CN110195209A - Outer broadband light absorbing material of a kind of visible red and preparation method thereof - Google Patents

Outer broadband light absorbing material of a kind of visible red and preparation method thereof Download PDF

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Publication number
CN110195209A
CN110195209A CN201910506818.3A CN201910506818A CN110195209A CN 110195209 A CN110195209 A CN 110195209A CN 201910506818 A CN201910506818 A CN 201910506818A CN 110195209 A CN110195209 A CN 110195209A
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copper
porous
mould plate
array mould
light absorbing
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任勇
沈娟
周睿
毛敏
代波
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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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
    • 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
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses broadband light absorbing materials outside a kind of visible red, it is characterized in that: the outer broadband light absorbing material of the visible red is the film of copper, it is the copper porous nanometer thin films for being generated copper through magnetron sputtering as template using porous aluminas array diaphragm plate.Preparation method includes: to prepare porous aluminas array mould plate；Copper is subjected to magnetron sputtering, porous aluminas array mould plate attachment copper film is prepared: being separated with chemical corrosion method, copper porous nanometer thin films are made.Reach 90% or more in the wave-length coverage internal absorptance of 200nm~2500nm using copper porous nanometer thin films prepared by the present invention, is functional, it can be used as ideal light absorber, have the characteristics that thin, light, suitable for fields such as solar battery light absorbing material, visible infrared dependent sensors, it can also be used directly as broadband light absorbing material outside visible red, it is practical.

Description

Outer broadband light absorbing material of a kind of visible red and preparation method thereof
Technical field
The invention belongs to light absorbing material and its preparations, are related to a kind of visible red broadband light absorbing material and its preparation outside Method.The outer broadband light absorbing material of visible red of the present invention is suitable for solar battery light absorbing material, the quick biography of visible infrared Sensor can also be used directly as broadband light absorbing material outside visible red.
Background technique
With the development of science and technology, the utilization and exploitation of the energy, the utilization of luminous energy is also increasingly taken seriously.Light absorption is light (electromagnetic radiation) interacts when passing through material with material, and electromagnetic radiation energy is partially converted into other energy The physical process of amount form.Photothermal conversion is exactly that absorbed light is released in the form of energy, generates the process of heat, does not have There is absorbed energy to be reflected by the object, scatter or transmits.Light can indicate that different frequencies is corresponding according to frequency and wavelength Opposite wave-length coverage and different principle of absorption.
The absorption of light is broadly divided into general absorption and selection absorbs.General absorb refers to absorption seldom, and a certain given It is almost unchanged in wave band.Selection, which absorbs, refers to absorption very much, and tempestuously changes with wavelength, for example quartz is to visible absorption spy It is not small, but the infrared light of 3.5-5.0 μ m wavelength range can but be absorbed strongly.It is ground to light absorbing material and its application In studying carefully, the technology based on nanophotonics is an important and active branch.When the scale of material structure constantly reduces, light Interaction between substance will show new speciality, such as the controllability of material effective refractive index, Localized field enhancement Effect and adjustable semiconductor material band gap etc..Herein on basis, unique light absorption is may be implemented in nano structural material Performance, such as the raising of absorption efficiency, the photothermal conversion of local, the adjusting etc. of absorption spectrum.Based on these characteristics, nanostructure Material is able to ascend or improves the performance of existing light absorption device.
In the prior art, the technology for preparing nano wire, nanotube and nano composite membrane has electrochemical deposition method, doughnuts Photoetching process, chemical etching, sol-gel auto-combustion technology, single solvent-thermal method combination coprecipitation, r. f. magnetron sputtering, Sol-gel and spin-coating method etc.；Used metal has gold, silver, copper, CdTe/CdS film, In2O3、SnO2Deng；What is obtained In the absorbing properties that product is tested, photo absorption performance is bad, the basic only photo absorption performance preference under some wavelength, and Absorbance not more than 88%.
According to literature survey, the metal for being used to prepare metal nano material at present is attached most importance to metal (such as Ag, Ni, Cd substantially Deng), the technics comparing of preparation it is complicated (step is more, and the requirement of some steps is harsh, is easy to be influenced by factors such as temperature, humidity, And most products are all composite membranes, and multiplicating is needed to prepare the technique of film, more complicated), obtained film is not Enough uniform (it is bad that film unevenly will lead to electrical and thermal conductivity performance)；These defects can be such that material inhales applied to solar battery light It is affected whens receiving material, visible infrared dependent sensor etc. to the response of light.
In short, the prior art has now been developed the absorbance of the metal nano material come mostly only in some wave-length coverage Interior absorbing properties are preferable, and the wave band being applicable in is not wide in range, and absorptance obtained is not high；And nanometer is prepared at present Linear array (concept of linear array is: the line unit that one group of similar linear structure is lined up, is spaced closely together), nanotube battle array The technique of column (concept of pipe array is: the tubular units that one group of similar tubular structure is lined up, is spaced closely together) all compares It is cumbersome.For example, sol-gal process prepares nano material, preparation process is as follows, first by the precursor solution for the nano wire of being prepared It is prepared into colloidal solution, then by colloidal solution by being immersed in alumina formwork or by modes such as suction filtrations, finally making Colloidal solution enters in the aperture of anodised aluminium aluminum alloy pattern plate, form one-dimensional nano structure after stove heats later, one As situation lower template be immersed in the time in colloidal sol and will affect the pattern to form nano material.Electro-deposition method prepares nano wire, Step is to place anodised aluminium in electrolyte, and metal to be generated, alloy or oxide are from it under electric field action It is deposited from electrode surface into the process in the hole of porous alumina formwork in electrolyte.AC electrodeposition nano wire The disadvantage is that the length for preparing nanowire is uncontrollable；The shortcomings that DC electrodeposition nanowire deposition is required alumina formwork The aluminium base of alumina formwork is generally passed through into mercury chloride or saturation copper chloride solution processing by complicated treatment process Fall, only remain porous alumina formwork part, the bottom of alumina formwork is sputtered into one layer of gold by the method for magnetron sputtering later Belong to (general gold), anodised aluminium is placed in electrolyte deposit later.Preparation step is more, complex process, practicability It is poor.
Summary of the invention
The purpose of the present invention is intended to overcome deficiency in the prior art, provides a kind of outer broadband light absorbing material of visible red And preparation method thereof.The present invention is by being template by copper with porous aluminas array diaphragm plate (or porous anodic alumina films plate) Copper porous nanometer thin films are generated through magnetron sputtering, so that it is equal to provide a kind of wave-length coverage internal absorptance in 200nm~2500nm Reach outer broadband light absorbing material of 90% or more, visible red of good performance and preparation method thereof.
The contents of the present invention are: a kind of outer broadband light absorbing material of visible red, it is characterized in that: the outer broadband of the visible red Light absorbing material is the film of copper.
In the contents of the present invention: the film of the copper is with porous aluminas array diaphragm plate (or porous anodic aluminium oxide Diaphragm plate) it is the copper porous nanometer thin films that template generates copper through magnetron sputtering.
In the contents of the present invention: the film of the copper with a thickness of 300nm~15 μm.
