CN102560650A - Porous aluminum oxide photonic crystal and preparation method and applications thereof - Google Patents
Porous aluminum oxide photonic crystal and preparation method and applications thereof Download PDFInfo
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- CN102560650A CN102560650A CN2010106170883A CN201010617088A CN102560650A CN 102560650 A CN102560650 A CN 102560650A CN 2010106170883 A CN2010106170883 A CN 2010106170883A CN 201010617088 A CN201010617088 A CN 201010617088A CN 102560650 A CN102560650 A CN 102560650A
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Abstract
The invention discloses a porous aluminum oxide photonic crystal and a preparation method and applications thereof. The crystal is composed of main layers and branch layers in a stacking mode, and defect layers arranged in a local area inside the crystal; wherein, the crystal is 75 to 85 microns thick, the main layers are composed of main holes, the branch layers are composed of two branch holes, two ends of one of the branch holes are respectively communicated with the main holes of an upper main layer and a lower main layer of the branch layer where the branch hole is in, and the defect layers are formed by straight holes and two ends of the straight holes are respectively communicated with the main holes. The preparation method includes firstly, oxidizing aluminum sheets, anodizing the oxidized aluminum sheets under periodic voltage, and obtaining alumina wafers containing main layers and branch layers; secondly, daubing grease on part of the front face of the alumina wafers, and anodizing the grease daubed alumina wafers under periodic voltage to obtain the alumina wafers containing defect layers in the local area; and thirdly, anodizing the alumina wafers containing defect layers under periodic voltage after removing the grease, and removing the redundant aluminum on the back face to obtain products. The porous aluminum oxide photonic crystal can be used for optical anti-counterfeiting of wave bands ranging from 780 nanometers to 1400 nanometers.
Description
Technical field
The present invention relates to a kind of photonic crystal and preparation method and purposes, especially a kind of porous alumina photonic crystal.
Background technology
As everyone knows, the photonic crystal that is made up of porous alumina membrane is because of the difference of its pore passage structure, is inequality to the transmittance of the light of different-waveband.Thus; People are in order to explore and expand the range of application of porous alumina photonic crystal; Some trials and effort have been done, like a kind of " having porous aluminum oxide film light filter of bifurcate holes and preparation method thereof " of mentioning among the disclosed Chinese invention patent Shen Qing Publication specification sheets CN 101520525A on September 2nd, 2009.This spectral filter is that the hole of porous alumina membrane is the linear pattern through hole of aperture 40～60nm; Be equipped with two-layer above bifurcate holes on its hole wall; The aperture of bifurcate holes is 20～40nm; Angle between itself and linear pattern through hole is 50～70 degree, and the trunk layer that the linear pattern through hole between bifurcate holes constitutes is periodically changed with the bifurcated layer of bifurcate holes formation, and the thickness of film is 60～180 μ m; The preparation method is the acid solution of 0.2～0.4M for aluminium flake is placed concentration; Anode is oxidizing to few 5min under the curved tooth wave voltage; Wherein, The wave amplitude of curved tooth wave voltage is that 22～50V, wavefront are that 45 degree, wave period are 2.5～3.5min, makes the porous aluminum oxide film light filter that has bifurcate holes.Though this spectral filter that is made up of porous alumina membrane can selectively filter the light of 500～1500nm wave band; Exist also and only can realize that same aluminum oxide film has identical optical property; Be that same aluminum oxide film can only carry out filtering deficiency to the light of a certain wave band; And can not use it for optical anti-counterfeiting, promptly same aluminum oxide film can be realized different optical properties at regional area; In addition, the preparation method can not make the aluminum oxide film that is used for optical anti-counterfeiting.
Summary of the invention
The technical problem that the present invention will solve provides a kind of and under visible light, has identical optical characteristics for overcoming weak point of the prior art, and the porous alumina photonic crystal that regional area has the different optical characteristic under infrared light.
Another technical problem that the present invention will solve is the preparation method that a kind of above-mentioned porous alumina photonic crystal is provided.
Technical problem in addition that the present invention will solve is the purposes that a kind of above-mentioned porous alumina photonic crystal is provided.
