CN103145095A - Preparation method of panchromatic structural color or color variation pattern array - Google Patents

Preparation method of panchromatic structural color or color variation pattern array Download PDF

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CN103145095A
CN103145095A CN2013100993861A CN201310099386A CN103145095A CN 103145095 A CN103145095 A CN 103145095A CN 2013100993861 A CN2013100993861 A CN 2013100993861A CN 201310099386 A CN201310099386 A CN 201310099386A CN 103145095 A CN103145095 A CN 103145095A
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array
noble metal
sample
color
etching
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张俊虎
张学民
叶顺盛
杨柏
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Jilin University
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Jilin University
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Abstract

The invention discloses a preparation method of a panchromatic structural color or color variation pattern array, belongs to the technical field of materials, and in particular relates to a method for preparing a panchromatic structural color or color variation pattern array by regulating the environment dielectric constants of an upper interface and a lower interface of a noble metal nanopore array. The preparation method comprises the following steps of: cleaning and surface hydrophilization treatment, the preparation of polystyrene single layer colloidal crystals, the construction for covering the noble metal nanopore array by a silicon oxide layer, the construction of a suspension noble metal nanopore array, selective regulation and control of the environment dielectric constant around the noble metal nanopore array and the like. The obtained noble metal nanopore array has a transmission peak adjustable within a visible light wave band (350nm-800nm), so that different single-color patterns or color patterns are shown, the apparent color of a single color sample can be changed along with the change of the external environment dielectric constant; and color change, disappear and reproduction of the array patterns can be realized for the color pattern sample along with the change of the external environment dielectric constant.

Description

The preparation method of a kind of panchromatic schemochrome or changeable colour color pattern array
Technical field
The invention belongs to the material technology field, be specifically related to prepare by the environment dielectric constant of regulating two interfaces, array up and down, noble metal nano hole a kind of method of panchromatic schemochrome or changeable colour color pattern array.
Background technology
Schemochrome based on the noble metal nanometer micrometer structure has colour stable, integrated level advantages of higher, has become independence of material science and important branch.Simultaneously, because this schemochrome derives from the peculiar surface plasma resonance character of noble metal, make structural color to produce significant change with the change of external environment dielectric constant, thereby have a wide range of applications in fields such as filtering, demonstration, photon paper and safety anti-fakes.
In the middle of all noble metal nano and micro materials, noble metal nano hole array is owing to having the different character of special optics, thereby becomes a kind of important materials of construction structure look.When white light incides noble metal nano hole array, see through the relating to parameters such as cycle, surrounding environment dielectric constant of light color and nanohole array.In relevant report before, people realize seeing through the change of light color (being the sample apparent colour) by the structural parameters such as cycle of regulation and control nanohole array, this just makes write-through technology such as need to adopting electron beam (E-Beam) etching, FIB (FIB) etching when constructing the sample with color pattern array.These technology cost on the one hand are expensive, and inefficiency, be unfavorable for large tracts of land preparation and the practical application of sample on the other hand.Therefore, be badly in need of a kind of novelty of development, with low cost, the construction method that can realize panchromatic schemochrome and color pattern array, this is significant for the application based on the schemochrome of noble metal nanometer micrometer structure.
Summary of the invention
But the purpose of this invention is to provide the preparation method that the simple large tracts of land of a kind of step realizes panchromatic schemochrome or changeable colour color pattern array.
Purpose of the present invention can be achieved through the following technical solutions: at first utilize non-closelypacked microballoon to be deposited on preparation noble metal nano hole array structure in the glass slide substrate for template in conjunction with metal, prepare silicon dioxide layer by sol-gal process subsequently and coat noble metal nano hole array structure, in conjunction with hydrofluoric acid, the selective etch of silicon dioxide layer and glass slide substrate is realized constructing of panchromatic schemochrome and color pattern array take the photoresist of patterning as template at last.Its principle is, by the silica layer thickness of regulation and control noble metal nano holes array upper surface and the etching state of lower surface glass slide substrate, can change the dielectric constant of nanohole array surrounding environment, thereby what can regulate and control sample sees through the peak-to-peak position, and finally realizes constructing of panchromatic schemochrome sample.Whole process operation is easy, and is with low cost, process low consumption cleaning, and controllability is high, and the gained sample has extraordinary mechanical stability.For the sample with color pattern array, color pattern is determined by the pattern of photoresist template; In pattern, each regional color is determined by this regional environment dielectric constant (or etch period).Utilize our method can prepare characteristic size in the color array structure of the 1 above arbitrary graphic pattern of μ m, still all have great importance in actual applications in scientific research.
Method of the present invention comprises six steps:
1. the cleaning of glass slide substrate and surface hydrophilic are processed: with glass slide acetone ultrasonic cleaning 10~15min, then use absolute ethyl alcohol ultrasonic cleaning 10~15min, then oven dry; Use again the acidic treatment liquid (mixed solution of mass fraction 98% concentrated sulfuric acid and mass fraction 30% hydrogen peroxide, the consumption volume ratio of two kinds of solution is 7:3) boil and process 20~30min, then through dry under nitrogen or air atmosphere after rinsed with deionized water, obtain the glass slide substrate of cleaning surfaces and hydrophilicity-imparting treatment.
