CN107012438A - A kind of preparation method of the reinforced porous silver-colored magnesium alloy film of heat endurance - Google Patents
A kind of preparation method of the reinforced porous silver-colored magnesium alloy film of heat endurance Download PDFInfo
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- CN107012438A CN107012438A CN201710254711.5A CN201710254711A CN107012438A CN 107012438 A CN107012438 A CN 107012438A CN 201710254711 A CN201710254711 A CN 201710254711A CN 107012438 A CN107012438 A CN 107012438A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
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Abstract
The invention discloses a kind of preparation method of thermally-stabilised reinforced porous silver-colored magnesium alloy film, it is related to optoelectronic materials technology.The present invention prepares silver-colored magnesium alloy film using film deposition techniques first, and the chemical constituent of the silver-colored magnesium alloy film includes：Mass fraction is 50%~60% magnesium elements, 3%~10% aluminium element and 30%~47% silver element；Then using de- alloy reaction corrosion active metal, and then the nano-porous structure of main adulterated with silver for skeleton a small amount of aluminium and magnesium is formed.Remain to keep loose structure after high-temperature process by porous silver-colored magnesium alloy film made from preparation method of the present invention, and then wider absorption spectrum and preferable assimilation effect can be kept.Preparation technology of the present invention is simple, reproducible, with low cost, can overcome the shortcomings of present in the porous silver-based film heat endurance of prior art, is conducive to porous silver-based film promoting the use in practice.
Description
Technical field
The present invention relates to optoelectronic materials technology, and in particular to a kind of thermally-stabilised reinforced porous silver-colored magnesium alloy film
Preparation method.
Background technology
Nano-porous materials are the nano materials that a class has pore character, its aperture be typically in the range of 0.1 to 100nm it
Between, for block materials, nano-porous materials are due to possessing the spies such as quantum size effect, skin effect and tunnel-effect
Different effect, allows that show the characteristic of special optical, electricity and magnetics, therefore in recent years increasingly by the wide of people
General concern, such as bibliography：What C.Fang et al. was delivered《Electrochemically prepared porous silver
and its application in surface-enhanced Raman scattering》(《Porous silver prepared by electrochemistry
And its application in SERS》).In numerous porous metal materials, nanoporous silverskin is due to its height ratio
The advantages of surface area, high-selenium corn, extremely-low density and excellent antibacterial characteristics, it is widely used in optics catalysis and surface enhanced is drawn
The technical fields such as graceful scattering substrate, the negative electrode of SOFC, minitype gas flow rate detector, therefore, nanometer is more
Kong Yin preparation has very important significance.
However, relative to other metal materials, silver element has low melting point and the spy of high electron transfer and flowing
Property, the heat endurance that result in argent is not high so that microstructure changes porous silver-based film at relatively high temperatures, and then
The problem of causing hydraulic performance decline in application process.Nanyang University of Singapore Chen Chiang Yu and its team (refer to document：
Yu C C, Baek J D, Su C H, et al.Acs Applied Materials＆Interfaces, 2016,8,10343-
10349) propose a kind of method based on ink-jet photoetching and reach the purpose for improving porous silver-based film heat stability, ink-jet photoetching
Method be to make silver atoms formation diameter be about 500~600 nanometers of chondritic by nanosphere lithography technology, it is obtained many
Silver atoms are stacked with the silver-based film of hole.Its microstructure is characterized using SEM in this article, can from figure
Go out：Obtained porous silver-based still keeps good microstructure under the annealing conditions of 400 DEG C of high temperature.But use
The method of ink-jet photoetching is complicated due to preparation flow, costly so that the large-scale production and application of porous silver-based film by
To limitation.In summary, heat endurance difference is porous silver-based film problem most urgently to be resolved hurrily in actually promoting the use, therefore,
Need a kind of method that can prepare thermally-stabilised enhanced porous silver-based film badly.
The content of the invention
The technical problems to be solved by the invention, which are that, overcomes the deficiencies in the prior art to strengthen there is provided a kind of heat endurance
The preparation method of the porous silver-colored magnesium alloy film of type, this method is made porous silver-colored magnesium alloy film and remains to keep many after high-temperature process
Pore structure, and then keep wider absorption spectrum and preferable assimilation effect.