For solving technical problem of the present invention, the technical scheme that is adopted is: the porous alumina photonic crystal was made up of trunk layer and bifurcated range upon range of adding, particularly,
The thickness of said photonic crystal is 75～85 μ m, and the mid-defectiveness layer of regional area in it;
The number of plies of said trunk layer and bifurcated layer is 375～425 layers, and its mutual thickness ratio is 2～3: 1;
Said trunk layer is made up of main aperture, and said bifurcated layer is made up of the bifurcated hole, and angle is 30～50 degree between the hole in said bifurcated hole, and the two ends of a bifurcate holes wherein are connected with the main aperture of the upper and lower trunk layer of its place bifurcated layer respectively;
The bore dia that is positioned at photonic crystal upper surface place of said main aperture is 80～110nm, and the bore dia of other each layer is linearity to be dwindled, and the bore dia until photonic crystal lower surface place is 17～20nm;
The bed thickness that is positioned at photonic crystal upper surface place of said trunk layer and bifurcated layer is respectively 300～350nm and 100～140nm, and the bed thickness of other each layer is linearity to be dwindled, and the bed thickness until photonic crystal lower surface place is respectively 130～150nm and 50～70nm;
Said defect layer is apart from photonic crystal upper surface 30～32 μ m, and it is that the straight hole of 60～70nm, Kong Changwei 260～1060nm constitutes by bore dia, and the two ends of said straight hole are connected with main aperture respectively.
As the further improvement of porous alumina photonic crystal, the axially bored line of the main aperture in the described trunk layer is perpendicular to the plane of photonic crystal; The axially bored line of the straight hole in the described defect layer is perpendicular to the plane of photonic crystal.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of above-mentioned porous alumina photonic crystal adopts anonizing, and particularly completing steps is following:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2～0.4M, anodic oxidation 2.5～3.5h under the volts DS of 51～55V is placed in the phosphorus chromic acid solution again and corrodes 4～5h, obtains containing the alumina wafer in solid matter hole;
Step 2; It is that 16～20 ℃, concentration are the oxalic acid solution of 0.2～0.4M that the alumina wafer that will contain the solid matter hole places temperature, depresses 74～78 cycles of anodic oxidation in the periodicity Asymmetric Electric, wherein; Periodically the waveform of asymmetric voltage does; Voltage is increased to 53V, during 180s, is reduced to 23V by the 53V linearity again from 23V according to sinusoidal wave rule during prior to 30s, and each cycle meter 210s obtains containing the alumina wafer of trunk layer and bifurcated layer;
Step 3, prior to place, the part apply grease in the front of the alumina wafer that contains trunk layer and bifurcated layer, will being coated with the greasy alumina wafer that contains trunk layer and bifurcated layer again, to place temperature be that 16～20 ℃, concentration are the oxalic acid solution of 0.2～0.4M; In 1～4 cycle of anodic oxidation under the periodicity specific voltage, wherein, periodically the waveform of specific voltage does; Voltage is after dropping to 38V by the 53V linearity during the 80s; The constant 100s of 23V place that maintains, each cycle is counted 180s, obtains containing in its inner regional area the alumina wafer of defect layer; Then, get rid of grease on the alumina wafer that contains defect layer in its inner regional area;
Step 4; To get rid of the butyrous alumina wafer that contains defect layer earlier, to place temperature be that 16～20 ℃, concentration are the oxalic acid solution of 0.2～0.4M; Depress 275～325 cycles of anodic oxidation in the periodicity Asymmetric Electric, wherein, periodically described in the synchronous waveform rapid 2 of asymmetric voltage; Be placed on again and get rid of the unnecessary aluminium in the back side in Cupric Chloride Solution or the tin chloride solution, make the porous alumina photonic crystal.
As the preparing method's of porous alumina photonic crystal further improvement, the purity of described aluminium flake is >=99.9%; Described phosphorus chromic acid solution is that concentration is that phosphoric acid and the concentration of 4～8wt% is the mixed solution of the chromic acid of 1.6～2wt%; Described part is the artificial pattern of setting; Described grease is a vacuum grease, or railway grease, or edible fat; Describedly get rid of grease on the alumina wafer that contains defect layer in the regional area for using acetone, ultrasonic cleaning and washed with de-ionized water successively.
For solving the technical problem that also has of the present invention, the technical scheme that also has that is adopted is: the purposes of above-mentioned porous alumina photonic crystal is the porous alumina photonic crystal to be used for the optical anti-counterfeiting of 780～1400nm wave band.