2. the preparation of substrate surface polystyrene individual layer microballoon: be that (preparation method of polystyrene microsphere is referring to J.H.Zhang for the polystyrene microsphere of 300~1000nm with size range, Z.Chen, Z.L.Wang, W.Y.Zhang, N.B.Ming, Mater.Lett.2003,57,4466.) after eccentric cleaning, the absolute ethyl alcohol and the deionized water mixed solution that are 1~2.5:1 with volume ratio disperse, and obtain mass percentage concentration and be 0.5~2.0% emulsion; Be added drop-wise to slowly in the glass culture dish that fills deionized water with the emulsion of syringe with 50~100 above-mentioned concentration of μ L, drip again 20~50 μ L mass percentage concentration and be the aqueous solution of 2.0~8.0% lauryl sodium sulfate, thereby obtain closelypacked individual layer polystyrene microsphere on the water surface; At last with at the bottom of the hydrophilic group that obtains in step 1, the polystyrene individual layer microballoon that floats on the surface being picked up, natural drying after, just obtained the surface and had the substrate sample of tightly packed individual layer polystyrene microsphere.
3. constructing of substrate surface noble metal nano hole array: the tightly packed individual layer polystyrene microsphere in surface is become non-tightly packed individual layer polystyrene microsphere with reactive ion etching, etching power is RF=20~60W, ICP=0~200W, chamber pressure is 5~15mTorr, oxygen flow is 40~60SCCM, etch period is 5~15min, and after etching, the diameter of polystyrene microsphere is reduced to full-sized 40~50%; Then (wherein the chromium layer plays the effect of adhesive for the gold that the chromium that vertical deposition 1.5~2nm is thick successively in the substrate of non-tightly packed polystyrene microsphere and 50~200nm are thick or silver, be used for strengthening the adhesion of gold or silver layer and substrate), remove again the metal of polystyrene microsphere and surface deposition thereof with chloroform, thereby obtained the orderly noble metal nano hole array of large area structure in substrate.
4. silicon dioxide layer coats constructing of noble metal nano hole array: be that (preparation method of silicon dioxide gel is referring to J.Jasieniak for 10~15% silicon dioxide gel with silica quality content, C.Sada, A.Chiasera, M.Ferrari, A.Martucci, P.Mulvaney, Adv.Funct.Mater.2008, 18, 3772.) the noble metal nano hole array surface that is spun on that step 3 obtains, then 5~20min is processed in gelation under 100~150 ℃ of conditions, thereby the noble metal nano hole array that obtains that silicon dioxide layer coats, wherein the silica layer thickness is 10~120nm,
5. constructing of suspension noble metal nano hole array: it is only to be exposed to outer glass slide substrate in this process of etching 10~90s(in 1~5% hydrofluoric acid aqueous solution to be etched that the noble metal nano hole array substrate that obtains in step 3 is immersed in mass fraction, and the glass of noble metal nano hole array and lower surface thereof is unaffected).After processing, the glass slide substrate of exposing in nanohole array vertically reaches and laterally all is etched away 10~90nm(etching is isotropism, namely vertically reaching on horizontal direction along nano-pore, the glass slide substrate all is etched), be suspended in substrate surface (in fact still have part to be connected between nanohole array and substrate, thereby guaranteed the mechanical stability of sample) showing as noble metal nano hole array on ESEM.The sample that etching is complete dries up with deionized water rinsing and with nitrogen subsequently, has just obtained suspension noble metal nano hole array substrate.
In like manner, the silicon dioxide layer that step 4 is obtained coats noble metal nano hole array sample, and to be immersed in mass fraction be etching 30~120s in the middle of 1~5% hydrofluoric acid aqueous solution, the sample that etching is complete dries up with deionized water rinsing and with nitrogen subsequently, also can obtain suspending noble metal nano hole array substrate (at the 20s that begins most, the top layer silicon dioxide layer is etched, and noble metal nano hole and the glass slide substrate below it are unaffected; 10~100s subsequently is in the time, and the upper surface silicon dioxide layer is etched away fully, and the glass slide substrate of exposing in the noble metal nano hole and the surface of glass slide substrate opposite side are etched; Noble metal nano hole and the glass slide substrate below it are unaffected).
The selective regulation of noble metal nano hole array surrounding environment dielectric constant: the orderly patterning photoresist sheet of surface construction (thickness is 0.2~2 μ m approximately) of silicon dioxide layer that the noble metal nano hole array that obtains in step 3 or step 4 obtain coats noble metal nano hole array, subsequently with this photoresist sheet as mask, it is etching 10~120s in the middle of 1~5% hydrofluoric acid aqueous solution that sample is immersed in mass fraction, and the glass slide substrate of exposing outside is etched; At last, the sample deionized water rinsing that etching is complete, then with ethanolic solution, photoresist sheet is removed, and dry up with nitrogen; The etching of upper strata silicon dioxide layer or lower floor's substrate of glass occurs in the zone of not protected by photoresist, and by the zone that photoresist is protected, etching is not occured, has realized the selective regulation of noble metal nano hole array surface zones of different environment dielectric constant.