To achieve the above object, the present invention provides following technical scheme：
A kind of preparation method of the reinforced porous silver-colored magnesium alloy film of heat endurance, comprises the following steps：
Using film deposition techniques in the silver-colored magnesium alloy film of deposition on substrate, wherein, the chemical constituent of silver-colored magnesium alloy film
Including：Mass fraction is 50%~60% magnesium elements, 3%~10% aluminium element and 30%~47% silver element；Then
Obtained silver-colored magnesium alloy film, which is placed in de- alloy solution, to react so that silver-colored magnesium alloy film formation loose structure；Question response is complete
Into, then immersion in absolute ethyl alcohol is placed in, immersion obtains porous silver-colored magnesium alloy film after completing through drying process.
Further, the present invention can take any suitable thin film deposition skill in the silver-colored magnesium alloy film of deposition on substrate
Art, specifically, use magnetron sputtering method prepare the operation of silver-colored magnesium alloy film for：
Substrate is subjected to the pre-heat treatment, the pressure of the base vacuum environment in the case where temperature is 100~120 DEG C of vacuum environment
It is strong to be better than 1 × 10-3Pa；After the completion of preheating, under operating air pressure, pre-sputtering is carried out to target using pure argon, pre-sputtering is completed
Afterwards, then sputtered on the substrate of preheating and obtain silver-colored magnesium alloy film.
According to embodiments of the present invention, the time of substrate the pre-heat treatment is 40~60 minutes.
Substrate is ITO, silicon chip, quartz, glass, aluminium foil or PET in the present invention.
The thickness of institute's deposition of silver magnesium alloy film is 100nm~1000nm on substrate in the present invention.
Further, when the present invention prepares loose structure using de- alloyage on silver-colored magnesium alloy film, alloy solution is taken off
The acetic acid solution for being 1%~6% for concentration.
Preferably, the time reacted in the acetic acid solution for being placed in 1%~6% is 30~60 seconds.
Compared with prior art, the invention has the advantages that：
It is by taking off the work in the silver-colored Mg-Al composite film of alloyage corrosion that what the present invention was provided, which prepares porous silver-colored magnesium alloy film,
Sprinkle magnesium metal, and the diffusion of silver-colored and a small amount of aluminium and freely assemble, so formed it is main with it is silver-colored be receiving for a small amount of aluminium of skeleton doping and magnesium
Rice loose structure.The preparation method can significantly improve the heat endurance of porous silver-based film, can see according to embodiments of the present invention
Go out：Porous metals silver-based film due to a small amount of aluminium of adulterating doping and one layer i.e. thin and alumina layer stably is formed therein,
The transfer ability of silver can be suppressed, so as to keep its microstructure not destroyed by the high temperature anneal, and then be ensure that porous
The optical absorptive character (wide spectrum, high-absorbility) of silver-colored magnesium alloy film.
Brief description of the drawings
Fig. 1 is provided the preparation technology schematic flow sheet of porous silver-colored magnesium alloy film by the embodiment of the present invention.
Fig. 2 is that SEM contrast of the embodiment of the present invention with comparative example respectively through microstructure before and after annealing is tied
Fruit is schemed, wherein, figure (a) is that SEM result figure of the porous silver-based laminated film without annealing is made in comparative example, is schemed
(b) SEM result figure of the porous silver-based laminated film by annealing is made for comparative example, figure (c) is implemented for the present invention
SEM result figure of the porous silver composite film without annealing is made in example, and figure (d) is that porous silver-based is made in the embodiment of the present invention
SEM result figure of the laminated film by annealing.
Embodiment
The principle of the invention is described in detail below in conjunction with the specific embodiment of the invention and Figure of description：
As shown in figure 1, the present embodiment specifically carries out preparing silver-colored magnesium alloy film, preparation flow bag using magnetron sputtering method
Include：Substrate heating, pre-sputtering and magnetron sputtering, prepare to use after silver-colored magnesium alloy film and go alloyage to carry out corroding active gold
Category, is controlled to the extent of reaction by the species and concentration and reaction time that take off alloy solution, then through over cleaning, used
Absolute ethyl alcohol or deionized water soaking and washing obtain porous silver-colored Mg-Al composite film to neutrality after processing is dried.