Beneficial effect with respect to prior art is; One of which; Use ESEM and ultraviolet-visible-near infrared sub-ray spectrometer to characterize respectively to the title product that makes; Can know that from its result title product is by trunk layer and bifurcated is range upon range of adds the porous alumina photonic crystal that the thickness that constitutes is 75～85 μ m, and the mid-defectiveness layer of regional area in the photonic crystal.Wherein, the number of plies of trunk layer and bifurcated layer is 375～425 layers, and its mutual thickness ratio is 2～3: 1; Trunk layer is made up of main aperture, and the bifurcated layer is made up of the bifurcated hole, and angle is 30～50 degree between the hole in bifurcated hole, and the two ends of a bifurcate holes wherein are connected with the main aperture of the upper and lower trunk layer of its place bifurcated layer respectively; The bore dia that is positioned at photonic crystal upper surface place of main aperture is 80～110nm, and the bore dia of other each layer is linearity to be dwindled, and the bore dia until photonic crystal lower surface place is 17～20nm; The bed thickness that is positioned at photonic crystal upper surface place of trunk layer and bifurcated layer is respectively 300～350nm and 100～140nm, and the bed thickness of other each layer is linearity to be dwindled, and the bed thickness until photonic crystal lower surface place is respectively 130～150nm and 50～70nm; Defect layer is apart from photonic crystal upper surface 30～32 μ m, and it is that the straight hole of 60～70nm, Kong Changwei 260～1060nm constitutes by bore dia, and the two ends of straight hole are connected with main aperture respectively.Photonic crystal has identical optical transmission performance to visible light, and in different zones, the zone that promptly is equipped with defect layer but has the performance that infrared rays is propagated simultaneously; They are two years old; Thisly add porous alumina photonic crystal that constitute and the mid-defectiveness layer of regional area in it by trunk layer and bifurcated are range upon range of; Because of trunk layer is different with the porosity of bifurcated layer, its effective medium refraction index is also different, has the cycle laminate structure that specific refractory power just distributes alternately thereby formed; It is the Bragg mirror structure; The microtexture defective of in addition introducing, promptly straight hole road unanimous between the higher and lower levels, aperture makes the infrared rays that can not propagate originally also can in the regional area of alumina wafer, propagate; Finally make photonic crystal possess different optical properties at regional area; Thereby obtained on same piece aluminum oxide class photonic crystal to realize that its each part under natural light or white light has identical optical characteristics, and each regional area of alumina wafer (can be layout, shape) has different optical characteristics under infrared ray radiation, as ultrared see through and by technique effect.It both can be used for storage information, can be used for the optical anti-counterfeiting of infrared rays wave band again, also have cost low, can disposablely use, read information convenient, with respect to the ultraviolet anti-fake technology to advantage such as the damage of human body is little, have splendid application prospect; Its three, preparing method's science, effectively, required equipment is simple, technology is convenient, and is controlled, good reproducibility, production cost is low, is suitable for large-scale industrial production.
As the further embodiment of beneficial effect, the one, the axially bored line preferred vertical of the main aperture in the trunk layer is in the plane of photonic crystal, and the axially bored line preferred vertical of the straight hole in the defect layer is beneficial to giving full play to of false proof effect in the plane of photonic crystal; The 2nd, the purity of aluminium flake is preferably >=99.9%, guaranteed the quality of photonic crystal; The 3rd, it is the mixed solution of the chromic acid of 1.6～2wt% that the phosphorus chromic acid solution is preferably phosphoric acid and the concentration that concentration is 4～8wt%, is beneficial to the formation in solid matter hole on the alumina wafer; The 4th, the part is preferably the pattern of artificial setting, is convenient to the identification of anti-counterfeiting mark; The 5th, grease is preferably vacuum grease, or railway grease, or edible fat, not only makes the source of raw material than horn of plenty, also makes preparation technology more be prone to implement and flexibly; The 6th, get rid of grease on the alumina wafer that contains defect layer in the regional area and be preferably and use acetone, ultrasonic cleaning and washed with de-ionized water successively, guaranteed to remove greasy effect.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses one of result that ESEM (SEM) characterizes to the title product that makes.Fig. 1 a is the SEM photo of title product surface topography, can be found out the about 100nm in the aperture of title product by it; Fig. 1 b, Fig. 1 c and Fig. 1 d are respectively the SEM photo of top, middle part and the bottom of title product vertical section, can find out that by these SEM photos the channel diameter of title product is reduced to 20nm gradually from 100nm, and bed thickness is reduced to 200nm gradually from 450nm.Shadow region among Fig. 1 c is the bifurcated layer, and middle portion is a trunk layer.
Fig. 2 uses one of result that ESEM characterizes to the rejected region of the title product that makes.Fig. 2 a is the SEM photo of the vertical section in the artificial pattern boundaries zone of setting; Can see by this SEM photo, no straight hole road, left side, border defective, there is straight hole road defective in the right side, border; Straight hole road length increases gradually to the right side from the left side, shown in the dotted line in the SEM photo.Fig. 2 b is the enlarged photograph of straight hole road defective among Fig. 2 a, can be known by it, and the zone between two dotted lines is a straight hole road defective.
Fig. 3 is the pattern synoptic diagram of Fig. 1, title product shown in Figure 2.
Fig. 4 uses one of result that ultraviolet-visible-the near infrared sub-ray spectrometer characterizes to the title product that makes.Solid-line curve among the figure is the position and the bandwidth of forbidden photon band, and dashed curve is the transmitted spectrum of area of the pattern; Dashed curve has explained that dropping on the interior infrared rays of forbidden photon band scope originally can propagate in the alumina type photonic crystal, alumina type photonic crystal All Ranges has identical optical transmission performance in visible spectrum.
