CN110735160A - Preparation method of up-conversion fluorescent anti-counterfeiting labels - Google Patents
Preparation method of up-conversion fluorescent anti-counterfeiting labels Download PDFInfo
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- CN110735160A CN110735160A CN201910390788.4A CN201910390788A CN110735160A CN 110735160 A CN110735160 A CN 110735160A CN 201910390788 A CN201910390788 A CN 201910390788A CN 110735160 A CN110735160 A CN 110735160A
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
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Abstract
The invention discloses a preparation method of up-conversion fluorescent anti-counterfeiting labels, which comprises the steps of conducting substrate surface treatment, patterned photoresist conducting substrate preparation, electrolyte preparation, electrochemical deposition preparation of patterned conducting substrate, photoresist removal and heat treatment, and finally obtaining a patterned film with up-conversion luminescence characteristics.
Description
Technical Field
The invention belongs to the field of photoelectronic information materials, and particularly relates to a preparation method of up-conversion fluorescent anti-counterfeiting labels.
Background
The fluorescence label can display specific fluorescence coding information under the irradiation of light, which is important commercial anti-counterfeiting technologies, the commonly used organic fluorescent dye molecules, semiconductor fluorescent quantum dots and other materials have the advantages of high luminous efficiency and adjustable luminous color, but face the limitation of the leakage toxicity and photobleaching of heavy metal ions, and in addition, the fluorescent dye has natural background color due to short wavelength absorption and is easy to leak coding information.
Up-conversion phosphor passing sensitizer (Yb)3+,Nd3+) And an activator (Er)3+,Tm3+, Ho3+And Eu3+) The fluorescent anti-counterfeiting label material is fluorescent anti-counterfeiting label materials with great commercial application potential, in recent years, the synthesis of upconversion nanocrystals and the improvement of optical performance regulation and control technology promote the application research of related anti-counterfeiting labelsThe method comprises the steps of preparing the fluorescent label by using an equal method, modifying hydrophobic ligand molecules on the surface of the fluorescent label, having good dispersibility in an organic solvent, adding a thickening agent to form ink, and printing a patterned up-conversion fluorescent label, wherein the resolution can reach 100 mu m, viscosity, surface tension and particle aggregation directly influence the printing performance of the ink.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of up-conversion fluorescent anti-counterfeiting labels, and the up-conversion fluorescent anti-counterfeiting labels have high spatial resolution and high concealment by combining a solution electrochemical deposition and microelectronic processing method.
The technical scheme adopted for realizing the purpose of the invention is as follows:
the preparation method of kinds of up-conversion fluorescent anti-counterfeiting labels comprises the following steps:
s1, sequentially carrying out ultrasonic cleaning on a conductive substrate by using deionized water, a glass cleaning agent, alcohol and acetone, and then carrying out wettability treatment on the surface of the conductive substrate by using plasma, or carrying out wettability treatment on the surface of the conductive substrate by using ultraviolet irradiation and ozone radiation;
s2, coating photoresist on the conductive substrate obtained in the step S1, baking for 3min at 97 ℃, and then exposing the patterned photoresist on the conductive substrate to expose the patterned conductive substrate for later use;
s3, preparing electrolyte; adding 0.1mol/L chloride/nitrate solution of a rare earth activator and 0.1mol/L chloride/nitrate solution of a rare earth sensitizer into 0.1mol/L yttrium nitrate or yttrium chloride solution to prepare a rare earth ion mixed solution; adjusting the pH value of 0.003-0.3 mol/L complexing agent solution to 7.0-9.0 by adopting 5mol/L sodium hydroxide solution, adding the solution into the rare earth ion mixed solution, reacting the complexing agent with rare earth ions to form complex solution, adding 0.5mol/L sodium ascorbate solution, adjusting the pH value of the mixed solution to 7.0-8.0 by adopting 5mol/L sodium hydroxide solution, wherein the volume ratio of the rare earth ion mixed solution to the complexing agent solution to the sodium ascorbate solution is 2: 1: and 2, adding ammonia fluoride or sodium fluoride solution to ensure that the molar ratio of fluorine ions to rare earth ions is 4-5: 1, adjusting the pH value to 5.0-7.0 by adopting a 5mol/L sodium hydroxide solution to obtain a transparent colloid electrolyte for later use;