In order the patterning photoresist sheet is to utilize with different size (characteristic size is more than 1 μ m) and different pattern shape (as band, circular, rectangle, square, triangle etc.) light is covered plate, and (the light substrate of covering plate is glass or quartz, therefore the selective thick metallic chromium layer of 100nm of having an appointment that deposits of its surperficial zones of different can form printing opacity and lighttight zone.Light is covered plate and can be designed arbitrarily as required, and commercialization is customized), by photoetching technique, light being covered pattern on plate copies on photoresist sheet and obtains that (preparation of the photoresist sheet of patterned surface is referring to document: A.Kumar, H.A.Biebuyck, G.M.Whitesides, Langmuir1994,10,1498.).
For the nanohole array sample that step 3 obtains, the upper surface of nano-pore is air (dielectric constant is 1), and lower surface is glass slide substrate (dielectric constant is about 2.25); Step 4 regulates and controls the average dielectric constant (adjustable between 1 and 2.25) of nano-pore upper surface by the thickness of controlling nano-pore sample upper surface silicon dioxide layer, this moment, the lower surface of sample still was glass slide substrate (dielectric constant is about 2.25); Step 5 realizes for the nanohole array regulation and control (all regulating and controlling between 1~2.25) of two surperficial environment dielectric constants up and down by the etching process of HF.The change of dielectric constant makes the noble metal nano hole characteristic see through peak generation marked change, and shows as the obvious change of apparent colour on macroscopic view.Therefore in the present invention, we need not to change the structural parameters of nanohole array, just simply just can realize the continuous variation of sample integral color by the variation of controlling its two surface dielectric constants in up and down.
Except the nanohole array sample of solid color, the method has obvious advantage for constructing the integrated sample surfaces of polychrome.As shown in step 6, utilize orderly patterning photoresist sheet just can realize the selective regulation of array sample surface, noble metal nano hole zones of different surrounding environment dielectric constant in conjunction with the selective etch of hydrofluoric acid as template, thereby realized constructing of particular color pattern array.Here the array structure that it is emphasized that gained color sample pattern in step 6 determined by photoresist sheet, and in pattern, each regional color is determined by the environment dielectric constant (or etch period) of this zone nanohole array.Therefore for the preparation process of the sample of particular color pattern, often not necessarily need to use above-mentioned institute in steps.As embodiment 1,3,4,5, the constructing of color described in 6 just do not need to use the silver nanoparticle hole sample of coated with silica.Simultaneously except listed 6 concrete steps and associated order, we can also develop the selective regulation that more means realize nano-pore surrounding environment dielectric constant on this basis, thereby make constructing of color pattern more versatile and flexible.As constructing of the color pattern described in embodiment 5,6, just need to use repeatedly photoetching and hf etching process.Corresponding with this method, traditional construction method needs to utilize the write-through technology to construct the nanohole array of Different structural parameters in zones of different, so cost is high and inefficiency.
Change because the schemochrome based on the noble metal nanometer micrometer structure can change with the external environment dielectric constant, so in the middle of step 4 and step 5, the apparent colour of gained solid color sample can present different colours in solvents with different dielectric constants; For step 6 gained color array sample, its main body color presents difference in solvents with different dielectric constants, and at the solvent dielectric constant higher than 1.85(ethanol) time, color pattern can become very fuzzy and even disappear.When solvent evaporates, the apparent colour of sample and color pattern can be replied original state (as Fig. 7, shown in 8,9).The method that the present invention relates to is simple, controlled, is with a wide range of applications low cost, large-area panchromatic schemochrome, erasable photon paper and constructing of changeable colour antifalsification label.
Description of drawings
Figure 1A: the method schematic diagram for preparing the color pattern array based on noble metal nano hole array;
Wherein, 1 surface preparation six closelypacked individual layer polystyrene microspheres 2 of side at the bottom of hydrophilic group at first; Process the non-closelypacked individual layer polystyrene microsphere 3 of preparation by oxygen gas plasma subsequently; Next carry out the deposition of noble metal and the removal of colloid micro ball, thereby obtain noble metal nano hole array 4 at substrate surface; Again by sol-gel technique coated silica layer 5 on the array 4 of noble metal nano hole; Construct subsequently patterning photoresist sheet 6 on silicon dioxide layer 5; At last sample is put into hydrofluoric acid aqueous solution and carry out etching, then photoresist sheet 6 use ethanol are removed, the patterned surface that the noble metal nano hole array structure 5 that has just obtained coated with silica is compound with suspension noble metal nano hole 7.Wherein, the pattern of pattern is determined by photoresist sheet.
Figure 1B: the formation mechanism of color pattern array.Shown in figure, when white light during to noble metal nano hole array, due to the different character of optics, make that to only have wavelength be that the light of (λ 1) can see through nano-pore, and make sample show the color that this wavelength light has.And when around nano-pore, dielectric constant changes (showing as in this experiment the selective etch of nano-pore upper strata silicon dioxide layer or substrate of glass), seeing through the peak-to-peak position and will change herein, change λ 2 into by the λ 1 that begins most, and then change color herein.Therefore, sample has presented specific color pattern.
