W/cm2, deposit layer of silicon dioxide medium
Layer, sedimentation time 5min.It is again started up gold target driving power, two target co-sputterings, the wherein sputtering of gold target and titanium dioxide silicon target
Power density is respectively 0.8W/cm2And 5W/cm2, substrate bias power density is 2.5W/cm2, after depositing 1h, close gold target, two
Silicon oxide target and bias driving power, finally obtain the multi-layer cermet film with structure color.
Above-mentioned film sample Cross Section Morphology is observed and analyzed by transmission electron microscope (TEM).Fig. 1 gives
The section TEM pattern of multilayered structure color film low power in embodiment 1, it can be seen that nano-wire array cermet is multiple from figure
Close the delamination and different-thickness of layer, dielectric layer and metal layer.Metal nanometer line array-ceramic thin film is with a thickness of 110
~120nm is in typical periodic arrangement structure, metal layer is as reflection wherein in nanowires of gold insertion silica substrate
Thickness degree is greater than 150nm.Fig. 2 is the section TEM pattern of multilayered structure color film high power in embodiment 1, and gold nano can be observed
Line average diameter is about 6nm, and edge 2.5~3nm of spacing, silicon dioxide dielectric layer thickness is within the scope of 5~7nm.
Fig. 3 is the optical photograph and corresponding absorption spectrum of multilayered structure color film in embodiment 1.Sample shows bright
Yellow, in yellow band reflectivity with higher.It can be found from Fig. 3, the main surface phasmon of sample absorbs peak position
Near 495nm.
Embodiment 2
It successively uses acetone, ethyl alcohol and deionized water to be cleaned by ultrasonic 15min respectively silicon wafer and quartz plate, removes surface contamination
Object；Silicon wafer after cleaning is fixed on substrate pallet with being dried with nitrogen；Tray loading is entered in magnetron sputtering apparatus settling chamber,
Forvacuum simultaneously is to 10-4Pa or less；Being passed through argon stream makes settling chamber's air pressure be maintained at 0.4Pa, cleans gold with radio-frequency sputtering
Target and silica target 10min, and it is biased cleaning substrate 5min；After etch cleaner, settling chamber's air pressure is adjusted
To 0.3Pa, silica target power supply is closed, the baffle before opening gold target starts to sputter, the power density for adjusting gold target is
3.5W/cm2, metal reflective layer, sedimentation time 25min.Gold target driving power is closed, while starting the drive of titanium dioxide silicon target
Dynamic power supply, power density are set as 5W/cm2, while applying substrate bias power density is 1W/cm2, deposit one layer of silica and be situated between
Matter layer, sedimentation time 10min.It is again started up gold target driving power, two target co-sputterings, wherein gold target and titanium dioxide silicon target splash
Penetrating power density is respectively 0.8W/cm2And 5W/cm2, substrate bias power density is 2.5W/cm2, after depositing 1.1h, close gold
Target, titanium dioxide silicon target and bias driving power, finally obtain the multi-layer cermet film with structure color.
Above-mentioned film sample Cross Section Morphology is observed and analyzed by TEM.Fig. 4 gives multilayer knot in embodiment 2
The section TEM pattern of structure color film high power, it is about 8nm, edge 2~2.5nm of spacing that nanowires of gold average diameter, which can be observed,.With
Embodiment 1 compares, it was demonstrated that passes through gold nano in the deposition parameters, that is, controllable metal ceramic composite beds such as the sputtering power of change target
The structural parameters such as diameter, the spacing of line.Fig. 5 is the optical photograph of sample and corresponding reflectance spectrum in embodiment 2.Sample is in
Reveal aubergine, compared with embodiment 1, surface phasmon absorption peak strength increases, and Dependent Red Shift about 40nm, it was demonstrated that gold
The color that the variation of nanowire structure can significantly affect multi-layer compound film is presented.
Embodiment 3
PET sheet is successively used acetone, ethyl alcohol and deionized water are cleaned by ultrasonic 15min respectively, removes surface contaminant；It cleans
Silicon wafer afterwards is fixed on substrate pallet with being dried with nitrogen；Tray loading is entered in magnetron sputtering apparatus settling chamber, while pre- pumping
Vacuum is to 10-4Pa or less；Being passed through argon stream makes settling chamber's air pressure be maintained at 0.4Pa, with d.c. sputtering cleaning silver target, and penetrates
The clear aluminium oxide target of RF sputtering, the time is 20min, and is biased cleaning substrate 5min；After etch cleaner, adjustment
Settling chamber's air pressure is to 0.25Pa, and baffle before opening silver-colored target and titanium dioxide silicon target starts cosputtering, while applying substrate bias.