Fig. 5 is opposite to one of result that the title product under the irradiation of visible light and infrared light sources characterizes respectively.Fig. 5 a is under visible light source (White LED light source) irradiation, the picture that camera collection arrives; Fig. 5 b is the picture that the infrared light sources irradiation photographs down, and title product demonstrates the different zone of light and shade, and transmit corresponding to infrared rays again in the high zone of brightness, and dark areas is corresponding to forbidden photon band, and infrared rays can not transmit within it.
Embodiment
At first buy or make with ordinary method from market:
The aluminium flake of purity >=99.9%; By concentration is mixed solution---the phosphorus chromic acid solution that the phosphoric acid of 4～8wt% and chromic acid that concentration is 1.6～2wt% are mixed with; As greasy vacuum grease, railway grease and edible fat; Acetone.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2M, anodic oxidation 3.5h under the volts DS of 51V; Wherein, the purity of aluminium flake is 99.9%.Be placed on again in the phosphorus chromic acid solution and corrode 4h, obtain containing the alumina wafer in solid matter hole.
It is that 16 ℃, concentration are the oxalic acid solution of 0.2M that step 2, the alumina wafer that will contain the solid matter hole place temperature, depresses 74 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically the waveform of asymmetric voltage does, voltage is increased to 53V, during 180s, is reduced to 23V by the 53V linearity again from 23V according to sinusoidal wave rule during prior to 30s, and each cycle meter 210s obtains containing the alumina wafer of trunk layer and bifurcated layer.
Step 3 is prior to place, the part apply grease in the front of the alumina wafer that contains trunk layer and bifurcated layer; Wherein, the part is the artificial pattern of setting, and grease is a vacuum grease.To be coated with the greasy alumina wafer that contains trunk layer and bifurcated layer again, to place temperature be that 16 ℃, concentration are the oxalic acid solution of 0.2M, 1 cycle of anodic oxidation under the periodicity specific voltage; Wherein, periodically the waveform of specific voltage does, voltage after dropping to 38V by the 53V linearity during the 80s, the constant 100s of 23V place that maintains, each cycle is counted 180s, obtains containing in its inner regional area the alumina wafer of defect layer.Then, get rid of grease on the alumina wafer that contains defect layer in its inner regional area; Wherein, get rid of grease on the alumina wafer that contains defect layer in the regional area for using acetone, ultrasonic cleaning and washed with de-ionized water successively.
Step 4, will getting rid of the butyrous alumina wafer that contains defect layer earlier, to place temperature be that 16 ℃, concentration are the oxalic acid solution of 0.2M, depresses 275 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically described in the synchronous waveform rapid 2 of asymmetric voltage.Be placed on again and get rid of the unnecessary aluminium in the back side in Cupric Chloride Solution or the tin chloride solution, make and be similar to Fig. 1, Fig. 2 and shown in Figure 3, and the porous alumina photonic crystal shown in the curve among Fig. 4.
Embodiment 2
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.25M, anodic oxidation 3.3h under the volts DS of 52V; Wherein, the purity of aluminium flake is 99.99%.Be placed on again in the phosphorus chromic acid solution and corrode 4h, obtain containing the alumina wafer in solid matter hole.
It is that 17 ℃, concentration are the oxalic acid solution of 0.25M that step 2, the alumina wafer that will contain the solid matter hole place temperature, depresses 75 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically the waveform of asymmetric voltage does, voltage prior to 30s during according to sinusoidal wave rule from 23V raise 53V, during 180s, be reduced to 23V again by the 53V linearity, each cycle meter 210s obtains containing the alumina wafer of trunk layer and bifurcated layer.
Step 3 is prior to place, the part apply grease in the front of the alumina wafer that contains trunk layer and bifurcated layer; Wherein, the part is the artificial pattern of setting, and grease is a vacuum grease.To be coated with the greasy alumina wafer that contains trunk layer and bifurcated layer again, to place temperature be that 17 ℃, concentration are the oxalic acid solution of 0.25M, 2 cycles of anodic oxidation under the periodicity specific voltage; Wherein, periodically the waveform of specific voltage does, voltage after dropping to 38V by the 53V linearity during the 80s, the constant 100s of 23V place that maintains, each cycle is counted 180s, obtains containing in its inner regional area the alumina wafer of defect layer.Then, get rid of grease on the alumina wafer that contains defect layer in its inner regional area; Wherein, get rid of grease on the alumina wafer that contains defect layer in the regional area for using acetone, ultrasonic cleaning and washed with de-ionized water successively.