Fig. 2 A: the flat scanning electromicroscopic photograph of glass slide substrate surface silver nanoparticle hole array sample (thickness 70nm, nanohole array lower surface are the glass slide substrate for cycle 450nm, aperture 250nm, and upper surface is air);
Fig. 2 B: glass slide substrate surface silver nanoparticle hole array sample (thickness 70nm, nanohole array lower surface are the glass slide substrate for cycle 450nm, aperture 250nm, and upper surface is air) see through spectrum.Wherein two are respectively silver/glass slide substrate (800nm), silver/air interface resonance through peak (520nm) through the peak;
Fig. 3 A: the side stereoscan photograph of glass slide substrate surface silver nanoparticle hole array sample (thickness 70nm, nanohole array lower surface are the glass slide substrate for cycle 450nm, aperture 250nm, and upper surface is air).Illustration is that sample sees through light color, is green, and seeing through optical wavelength in its visible region is 520nm;
Fig. 3 B: the atomic force photo of glass slide substrate surface silver nanoparticle hole array (thickness 70nm, nanohole array lower surface are the glass slide substrate for cycle 450nm, aperture 250nm, and upper surface is air) and height analysis chart.Can find out that by altitude curve silver-colored perforated membrane thickness is about 70nm;
Fig. 3 C: the side stereoscan photograph of Fig. 2 A sample obtains after etching glass slide substrate 30s in hydrofluoric acid aqueous solution suspension silver nanoparticle hole array.As shown in the figure, silver nanoparticle hole itself is unaffected, and vertical etching depth and the lateral erosion length in its glass base, below all are about 30nm.In etching process, the variation of glass substrate opposite side can be ignored substantially for the not impact of nano-pore optical property.Illustration is that sample sees through light color, is redness, and seeing through optical wavelength in its visible region is 710nm;
Fig. 3 D: the corresponding atomic force photo of Fig. 3 C sample and height analysis chart.Can find out that by altitude curve before and after silver-colored perforated membrane etching, its degree of depth has increased approximately 30nm;
Fig. 3 E: the side stereoscan photograph of Fig. 2 A sample obtains after etching glass slide substrate 90s in hydrofluoric acid aqueous solution suspension silver nanoparticle hole array.As shown in the figure, silver nanoparticle hole itself is unaffected, and vertical etching depth and the lateral erosion length in its glass base, below all are about 90nm.Illustration is that sample sees through light color, is yellow.Seeing through optical wavelength in its visible region is 630nm;
Fig. 3 F: the corresponding atomic force photo of Fig. 3 E sample and height analysis chart.Can find out that by altitude curve before and after silver-colored perforated membrane etching, its degree of depth has increased approximately 90nm;
Fig. 4 A: the side stereoscan photograph of the coated with silica silver nanoparticle hole array sample that obtains after Fig. 2 A sample upper surface coated silica gel (nano-pore upper strata be 120nm thick silicon dioxide layer, lower floor is the glass slide substrate).Illustration is that sample sees through light color, is blueness, and seeing through optical wavelength in its visible region is 490nm;
Fig. 4 B: the atomic force photo of Fig. 4 A sample and highly analysis.Can find out the upper surface with opposed flattened by altitude curve;
Fig. 4 C: Fig. 4 A sample is put into the side stereoscan photograph (nano-pore upper strata be 60nm thick silicon dioxide layer, lower floor is the glass slide substrate) of the sample that obtains after hydrofluoric acid aqueous solution etching upper strata silicon dioxide layer 10s.Illustration is that sample sees through light color, is purple, and seeing through optical wavelength in its visible region is 450nm;
Fig. 4 D: the atomic force photo of Fig. 4 C sample and highly analysis;
Fig. 5 A: the optical microscope photograph of the double-colored integrating colour pattern array of red (delta-shaped region 501 sees through optical wavelength 710nm)/green (continuum 502 sees through optical wavelength 520nm).Scale is 50 μ m;
Fig. 5 B: the optical microscope photograph of the double-colored integrating colour pattern array of orange (zone 503 sees through optical wavelength 650nm)/green (zone 504 sees through optical wavelength 520nm).Scale is 50 μ m;
Fig. 5 C: the optical microscope photograph of the double-colored integrating colour pattern array of yellow (zone 505 sees through optical wavelength 630nm)/red (zone 506 sees through optical wavelength 710nm).Scale is 50 μ m;
Fig. 5 D: the optical microscope photograph of yellow (zone 507 sees through optical wavelength 630nm)/red (zone 508 sees through optical wavelength 710nm)/green (zone 509 sees through optical wavelength 520nm) three look integrating colour pattern array.Scale is 50 μ m;
Fig. 6 A: the optical microscope photograph of the double-colored integrating colour pattern array of blue (zone 601 sees through optical wavelength 490nm)/green (zone 602 sees through optical wavelength 520nm).Scale is 50 μ m;
Fig. 6 B: the optical microscope photograph of blue (zone 603 sees through optical wavelength 490nm)/green (zone 604 sees through optical wavelength 520nm)/red (zone 605 sees through optical wavelength 710nm) three look integrating colour pattern array.Scale is 50 μ m;
Fig. 6 C: blue (zone 606, see through optical wavelength 490nm)/green (zone 607, see through optical wavelength 520nm)/optical microscope photograph of red (zone 608 sees through optical wavelength 710nm)/yellow (zone 609 sees through optical wavelength 630nm) four look integrating colour pattern array.Scale is 50 μ m;
Fig. 6 D: yellow (zone 610, see through optical wavelength 630nm)/red (zone 611, see through optical wavelength 710nm)/optical microscope photograph of green (zone 613 sees through optical wavelength 520nm)/purple (zone 612 sees through optical wavelength 450nm) four look integrating colour pattern array.Scale is 100 μ m;