s4, taking the patterned conductive substrate in the step S2 as a working electrode, a platinum electrode as a counter electrode and an Ag/AgCl electrode as a reference electrode, and carrying out electrodeposition in the electrolyte in the step S3, wherein the deposition potential of the electrolyte is 0.6-1.2V relative to that of the Ag/AgCl electrode, the deposition time is 5-10 min, the water bath deposition temperature is 20-80 ℃, and the rare earth doped up-conversion fluorescent nano-crystals are deposited and grown on the exposed conductive substrate to prepare an up-conversion fluorescent film;
s5, placing the patterned conductive substrate in an acetone solution, and dissolving to remove the residual photoresist on the surface of the conductive substrate;
s6, placing the patterned conductive substrate processed in the step S5 in a tube furnace for annealing for 1-5 hours at the annealing temperature of 300-600 ℃, or selectively and rapidly heat-treating the film on the conductive substrate by using a 100-300 ℃ low-temperature near infrared sintering method by utilizing the absorption difference of the upconversion fluorescent film and the conductive layer substrate to near infrared band light to obtain the rare earth doped upconversion fluorescent film with the upconversion luminescence characteristic.
In the scheme, in step , the conductive substrate is made of ITO (indium tin oxide), FTO (fluorine-doped tin oxide) conductive glass or flexible conductive glass such as PET-ITO (polyethylene terephthalate-indium tin oxide) and PI-ITO;
in the scheme, steps are further included, and the step of baking the conductive substrate at 110 ℃ for 80S for hardening is further included between the steps S2 and S3.
In the above scheme, preferably, the rare earth-doped up-conversion fluorescent film is a sodium yttrium fluoride film co-doped with a rare earth activator and a rare earth sensitizer, the rare earth activator is erbium and thulium, and the rare earth sensitizer is ytterbium and neodymium.
In the above scheme, preferably, the rare earth-doped upconversion fluorescent film is a ytterbium and erbium-codoped sodium yttrium fluoride film, the molar content of ytterbium is 20%, the molar content of erbium is 2%, and the film emits green fluorescence under laser irradiation with a wavelength of 980 nm;
the rare earth doped up-conversion fluorescent film is an ytterbium and thulium co-doped sodium yttrium fluoride film, the molar content of ytterbium is 20%, the molar content of thulium is 0.2-2%, and blue fluorescence is emitted under the irradiation of laser with the wavelength of 980 nm;
the rare earth doped up-conversion fluorescent film is a ytterbium and erbium co-doped sodium yttrium fluoride film, the molar content of ytterbium is 60%, the molar content of erbium is 2%, and red fluorescence is emitted under laser irradiation with the wavelength of 980 nm;
the rare earth doped up-conversion fluorescent film is a ytterbium neodymium thulium co-doped sodium yttrium fluoride film, the molar content of ytterbium is 2-20%, the molar content of neodymium is 3%, the molar content of erbium is 0.2-2%, and green fluorescence is emitted under laser irradiation with wavelength of 808 nm.
In the above scheme, preferably, the mixed solution in step S3 includes the following mole contents of ions:
Y3+38～88％
Er3+2％。
in the above scheme, preferably, the mixed solution in step S3 includes the following mole contents of ions:
Y3+78～79.8％
Tm3+0.2～2％。
in the above scheme, preferably, the mixed solution in step S3 includes the following mole contents of ions:
in the above scheme, preferably, the complex is disodium edetate or ethylenediaminetetraacetic acid.
In the above scheme, preferably, in the step S2, the photoresist patterning is performed by any one of methods, that is, exposing the patterned photoresist by ultraviolet light exposure on the conductive substrate after photoresist leveling with a mask, developing, and finally baking to obtain a patterned conductive substrate with the patterned photoresist attached on the surface, or directly exposing the patterned conductive substrate by Electron Beam Lithography (EBL) and X-ray lithography (XRL), and then developing to dissolve the photoresist in the exposed region to leak the patterned conductive substrate.