Step 4, will getting rid of the butyrous alumina wafer that contains defect layer earlier, to place temperature be that 17 ℃, concentration are the oxalic acid solution of 0.25M, depresses 288 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically described in the synchronous waveform rapid 2 of asymmetric voltage.Be placed on again and get rid of the unnecessary aluminium in the back side in Cupric Chloride Solution or the tin chloride solution, make and be similar to Fig. 1, Fig. 2 and shown in Figure 3, and the porous alumina photonic crystal shown in the curve among Fig. 4.
Embodiment 3
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.3M, anodic oxidation 3h under the volts DS of 53V; Wherein, the purity of aluminium flake is >=99.9%.Be placed on again in the phosphorus chromic acid solution and corrode 4.5h, obtain containing the alumina wafer in solid matter hole.
It is that 18 ℃, concentration are the oxalic acid solution of 0.3M that step 2, the alumina wafer that will contain the solid matter hole place temperature, depresses 76 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically the waveform of asymmetric voltage does, voltage prior to 30s during according to sinusoidal wave rule from 23V raise 53V, during 180s, be reduced to 23V again by the 53V linearity, each cycle meter 210s obtains containing the alumina wafer of trunk layer and bifurcated layer.
Step 3 is prior to place, the part apply grease in the front of the alumina wafer that contains trunk layer and bifurcated layer; Wherein, the part is the artificial pattern of setting, and grease is a vacuum grease.To be coated with the greasy alumina wafer that contains trunk layer and bifurcated layer again, to place temperature be that 18 ℃, concentration are the oxalic acid solution of 0.3M, 3 cycles of anodic oxidation under the periodicity specific voltage; Wherein, periodically the waveform of specific voltage does, voltage after dropping to 38V by the 53V linearity during the 80s, the constant 100s of 23V place that maintains, each cycle is counted 180s, obtains containing in its inner regional area the alumina wafer of defect layer.Then, get rid of grease on the alumina wafer that contains defect layer in its inner regional area; Wherein, get rid of grease on the alumina wafer that contains defect layer in the regional area for using acetone, ultrasonic cleaning and washed with de-ionized water successively.
Step 4, will getting rid of the butyrous alumina wafer that contains defect layer earlier, to place temperature be that 18 ℃, concentration are the oxalic acid solution of 0.3M, depresses 300 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically described in the synchronous waveform rapid 2 of asymmetric voltage.Be placed on again and get rid of the unnecessary aluminium in the back side in Cupric Chloride Solution or the tin chloride solution, make like Fig. 1, Fig. 2 and shown in Figure 3, and the porous alumina photonic crystal shown in the curve among Fig. 4.
Embodiment 4
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.35M, anodic oxidation 2.8h under the volts DS of 54V; Wherein, the purity of aluminium flake is >=99.99%.Be placed on again in the phosphorus chromic acid solution and corrode 5h, obtain containing the alumina wafer in solid matter hole.
It is that 19 ℃, concentration are the oxalic acid solution of 0.35M that step 2, the alumina wafer that will contain the solid matter hole place temperature, depresses 77 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically the waveform of asymmetric voltage does, voltage is increased to 53V, during 180s, is reduced to 23V by the 53V linearity again from 23V according to sinusoidal wave rule during prior to 30s, and each cycle meter 210s obtains containing the alumina wafer of trunk layer and bifurcated layer.
Step 3 is prior to place, the part apply grease in the front of the alumina wafer that contains trunk layer and bifurcated layer; Wherein, the part is the artificial pattern of setting, and grease is a vacuum grease.To be coated with the greasy alumina wafer that contains trunk layer and bifurcated layer again, to place temperature be that 19 ℃, concentration are the oxalic acid solution of 0.35M, 4 cycles of anodic oxidation under the periodicity specific voltage; Wherein, periodically the waveform of specific voltage does, voltage after dropping to 38V by the 53V linearity during the 80s, the constant 100s of 23V place that maintains, each cycle is counted 180s, obtains containing in its inner regional area the alumina wafer of defect layer.Then, get rid of grease on the alumina wafer that contains defect layer in its inner regional area; Wherein, get rid of grease on the alumina wafer that contains defect layer in the regional area for using acetone, ultrasonic cleaning and washed with de-ionized water successively.
Step 4, will getting rid of the butyrous alumina wafer that contains defect layer earlier, to place temperature be that 19 ℃, concentration are the oxalic acid solution of 0.35M, depresses 313 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically described in the synchronous waveform rapid 2 of asymmetric voltage.Be placed on again and get rid of the unnecessary aluminium in the back side in Cupric Chloride Solution or the tin chloride solution, make and be similar to Fig. 1, Fig. 2 and shown in Figure 3, and the porous alumina photonic crystal shown in the curve among Fig. 4.
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.4M, anodic oxidation 2.5h under the volts DS of 55V; Wherein, the purity of aluminium flake is >=99.9%.Be placed on again in the phosphorus chromic acid solution and corrode 5h, obtain containing the alumina wafer in solid matter hole.