Another content of the invention is: a kind of preparation method of the outer broadband light absorbing material of visible red, comprising:
A, porous aluminas array mould plate (or porous anodic aluminium oxide array mould plate) is prepared；
The preparation method of porous aluminas array mould plate is using Two-step anodization, is the prior art；
The preparation method of porous aluminas array mould plate is divided into 3 steps: (1) by aluminium flake (preferably use purity for 99.99% high-purity aluminium flake) it is cleaned and (is cleaned mainly using the method for ultrasonic cleaning, step is: first by aluminium flake in ethyl alcohol Middle cleaning 5min~30min is to remove the grease outside aluminium flake；Aluminium flake is placed on the sodium hydroxide that concentration is 0.5~2mol/L again 5min~30min is cleaned in aqueous solution to remove the oxide and other chemical substances on its surface)；(2) then aluminium flake is carried out Annealing (keeps the temperature 1h~3h under the conditions of 400 DEG C~600 DEG C of temperature to be made annealing treatment), carries out electrochemical polish later (electrochemical polish is carried out on electrochemistry platform, polishing fluid is ethyl alcohol and perchloric acid volume ratio is the mixture of 5:1~27:9, with Aluminium flake after annealing is anode, and aluminium flake is cathode, and is subject to 10V or more voltage electrochemical polishing 10min~20min), (3) once oxidation is carried out after, and (condition, the parameter of once oxidation are: using the aluminium flake after electrochemical polish as anode, aluminium flake is yin Pole, using concentration for 0.1mol/L~1mol/L oxalic acid aqueous solution as electrolyte, oxidation voltage is 40V~60V, oxidizing temperature is 2 DEG C~8 DEG C, oxidization time be 1h~4h carry out once oxidation.), after removing once oxidation layer, carry out secondary oxidation (secondary oxidation Condition, parameter be: the conditions such as electrolyte temperature, electrolyte, oxidation voltage of second oxidation and the phase aoxidized for the first time Together), drop voltage processing is then carried out, is reduced to the 90%~98% of original voltage every time, time interval is 60s~120s, directly To power supply is closed when dropping to 2V~8V, finally cleans, obtain porous aluminas array mould plate；
It is characterized in that further including the following steps:
B, porous aluminas array mould plate attachment copper film is prepared:
Porous aluminas array mould plate (specification can be long 1cm x wide 1cm~long 4cm x wide 3cm) cleaning is dry It is dry after net, then by the porous aluminas array mould plate fixed placement after drying in magnetron sputtering apparatus (magnetron sputtering apparatus Offer enterprise be CAS Shenyang Scientific Instruments Co., Ltd., model can be JGP-450A, MPS-4000- C4 it is vacuumized in vacuum cavity), until (vacuum degree) pressure is in 2x 10-4After Pa or less, by copper, (i.e. copper target is directly installed in On target chamber in magnetron sputtering apparatus；Copper target preferably use purity for 99.99% copper；It is 3 English that copper target, which can be diameter, Very little, cylindrical body with a thickness of 3mm or other prior art shapes) magnetron sputtering is carried out, it controls sputtering power (or invariable power) For 30W~150W, sputter rate be 0.1nm/s~2nm/s, sputtering time is 10~360min, obtains porous aluminas battle array Column template adheres to copper film (thickness 300nm~15 μm)；(magnetron sputtering is exactly by target as sputter to base material, to be formed Corresponding film；The target of magnetron sputtering selection of the present invention is copper target, and base material is porous aluminas array mould plate, therefore, Product obtained is exactly to adhere to copper film in porous aluminas array mould plate).
C, copper porous nanometer thin films are prepared:
Porous aluminas array mould plate obtained attachment copper film is separated with chemical corrosion method；Step is: preparing dense Degree is the sodium hydrate aqueous solution of 0.2mol/L~0.8mol/L as sodium hydroxide corrosive liquid, by aluminium oxide array mould obtained Plate attachment copper film is soaked into sodium hydroxide corrosive liquid, is impregnated 10min~360min at room temperature, is made porous aluminas array mould Copper film part in plate attachment copper film is partially separated the individual copper film for coming, obtaining with porous aluminas array mould plate, later Corrosive liquid is washed with water again, and by copper film surface with being dried with nitrogen, obtains copper porous nanometer thin films；Copper obtained is porous to be received In rice film, the surface of entire copper porous nanometer thin films has numerous copper porous nanometer structure tightly to stick together to be formed, And the overall diameter of each copper porous nanometer structure is substantially consistent with the diameter in the hole of porous aluminas array mould plate.Copper is more The structure of hole nano thin-film arrangement is consistent with the arrangement in hole of used porous aluminas array mould plate, is hexagonal structure. Copper porous nanometer thin films are as follows: what is contacted with porous aluminas array mould plate is nano aperture structure on one side, and another side is sealing State.Different pore size, different-thickness the absorbing properties test results of copper porous nanometer thin films show: absorptance exists Within the scope of 90%-99%.
In another content of the invention: by the porous aluminas array mould plate fixed placement of drying in magnetic described in step b It is vacuumized in the vacuum cavity of control sputtering instrument, until (vacuum degree) pressure is in 2x 10-4After Pa or less, copper is subjected to magnetic control Sputtering, preferably: by the porous aluminas array mould plate fixed placement of drying in the vacuum cavity of magnetron sputtering apparatus into Row vacuumizes, until (vacuum degree) pressure is in 2x 10-4After Pa or less, it is passed through argon gas, then (i.e. copper target is directly installed in magnetic control and splashes by copper It penetrates on the target chamber in instrument；The copper that copper target is preferably 99.99% by purity；Copper target can be diameter be 3 inches, with a thickness of The cylindrical body of 3mm or other prior art shapes) carry out magnetron sputtering.
In another content of the invention: it is dry after cleaning up porous aluminas array mould plate described in step b, preferably : at normal temperatures and pressures, porous aluminas array mould plate is impregnated into 2~4h in water and washes surface smut；Again will later Porous aluminas array mould plate is dipped into the grease etc. that 2~4h in acetone removes surface；Later again by porous aluminas array mould Plate is dipped into 2~4h in ethyl alcohol (referring to dehydrated alcohol) and does last cleaning；Porous aluminas array mould plate is dried up with nitrogen later.
In another content of the invention: water described in step b and step c can be ultrapure water, and (ultrapure water, being will be in water Conducting medium almost removes, and the colloidal substance not dissociated in water, gas and organic matter are removed to very low degree Water, using prior art preparation), distilled water or deionized water.
Compared with prior art, the present invention have following features and the utility model has the advantages that
(1) using the present invention, the porous aluminas array mould plate of selection (or it is porous anodic aluminium oxide array mould plate, more Porous aluminum oxide array films, porous anodic alumina template are generally made of porous aluminas membrane part, barrier layer and aluminium substrate, tool There are hexangular ordered hole arrangement, corrosion resistance, the good transparency and mechanical performance, in nano material preparation and photonic device side Mask has wide practical use) with unique nanometer scale porous structure, can be used as prepare nano wire nanotube and The template of nano-wire array system material is that nano-copy technology (refers within the scope of nanoscale, by manipulation atom, divides Son, atomic group and micel, make it rearrange the technology for being combined into novel substance；Its final goal is directly with atom, molecule Variation, so that substance is shown novel physical, chemical and biological properties on nanoscale, produce with specific function Product；Nano-copy technology is the development of nanotechnology, can position assembly and self-replacation, positioning assembly is exactly suitably Put molecule part appropriate in side) one of key；The hole pore size of porous alumina formwork is consistent, it is orderly aligned, point Cloth uniformly (referring to Fig. 1), therefore prepares zero micro Nano material, monodimension nanometer material, nano wire, nanotube with the alumina formwork Deng have the advantages that preparation be easy, method it is simple；
(2) using the present invention, using porous aluminas array films as the antipoints array films of template generation, system arrangement is improved Order, and have very high planarization, make the system have stronger absorbing properties (referring to figs. 2 and 3)；This is received Rice material may be directly applied to the outer broadband light absorbing material of visible red；
(3) present invention used in raw metal it is cheap and easy to get (metallic copper of use is common metal, cheap, hold Be easy to get to), preparation process is simple (only need to prepare one layer of copper film and just obtained product), and obtained film is uniformly (from scanning electricity Sem observation can obtain, and copper film prepared by the present invention is the copper nano-tube array of one layer of marshalling, visibly homogeneous), there is photo absorption performance Very well, it is easy the superperformance of preparation, whens for solar battery light absorbing material, visible infrared dependent sensor etc., makes material Material is higher to the sensitivity of photoinduction, larger to the wave-length coverage of photoresponse, and the conduction of material, heating conduction are stronger；
(4) using the present invention, copper film (i.e. copper porous nanometer thin films) obtained is exactly the outer broadband light absorption material of visible red Material, apparent condition is: the surface of entire Copper thin film is that one group of copper nanotube tightly sticks together to be formed, and each copper nanometer The overall diameter of pipe is substantially consistent with the diameter in the hole of porous aluminas array mould plate；The structure of copper Nanotube alignment with made Arrangement with the hole of porous aluminas array mould plate is consistent, is hexagonal structure；Copper film exterior appearance obtained is good, nanotube Marshalling is uniform, has the superperformances such as photoinduction high sensitivity, photoresponse wave-length coverage are big, there are no pollution to the environment, The wave-length coverage internal absorptance of 200nm~2500nm reaches 90% or more (90%~99%), and the absorbent properties of light are good；
(5) preparation method preparation process of the present invention is simple, low in cost, prepares copper film using the method for magnetron sputtering, behaviour It is simple to make step, does not also need to prepare composite membrane, extinction weight is lighter, thinner, and photo absorption performance is stablized, and it is environmental-friendly, Resulting materials have broad application prospects in the fields such as solar battery light absorbing material and visible infrared dependent sensor, real It is strong with property.
Detailed description of the invention
Fig. 1 is that the porous alumina formwork in (embodiment 1) of the embodiment of the present invention measured using scanning electron microscope is (or more Porous aluminum oxide array mould plate, porous anodic aluminium oxide array mould plate, porous aluminas array films)；Its bright hole configurations of the chart It is more obvious；
Fig. 2 is that (i.e. copper porous nano is thin for copper film in (embodiment 4) of the embodiment of the present invention measured using scanning electron microscope Film)；Its bright structural arrangement of the chart is orderly；
Fig. 3 is copper film absorption spectrum in (embodiment 4) of the embodiment of the present invention measured using ultraviolet specrophotometer；The figure Show that its photo absorption performance is more preferable, extinction wave band is wider.