In the above scheme, it is preferable that steps S2 to S5 are further repeated a plurality of times in sequence between steps S5 and S6.
Specifically, A method for preparing mask by direct laser writing includes using pulse fiber laser (SPILases)G420W) was directly written on the Al film-plated quartz with a pulse width of 100ns, a repetition frequency of 50kHz, an average power of 3W (1062. + -.3 nm), and a writing speed controlled at 1000 mm/s. And taking the laser direct writing Al film quartz mirror as a mask.
Specifically, steps are carried out, EBL electron beam exposure etching is carried out to prepare patterned photoresist on a conductive substrate, firstly, a spin coater is arranged to rotate at a low speed of 500rpm for 6 seconds and at a high speed of 4000rpm for 30 seconds, polymethyl methacrylate (PMMA) electron beam resist is uniformly coated on the conductive substrate obtained in the S1 step, a pattern generating system (NPGS) is used for designing a pattern, generating a running file, aligning and engraving the pattern, the conductive substrate is directly patterned with the photoresist on the surface of the conductive substrate after exposure for 1.5 hours by adopting 30keV accelerating voltage and 2.5nA electron beam current, and finally, development and film hardening are carried out for 60 seconds, and the patterning of the conductive substrate is realized through the patterning of the photoresist on the surface.
Specifically, steps are carried out, ion beam etching is carried out to prepare patterned photoresist on the conductive substrate, firstly, a spin coater is arranged to rotate at a low speed of 500rpm for 6 seconds and at a high speed of 4000rpm for 30 seconds, polymethyl methacrylate (PMMA) electron beam resist is uniformly coated on the conductive substrate obtained in the S1 step, then a graph designed by CAD is introduced into a system, an etching cabin is vacuumized, 30keV accelerating voltage and 65nA ion beam current are adopted to directly etch the photoresist on the surface of the conductive substrate for 8 minutes, finally, 60 seconds of developing and film hardening are carried out to obtain the patterned photoresist, and patterning of the conductive substrate is realized through patterning of the photoresist on the surface.
Specifically, steps are carried out, wherein, the patterned photoresist is prepared on the conductive substrate by X-ray lithography (XRL), firstly, a spin coater is arranged to rotate at a low speed of 500rpm for 6 seconds and at a high speed of 4000rpm for 30 seconds, polymethyl methacrylate (PMMA) electron beam resist is uniformly coated on the conductive substrate obtained in the S1 step, then, the graph designed by CAD is led into a system, X photons with the energy of 1-4kev are obtained by regulating and controlling to directly etch the photoresist on the surface of the conductive substrate for 2-5 minutes, and finally, the developing is carried out for 60 seconds, the film is hardened to obtain the patterned photoresist, and the patterning of the conductive substrate is realized through the patterning of the photoresist on the surface.
Specifically, steps are carried out, Laser Direct Writing (LDW) is carried out to prepare patterned photoresist on the conductive substrate, firstly, a spin coater is arranged for 500rpm time 6 seconds at low speed and 4000rpm time 30 seconds at high speed, polymethyl methacrylate (PMMA) photoresist is uniformly coated on the conductive substrate obtained in S1 step, the graph designed by CAD is led into the system, and a pulse fiber laser (SPI Lasers) is adoptedG420W) directly etching the photoresist, controlling the pulse width to be 100ns, the repetition frequency to be 50kHz, the average power to be 1W (1062 +/-3 nm), controlling the writing speed to be 1000mm/s, finally developing for 60 seconds, hardening to obtain the patterned photoresist, and realizing the patterning of the conductive substrate through the patterning of the surface photoresist.
Compared with the prior art, the invention has the following beneficial effects:
the conductive substrate processed by the step S1 has improved wettability and adhesion, and uses flexible conductive glass: PET-ITO and PI-ITO can be made into anti-counterfeiting label films with ductility.