It is that 20 ℃, concentration are the oxalic acid solution of 0.4M that step 2, the alumina wafer that will contain the solid matter hole place temperature, depresses 78 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically the waveform of asymmetric voltage does, voltage is increased to 53V, during 180s, is reduced to 23V by the 53V linearity again from 23V according to sinusoidal wave rule during prior to 30s, and each cycle meter 210s obtains containing the alumina wafer of trunk layer and bifurcated layer.
Step 3 is prior to place, the part apply grease in the front of the alumina wafer that contains trunk layer and bifurcated layer; Wherein, the part is the artificial pattern of setting, and grease is a vacuum grease.To be coated with the greasy alumina wafer that contains trunk layer and bifurcated layer again, to place temperature be that 20 ℃, concentration are the oxalic acid solution of 0.4M, 4 cycles of anodic oxidation under the periodicity specific voltage; Wherein, periodically the waveform of specific voltage does, voltage after dropping to 38V by the 53V linearity during the 80s, the constant 100s of 23V place that maintains, each cycle is counted 180s, obtains containing in its inner regional area the alumina wafer of defect layer.Then, get rid of grease on the alumina wafer that contains defect layer in its inner regional area; Wherein, get rid of grease on the alumina wafer that contains defect layer in the regional area for using acetone, ultrasonic cleaning and washed with de-ionized water successively.
Step 4, will getting rid of the butyrous alumina wafer that contains defect layer earlier, to place temperature be that 20 ℃, concentration are the oxalic acid solution of 0.4M, depresses 325 cycles of anodic oxidation in the periodicity Asymmetric Electric; Wherein, periodically described in the synchronous waveform rapid 2 of asymmetric voltage.Be placed on again and get rid of the unnecessary aluminium in the back side in Cupric Chloride Solution or the tin chloride solution, make and be similar to Fig. 1, Fig. 2 and shown in Figure 3, and the porous alumina photonic crystal shown in the curve among Fig. 4.
Select for use respectively again as greasy vacuum grease or railway grease or edible fat, repeat the foregoing description 1～5, made equally as or be similar to Fig. 1, Fig. 2 and shown in Figure 3, and the porous alumina photonic crystal shown in the curve among Fig. 4.
The purposes of porous alumina photonic crystal is the porous alumina photonic crystal to be used for the optical anti-counterfeiting of 780～1400nm wave band.
Obviously, those skilled in the art can to porous alumina photonic crystal of the present invention and its production and use carry out various changes and modification and do not break away from the spirit and scope of the present invention.Like this, belong within the scope of claim of the present invention and equivalent technologies thereof if of the present invention these are revised with modification, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. porous alumina photonic crystal was made up of trunk layer and bifurcated range upon range of adding, and it is characterized in that:
The thickness of said photonic crystal is 75～85 μ m, and the mid-defectiveness layer of regional area in it;
The number of plies of said trunk layer and bifurcated layer is 375～425 layers, and its mutual thickness ratio is 2～3: 1;
Said trunk layer is made up of main aperture, and said bifurcated layer is made up of the bifurcated hole, and angle is 30～50 degree between the hole in said bifurcated hole, and the two ends of a bifurcate holes wherein are connected with the main aperture of the upper and lower trunk layer of its place bifurcated layer respectively;
The bore dia that is positioned at photonic crystal upper surface place of said main aperture is 80～110nm, and the bore dia of other each layer is linearity to be dwindled, and the bore dia until photonic crystal lower surface place is 17～20nm;
The bed thickness that is positioned at photonic crystal upper surface place of said trunk layer and bifurcated layer is respectively 300～350nm and 100～140nm, and the bed thickness of other each layer is linearity to be dwindled, and the bed thickness until photonic crystal lower surface place is respectively 130～150nm and 50～70nm;
Said defect layer is apart from photonic crystal upper surface 30～32 μ m, and it is that the straight hole of 60～70nm, Kong Changwei 260～1060nm constitutes by bore dia, and the two ends of said straight hole are connected with main aperture respectively.
2. porous alumina photonic crystal according to claim 1 is characterized in that the plane of the axially bored line of the main aperture in the trunk layer perpendicular to photonic crystal.
3. porous alumina photonic crystal according to claim 1 is characterized in that the plane of the axially bored line of the straight hole in the defect layer perpendicular to photonic crystal.