Specific embodiment
The embodiments given below are intended to further illustrate the invention, but is not to be construed as to the scope of the present invention Limitation, some nonessential improvement and tune that person skilled in art makes the present invention according to the content of aforementioned present invention It is whole, still fall within protection scope of the present invention.
Embodiment 1:
A kind of outer broadband light absorbing material of visible red, is the antipoints array using porous aluminas array films as template generation Film；
The preparation method of the outer broadband light absorbing material of the visible red includes the following steps:
A, prepare porous aluminas array mould plate (or porous anodic aluminium oxide array mould plate, porous aluminas array films, Alumina formwork, rear same)；
The porous alumina formwork is prepared using Two-step anodization, compared with technology；
Porous alumina formwork preparation process is divided into three steps: the high-purity aluminium flake that purity is 99.99% being carried out clear It washes, cleans mainly using the method for ultrasonic cleaning, this process is divided into two steps, aluminium flake is first cleaned to 14min in alcohol to remove Grease outside aluminium flake；Aluminium flake is placed on again in the sodium hydroxide solution of 1mol/L and cleans 8min to remove the oxide on its surface With other chemical substances；The annealing of 1.5h, the electricity oneself built at us later are kept the temperature under the conditions of carrying out 550 DEG C to it afterwards Electrochemical polish is carried out in chemical platform, polishing fluid is ethyl alcohol and perchloric acid volume ratio is 15:4, with the high-purity aluminium flake handled well For anode, homemade aluminium flake is cathode, and is subject to 15V voltage electrochemical polishing 12min, later using processed aluminium flake as anode, Homemade aluminium flake uses oxidation voltage for 50V, oxidizing temperature 8 for cathode using the oxalic acid solution of 0.1mol/L as electrolyte DEG C, oxidization time be that 2h carries out once oxidation, after removing once oxidation layer, carry out secondary oxidation, the electrolyte temperature of second oxidation The conditions such as degree, electrolyte, oxidation voltage are identical as first time oxidation, and drop voltage is reduced to the 90% of original voltage every time, when Between between be divided into 85s, until while dropping to 4V closes power supply, then decompression is handled, and is finally cleaned.
Further include the following steps:
B, alumina formwork attachment copper film is prepared:
Porous alumina formwork is cleaned up through ethyl alcohol, i.e., at normal temperatures and pressures, by alumina formwork in ultrapure water logging 2h is steeped, surface smut is washed；Porous alumina formwork is dipped into the grease etc. that 2h in acetone soln removes surface again later； Porous alumina formwork is dipped into 2h in ethanol solution again later and does last cleaning.Sample is dried up with nitrogen later.It will place The porous alumina formwork managed, which fixes, to be placed in the vacuum cavity of magnetron sputtering apparatus, is vacuumized, and waits until vacuum Degree reach to a certain degree after, sputtering power be range be 40W, sputter rate 0.21nm/s, sputtering time 60min, carry out Magnetron sputtering grows certain thickness copper film.
C, the preparation of independent copper film (i.e. copper porous nanometer thin films, rear same):
The sample prepared is separated with chemical corrosion method.The concentration of sodium hydroxide solution of configuration is 0.5mol/L, By the porous alumina formwork of magnetron sputtering copper film, it is placed in configured sodium hydroxide corrosive liquid, corrodes one at room temperature The section time, so that copper film part is partially separated with porous alumina formwork and comes, obtained individual copper film.Later again with ultrapure Water washes corrosive liquid, and the ultrapure water process by copper film on surface is completely made.
The copper film of preparation is the outer broadband light absorbing material of visible red, and absorptance reaches 90%, and product shape is relatively beautiful It sees.
Embodiment 2:
A kind of outer broadband light absorbing material of visible red, is the antipoints array using porous aluminas array films as template generation Film；
The preparation method of the outer broadband light absorbing material of the visible red includes the following steps:
A, porous aluminas array mould plate is prepared；
The porous alumina formwork is prepared using Two-step anodization, compared with technology；
Porous alumina formwork preparation process is divided into three steps: the high-purity aluminium flake that purity is 99.99% being carried out clear It washes, cleans mainly using the method for ultrasonic cleaning, this process is divided into two steps, aluminium flake is first cleaned to 16min in alcohol to remove Grease outside aluminium flake；Aluminium flake is placed on again in the sodium hydroxide solution of 1.5mol/L and cleans 12min to remove the oxygen on its surface Compound and other chemical substances；The annealing that 2h is kept the temperature under the conditions of carrying out 500 DEG C to it afterwards, oneself builds at us later Electrochemical polish is carried out on electrochemistry platform, polishing fluid is ethyl alcohol and perchloric acid volume ratio is 16:5, with the rafifinal handled well Piece is anode, and homemade aluminium flake is cathode, and is subject to 14V voltage electrochemical polishing 13min, is later sun with processed aluminium flake Pole, homemade aluminium flake is cathode, using the oxalic acid solution of 0.2mol/L as electrolyte, uses the oxidation voltage to be for 45V, oxidizing temperature 8 DEG C, oxidization time be that 3h carries out once oxidation, after removing once oxidation layer, carry out secondary oxidation, the electrolyte temperature of second oxidation The conditions such as degree, electrolyte, oxidation voltage are identical as first time oxidation, and drop voltage is reduced to the 90% of original voltage every time, when Between between be divided into 80s, until while dropping to 6V closes power supply, then decompression is handled, and is finally cleaned.
Further include the following steps:
B, alumina formwork attachment copper film is prepared:
Porous alumina formwork is cleaned up through ethyl alcohol, i.e., at normal temperatures and pressures, by alumina formwork in ultrapure water logging 3h is steeped, surface smut is washed；Porous alumina formwork is dipped into the grease etc. that 3h in acetone soln removes surface again later； Porous alumina formwork is dipped into 3h in ethanol solution again later and does last cleaning.Sample is dried up with nitrogen later.It will place The porous alumina formwork managed, which fixes, to be placed in the vacuum cavity of magnetron sputtering apparatus, is vacuumized, and waits until vacuum Degree reach to a certain degree after, sputtering power be range be 60W, sputter rate 0.38nm/s, sputtering time 60min, carry out Magnetron sputtering grows certain thickness copper film.
C, the preparation of independent copper film:
The sample prepared is separated with chemical corrosion method.The concentration of sodium hydroxide solution of configuration is 0.5mol/L, By the porous alumina formwork of magnetron sputtering copper film, it is placed in configured sodium hydroxide corrosive liquid, corrodes one at room temperature The section time, so that copper film part is partially separated with porous alumina formwork and comes, obtained individual copper film.Later again with ultrapure Water washes corrosive liquid, and the ultrapure water process by copper film on surface is completely made.
The copper film of preparation is exactly the outer broadband light absorbing material of visible red, and absorptance reaches 92%, and product shape is relatively beautiful It sees.
Embodiment 3:
A kind of outer broadband light absorbing material of visible red, is the antipoints array using porous aluminas array films as template generation Film；
The preparation method of the outer broadband light absorbing material of the visible red includes the following steps:
A, porous aluminas array mould plate is prepared；
The porous alumina formwork is prepared using Two-step anodization, compared with technology；
Porous alumina formwork preparation process is divided into three steps: the high-purity aluminium flake that purity is 99.99% being carried out clear It washes, cleans mainly using the method for ultrasonic cleaning, this process is divided into two steps, aluminium flake is first cleaned to 10min in alcohol to remove Grease outside aluminium flake；Aluminium flake is placed on again in the sodium hydroxide solution of 1mol/L and cleans 15min to remove the oxidation on its surface Object and other chemical substances；The annealing of 3h, the electricity oneself built at us later are kept the temperature under the conditions of carrying out 600 DEG C to it afterwards Electrochemical polish is carried out in chemical platform, polishing fluid is ethyl alcohol and perchloric acid volume ratio is 3:1, is with the high-purity aluminium flake handled well Anode, homemade aluminium flake are cathode, and are subject to 15V voltage electrochemical polishing 8min, later using processed aluminium flake as anode, self-control Aluminium flake be cathode, using the oxalic acid solution of 0.15mol/L as electrolyte, using oxidation voltage for 50V, oxidizing temperature is 8 DEG C, oxygen Changing the time is that 2h carries out once oxidation, after removing once oxidation layer, carries out secondary oxidation, electrolyte temperature, the electricity of second of oxidation It is identical as first time oxidation to solve the conditions such as liquid, oxidation voltage, drop voltage is reduced to the 90% of original voltage every time, time interval For 90s, power supply is closed when until dropping to 4V, then decompression is handled, and is finally cleaned.