Embodiment 1：
Step A：The preparation of silver-colored magnesium alloy film；
The substrate is placed in vacuum excellent by the quartz substrate for having 100 Ni nanoparticle Cr reflecting layer using deposition as substrate
In 1 × 10-3Under conditions of Pa, heating substrate to 120 DEG C of progress the pre-heat treatments, the pre-heat treatment time is 60 minutes；Complete preheating
Using magnetron sputtering technique to deposit on the substrate after processing, to obtain Mg contents for 54%, Al content be that 6%, Ag contents are
40% silver-colored Mg-Al composite film, the thickness of the film is 300 nanometers；
Step B：The preparation of porous silver-colored magnesium alloy film；
Silver-colored magnesium laminated film made from step A is placed in the acetic acid solution that concentration is 2%, corroded 1 minute；Then take out
Cleaned using deionized water, then be placed in immersion 3~5 minutes in absolute ethyl alcohol, immersion obtains porous silver after completing through drying process
Mg-Al composite film.
Porous silver-colored Mg-Al composite film made from embodiment is made annealing treatment 60 minutes in the case where annealing temperature is 300 DEG C, system
Obtain the porous silver-colored Mg-Al composite film of annealed processing.
This implementation is made using model Tensor 27 spectrometer the porous silver-colored Mg-Al composite without annealing
Film and the reflectance spectrum for being 350nm~850nm by the porous silver-colored Mg-Al composite film progress wave-length coverage made annealing treatment are surveyed
Examination, measures corresponding reflectivity, because transmissivity is 0, according to absorptivity calculation formula：(wherein A is absorptivity to A=1-R, and R is anti-
Penetrate rate), it is 96.77% to be computed without the average absorption ratio of the porous silver-colored Mg-Al composite film of annealing, by moving back
The average absorption ratio of the porous silver-colored Mg-Al composite film of fire processing is 92.01%.
Embodiment 2：
Step A：The preparation of silver-colored magnesium alloy film；
The substrate is placed in vacuum excellent by the quartz substrate for having 100 Ni nanoparticle Cr reflecting layer using deposition as substrate
In 1 × 10-3Under conditions of Pa, heating substrate to 120 DEG C of progress the pre-heat treatments, the pre-heat treatment time is 60 minutes；Complete preheating
Using magnetron sputtering technique to deposit on the substrate after processing, to obtain Mg contents for 50%, Al content be that 10%, Ag contents are
40% silver-colored Mg-Al composite film, the thickness of the film is 300 nanometers；
Step B：The preparation of porous silver-colored magnesium alloy film；
Silver-colored magnesium laminated film made from step A is placed in the acetic acid solution that concentration is 2%, corroded 1 minute；Then take out
Cleaned using deionized water, then be placed in immersion 3~5 minutes in absolute ethyl alcohol, immersion obtains porous silver after completing through drying process
Mg-Al composite film.
Porous silver-colored Mg-Al composite film made from embodiment is made annealing treatment 60 minutes in the case where annealing temperature is 300 DEG C, system
Obtain the porous silver-colored Mg-Al composite film of annealed processing.
This implementation is made using model Tensor 27 spectrometer the porous silver-colored Mg-Al composite without annealing
Film and the reflectance spectrum for being 350nm~850nm by the porous silver-colored Mg-Al composite film progress wave-length coverage made annealing treatment are surveyed
Examination, measures corresponding reflectivity, because transmissivity is 0, according to absorptivity calculation formula：(wherein A is absorptivity to A=1-R, and R is anti-
Penetrate rate), it is 92.54% to be computed without the average absorption ratio of the porous silver-colored Mg-Al composite film of annealing, by moving back
The average absorption ratio of the porous silver-colored Mg-Al composite film of fire processing is 91.13%.