4. the preparation method of the said porous alumina photonic crystal of claim 1 adopts anonizing, it is characterized in that completing steps is following:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2～0.4M, anodic oxidation 2.5～3.5h under the volts DS of 51～55V is placed in the phosphorus chromic acid solution again and corrodes 4～5h, obtains containing the alumina wafer in solid matter hole;
Step 2; It is that 16～20 ℃, concentration are the oxalic acid solution of 0.2～0.4M that the alumina wafer that will contain the solid matter hole places temperature, depresses 74～78 cycles of anodic oxidation in the periodicity Asymmetric Electric, wherein; Periodically the waveform of asymmetric voltage does; Voltage is increased to 53V, during 180s, is reduced to 23V by the 53V linearity again from 23V according to sinusoidal wave rule during prior to 30s, and each cycle meter 210s obtains containing the alumina wafer of trunk layer and bifurcated layer;
Step 3, prior to place, the part apply grease in the front of the alumina wafer that contains trunk layer and bifurcated layer, will being coated with the greasy alumina wafer that contains trunk layer and bifurcated layer again, to place temperature be that 16～20 ℃, concentration are the oxalic acid solution of 0.2～0.4M; In 1～4 cycle of anodic oxidation under the periodicity specific voltage, wherein, periodically the waveform of specific voltage does; Voltage is after dropping to 38V by the 53V linearity during the 80s; The constant 100s of 23V place that maintains, each cycle is counted 180s, obtains containing in its inner regional area the alumina wafer of defect layer; Then, get rid of grease on the alumina wafer that contains defect layer in its inner regional area;
Step 4; To get rid of the butyrous alumina wafer that contains defect layer earlier, to place temperature be that 16～20 ℃, concentration are the oxalic acid solution of 0.2～0.4M; Depress 275～325 cycles of anodic oxidation in the periodicity Asymmetric Electric, wherein, periodically described in the synchronous waveform rapid 2 of asymmetric voltage; Be placed on again and get rid of the unnecessary aluminium in the back side in Cupric Chloride Solution or the tin chloride solution, make the porous alumina photonic crystal.
5. the preparation method of porous alumina photonic crystal according to claim 4, the purity that it is characterized in that aluminium flake is >=99.9%.
6. the preparation method of porous alumina photonic crystal according to claim 4 is characterized in that the phosphorus chromic acid solution is that concentration is that phosphoric acid and the concentration of 4～8wt% is the mixed solution of the chromic acid of 1.6～2wt%.
7. the preparation method of porous alumina photonic crystal according to claim 4 is characterized in that the local artificial pattern of setting that is.
8. the preparation method of porous alumina photonic crystal according to claim 4 is characterized in that grease is a vacuum grease, or railway grease, or edible fat.
9. the preparation method of porous alumina photonic crystal according to claim 4 is characterized in that getting rid of grease on the alumina wafer that contains defect layer in the regional area for using acetone, ultrasonic cleaning and washed with de-ionized water successively.
10. the purposes of the said porous alumina photonic crystal of claim 1 is characterized in that:
The optical anti-counterfeiting that the porous alumina photonic crystal is used for 780～1400nm wave band.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305890A (en) * | 2013-06-06 | 2013-09-18 | 安徽大学 | Preparation method of three-dimensional penetrating anode aluminum oxide template |
| CN105088306A (en) * | 2015-08-31 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Anodised aluminium nano-structure with coatings on double sides and preparation method and application thereof |
| CN107620104A (en) * | 2017-09-30 | 2018-01-23 | 佛山科学技术学院 | The preparation method of AAO photonic crystal coating for selective absorption of sunlight spectrum |
| CN107779921A (en) * | 2017-09-30 | 2018-03-09 | 佛山科学技术学院 | The preparation method of the compound heat absorbing coating of AAO photonic crystal based high-temp-resistant ternary nanos |
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| CN109989086A (en) * | 2019-04-19 | 2019-07-09 | 河北工业大学 | A kind of preparation method of the porous aluminas photon crystal film with high saturation schemochrome |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041708A (en) * | 1988-10-03 | 1990-05-02 | 艾尔坎国际有限公司 | Porous anodic aluminium oxide membranes |
| JP2000254900A (en) * | 1999-01-06 | 2000-09-19 | Canon Inc | Manufacture of structural body having pore and structural body manufactured by the same |
| JP2003113497A (en) * | 2001-10-09 | 2003-04-18 | Canon Inc | Porous structure and manufacturing method therefor |