Further include the following steps:
B, alumina formwork attachment copper film is prepared:
Porous alumina formwork is cleaned up through ethyl alcohol, i.e., at normal temperatures and pressures, by alumina formwork in ultrapure water logging 3h is steeped, surface smut is washed；Porous alumina formwork is dipped into the grease etc. that 3h in acetone soln removes surface again later； Porous alumina formwork is dipped into 3h in ethanol solution again later and does last cleaning.Sample is dried up with nitrogen later.It will place The porous alumina formwork managed, which fixes, to be placed in the vacuum cavity of magnetron sputtering apparatus, is vacuumized, and waits until vacuum Degree reach to a certain degree after, sputtering power be range be 70W, sputter rate 0.47nm/s, sputtering time 60min, carry out Magnetron sputtering grows certain thickness copper film.
C, the preparation of independent copper film:
The sample prepared is separated with chemical corrosion method.The concentration of sodium hydroxide solution of configuration is 0.6mol/L, By the porous alumina formwork of magnetron sputtering copper film, it is placed in configured sodium hydroxide corrosive liquid, corrodes one at room temperature The section time, so that copper film part is partially separated with porous alumina formwork and comes, obtained individual copper film.Later again with ultrapure Water washes corrosive liquid, and the ultrapure water process by copper film on surface is completely made.
The copper film of preparation is exactly the outer broadband light absorbing material of visible red, and absorptance reaches 91%, and product shape is relatively beautiful It sees.
Embodiment 4:
A kind of outer broadband light absorbing material of visible red, is the antipoints array using porous aluminas array films as template generation Film；
The preparation method of the outer broadband light absorbing material of the visible red includes the following steps:
A, porous aluminas array mould plate is prepared；
The porous alumina formwork is prepared using Two-step anodization, compared with technology；
Porous alumina formwork preparation process is divided into three steps: the high-purity aluminium flake that purity is 99.99% being carried out clear It washes, cleans mainly using the method for ultrasonic cleaning, this process is divided into two steps, aluminium flake is first cleaned to 15min in alcohol to remove Grease outside aluminium flake；Aluminium flake is placed on again in the sodium hydroxide solution of 1mol/L and cleans 10min to remove the oxidation on its surface Object and other chemical substances；The annealing that 2.5h is kept the temperature under the conditions of carrying out 400 DEG C to it afterwards, oneself builds at us later Electrochemical polish is carried out on electrochemistry platform, polishing fluid is ethyl alcohol and perchloric acid volume ratio is 8:3, with the high-purity aluminium flake handled well For anode, homemade aluminium flake is cathode, and is subject to 16V voltage electrochemical polishing 12min, later using processed aluminium flake as anode, Homemade aluminium flake uses oxidation voltage for 45V, oxidizing temperature 5 for cathode using the oxalic acid solution of 0.15mol/L as electrolyte DEG C, oxidization time be that 2h carries out once oxidation, after removing once oxidation layer, carry out secondary oxidation, the electrolyte temperature of second oxidation The conditions such as degree, electrolyte, oxidation voltage are identical as first time oxidation, and drop voltage is reduced to the 95% of original voltage every time, when Between between be divided into 90s, until while dropping to 8V closes power supply, then decompression is handled, and is finally cleaned.
Further include the following steps:
B, alumina formwork attachment copper film is prepared:
Porous alumina formwork is cleaned up through ethyl alcohol, i.e., at normal temperatures and pressures, by alumina formwork in ultrapure water logging 3h is steeped, surface smut is washed；Porous alumina formwork is dipped into the grease etc. that 3h in acetone soln removes surface again later； Porous alumina formwork is dipped into 3h in ethanol solution again later and does last cleaning.Sample is dried up with nitrogen later.It will place The porous alumina formwork managed, which fixes, to be placed in the vacuum cavity of magnetron sputtering apparatus, is vacuumized, and waits until vacuum Degree reach to a certain degree after, sputtering power be range be 80W, sputter rate 0.59nm/s, sputtering time 55min, carry out Magnetron sputtering grows certain thickness copper film.
C, the preparation of independent copper film:
The sample prepared is separated with chemical corrosion method.The concentration of sodium hydroxide solution of configuration is 0.6mol/L, By the porous alumina formwork of magnetron sputtering copper film, it is placed in configured sodium hydroxide corrosive liquid, corrodes one at room temperature The section time, so that copper film part is partially separated with porous alumina formwork and comes, obtained individual copper film.Later again with ultrapure Water washes corrosive liquid, and the ultrapure water process by copper film on surface is completely made.
The copper film of preparation is exactly the outer broadband light absorbing material of visible red, and absorbance reaches 98%, and product shape is more beautiful It sees.
Embodiment 5:
A kind of outer broadband light absorbing material of visible red, is the antipoints array using porous aluminas array films as template generation Film；
The preparation method of the outer broadband light absorbing material of the visible red includes the following steps:
A, porous aluminas array mould plate is prepared；
The porous alumina formwork is prepared using Two-step anodization, compared with technology；
Porous alumina formwork preparation process is divided into three steps: the high-purity aluminium flake that purity is 99.99% being carried out clear It washes, cleans mainly using the method for ultrasonic cleaning, this process is divided into two steps, aluminium flake is first cleaned to 16min in alcohol to remove Grease outside aluminium flake；Aluminium flake is placed on again in the sodium hydroxide solution of 1.5mol/L and cleans 12min to remove the oxygen on its surface Compound and other chemical substances；The annealing that 1h is kept the temperature under the conditions of carrying out 500 DEG C to it afterwards, oneself builds at us later Electrochemical polish is carried out on electrochemistry platform, polishing fluid is ethyl alcohol and perchloric acid volume ratio is 7:2, with the high-purity aluminium flake handled well For anode, homemade aluminium flake is cathode, and is subject to 20V voltage electrochemical polishing 10min, later using processed aluminium flake as anode, Homemade aluminium flake uses oxidation voltage for 40V, oxidizing temperature 8 for cathode using the oxalic acid solution of 0.2mol/L as electrolyte DEG C, oxidization time be that 2h carries out once oxidation, after removing once oxidation layer, carry out secondary oxidation, the electrolyte temperature of second oxidation The conditions such as degree, electrolyte, oxidation voltage are identical as first time oxidation, and drop voltage is reduced to the 90% of original voltage every time, when Between between be divided into 80s, until while dropping to 8V closes power supply, then decompression is handled, and is finally cleaned.
Further include the following steps:
B, alumina formwork attachment copper film is prepared:
Porous alumina formwork is cleaned up through ethyl alcohol, i.e., at normal temperatures and pressures, by alumina formwork in ultrapure water logging 4h is steeped, surface smut is washed；Porous alumina formwork is dipped into the grease etc. that 3h in acetone soln removes surface again later； Porous alumina formwork is dipped into 3h in ethanol solution again later and does last cleaning.Sample is dried up with nitrogen later.It will place The porous alumina formwork managed, which fixes, to be placed in the vacuum cavity of magnetron sputtering apparatus, is vacuumized, and waits until vacuum Degree reach to a certain degree after, sputtering power be range be 85W, sputter rate 0.66nm/s, sputtering time 55min, carry out Magnetron sputtering grows certain thickness copper film.
C, the preparation of independent copper film:
The sample prepared is separated with chemical corrosion method.The concentration of sodium hydroxide solution of configuration is 0.7mol/L, By the porous alumina formwork of magnetron sputtering copper film, it is placed in configured sodium hydroxide corrosive liquid, corrodes one at room temperature The section time, so that copper film part is partially separated with porous alumina formwork and comes, obtained individual copper film.Later again with ultrapure Water washes corrosive liquid, and the ultrapure water process by copper film on surface is completely made.
The copper film of preparation is exactly the outer broadband light absorbing material of visible red, and absorptance reaches 96%, and product shape is more beautiful It sees.
Embodiment 6~13:
A kind of outer broadband light absorbing material of visible red, is the antipoints array using porous aluminas array films as template generation Film；
The preparation method of the outer broadband light absorbing material of the visible red includes the following steps:
A, porous aluminas array mould plate is prepared；
The porous alumina formwork is prepared using Two-step anodization, compared with technology；
Porous alumina formwork preparation process is divided into three steps: the high-purity aluminium flake that purity is 99.99% being carried out clear It washes, cleans mainly using the method for ultrasonic cleaning, this process is divided into two steps, aluminium flake is first cleaned to 16min in alcohol to remove Grease outside aluminium flake；Aluminium flake is placed on again in the sodium hydroxide solution of 1mol/L and cleans 9min to remove the oxide on its surface With other chemical substances；The annealing of 2h, the electrification oneself built at us later are kept the temperature under the conditions of carrying out 450 DEG C to it afterwards It learns and carries out electrochemical polish on platform, polishing fluid is ethyl alcohol and perchloric acid volume ratio is 5:1, is positive with the high-purity aluminium flake handled well Pole, homemade aluminium flake are cathode, and are subject to 16V voltage electrochemical polishing 25min, later using processed aluminium flake as anode, self-control Aluminium flake be cathode, using the oxalic acid solution of 0.2mol/L as electrolyte, using oxidation voltage for 48V, oxidizing temperature is 8 DEG C, oxygen Changing the time is that 2h carries out once oxidation, after removing once oxidation layer, carries out secondary oxidation, electrolyte temperature, the electricity of second of oxidation It is identical as first time oxidation to solve the conditions such as liquid, oxidation voltage, drop voltage is reduced to the 90% of original voltage every time, time interval For 85s, power supply is closed when until dropping to 4V, then decompression is handled, and is finally cleaned.