Embodiment 3：
Step A：The preparation of silver-colored magnesium alloy film；
The substrate is placed in vacuum excellent by the quartz substrate for having 100 Ni nanoparticle Cr reflecting layer using deposition as substrate
Under conditions of 1 × 10-3Pa, heating substrate to 120 DEG C of progress the pre-heat treatments, the pre-heat treatment time is 60 minutes；Complete preheating
Using magnetron sputtering technique to deposit on the substrate after processing, to obtain Mg contents for 57%, Al content be that 3%, Ag contents are
40% silver-colored Mg-Al composite film, the thickness of the film is 500 nanometers；
Step B：The compound preparation of porous silver-based；
Silver-colored magnesium laminated film made from step A is placed in the acetic acid solution that concentration is 2%, corroded 1 minute；Then take out
Cleaned using deionized water, then be placed in immersion 3~5 minutes in absolute ethyl alcohol, immersion obtains porous silver after completing through drying process
Mg-Al composite film.
Porous silver-colored Mg-Al composite film made from embodiment 3 is made annealing treatment 60 minutes in the case where annealing temperature is 300 DEG C, system
Obtain the porous silver-colored Mg-Al composite film of annealed processing.
This implementation is made using model Tensor 27 spectrometer the porous silver-colored Mg-Al composite without annealing
Film and the reflectance spectrum for being 350nm~850nm by the porous silver-colored Mg-Al composite film progress wave-length coverage made annealing treatment are surveyed
Examination, measures corresponding reflectivity, because transmissivity is 0, according to absorptivity calculation formula：(wherein A is absorptivity to A=1-R, and R is anti-
Penetrate rate), it is 95.79% to be computed without the average absorption ratio of the porous silver-colored Mg-Al composite film of annealing, by moving back
The average absorption ratio of the porous silver-colored Mg-Al composite film of fire processing is 87.53%.
The porous silver-colored Mg-Al composite film of annealed processing is characterized using SEM means, in SEM results such as Fig. 2 (c)
Shown in (d).
Embodiment 4：
The present embodiment embodiment as a comparison, silver-based film, which is made, has aluminium element external sediment process conditions except undoping and de-
Alloy reaction condition be the same as Example 3, concrete operations are as follows：
Step A：The preparation of silver-colored magnesium alloy film；
The substrate is placed in vacuum excellent by the quartz substrate for having 100 Ni nanoparticle Cr reflecting layer using deposition as substrate
In 1 × 10-3Under conditions of Pa, heating substrate to 120 DEG C of progress the pre-heat treatments, the pre-heat treatment time is 60 minutes；Complete preheating
Use magnetron sputtering technique to deposit on the substrate after processing to obtain silver-colored magnesium that Mg contents are 40% for 60%, Ag contents and be combined
Film, the thickness of the film is 500 nanometers；
Step B：The compound preparation of porous silver-based；
Silver-colored magnesium laminated film made from step A is placed in the acetic acid solution that concentration is 2%, corroded 1 minute；Then take out
Cleaned using deionized water, then be placed in immersion 3~5 minutes in absolute ethyl alcohol, immersion obtains porous silver after completing through drying process
Magnesium laminated film.
Porous silver-based laminated film made from embodiment 4 is made annealing treatment at 300 DEG C of annealing temperature, 60 points are handled
Clock, is made the porous silver-colored Mg-Al composite film of annealed processing.
This implementation is made using model Tensor 27 spectrometer the porous silver-colored magnesium THIN COMPOSITE without annealing
Film and the reflectance spectrum for being 350nm~850nm by 300 DEG C of porous silver-colored magnesium laminated films progress wave-length coverages made annealing treatment are surveyed
Examination, measures corresponding reflectivity, because transmissivity is 0, according to absorptivity calculation formula：(wherein A is absorptivity to A=1-R, and R is anti-
Penetrate rate), it is 97.59% to be computed without the average absorption ratio of the porous silver-colored magnesium laminated film of annealing, by annealing
The average absorption ratio of the porous silver-colored magnesium laminated film of processing is 75.24%.