| JP2004285404A (en) * | 2003-03-20 | 2004-10-14 | Kanagawa Acad Of Sci & Technol | Anodically oxidized porous alumina and manufacturing method therefor |
| CN1548589A (en) * | 2003-05-19 | 2004-11-24 | 中国科学院物理研究所 | Production process of alumina template with nano holes |
| CN1752296A (en) * | 2005-06-08 | 2006-03-29 | 武汉大学 | Method for preparing aluminium oxide nano-form photon crystal |
| CN101016641A (en) * | 2006-12-31 | 2007-08-15 | 武汉大学 | Method of preparing three-dimensional aluminum oxide nano template by constant-current decompression |
| CN101104944A (en) * | 2007-04-19 | 2008-01-16 | 上海交通大学 | Process for preparing ordered porous aluminum oxide thin film |
| CN101220510A (en) * | 2007-09-26 | 2008-07-16 | 武汉大学 | Method for manufacturing high quality aluminum oxide photon crystal |
| CN101451260A (en) * | 2008-12-18 | 2009-06-10 | 安徽大学 | Method for preparing porous alumina formwork with Y type structure |
| CN101520525A (en) * | 2008-02-25 | 2009-09-02 | 中国科学院合肥物质科学研究院 | Porous aluminum oxide film light filter with bifurcate holes and preparation method thereof |
| JP2009256751A (en) * | 2008-04-18 | 2009-11-05 | Kanagawa Acad Of Sci & Technol | Anodically oxidized porous alumina and production method therefor |
-
2010
- 2010-12-29 CN CN201010617088.3A patent/CN102560650B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041708A (en) * | 1988-10-03 | 1990-05-02 | 艾尔坎国际有限公司 | Porous anodic aluminium oxide membranes |
| JP2000254900A (en) * | 1999-01-06 | 2000-09-19 | Canon Inc | Manufacture of structural body having pore and structural body manufactured by the same |
| JP2003113497A (en) * | 2001-10-09 | 2003-04-18 | Canon Inc | Porous structure and manufacturing method therefor |
| JP2004285404A (en) * | 2003-03-20 | 2004-10-14 | Kanagawa Acad Of Sci & Technol | Anodically oxidized porous alumina and manufacturing method therefor |
| CN1548589A (en) * | 2003-05-19 | 2004-11-24 | 中国科学院物理研究所 | Production process of alumina template with nano holes |
| CN1752296A (en) * | 2005-06-08 | 2006-03-29 | 武汉大学 | Method for preparing aluminium oxide nano-form photon crystal |
| CN101016641A (en) * | 2006-12-31 | 2007-08-15 | 武汉大学 | Method of preparing three-dimensional aluminum oxide nano template by constant-current decompression |
| CN101104944A (en) * | 2007-04-19 | 2008-01-16 | 上海交通大学 | Process for preparing ordered porous aluminum oxide thin film |
| CN101220510A (en) * | 2007-09-26 | 2008-07-16 | 武汉大学 | Method for manufacturing high quality aluminum oxide photon crystal |
| CN101520525A (en) * | 2008-02-25 | 2009-09-02 | 中国科学院合肥物质科学研究院 | Porous aluminum oxide film light filter with bifurcate holes and preparation method thereof |
| JP2009256751A (en) * | 2008-04-18 | 2009-11-05 | Kanagawa Acad Of Sci & Technol | Anodically oxidized porous alumina and production method therefor |
| CN101451260A (en) * | 2008-12-18 | 2009-06-10 | 安徽大学 | Method for preparing porous alumina formwork with Y type structure |
Non-Patent Citations (2)
| Title |
|---|
| WEN JUN ZHENG ET AL.: "Modulation of Transmission Spectra of Anodized Alumina Membrane Distributed Bragg Reflector by Controlling Anodization Temperature", 《NANOSCALE RESEARCH LETTERS》 * |
| WEN JUN ZHENG ET AL.: "Modulation of Transmission Spectra of Anodized Alumina Membrane Distributed Bragg Reflector by Controlling Anodization Temperature", 《NANOSCALE RESEARCH LETTERS》, vol. 4, no. 7, 24 March 2009 (2009-03-24), pages 665 - 667 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305890A (en) * | 2013-06-06 | 2013-09-18 | 安徽大学 | Preparation method of three-dimensional penetrating anode aluminum oxide template |
| CN103305890B (en) * | 2013-06-06 | 2016-03-02 | 安徽大学 | The preparation method of the anodic oxidation aluminium formwork that three-dimensional runs through |
| CN105088306A (en) * | 2015-08-31 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Anodised aluminium nano-structure with coatings on double sides and preparation method and application thereof |
| CN107620104A (en) * | 2017-09-30 | 2018-01-23 | 佛山科学技术学院 | The preparation method of AAO photonic crystal coating for selective absorption of sunlight spectrum |
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| CN107794557A (en) * | 2017-09-30 | 2018-03-13 | 佛山科学技术学院 | A kind of preparation method of light alloy-based photonic crystal Infrared stealthy materials |
| CN107794557B (en) * | 2017-09-30 | 2019-12-06 | 佛山科学技术学院 | Preparation method of light alloy-based photonic crystal infrared stealth material |
| CN109989086A (en) * | 2019-04-19 | 2019-07-09 | 河北工业大学 | A kind of preparation method of the porous aluminas photon crystal film with high saturation schemochrome |
| CN109989086B (en) * | 2019-04-19 | 2020-11-03 | 河北工业大学 | Preparation method of porous alumina photonic crystal film with high-saturation structural color |
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