Fig. 7 A-Fig. 7 F: the apparent colour of three look integrating colour pattern array samples shown in Fig. 5 D in the differing dielectric constant environment changes.Sample environment of living in is followed successively by air, methyl alcohol, water, chloroform, toluene and carbon disulfide.When the external environment dielectric constant during higher than water or methyl alcohol (approximately 1.85), color pattern disappears, and integral color presents purple (seeing through optical wavelength 478nm) in methyl alcohol and water, present blue-green (seeing through optical wavelength 509nm) in chloroform, present green (seeing through optical wavelength 522nm) in toluene, present green (seeing through optical wavelength 563nm) in carbon disulfide;
Fig. 8 A-Fig. 8 C: three look integrated samples shown in Fig. 5 D are along with the volatilization of surperficial ethanol, and color pattern is by disappearing to the dynamic process of replying.When sample surfaces is covered by ethanol (as Fig. 8 A), the sample surfaces integral color presents purple (seeing through optical wavelength 478nm), and pattern is very fuzzy.Along with the volatilization gradually of ethanol, sample surfaces partly comes out, and demonstrates multicolor patterns array (as Fig. 8 B, 8C) originally, and the remaining place that is covered by ethanol is still keeping the purple as shown in Fig. 8 A;
Fig. 8 D-Fig. 8 F: three look integrated samples shown in Fig. 5 D are along with the volatilization of surperficial toluene, and color pattern is by disappearing to the dynamic process of replying.When sample surfaces is covered by ethanol (as Fig. 8 D), the sample surfaces integral color presents green (seeing through optical wavelength 522nm), does not almost observe the surface and has pattern array.Along with the volatilization gradually of toluene, sample surfaces partly comes out, and demonstrates multicolor patterns array (as Fig. 8 E, 8F) originally, and the remaining place that is covered by toluene is still keeping the green as shown in Fig. 8 D;
Fig. 9 A-Fig. 9 D: the apparent colour of four look integrated samples shown in Fig. 7 C in the differing dielectric constant environment changes.Sample environment of living in is followed successively by methyl alcohol, chloroform, toluene and carbon disulfide.Compare with Fig. 7 C, when the sample surfaces dielectric constant raise, it is very fuzzy that the sample surfaces color pattern becomes.During higher than methyl alcohol (approximately 1.85), color pattern disappears substantially when the external environment dielectric constant, and integral color is at methyl alcohol, and chloroform all presents blueness (seeing through optical wavelength 500nm) in toluene, present blue-green (seeing through optical wavelength 520nm) in carbon disulfide.
The specific embodiment
Embodiment 1:
1. the cleaning of glass slide substrate and surface hydrophilic are processed:
Glass slide is passed through acetone ultrasonic cleaning 10min, absolute ethyl alcohol ultrasonic cleaning 10min, oven dry, the acidic treatment liquid (mixed solution of mass fraction 98% concentrated sulfuric acid and mass fraction 30% hydrogen peroxide successively, the consumption volume ratio of two kinds of solution is 7:3) boil and process 20min, through dry under nitrogen or air atmosphere after rinsed with deionized water, obtain the glass slide substrate of cleaning surfaces and hydrophilicity-imparting treatment again;
2. the preparation method of polystyrene microsphere:
Under nitrogen protection, take the absolute ethyl alcohol of 100mL and 40mL deionized water as decentralized medium, with 10.5mL styrene; 0.2222g potassium peroxydisulfate; 0.2445g dodecyl sodium sulfate, add in the reactor that mechanical agitator and reflux condensing tube are housed, mechanical agitation speed is at 300r/min.Carry out dispersion polymerization in the water-bath of 70 ℃, obtain stablizing the emulsion of milky monodisperse polystyrene microsphere after reaction 10h, the diameter of microballoon is 450nm;
3. the preparation of glass slide substrate surface polystyrene individual layer microballoon:
With the polystyrene microsphere centrifuge washing that makes, the absolute ethyl alcohol and the deionized water mixed solution that are 1.5:1 with volume ratio again disperse, solid content is the 0.5%(mass fraction) emulsion of monodisperse polystyrene microsphere, get the emulsion of 50 μ L with syringe, being added drop-wise to slowly the diameter that fills deionized water is in the glass culture dish of 9cm, then to drip 20 μ L mass percentage concentration be 5.0% sodium dodecyl sulfate solution; The glass slide substrate of the clean and surface hydrophilic of processing with step 1 picks up the polystyrene individual layer of keeping afloat, natural drying after, just obtained the closelypacked polystyrene microsphere of individual layer, thickness is 450nm;
4. apparent colour is the preparation of green silver nanoparticle hole array sample:
With the oxygen plasma etching, closelypacked polystyrene microsphere is become non-closelypacked microballoon (diameter is reduced to full-sized 50%), etching power is RF=60W, and chamber pressure is 10mTorr, and oxygen flow is 50SCCM, and etch period is 10min; And then in substrate successively vertical deposition 1.5nm crome metal and the thick noble silver of 70nm (wherein metallic chromium layer plays the effect of adhesive, is used for strengthening the adhesion (pressure 5 * 10 of settling chamber of noble metal silver layer and glass slide substrate -4Pa, sedimentation rate 0.1nm/s; But reference literature X.M.Zhang, Z.B.Li, S.S.Ye, S.Wu, J.H.Zhang, L.Y.Cui, A.R.Li, T.Q.Wang, S.Z.Li, B.Yang, J.Mater.Chem2012,22,8903.), remove polystyrene microsphere and top layer metal thereof with chloroform, just obtained large-area ordered nanohole array in the glass slide substrate.Gained silver nanoparticle hole array cycle this moment is 450nm, and the aperture is 250nm.When the white light vertical incidence, its spectrum is as shown in Fig. 2 B, and its apparent colour is green (as Fig. 3 A).It is worthy of note, the apparent colour of gained nanohole array is relevant to the cycle size of nano-pore at this moment.For example, the polystyrene microsphere take diameter as 275nm is as the priming color of template gained nanohole array as red.In follow-up embodiment, we fixedly the nano-pore cycle be 450nm, only change its surrounding environment dielectric constant, realize the adjustable continuously of color sample with this.