In step S2, a positive photoresist is used, for example, an ultraviolet lithography mask method is adopted, the irradiated photoresist is dissolved after being irradiated by ultraviolet light, the pattern on the lithography mask is transferred to the conductive substrate in aspect, the transferred pattern has millimeter/micron level resolution, the conductive substrate needing electrodeposition is exposed in aspect, the photoresist dissolved by light exposure can also use EBL electron beam exposure etching method, FIB focused ion beam photoetching method, X-ray lithography (XRL) and Laser Direct Writing (LDW) can directly pattern the etched photoresist without making a mask, and the patterning of the conductive substrate is realized through the patterning of the surface photoresist.
The electrolyte in the step S3 and the conductive substrate exposed in the step S2 are used, the exposed conductive substrate has high wettability and adhesion, and the rare earth doped up-conversion fluorescent nano-crystal is uniformly deposited on the exposed conductive substrate in the step S4 to form the patterned up-conversion fluorescent film, so that the pattern distribution is uniform, the resolution is high, and the problems of nano-particle agglomeration and precipitation and coffee ring effect in the existing ink-jet anti-counterfeiting technology are solved.
The pattern of the patterned film prepared in the step S4 is uniformly distributed, the resolution can reach about 20 microns, and the problems of nanoparticle agglomeration and precipitation and coffee ring effect in the existing ink-jet anti-counterfeiting technology are solved.
Ytterbium and erbium co-doped sodium yttrium fluoride film NaYF4:Yb,Er(78:20:2)]Visible green fluorescence is excited by near infrared light, cannot be seen under the irradiation of visible light and ultraviolet light, can be hidden under the visible light and is used for anti-counterfeiting marks;
ytterbium and erbium co-doped sodium yttrium fluoride nanoparticle loaded thin film NaYF4:Yb, Er(38:60:2)]The film can excite visible red fluorescence under near infrared light, cannot be seen under the irradiation of visible light and ultraviolet light, can be hidden under the visible light and is used for anti-counterfeiting marks;
yb-thulium-codoped sodium yttrium fluoride nanoparticle loaded film [ NaYF4:Yb, Tm(79.8:20:0.2)]And [ NaYF4:Yb,Tm(79.5:20:0.5)]Exciting visible blue fluorescence in near infrared light, visible light and violetThe anti-counterfeiting label does not emit light under the irradiation of external light, has concealment under visible light and ultraviolet light, and can be used for anti-counterfeiting labels;
Yb-Nd-Tm-codoped sodium yttrium fluoride nanoparticle loaded film [ NaYF4:Nb,Yb,Tm (76.8～94.8:3:2～20:0.2～2)]The fluorescent material can excite green fluorescence under near infrared light, does not emit light under the irradiation of visible light and ultraviolet light, has concealment under the irradiation of visible light and ultraviolet light, and can be used for anti-counterfeiting marks.
The patterned film obtained in steps S2 to S5 is repeated several times between steps S5 and S6, and has a plurality of sub-patterns capable of emitting different fluorescence, and each sub-pattern excites visible fluorescence of different colors under the irradiation of the near-infrared light with the same wavelength.
In step S6, the conductive layer substrate does not absorb the near-infrared light, and the upconversion fluorescent film absorbs the near-infrared light, so that the upconversion fluorescent film can be differentially heated without heating the flexible conductive substrate.