Further include the following steps:
B, alumina formwork attachment copper film is prepared:
Porous alumina formwork is cleaned up through ethyl alcohol, i.e., at normal temperatures and pressures, by alumina formwork in ultrapure water logging 2.5h is steeped, surface smut is washed；Porous alumina formwork is dipped into the oil that 2.5h in acetone soln removes surface again later Rouge etc.；Porous alumina formwork is dipped into 2.5h in ethanol solution again later and does last cleaning.Sample is blown with nitrogen later It is dry.The porous alumina formwork handled well is fixed in the vacuum cavity for being placed on magnetron sputtering apparatus, is vacuumized, etc. To vacuum degree reach to a certain degree after, sputtering power be range be 30W-150W, sputter rate is 0.1nm/s~2nm/s, sputtering Time is 10min-360min, carries out magnetron sputtering and grows certain thickness copper film.
C, the preparation of independent copper film:
The sample prepared is separated with chemical corrosion method.The concentration of sodium hydroxide solution range of configuration is The porous alumina formwork of magnetron sputtering copper film is placed on configured sodium hydroxide corrosive liquid by 0.2mol/L-0.8mol In, at room temperature corrosion a period of time, so that copper film part is partially separated with porous alumina formwork and comes, what is obtained is individual Copper film.Corrosive liquid is washed with ultrapure water again later, and the ultrapure water process by copper film on surface is completely made.
The copper film of preparation is exactly the outer broadband light absorbing material of visible red, and absorptance is in 90%~99% range, product Good appearance；
In embodiment 6~13: sputtering power (W), sputtering time (min) see the table below:
Embodiment number 6 7 8 9 10 11 12 13
Sputtering power (W) 90 95 100 105 110 115 120 125
Sputter rate (nm/s) 0.74 0.85 0.96 1.03 1.19 1.23 1.38 1.49
Sputtering time (min) 60 60 55 55 50 50 45 45
In embodiment 6~13: the concentration range of the sodium hydrate aqueous solution of the configuration is 0.2mol/L~0.8mol/L In any concentration.
Embodiment 14:
A kind of outer broadband light absorbing material of visible red, the outer broadband light absorbing material of the visible red are the films of copper.
Embodiment 15:
A kind of outer broadband light absorbing material of visible red, the outer broadband light absorbing material of the visible red are the film of copper, institute State copper film be with porous aluminas array diaphragm plate (or porous anodic alumina films plate) be template by copper through magnetron sputtering The copper porous nanometer thin films of generation.
Embodiment 16:
A kind of outer broadband light absorbing material of visible red, the film of the copper with a thickness of 15 μm；The other the same as in Example 14 Or embodiment 15, it omits.
Embodiment 17:
A kind of outer broadband light absorbing material of visible red, the film of the copper with a thickness of 300nm；The other the same as in Example 14 Or embodiment 15, it omits.
Embodiment 18:
A kind of outer broadband light absorbing material of visible red, the film of the copper with a thickness of 500nm；The other the same as in Example 14 Or embodiment 15, it omits.
Embodiment 19:
A kind of outer broadband light absorbing material of visible red, the film of the copper with a thickness of 7.5 μm；The other the same as in Example 14 Or embodiment 15, it omits.
Embodiment 20:
A kind of outer broadband light absorbing material of visible red, the film of the copper with a thickness of 5 μm；The other the same as in Example 14 or Embodiment 15 is omitted.
Embodiment 21:
A kind of outer broadband light absorbing material of visible red, the film of the copper with a thickness of any in 300nm~15 μm Numerical value；The other the same as in Example 14 or embodiment 15 are omitted.
Embodiment 22:
A kind of preparation method of the outer broadband light absorbing material of visible red, comprising:
A, porous aluminas array mould plate (or porous anodic aluminium oxide array mould plate) is prepared；
The preparation method of porous aluminas array mould plate is using Two-step anodization, is the prior art；
The preparation method of porous aluminas array mould plate is divided into 3 steps: (1) by aluminium flake (preferably use purity for 99.99% high-purity aluminium flake) it is cleaned and (is cleaned mainly using the method for ultrasonic cleaning, step is: first by aluminium flake in ethyl alcohol Middle cleaning 5min is to remove the grease outside aluminium flake；Aluminium flake is placed in the sodium hydrate aqueous solution that concentration is 0.5 again and is cleaned 30min with remove its surface oxide and other chemical substances)；(2) then aluminium flake is made annealing treatment (in 400 DEG C of temperature 3h is kept the temperature under the conditions of degree to be made annealing treatment), electrochemical polish is carried out later (to carry out electrochemical polish on electrochemistry platform, throw Light liquid is ethyl alcohol and perchloric acid volume ratio is the mixture of 5:1, and using the aluminium flake after making annealing treatment as anode, aluminium flake is cathode, and Be subject to 10V or more voltage electrochemical polishing 10min), carry out after (3) once oxidation (condition, the parameter of once oxidation are: with Aluminium flake after electrochemical polish is anode, and aluminium flake is cathode, using concentration for 0.1mol/L oxalic acid aqueous solution as electrolyte, oxidation Voltage is 40V, oxidizing temperature is 2 DEG C, oxidization time is that 4h carries out once oxidation.), after removing once oxidation layer, carry out secondary oxygen (condition, the parameter of secondary oxidation are: the conditions such as electrolyte temperature, electrolyte, oxidation voltage of second of oxidation and first time for change What is aoxidized is identical), drop voltage processing is then carried out, is reduced to the 90% of original voltage, time interval 120s, until drop every time Power supply is closed when to 2V, finally cleans, obtains porous aluminas array mould plate；
Further include the following steps:
B, porous aluminas array mould plate attachment copper film is prepared:
It is dry after porous aluminas array mould plate (specification can be long 1cm x wide 1cm) is cleaned up, then will In magnetron sputtering apparatus, (the offer enterprise of magnetron sputtering apparatus is China to porous aluminas array mould plate fixed placement after drying Shenyang scientific instrument limited liability company, the academy of sciences, model can be JGP-450A, MPS-4000-C4) vacuum cavity in into Row vacuumizes, until (vacuum degree) pressure is in 2x 10-4After Pa or less, by copper, (i.e. copper target is directly installed in magnetron sputtering apparatus On target chamber；Copper target preferably use purity for 99.99% copper；It is 3 inches, with a thickness of the circle of 3mm that copper target, which can be diameter, Cylinder or other prior art shapes) magnetron sputtering is carried out, control sputtering power (or invariable power) is 30W, sputter rate is 0.1nm/s, sputtering time 360min obtain porous aluminas array mould plate attachment copper film；(magnetron sputtering is exactly by target It is splashed on base material, to form corresponding film；The target of magnetron sputtering selection of the present invention is copper target, and base material is Porous aluminas array mould plate, therefore, product obtained are exactly to adhere to copper film in porous aluminas array mould plate).
C, copper porous nanometer thin films are prepared:
Porous aluminas array mould plate obtained attachment copper film is separated with chemical corrosion method；Step is: preparing dense The sodium hydrate aqueous solution that degree is 0.2mol/L adheres to copper film as sodium hydroxide corrosive liquid, by aluminium oxide array mould plate obtained It is soaked into sodium hydroxide corrosive liquid, impregnates 360min at room temperature, make the copper in porous aluminas array mould plate attachment copper film Membrane part is partially separated with porous aluminas array mould plate and comes, and obtained individual copper film washes with water corrosion again later Liquid, and by copper film surface with being dried with nitrogen, obtain copper porous nanometer thin films；In copper porous nanometer thin films obtained, entire copper The surface of porous nanometer thin films has numerous copper porous nanometer structure tightly to stick together to be formed, and each copper is porous receives The overall diameter of rice structure is substantially consistent with the diameter in the hole of porous aluminas array mould plate.The arrangement of copper porous nanometer thin films Structure is consistent with the arrangement in hole of used porous aluminas array mould plate, is hexagonal structure.Copper porous nanometer thin films are as follows: What is contacted with porous aluminas array mould plate is nano aperture structure on one side, and another side is sealing state.