5. apparent colour is red, the preparation of orange and yellow silver nanoparticle hole array sample:
Be etching 30s successively in the middle of 1% hydrofluoric acid aqueous solution with the apparent colour that obtains in step 4 for green silver nanoparticle hole array immerses mass fraction, 50s and 90s, the sample that etching is complete dries up with deionized water rinsing and with nitrogen subsequently, just obtained apparent colour and be red (as Fig. 3 C), the suspension silver nanoparticle hole array sample of orange and yellow (as Fig. 3 E).In etching process, silver nanoparticle hole itself is unaffected, and vertical etch rate and the lateral erosion speed in its glass base, below all are about 1nm/s.In observed time range, the variation of glass substrate opposite side can be ignored substantially for the not impact of nano-pore optical property in experiment.
Embodiment 2:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene individual layer microballoon sees embodiment 1.
2. apparent colour is seen embodiment 1 for the preparation method of green silver nanoparticle hole array sample.
3. apparent colour is the preparation of the silicon dioxide layer coated with silver nanohole array sample of blueness:
Silver nanoparticle hole array surface silicon dioxide layer is by after sample surfaces spin coating silicon dioxide gel, prepares after gelation 10min in 135 ℃ of baking ovens.The preparation method of silicon dioxide gel is summarized as follows.At first with 5mLSi (OC 2H 5) 4Be dissolved in 5mL ethanol and prepare solution A; 81 μ L concentrated hydrochloric acids are added in 1.935mL water be mixed with solution B.Afterwards under 70 ℃ of stirrings, with solution A in 20min slowly is added dropwise to solution B in the time and react 2h.At last, system is cooled to room temperature and continuation reaction 24h.During spin coating, silicon dioxide gel is carried out (volume ratio 1:1) dilution with ethanol, dilution ratio has determined the thickness of the silicon dioxide layer that obtains at last.The spin coating condition is 2000rpm, 1min.The silica layer thickness that obtains in experiment is 120nm, and this moment, the sample apparent colour was blue (as Fig. 4 A).
4. apparent colour is the preparation of the silicon dioxide layer coated with silver nanohole array sample of purple:
Be etching upper strata silicon dioxide layer 10s in the middle of 1% hydrofluoric acid aqueous solution with the apparent colour that obtains in step 3 for blue coated with silica silver nanoparticle hole array immerses mass fraction, after etching, upper strata silica layer thickness is reduced to 60nm, the sample that etching is complete dries up with deionized water rinsing and with nitrogen subsequently, has just obtained apparent colour and be (as Fig. 4 C) the coated with silica silver nanoparticle hole array sample of purple.
Embodiment 3:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene individual layer microballoon sees embodiment 1.
2. apparent colour is seen embodiment 1 for the preparation method of green silver nanoparticle hole array sample.
Silver nanoparticle hole surface patterning photoresist sheet preparation:
We make positive photoresist (BP212-37 with the speed spin coating 1min of 4000rpm/min, Beijing Microtronics A/S) tiling is to array sample surface, silver nanoparticle hole (this moment, photoresist thickness was approximately 2 μ m), afterwards by the exposure of traditional photoetching technique, and with mass fraction 0.5% sodium hydrate aqueous solution as developing liquid developing.After development, the photoresist of exposure area is washed off, exposes substrate, and unexposed place is still covered by photoresist.The pattern of photoresist sheet is to be determined by business-like photolithography plate, variation by the photolithography plate pattern, we can obtain characteristic size, and (in experiment, applied photolithography plate pattern comprises that width is at the ribbon structure of 15 μ m at the photoresist sheet of the 1 above arbitrary graphic pattern of μ m, the length of side is the equilateral triangle of 20 μ m, and elongated be the square etc. of 20 μ m).