Drawings
FIG. 1 is a NaYF4:Yb3+,Er3+(78:20:2) field emission scanning electron micrographs of the film surface;
FIG. 2 is a NaYF4:Yb3+,Er3+(78:20:2) transverse sectional field emission scanning electron micrographs of the film;
FIG. 3 is a NaYF4:Yb3+,Er3+(78:20:2) X-ray diffraction pattern of the film;
FIG. 4 is a NaYF4:Yb3+,Er3+(78:20:2) a photograph and a UV-VIS near IR transmission spectrum of the film;
FIG. 5 is a NaYF4:Yb3+,Tm3+(79.8:20:0.2)，NaYF4:Yb3+, Er3+(78:20:2)，NaYF4:Yb3+,Er3 +(38:60:2) fluorescence photograph and up-conversion fluorescence emission spectrum of the film under 980nm near infrared light irradiation;
FIG. 6 is a NaYF4:Nd3+,Yb3+,Tm3+(92.8:3:4:0.2) fluorescent photograph and up-conversion fluorescence emission spectrum of the film under 808nm near infrared light irradiation;
FIG. 7 shows (a) a mask for preparing a single-color bar code pattern and (b) to (d) masks for preparing a multi-color bar code pattern, respectively;
FIG. 8 is a photograph of (a) "barcode" patterned photoresist in white light and (b) NaYF, respectively4:Yb3+,Tm3+(79.5:20:0.5)、(c)NaYF4:Yb3+,Er3+(78:20:2)、(d) NaYF4:Yb3+,Er3+(38:60:2) thin film and (e) patterning of rare earth doped NaYF by multi-step photolithography and electrochemical deposition4Up-conversion fluorescence photograph (scale bar 500 μm) of the film at 980nm near infrared.
Detailed Description
The invention is further described with reference to the figures and the specific embodiments.
Example 1
A preparation method of the up-conversion fluorescent anti-counterfeiting label comprises the following implementation steps:
(1) the plasma is used for processing a conductive substrate (ITO or FTO), step , the conductive substrate (FTO) is respectively subjected to ultrasonic cleaning by deionized water, glass cleaning agent, alcohol and acetone, step two, nitrogen or argon is activated by using a plasma generator under the vacuum condition of 100Pa, the activated nitrogen or argon is used for flushing the surface of the conductive substrate (ITO or FTO), step ①, the wettability of the surface of organic compounds has great influence on the performances of pigments, ink, adhesives and the like, such as flashover voltage and surface leakage current of the surface of materials, and the wettability is measured by contact angle, the bonding strength of ② is strong, after the polymer and metal are processed by plasma activated gas, the bonding strength of the materials and the adhesive is enhanced, the bonding strength of the material and the adhesive can be enhanced because the cross-linking of the surface of the polymer strengthens the bonding force of a boundary layer, or the bonding strength of the polymer is enhanced by introducing dipoles during plasma processing, the bonding strength of the surface of the polymer can be enhanced by plasma processing, the adhesion strength of the polymer is enhanced by using plasma processing of helium, the plasma, the adhesion strength of the polymer and the rubber is enhanced by using 233, and the plasma processing of the rubber, and the rubber, the rubber is enhanced by using plasma processing.
(2) Preparing a patterned photoresist conductive substrate: the spin coating is carried out for 6s at the initial rotation speed of 600rpm of a spin coater, then 30s at the second rotation speed of 2000rpm, AZ5214 photoresist (Suzhou Fuji film electronic materials Co., Ltd.) is spin-coated on the conductive substrate, and the conductive substrate is baked for 3min at the temperature of 97 ℃. And then covering the mask with the coding pattern on the conductive substrate after the photoresist is homogenized, carrying out ultraviolet exposure with the wavelength of 350-450 nm, setting the power of a mercury lamp to be 350W, setting the exposure time to be 10s, taking down the photoetching mask, developing, and finally baking at 110 ℃ for 80s to harden the film for later use.
The scheme can also adopt a photoresist negative glue, but the pattern resolution of the photoresist negative glue transfer is lower.
The mask is prepared by adopting a laser direct writing technology, and pulsed fiber Lasers (SPI Lasers)
G420W) was directly written on a silicon mirror covered with an Al film, with a pulse width of 100ns, a repetition frequency of 50kHz, an average power of 3W (1062 ± 3nm), and a writing speed controlled at 1000 mm/s. An Al film quartz mirror for laser direct writing is used as a mask plate.