Embodiment 23:
A kind of preparation method of the outer broadband light absorbing material of visible red, comprising:
A, porous aluminas array mould plate (or porous anodic aluminium oxide array mould plate) is prepared；
The preparation method of porous aluminas array mould plate is using Two-step anodization, is the prior art；
The preparation method of porous aluminas array mould plate is divided into 3 steps: (1) by aluminium flake (preferably use purity for 99.99% high-purity aluminium flake) it is cleaned and (is cleaned mainly using the method for ultrasonic cleaning, step is: first by aluminium flake in ethyl alcohol Middle cleaning 30min is to remove the grease outside aluminium flake；Aluminium flake is placed on again clear in the sodium hydrate aqueous solution that concentration is 2mol/L 5min is washed to remove the oxide on its surface and other chemical substances)；(2) then aluminium flake is made annealing treatment (in 600 DEG C of temperature 1h is kept the temperature under the conditions of degree to be made annealing treatment), electrochemical polish is carried out later (to carry out electrochemical polish on electrochemistry platform, throw Light liquid is ethyl alcohol and perchloric acid volume ratio is the mixture of 27:9, and using the aluminium flake after making annealing treatment as anode, aluminium flake is cathode, and Be subject to 10V or more voltage electrochemical polishing 20min), carry out after (3) once oxidation (condition, the parameter of once oxidation are: with Aluminium flake after electrochemical polish is anode, and aluminium flake is cathode, using concentration for 1mol/L oxalic acid aqueous solution as electrolyte, oxidation electricity Pressure is 60V, oxidizing temperature is 8 DEG C, oxidization time is that 1h carries out once oxidation.), after removing once oxidation layer, carry out secondary oxidation (condition, the parameter of secondary oxidation are: conditions and the first time oxygen such as electrolyte temperature, electrolyte, oxidation voltage of second of oxidation That changes is identical), drop voltage processing is then carried out, the 98% of original voltage, time interval 60s are reduced to every time, until dropping to Power supply is closed when 8V, is finally cleaned, and porous aluminas array mould plate is obtained；
Further include the following steps:
B, porous aluminas array mould plate attachment copper film is prepared:
It is dry after porous aluminas array mould plate (specification can be long 4cm x wide 3cm) is cleaned up, then will In magnetron sputtering apparatus, (the offer enterprise of magnetron sputtering apparatus is China to porous aluminas array mould plate fixed placement after drying Shenyang scientific instrument limited liability company, the academy of sciences, model can be JGP-450A, MPS-4000-C4) vacuum cavity in into Row vacuumizes, until (vacuum degree) pressure is in 2x 10-4After Pa or less, by copper, (i.e. copper target is directly installed in magnetron sputtering apparatus On target chamber；Copper target preferably use purity for 99.99% copper；It is 3 inches, with a thickness of the circle of 3mm that copper target, which can be diameter, Cylinder or other prior art shapes) magnetron sputtering is carried out, control sputtering power (or invariable power) is 150W, sputter rate is 2nm/s, sputtering time 10min obtain porous aluminas array mould plate attachment copper film；(magnetron sputtering exactly splashes target It is mapped on base material, to form corresponding film；The target of magnetron sputtering selection of the present invention is copper target, and base material is more Porous aluminum oxide array mould plate, therefore, product obtained are exactly to adhere to copper film in porous aluminas array mould plate).
C, copper porous nanometer thin films are prepared:
Porous aluminas array mould plate obtained attachment copper film is separated with chemical corrosion method；Step is: preparing dense The sodium hydrate aqueous solution that degree is 0.8mol/L adheres to copper film as sodium hydroxide corrosive liquid, by aluminium oxide array mould plate obtained It is soaked into sodium hydroxide corrosive liquid, impregnates 10min at room temperature, make the copper film in porous aluminas array mould plate attachment copper film Part is partially separated the individual copper film for coming, obtaining with porous aluminas array mould plate, washes with water corrosive liquid again later, And by copper film surface with being dried with nitrogen, copper porous nanometer thin films are obtained；In copper porous nanometer thin films obtained, entire copper is porous The surface of nano thin-film has numerous copper porous nanometer structure tightly to stick together to be formed, and each copper porous nano knot The overall diameter of structure is substantially consistent with the diameter in the hole of porous aluminas array mould plate.The structure of copper porous nanometer thin films arrangement It is consistent with the arrangement in hole of used porous aluminas array mould plate, it is hexagonal structure.Copper porous nanometer thin films are as follows: with it is more The contact of porous aluminum oxide array mould plate is nano aperture structure on one side, and another side is sealing state.
Embodiment 24:
A kind of preparation method of the outer broadband light absorbing material of visible red, comprising:
A, porous aluminas array mould plate (or porous anodic aluminium oxide array mould plate) is prepared；
The preparation method of porous aluminas array mould plate is using Two-step anodization, is the prior art；
The preparation method of porous aluminas array mould plate is divided into 3 steps: (1) by aluminium flake (preferably use purity for 99.99% high-purity aluminium flake) it is cleaned and (is cleaned mainly using the method for ultrasonic cleaning, step is: first by aluminium flake in ethyl alcohol Middle cleaning 18min is to remove the grease outside aluminium flake；Aluminium flake is placed in the sodium hydrate aqueous solution that concentration is 1.2mol/L again 18min is cleaned to remove the oxide and other chemical substances on its surface)；(2) then aluminium flake is made annealing treatment (500 Heat preservation 2h is made annealing treatment under the conditions of DEG C temperature), electrochemical polish is carried out later (electrochemistry throwing is carried out on electrochemistry platform Light, polishing fluid is ethyl alcohol and perchloric acid volume ratio is the mixture of 4:1, and using the aluminium flake after making annealing treatment as anode, aluminium flake is yin Pole, and it is subject to 10V or more voltage electrochemical polishing 15min), once oxidation (condition, the parameter of once oxidation is carried out after (3) Be: using the aluminium flake after electrochemical polish as anode, aluminium flake is cathode, using concentration for 0.5mol/L oxalic acid aqueous solution as electrolysis Liquid, oxidation voltage 50V, oxidizing temperature are 5 DEG C, oxidization time is that 2.5h carries out once oxidation.), after removing once oxidation layer, into (condition, the parameter of secondary oxidation are row secondary oxidation: the conditions such as electrolyte temperature, electrolyte, oxidation voltage of second of oxidation It is identical as first time oxidation), drop voltage processing is then carried out, is reduced to the 95% of original voltage every time, time interval is 90s closes power supply when until dropping to 5V, finally cleans, obtain porous aluminas array mould plate；
Further include the following steps:
B, porous aluminas array mould plate attachment copper film is prepared:
It is dry after porous aluminas array mould plate (specification can be long 4cm x wide 3cm) is cleaned up, then will In magnetron sputtering apparatus, (the offer enterprise of magnetron sputtering apparatus is China to porous aluminas array mould plate fixed placement after drying Shenyang scientific instrument limited liability company, the academy of sciences, model can be JGP-450A, MPS-4000-C4) vacuum cavity in into Row vacuumizes, until (vacuum degree) pressure is in 2x 10-4After Pa or less, by copper, (i.e. copper target is directly installed in magnetron sputtering apparatus On target chamber；Copper target preferably use purity for 99.99% copper；It is 3 inches, with a thickness of the circle of 3mm that copper target, which can be diameter, Cylinder or other prior art shapes) magnetron sputtering is carried out, control sputtering power (or invariable power) is 80W, sputter rate is 1nm/s, sputtering time 185min obtain porous aluminas array mould plate attachment copper film；(magnetron sputtering exactly splashes target It is mapped on base material, to form corresponding film；The target of magnetron sputtering selection of the present invention is copper target, and base material is more Porous aluminum oxide array mould plate, therefore, product obtained are exactly to adhere to copper film in porous aluminas array mould plate).
C, copper porous nanometer thin films are prepared:
Porous aluminas array mould plate obtained attachment copper film is separated with chemical corrosion method；Step is: preparing dense The sodium hydrate aqueous solution that degree is 0.5mol/L adheres to copper film as sodium hydroxide corrosive liquid, by aluminium oxide array mould plate obtained It is soaked into sodium hydroxide corrosive liquid, impregnates 185min at room temperature, make the copper in porous aluminas array mould plate attachment copper film Membrane part is partially separated with porous aluminas array mould plate and comes, and obtained individual copper film washes with water corrosion again later Liquid, and by copper film surface with being dried with nitrogen, obtain copper porous nanometer thin films；In copper porous nanometer thin films obtained, entire copper The surface of porous nanometer thin films has numerous copper porous nanometer structure tightly to stick together to be formed, and each copper is porous receives The overall diameter of rice structure is substantially consistent with the diameter in the hole of porous aluminas array mould plate.The arrangement of copper porous nanometer thin films Structure is consistent with the arrangement in hole of used porous aluminas array mould plate, is hexagonal structure.Copper porous nanometer thin films are as follows: What is contacted with porous aluminas array mould plate is nano aperture structure on one side, and another side is sealing state.