For comparing embodiment and the heat endurance of the porous silver-based film of comparative example, figure (a) is comparative example in Fig. 2
SEM result figure of the porous silver-colored magnesium film without annealing is made in (i.e. embodiment 4), and figure (b) is that comparative example is made many
SEM result figure of the hole silver magnesium laminated film by annealing, figure (c) is that porous silver-colored Mg-Al composite is made in the embodiment of the present invention 3
Film is without the SEM result figures of annealing, and figure (d) is that porous silver-colored Mg-Al composite film process is made in the embodiment of the present invention 3
The SEM result figures of annealing.By contrast, it can be clearly seen that：Doped with the porous silver-based film heat stability of Al elements
It is higher, remaining able to maintain its microcosmic loose structure after the high temperature anneal, therefore its optical property does not substantially decay,
Its average absorption ratio in wider absorption spectrum ranges is higher；Porous silver-based film without the Al elements that adulterate is passing through
Microstructure is substantially destroyed after the high temperature anneal, and its average absorption ratio in wider absorption spectrum ranges is substantially reduced,
Heat endurance is poor.
Embodiments of the invention are set forth above in association with accompanying drawing, but the invention is not limited in above-mentioned specific
Embodiment, above-mentioned embodiment is only schematical, rather than restricted, and one of ordinary skill in the art exists
Under the enlightenment of the present invention, in the case of present inventive concept and scope of the claimed protection is not departed from, many shapes can be also made
Formula, these are belonged within the protection of the present invention.
Claims (7)
1. a kind of preparation method of the reinforced porous silver-colored magnesium alloy film of heat endurance, it is characterised in that use thin film deposition skill
Art in the silver-colored magnesium alloy film of deposition on substrate, wherein, the chemical constituent of silver-colored magnesium alloy film includes：Mass fraction be 50%~
60% magnesium elements, 3%~10% aluminium element and 30%~47% silver element；Then obtained silver-colored magnesium alloy film is placed in
Reacted in de- alloy solution so that silver-colored magnesium alloy film formation loose structure；Question response is completed, then is placed in leaching in absolute ethyl alcohol
Bubble, immersion obtains porous silver-colored magnesium alloy film after completing through drying process.
2. a kind of preparation method of the reinforced porous silver-colored magnesium alloy film of heat endurance according to claim 1, its feature
It is, the substrate is ITO, silicon chip, quartz, glass, aluminium foil or PET.
3. a kind of preparation method of the reinforced porous silver-colored magnesium alloy film of heat endurance according to claim 1, its feature
It is, the concrete operations of deposition on substrate silver magnesium alloy film are：
Substrate is subjected to the pre-heat treatment in the case where temperature is 100 DEG C~120 DEG C of vacuum environment, the base vacuum environment is better than 1
×10-3Pa；After the completion of preheating, under operating air pressure, pre-sputtering is carried out to target using pure argon, after the completion of pre-sputtering, then
Sputtering obtains silver-based laminated film on the substrate of preheating.
4. a kind of preparation method of the reinforced porous silver-colored magnesium alloy film of heat endurance according to claim 3, its feature
It is, the time of the pre-heat treatment is 40~60 minutes.
5. a kind of preparation method of the reinforced porous silver-colored magnesium alloy film of heat endurance according to claim 1, its feature
It is, the thickness of the silver-colored magnesium alloy film is 100nm~1000nm.
6. a kind of preparation side of the reinforced porous silver-colored magnesium alloy film of heat endurance according to any one of claim 1 to 5
Method, it is characterised in that de- alloy solution is the acetic acid solution that concentration is 1%~6%.
7. a kind of preparation method of the reinforced porous silver-colored magnesium alloy film of heat endurance according to claim 6, its feature
It is, it is 30~120 seconds to be placed in the time reacted in de- alloy solution.
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| CN110484764A (en) * | 2019-08-08 | 2019-11-22 | 哈尔滨工业大学（深圳） | Nanoporous high-entropy alloy and preparation method thereof |
| CN111139062A (en) * | 2020-01-07 | 2020-05-12 | 江苏理工学院 | Preparation method of silver-containing nano porous metal loaded chlorine-containing perovskite quantum dot film |
| CN111139062B (en) * | 2020-01-07 | 2022-11-22 | 江苏理工学院 | Preparation method of silver-containing nano porous metal loaded chlorine-containing perovskite quantum dot film |
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