4. the preparation of the double-colored integrating colour pattern array of red/green:
It is that in the middle of 1% hydrofluoric acid aqueous solution, vertical etching depth and the lateral erosion length of its below substrate of glass of etching glass slide substrate 30s(all is about 30nm that the silver nanoparticle hole array sample that step 3 is obtained surface coverage and have the patterning photoresist sheet immerses mass fraction); the sample deionized water rinsing that etching is complete subsequently; with ethanolic solution, photoresist sheet is removed again; and dry up with nitrogen; become redness after the regional etching of not protected by photoresist sheet, just having obtained apparent colour is the double-colored integrating colour pattern array of red/green sample (as Fig. 5 A).
Embodiment 4:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene individual layer microballoon sees embodiment 1.
2. apparent colour is seen embodiment 1 for the preparation method of green silver nanoparticle hole array sample.
Silver nanoparticle hole surface patterning photoresist sheet preparation see embodiment 3.
4. the preparation of orange/green double-colored integrating colour pattern array:
It is etching glass slide substrate 50s in the middle of 1% hydrofluoric acid aqueous solution that the silver nanoparticle hole array sample that step 3 is obtained surface coverage and have the patterning photoresist sheet immerses mass fraction; (vertical etching depth and the lateral erosion length in its glass base, below all are about 50nm); the sample deionized water rinsing that etching is complete subsequently; with ethanolic solution, photoresist sheet is removed again; and dry up with nitrogen; become orangely after the regional etching of not protected by photoresist sheet, just having obtained apparent colour is orange/green double-colored integrating colour pattern array sample (as Fig. 5 B).
Embodiment 5:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene individual layer microballoon sees embodiment 1.
2. apparent colour is seen embodiment 1 for the preparation method of green silver nanoparticle hole array sample.
Silver nanoparticle hole surface patterning photoresist sheet preparation see embodiment 3.
4. the preparation of yellow/red double-colored integrating colour pattern array:
It is etching glass slide substrate 40s in the middle of 1% hydrofluoric acid aqueous solution that the silver nanoparticle hole array sample that step 3 is obtained surface coverage and have the patterning photoresist sheet immerses mass fraction; (vertical etching depth and the lateral erosion length in its glass base, below all are about 40nm); the sample deionized water rinsing that etching is complete subsequently; with ethanolic solution, photoresist sheet is removed again; and dry up with nitrogen; become orange redly after the regional etching of not protected by photoresist sheet, just having obtained apparent colour is orange red/green double-colored integrating colour pattern array sample.
Subsequently sample is immersed again mass fraction and is etching 30s in the middle of 1% hydrofluoric acid aqueous solution.After twice etching, just formed etch period at sample surfaces and be respectively the 30s(redness) and 70s(yellow) the zone, just having obtained apparent colour is yellow/red double-colored integrating colour pattern array sample (as Fig. 5 C).
Embodiment 6:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene individual layer microballoon sees embodiment 1.
2. apparent colour is seen embodiment 1 for the preparation method of green silver nanoparticle hole array sample.
3. embodiment 3 is seen in the preparation of silver nanoparticle hole surface ribbon photoresist sheet.
4. the preparation of yellow/red/green three look integrating colour pattern array:
It is etching glass slide substrate 40s in the middle of 1% hydrofluoric acid aqueous solution that the silver nanoparticle hole array sample that step 3 is obtained surface coverage and have the ribbon photoresist sheet immerses mass fraction, and etching depth is~40nm, thereby obtains green red band.
Utilize afterwards the ribbon photolithography plate, expose on the direction perpendicular to photoetching for the first time, obtain square shape photoetching agent pattern after developing.This moment, the photoresist square was distributed on green stripes.At last sample is continued etching glass slide substrate 30s in the HF aqueous acid, and with ethanol, the photoresist template is washed off.At this moment; red stripes obtained in the previous step zone is meeting yellowing (etch period 70s) after increasing etch period; on green stripes, not protected zone can become redness after etching 30s; it is green that the zone of being protected by photoresist on green stripes still keeps, thereby obtained three looks integrated pattern (as Fig. 5 D).
Embodiment 7:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene individual layer microballoon sees embodiment 1.
2. apparent colour is seen embodiment 2 for the preparation method of blue silicon dioxide layer coated with silver nanohole array sample.
3. embodiment 3 is seen in the preparation of blue silicon dioxide layer coated with silver nanohole array sample surfaces patterning photoresist sheet.
4. the preparation of yellow/red/green four look integrating colour pattern array samples:
It is etching 20s, 50s, 90s successively in the middle of 1% hydrofluoric acid aqueous solution that the blue sample that step 3 is obtained surface coverage and have the patterning photoresist sheet immerses mass fraction, the sample deionized water rinsing that etching is complete subsequently, with ethanolic solution, photoresist sheet is removed again, and dry up with nitrogen, just can obtain successively double-colored integrated, the color pattern array sample (as Fig. 6 A-6C) that red/green three looks integrated, yellow/red/green four looks integrated of green/blue.
Embodiment 8:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene individual layer microballoon sees embodiment 1.
2. apparent colour is that the preparation method of the coated with silica silver nanoparticle hole array sample of purple sees embodiment 2.