Embodiment 25:
A kind of preparation method of the outer broadband light absorbing material of visible red, comprising:
A, porous aluminas array mould plate (or porous anodic aluminium oxide array mould plate) is prepared；
The preparation method of porous aluminas array mould plate is using Two-step anodization, is the prior art；
The preparation method of porous aluminas array mould plate is divided into 3 steps: (1) by aluminium flake (preferably use purity for 99.99% high-purity aluminium flake) it is cleaned and (is cleaned mainly using the method for ultrasonic cleaning, step is: first by aluminium flake in ethyl alcohol Middle cleaning 16min is to remove the grease outside aluminium flake；Aluminium flake is placed on again clear in the sodium hydrate aqueous solution that concentration is 1mol/L 15min is washed to remove the oxide on its surface and other chemical substances)；(2) then aluminium flake is made annealing treatment (at 500 DEG C Under the conditions of temperature keep the temperature 2h made annealing treatment), later carry out electrochemical polish (electrochemical polish is carried out on electrochemistry platform, Polishing fluid is ethyl alcohol and perchloric acid volume ratio is the mixture of 4:1, and using the aluminium flake after making annealing treatment as anode, aluminium flake is cathode, And be subject to 10V or more voltage electrochemical polishing 16min), carry out after (3) once oxidation (condition, the parameter of once oxidation are: Using the aluminium flake after electrochemical polish as anode, aluminium flake is cathode, using concentration for 0.5mol/L oxalic acid aqueous solution as electrolyte, oxygen Change voltage is 50V, oxidizing temperature is 5 DEG C, oxidization time is that 3h carries out once oxidation), after removing once oxidation layer, carry out secondary oxygen (condition, the parameter of secondary oxidation are: the conditions such as electrolyte temperature, electrolyte, oxidation voltage of second of oxidation and first time for change What is aoxidized is identical), drop voltage processing is then carried out, is reduced to the 95% of original voltage, time interval 90s, until drop every time Power supply is closed when to 5V, finally cleans, obtains porous aluminas array mould plate；
Further include the following steps:
B, porous aluminas array mould plate attachment copper film is prepared:
It is dry after porous aluminas array mould plate (specification can be long 1cm x wide 1cm) is cleaned up, then will In magnetron sputtering apparatus, (the offer enterprise of magnetron sputtering apparatus is China to porous aluminas array mould plate fixed placement after drying Shenyang scientific instrument limited liability company, the academy of sciences, model can be JGP-450A, MPS-4000-C4) vacuum cavity in into Row vacuumizes, until (vacuum degree) pressure is in 2x 10-4After Pa or less, by copper, (i.e. copper target is directly installed in magnetron sputtering apparatus On target chamber；Copper target preferably use purity for 99.99% copper；It is 3 inches, with a thickness of the circle of 3mm that copper target, which can be diameter, Cylinder or other prior art shapes) magnetron sputtering is carried out, control sputtering power (or invariable power) is 90W, sputter rate is 1.1nm/s, sputtering time 180min obtain porous aluminas array mould plate attachment copper film；(magnetron sputtering is exactly by target It is splashed on base material, to form corresponding film；The target of magnetron sputtering selection of the present invention is copper target, and base material is Porous aluminas array mould plate, therefore, product obtained are exactly to adhere to copper film in porous aluminas array mould plate).
C, copper porous nanometer thin films are prepared:
Porous aluminas array mould plate obtained attachment copper film is separated with chemical corrosion method；Step is: preparing dense The sodium hydrate aqueous solution that degree is 0.6mol/L adheres to copper film as sodium hydroxide corrosive liquid, by aluminium oxide array mould plate obtained It is soaked into sodium hydroxide corrosive liquid, impregnates 180min at room temperature, make the copper in porous aluminas array mould plate attachment copper film Membrane part is partially separated with porous aluminas array mould plate and comes, and obtained individual copper film washes with water corrosion again later Liquid, and by copper film surface with being dried with nitrogen, obtain copper porous nanometer thin films；In copper porous nanometer thin films obtained, entire copper The surface of porous nanometer thin films has numerous copper porous nanometer structure tightly to stick together to be formed, and each copper is porous receives The overall diameter of rice structure is substantially consistent with the diameter in the hole of porous aluminas array mould plate.The arrangement of copper porous nanometer thin films Structure is consistent with the arrangement in hole of used porous aluminas array mould plate, is hexagonal structure.Copper porous nanometer thin films are as follows: What is contacted with porous aluminas array mould plate is nano aperture structure on one side, and another side is sealing state.
Embodiment 26:
A kind of preparation method of the outer broadband light absorbing material of visible red, comprising:
A, porous aluminas array mould plate (or porous anodic aluminium oxide array mould plate) is prepared；
The preparation method of porous aluminas array mould plate is using Two-step anodization, is the prior art；
The preparation method of porous aluminas array mould plate is divided into 3 steps: (1) by aluminium flake (preferably use purity for 99.99% high-purity aluminium flake) it is cleaned and (is cleaned mainly using the method for ultrasonic cleaning, step is: first by aluminium flake in ethyl alcohol Middle cleaning 5min~30min (any value therein) is to remove the grease outside aluminium flake；Again by aluminium flake be placed on concentration be 0.5~ 5min~30min (any value therein) is cleaned in the sodium hydrate aqueous solution of 2mol/L (any value therein) to remove its table The oxide in face and other chemical substances)；(2) aluminium flake is then made annealing treatment into (any value in 400 DEG C~600 DEG C Any value kept the temperature in 1h~3h under the conditions of temperature is made annealing treatment), carrying out electrochemical polish later, (electrochemistry platform is enterprising Row electrochemical polish, polishing fluid is ethyl alcohol and perchloric acid volume ratio is the mixture of 5:1~27:9 (any value therein), to move back Fire treated aluminium flake is anode, and aluminium flake is cathode, and is subject to appointing in 10V or more voltage electrochemical polishing 10min~20min One value), carry out after (3) once oxidation (condition, the parameter of once oxidation are: using the aluminium flake after electrochemical polish as anode, aluminium Piece is cathode, using concentration for any value in 0.1mol/L~1mol/L oxalic acid aqueous solution as electrolyte, oxidation voltage 40V Any value, oxidizing temperature in~60V are that any value, the oxidization time in 2 DEG C~8 DEG C are that any value in 1h~4h carries out one Secondary oxidation.), after removing once oxidation layer, carrying out secondary oxidation, (condition, the parameter of secondary oxidation are: the electrolyte of second of oxidation The conditions such as temperature, electrolyte, oxidation voltage are identical as first time oxidation), drop voltage processing is then carried out, is reduced to original every time Carry out any value in the 90%~98% of voltage, time interval is any value in 60s~120s, until dropping in 2V~8V Power supply is closed when any value, is finally cleaned, and porous aluminas array mould plate is obtained；
Further include the following steps:
B, porous aluminas array mould plate attachment copper film is prepared:
Porous aluminas array mould plate (specification can be long 1cm x wide 1cm~long 4cm x wide 3cm) cleaning is dry It is dry after net, then by the porous aluminas array mould plate fixed placement after drying in magnetron sputtering apparatus (magnetron sputtering apparatus Offer enterprise be CAS Shenyang Scientific Instruments Co., Ltd., model can be JGP-450A, MPS-4000- C4 it is vacuumized in vacuum cavity), until (vacuum degree) pressure is in 2x 10-4After Pa or less, by copper, (i.e. copper target is directly installed in On target chamber in magnetron sputtering apparatus；Copper target preferably use purity for 99.99% copper；It is 3 English that copper target, which can be diameter, Very little, cylindrical body with a thickness of 3mm or other prior art shapes) magnetron sputtering is carried out, it controls sputtering power (or invariable power) It is any value, sputtering time in 0.1nm/s~2nm/s for any value, the sputter rate in 30W~150W is 10~360min In any value, obtain porous aluminas array mould plate attachment copper film；(magnetron sputtering is exactly by target as sputter to base material On, to form corresponding film；The target of magnetron sputtering selection of the present invention is copper target, and base material is porous aluminas array Template, therefore, product obtained are exactly to adhere to copper film in porous aluminas array mould plate).