Wherein the Sputtering power density of silver-colored target and aluminium oxide target is respectively 1.5W/cm2And 4.5W/cm2, substrate bias power density is
2.4W/cm2.After depositing 1.5h, silver-colored target driving power is closed, continues to deposit one layer of silicon oxide dielectric layer, sedimentation time is
15min.Aluminium oxide target driving power and grid bias power supply are closed, silver-colored target driving power is started, adjusts the Sputtering power density of silver-colored target
For 2.8W/cm2, metal reflective layer, sedimentation time 30min.Silver-colored target driving power is closed, is finally obtained in flexible substrate
Schemochrome film.
Fig. 6 is the optical photograph of schemochrome film in the bent state on large area PET substrate in embodiment 3, it was demonstrated that this
Invention preparation method used is suitable for a variety of substrates such as flexible, rigidity, and can large area preparation, obtained schemochrome is thin
Film has preferable mechanical performance.
Technical solution of the present invention and beneficial effect is described in detail in above-described specific embodiment, Ying Li
Solution is not intended to restrict the invention the foregoing is merely presently most preferred embodiment of the invention, all in principle model of the invention
Interior done any modification, supplementary, and equivalent replacement etc. are enclosed, should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of multi-layer cermet film with structure color, which is characterized in that from substrate outward successively include metal layer,
Dielectric layer and metal nanometer line array-ceramic thin film；
In the metal nanometer line array-ceramic thin film, metal nanometer line is uprightly distributed in ceramic phase, metal nanometer line
Diameter is not less than 2nm, highly identical as the thickness of the metal nanometer line array-ceramic thin film, between metal nanometer line
Spacing is 1.5~20nm.
2. as described in claim 1 with the multi-layer cermet film of structure color, which is characterized in that metal nanometer line is straight
Diameter is 3~7nm, and the spacing between metal nanometer line is 2.5~10nm.
3. as described in claim 1 with the multi-layer cermet film of structure color, which is characterized in that the metal nano
Linear array-ceramic thin film with a thickness of 50~300nm, the dielectric layer with a thickness of 0.5~30nm, the metal layer
With a thickness of 3~200nm.
4. as described in claim 1 with the multi-layer cermet film of structure color, which is characterized in that the metal layer material
Material is identical with metal nano wire material, and the dielectric layer material is identical with ceramic phase material.
5. the multi-layer cermet film as described in claim 1 or 4 with structure color, which is characterized in that metal material
For one in gold, platinum, silver, copper, aluminium, or the alloy of both any composition；Dielectric layer material is oxide, nitride, carbonization
Object, boride or silica；Ceramic phase is oxide, nitride, carbide, boride or silica.
6. a kind of preparation method of the described in any item multi-layer cermet films with structure color of Claims 1 to 5, packet
Include following steps:
(1) pre-processed substrate；
(2) it chooses metal and ceramics is used as target, control metallic target work carries out magnetic in the processed substrate surface of step (1)
Sputtering sedimentation is controlled, metal layer is obtained；Then, control ceramic target work, carries out magnetron sputtering deposit dielectric layer on the metal layer；
Finally, control metallic target and ceramic target work at the same time, magnetron sputtering deposited metal nano-wire array-ceramics are multiple on the dielectric layer
Layer is closed, multi-layer cermet film is obtained；
When magnetron sputtering, metallic target is driven using pulse, radio frequency or DC power supply driving, ceramic target using radio-frequency power supply.
7. the preparation method of the multi-layer cermet film with structure color as claimed in claim 6, sputtering sedimentation metal
When nano-wire array-ceramic thin film, power density range used in splash-proofing sputtering metal target is 0.3~1.5W/cm2；Sputtering ceramics
Power density range used in target is 2.5~15W/cm2, sputtering pressure range is 0.1~1Pa, and target-substrate distance is higher than 70mm.
8. the preparation method of the multi-layer cermet film with structure color as claimed in claim 6, when substrate is insulation
When transparent substrates, the type of substrate bias is rf bias；When substrate is exhausted conductive transparent substrate, the type of substrate bias is
Rf bias or pulsed bias；Substrate bias power density range is 0.5~3W/cm2, automatic bias is higher than -50V.
9. the preparation method of the multi-layer cermet film with structure color as claimed in claim 6, sputtering sedimentation metal
When nano-wire array-ceramic thin film, power density range used in splash-proofing sputtering metal target is 0.5~1.2W/cm2；Sputtering ceramics
Power density range used in target is 5~12W/cm2, sputtering pressure range is 0.15~0.6Pa, and target-substrate distance is higher than 90mm, lining
Substrate biasing power density range is 1~2.5W/cm2, automatic bias is higher than -70V.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113249700A (en) * | 2021-05-28 | 2021-08-13 | 中国科学院宁波材料技术与工程研究所 | Metamaterial with infrared high refractive index and low dispersion and preparation method thereof |
| CN115478247A (en) * | 2021-05-28 | 2022-12-16 | 上海日岳新能源有限公司 | Wear-resistant high-temperature-resistant large-lattice ceramic film heat-insulating structure |
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