(3) Preparing electrolyte: adjusting the pH value of 10mL of disodium ethylene diamine tetraacetate (EDTA-2Na) solution with the concentration of 0.2mol/L to 7.0-9.0, respectively preparing yttrium chloride or yttrium nitrate solution, ytterbium chloride or ytterbium nitrate solution and chlorinated bait or nitric bait solution with the concentration of 0.1mol/L, preparing a rare earth ion mixed solution formed by yttrium ions, ytterbium ions and bait ions with the molar ratio of 78:20:2 by taking the rare earth nitrate or chloride as a precursor, adding 20mL of the rare earth ion mixed solution into the EDTA-2Na solution with the adjusted pH value to form a stable complex solution, then adding 20mL of sodium ascorbate with the concentration of 0.5mol/L, adjusting the pH value of the complex solution to be alkalescent 7.0-8.0, and then adding 20-25 mL of ammonium fluoride (NH) with the concentration of 0.4mol/L4F) And adjusting the pH value of the solution to 5.0-7.0 to obtain transparent colloid electrolyte for later use.
(4) Electrochemical deposition of the film: and forming a three-electrode system by using a conductive substrate with patterned photoresist as a working electrode and a platinum electrode as a counter electrode, and placing the three-electrode system in an electrolyte for electrodeposition, wherein an Ag/AgCl electrode is used as a reference electrode for electrodeposition, the deposition potential is 0.6V-1.2V relative to that of the Ag/AgCl electrode, the deposition time is 5-10 min, and the water bath deposition temperature is 20-80 ℃.
(5) Removing the photoresist: and immersing the patterned thin film subjected to electrochemical deposition in an acetone solution at normal temperature for 10 seconds, washing the patterned thin film for 3 times by using acetone, alcohol and deionized water in sequence, removing the photoresist on the surface of the substrate, and drying for later use.
(6) And (3) heat treatment: annealing the film prepared on the high-temperature resistant substrate (ITO or FTO) for 1-5 h in a tube furnace at the annealing temperature of 300-600 ℃ to obtain the NaYF4Yb, Er upconversion luminescence characteristics.
As shown in FIG. 1, NaYF4Yb and Er (78:20:2) thin films are composed of dense spherical nano-particles with the particle size of 510 +/-180 nm. As shown in FIG. 2, in cross section, NaYF with a thickness of about 5.8 μm is grown on the FTO layer4Yb, Er (78:20:2) thin film As shown in FIG. 3, the thin film has three distinct peaks of 28.401 DEG, 47.149 DEG and 56.065 DEG, corresponding to α -NaYF, respectively, except for the diffraction peak of the FTO substrate (JCPDS card number 41-1445)4(111) (220) and (311) (JCPDS card number 06-0342) and shows that the electrochemical deposition method can prepare high-crystalline pure cubic phase NaYF in a liquid environment4An inorganic thin film. As shown in FIG. 4, the average transmittance in the visible light band is about 76.2%, and the insets also show that the film has higher transparency, which is beneficial to the preparation of the high-concealment fluorescent anti-counterfeiting label. As shown in FIG. 5, as the wavelength of the electromagnetic wave increases, the encoding region emits tunable visible fluorescence under the excitation of invisible near infrared light (808,980nm), and the film emits strong green light emission with the wavelength of 510-575 nm and weak red light emission with the wavelength of 625-700 nm under the irradiation of 980nm near infrared light. As shown in FIG. 8(b), NaYF4Under the irradiation of near infrared light with the wavelength of 980nm, the Yb and Er (78:20:2) patterned thin film emits green visible fluorescence in a coding region, and the resolution reaches about 50 mu m.
Example 2
A preparation method of the up-conversion fluorescent anti-counterfeiting label comprises the following implementation steps:
(1) the method comprises the steps of , respectively carrying out ultrasonic cleaning on a conductive substrate (FTO) by using deionized water, a glass cleaning agent, alcohol and acetone, and secondly, activating nitrogen or argon by using a plasma generator to output voltage of 600-800V under the vacuum condition of 100Pa, and flushing the surface of the conductive substrate (flexible PET-ITO or flexible PI-ITO) by using the activated nitrogen or argon.