C, copper porous nanometer thin films are prepared:
Porous aluminas array mould plate obtained attachment copper film is separated with chemical corrosion method；Step is: preparing dense Degree is the sodium hydrate aqueous solution of any value in 0.2mol/L~0.8mol/L as sodium hydroxide corrosive liquid, by oxygen obtained Change aluminium array mould plate attachment copper film to be soaked into sodium hydroxide corrosive liquid, impregnates any in 10min~360min at room temperature Value is partially separated the copper film part in porous aluminas array mould plate attachment copper film with porous aluminas array mould plate and comes, Obtained individual copper film washes with water corrosive liquid again later, and by copper film surface with being dried with nitrogen, and obtains that copper is porous to be received Rice film；In copper porous nanometer thin films obtained, the surface of entire copper porous nanometer thin films is that have numerous copper porous nano knot Structure, which tightly sticks together, to be formed, and the overall diameter of each copper porous nanometer structure is substantially the same as porous aluminas array mould plate The diameter in hole is consistent.The arrangement in the hole of the structure and used porous aluminas array mould plate of copper porous nanometer thin films arrangement It unanimously, is hexagonal structure.Copper porous nanometer thin films are as follows: what is contacted with porous aluminas array mould plate is nano aperture on one side Structure, and another side is sealing state.
Embodiment 27:
A kind of preparation method of the outer broadband light absorbing material of visible red, by the porous aluminas of drying described in step b Array mould plate fixed placement is vacuumized in the vacuum cavity of magnetron sputtering apparatus, until (vacuum degree) pressure is in 2x 10-4Pa After below, copper is subjected to magnetron sputtering, preferably: by the porous aluminas array mould plate fixed placement of drying in magnetron sputtering It is vacuumized in the vacuum cavity of instrument, until (vacuum degree) pressure is in 2x 10-4After Pa or less, it is passed through argon gas, then (i.e. by copper Copper target is directly installed on the target chamber in magnetron sputtering apparatus；The copper that copper target is preferably 99.99% by purity；Copper target can be with Be diameter it is 3 inches, the cylindrical body with a thickness of 3mm or other prior art shapes) carry out magnetron sputtering；The other the same as in Example 22 It is any in~26, it omits.
Embodiment 28:
A kind of preparation method of the outer broadband light absorbing material of visible red, by porous aluminas array mould described in step b Plate is dry after cleaning up, and is: at normal temperatures and pressures, porous aluminas array mould plate being impregnated 2~4h in water and washes table Face dirt；Porous aluminas array mould plate is dipped into the grease etc. that 2~4h in acetone removes surface again later；It later again will be more Porous aluminum oxide array mould plate is dipped into 2~4h in ethyl alcohol (referring to dehydrated alcohol) and does last cleaning；Later with nitrogen by porous oxidation The drying of aluminium array mould plate；It is any in the other the same as in Example 2 2~27, it omits.
Embodiment 29:
A kind of preparation method of the outer broadband light absorbing material of visible red, by porous aluminas array mould described in step b Plate is dry after cleaning up, and is: at normal temperatures and pressures, porous aluminas array mould plate being impregnated 3h in water and washes surface dirt Dirt；Porous aluminas array mould plate is dipped into the grease etc. that 3h in acetone removes surface again later；Later again by porous oxidation Aluminium array mould plate is dipped into 3h in ethyl alcohol (referring to dehydrated alcohol) and does last cleaning；Later with nitrogen by porous aluminas array mould plate Drying；It is any in the other the same as in Example 2 2~27, it omits.
In above-described embodiment: water described in step b and step c is that (ultrapure water is that the conducting medium in water is several to ultrapure water It completely removes, and the colloidal substance not dissociated in water, gas and organic matter is removed to the water of very low degree, use is existing Technology preparation), distilled water or deionized water.
The thickness of the attachment copper film of porous aluminas array mould plate made from above-described embodiment can be in 300nm~15 μm Any value.
The copper film prepared in above-described embodiment is exactly the outer broadband light absorbing material of visible red, and absorptance is 90%~99% In range, product shape is beautiful；
In above-described embodiment: used each raw material is commercial product.
In above-described embodiment: it is not specifically specified in used percentage, be quality (weight) percentage or Well known to a person skilled in the art percentages；Described quality (weight) part can be gram or kilogram.
In above-described embodiment: technological parameter (temperature, time, pressure, concentration etc.) and dosage of each component number in each step Value etc. is range, and any point is applicable.
The technology contents being not specifically delineated in the content of present invention and above-described embodiment are compared with technology.
The present invention is not limited to the above embodiments, can be implemented described in the content of present invention and has the good result.

Claims (8)

1. the outer broadband light absorbing material of a kind of visible red, it is characterized in that: the outer broadband light absorbing material of the visible red is copper Film.
2. the outer broadband light absorbing material of visible red according to claim 1, it is characterized in that: the film of the copper is with porous Aluminium oxide array diaphragm plate is the copper porous nanometer thin films that template generates copper through magnetron sputtering.
3. the outer broadband light absorbing material of visible red as described in claim 1 or 2, it is characterized in that: the thickness of the film of the copper Degree is 300nm~15 μm.
4. a kind of preparation method of the outer broadband light absorbing material of visible red, comprising:
A, porous aluminas array mould plate is prepared；
It is characterized in that further including the following steps:
B, porous aluminas array mould plate attachment copper film is prepared:
It is dry after porous aluminas array mould plate is cleaned up, then the porous aluminas array mould plate fixation after drying is put It sets and is vacuumized in the vacuum cavity of magnetron sputtering apparatus, until pressure is in 2 x 10-4After Pa or less, copper is subjected to magnetic control Sputtering, control sputtering power is 30W~150W, sputter rate is 0.1nm/s~2nm/s, sputtering time is 10~360min, i.e., Porous aluminas array mould plate is made and adheres to copper film；
C, copper porous nanometer thin films are prepared:
Porous aluminas array mould plate obtained attachment copper film is separated with chemical corrosion method；Step is: compound concentration is The sodium hydrate aqueous solution of 0.2mol/L~0.8mol/L is attached by aluminium oxide array mould plate obtained as sodium hydroxide corrosive liquid Copper film be soaked into sodium hydroxide corrosive liquid, at room temperature impregnate 10min~360min, keep porous aluminas array mould plate attached Copper film part in copper film the individual copper film for coming, obtaining is partially separated with porous aluminas array mould plate, use again later Water washes corrosive liquid, and by copper film surface with being dried with nitrogen, obtains copper porous nanometer thin films.
5. by the preparation method of the outer broadband light absorbing material of visible red described in claim 4, it is characterized in that: described in step b The porous aluminas array mould plate fixed placement of drying is vacuumized in the vacuum cavity of magnetron sputtering apparatus, until pressure In 2 x 10-4After Pa or less, copper is subjected to magnetron sputtering, is: by the porous aluminas array mould plate fixed placement of drying in magnetic It is vacuumized in the vacuum cavity of control sputtering instrument, until pressure is in 2 x 10-4After Pa or less, it is passed through argon gas, then copper is carried out Magnetron sputtering.
6. by the preparation method of the outer broadband light absorbing material of the visible red of claim 4 or 5, it is characterized in that: institute in step b Drying after cleaning up porous aluminas array mould plate is stated, is: at normal temperatures and pressures, by porous aluminas array mould plate in water 2~4 h of middle immersion wash surface smut；Porous aluminas array mould plate is dipped into 2~4 h removing table in acetone again later The grease etc. in face；Porous aluminas array mould plate is dipped into 2~4 h in ethyl alcohol again later and does last cleaning；Nitrogen is used later Porous aluminas array mould plate is dried up.
7. by the preparation method of the outer broadband light absorbing material of the visible red of claim 4 or 5, it is characterized in that: step b and step Water described in rapid c is ultrapure water, distilled water or deionized water.
8. by the preparation method of the outer broadband light absorbing material of visible red described in claim 6, it is characterized in that: step b and step c Described in water be ultrapure water, distilled water or deionized water.
CN201910506818.3A 2019-06-12 2019-06-12 Outer broadband light absorbing material of a kind of visible red and preparation method thereof Pending CN110195209A (en)

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CN110488401A (en) * 2019-09-09 2019-11-22 南开大学 The two-sided random nano aluminium oxide hole wave absorbing device part in part
CN114540754A (en) * 2022-04-02 2022-05-27 西南科技大学 Cu/Ti-W/ceramic composite material and preparation method thereof

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CN105543796A (en) * 2016-02-01 2016-05-04 山东大学 Method for preparing nano porous copper thin film material by magnetron sputtering

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* Cited by examiner, † Cited by third party
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CN110488401A (en) * 2019-09-09 2019-11-22 南开大学 The two-sided random nano aluminium oxide hole wave absorbing device part in part
CN114540754A (en) * 2022-04-02 2022-05-27 西南科技大学 Cu/Ti-W/ceramic composite material and preparation method thereof

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Application publication date: 20190903