The coated with silica silver nanoparticle hole array sample patterned surface photoresist sheet of purple preparation see embodiment 3.
4. the preparation of yellow/red/green/purple four look integrating colour pattern array samples:
It is etching 80s successively in the middle of 1% hydrofluoric acid aqueous solution that the purple sample that step 3 is obtained surface coverage and have the patterning photoresist sheet immerses mass fraction, the sample deionized water rinsing that etching is complete subsequently, with ethanolic solution, photoresist sheet is removed again, and dry up with nitrogen, just can obtain successively yellow/red/green/purple four looks integrated color pattern array sample (as Fig. 6 D).
The above is only preferred embodiment of the present invention, is not technical scheme of the present invention is done any pro forma restriction.Any simple modification that every foundation technical spirit of the present invention is done above embodiment, be equal to and change and modify, all fall within the scope of protection of the present invention.

Claims (4)

1. the preparation method of a panchromatic schemochrome or changeable colour color pattern array, its step is as follows:
1) cleaning of glass slide substrate and surface hydrophilic are processed: with glass slide acetone ultrasonic cleaning 10~15min, then use absolute ethyl alcohol ultrasonic cleaning 10~15min, then oven dry; Boil with acidic treatment liquid again and process 20~30min, then through dry under nitrogen or air atmosphere after rinsed with deionized water, obtain the glass slide substrate of cleaning surfaces and hydrophilicity-imparting treatment;
2) preparation of substrate surface polystyrene individual layer microballoon: be after the polystyrene microsphere eccentric cleaning of 300~1000nm with size range, be that the absolute ethyl alcohol of 1~2.5:1 and deionized water mixed solution disperse with volume ratio, obtain mass percentage concentration and be 0.5~2.0% emulsion; Be added drop-wise to slowly in the glass culture dish that fills deionized water with the emulsion of syringe with 50~100 above-mentioned concentration of μ L, drip again 20~50 μ L mass percentage concentration and be the aqueous solution of 2.0~8.0% lauryl sodium sulfate, thereby obtain closelypacked individual layer polystyrene microsphere on the water surface; At last with at the bottom of the hydrophilic group that obtains in step 1), the polystyrene individual layer microballoon that floats on the surface being picked up, natural drying after, just obtained the surface and had the substrate sample of tightly packed individual layer polystyrene microsphere;
3) constructing of substrate surface noble metal nano hole array: with reactive ion etching, the tightly packed individual layer polystyrene microsphere in surface is become non-tightly packed individual layer polystyrene microsphere, after etching, the diameter of polystyrene microsphere is reduced to full-sized 40~50%; Then the gold that the chromium that vertical deposition 1.5~2nm is thick successively in the substrate of non-tightly packed polystyrene microsphere and 50~200nm are thick or silver-colored, remove again the metal of polystyrene microsphere and surface deposition thereof with chloroform, thereby obtained the orderly noble metal nano hole array of large area structure in substrate;
4) constructing of suspension noble metal nano hole array: it is etching 10~90s in 1~5% hydrofluoric acid aqueous solution that the noble metal nano hole array substrate that obtains in step 3) is immersed in mass fraction; After processing, the glass slide substrate of exposing in nanohole array vertically and laterally all be etched away 10~90nm, thereby make noble metal nano hole array be suspended in glass basic surface; The sample that etching is complete dries up with deionized water rinsing and with nitrogen subsequently, and the noble metal nano hole array substrate that obtains suspending namely prepares panchromatic schemochrome or changeable colour color pattern array.
2. the preparation method of a kind of panchromatic schemochrome as claimed in claim 1 or changeable colour color pattern array, it is characterized in that: be the noble metal nano hole array surface that 10~15% silicon dioxide gel is spun on that step 3) obtains with silica quality content, then 5~20min is processed in gelation under 100~150 ℃ of conditions, thereby the noble metal nano hole array that obtains that silicon dioxide layer coats, wherein the silica layer thickness is 10~120nm; Then silicon dioxide layer being coated noble metal nano hole array, to be immersed in mass fraction be etching 30~120s in the middle of 1~5% hydrofluoric acid aqueous solution, the sample that etching is complete dries up with deionized water rinsing and with nitrogen again, and noble metal nano hole array substrate obtains suspending.
3. the preparation method of a kind of panchromatic schemochrome as claimed in claim 1 or 2 or changeable colour color pattern array, it is characterized in that: the orderly patterning photoresist sheet of surface construction of the noble metal nano hole array that obtains in step 3) or silicon dioxide layer coat noble metal nano hole array, subsequently with this photoresist sheet as mask, it is etching 10~120s in the middle of 1~5% hydrofluoric acid aqueous solution that sample is immersed in mass fraction, and the glass slide substrate of exposing outside is etched; At last, the sample deionized water rinsing that etching is complete, then with ethanolic solution, photoresist sheet is removed, and dry up with nitrogen.
4. the preparation method of a kind of panchromatic schemochrome as claimed in claim 1 or changeable colour color pattern array, it is characterized in that: the etching power of step 3) is RF=20~60W, ICP=0~200W, chamber pressure is 5~15mTorr, oxygen flow is 40~60SCCM, and etch period is 5~15min.
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