(2) Preparing a patterned photoresist conductive substrate (prepared by adopting a Laser Direct Writing (LDW) technology), preparing a patterned photoresist on the conductive substrate: firstly, setting the low speed 500rpm time of a spin coater for 6 seconds and the high speed 4000rpm time of 30 seconds, and uniformly spin-coating polymethyl methacrylate (PMMA) photoresist on the conductive substrate obtained in the step S1. And introducing the graph designed by the CAD into a system, adopting a pulse optical fiber laser to directly etch the graph on the photoresist, controlling the pulse width to be 100ns, the repetition frequency to be 50kHz, the average power to be 0.5W (1062 +/-3 nm), controlling the writing speed to be 1000mm/s, finally developing for 60 seconds, hardening to obtain the patterned photoresist, and realizing the patterning of the conductive substrate through the patterning of the surface photoresist.
(3) Preparing electrolyte: adjusting the pH value of 10mL of disodium ethylene diamine tetraacetate (EDTA-2Na) of a complexing agent solution with the concentration of 0.3mol/L to 7.0-9.0, respectively preparing a yttrium chloride or yttrium nitrate solution, a ytterbium chloride or ytterbium nitrate solution and a chlorinated bait or nitric bait solution with the concentration of 0.1mol/L, preparing a rare earth ion mixed solution formed by yttrium ions, ytterbium ions and bait ions with the molar ratio of 38:60:2 by taking the rare earth nitrate or chloride as a precursor, adding 20mL of the rare earth ion mixed solution into the EDTA-2Na solution with the adjusted pH value to form a stable complex solution, then adding 20mL of sodium ascorbate with the concentration of 0.5mol/L, adjusting the pH value of the complex solution to be alkalescent 7.0-8.0, and then adding 20-25 mL of ammonium fluoride (NH) with the concentration of 0.4mol/L4F) And adjusting the pH value of the solution to 5.0-7.0 to obtain transparent colloid electrolyte for later use.
(4) Electrochemical deposition: and forming a three-electrode system by using a conductive substrate with patterned photoresist as a working electrode and a platinum electrode as a counter electrode, and placing the three-electrode system in an electrolyte for electrodeposition, wherein an Ag/AgCl electrode is used as a reference electrode for electrodeposition, the deposition potential is 0.6V-1.2V relative to that of the Ag/AgCl electrode, the deposition time is 5-10 min, and the water bath deposition temperature is 20-80 ℃.
(5) Removing the photoresist: and immersing the patterned thin film subjected to electrochemical deposition in an acetone solution at normal temperature for 10 seconds, washing the patterned thin film for 3 times by using acetone, alcohol and deionized water in sequence, removing the photoresist on the surface of the substrate, and drying for later use.
(6) And (3) heat treatment: the flexible conductive substrate (flexible PET-ITO, PI-ITO) adopts 300 deg.C low temperature near infrared sintering technology to realize extremely high energy density (up to 1000 kW/m)2) Rapidly sintering to obtain the NaYF4Yb, Er upconversion luminescence characteristics.
As shown in FIG. 5, the film emits visible red light with a wavelength of 640-700 nm under 980nm near-infrared light. As shown in FIG. 8(c), NaYF4Under the irradiation of near infrared light with the wavelength of 980nm, the Yb and Er (38:60:2) patterned thin film emits red visible fluorescence in a coding region, and the resolution reaches about 20 mu m.
Example 3
A preparation method of the up-conversion fluorescent anti-counterfeiting label comprises the following implementation steps:
(1) the method comprises the steps of , respectively carrying out ultrasonic cleaning on a conductive substrate (ITO or FTO or PI-ITO) by using deionized water, a glass cleaning agent, alcohol and acetone, and secondly, activating nitrogen or argon by using a plasma generator to output voltage of 600-800V under the vacuum condition of 100Pa, and flushing the surface of the conductive substrate (ITO or FTO or PI-ITO) by using the activated nitrogen or argon.
(2) Preparation of patterned photoresist conductive substrate (ion beam etching preparation of patterned conductive substrate): firstly, setting a spin coater for 6 seconds at a low speed of 500rpm and 30 seconds at a high speed of 4000rpm, and uniformly spin-coating a polymethyl methacrylate (PMMA) electron beam resist on the conductive substrate obtained in the step S1. And introducing the graph designed by the CAD into the system, and vacuumizing the etching cabin. And directly etching the photoresist on the surface of the conductive substrate by adopting 30keV accelerating voltage and 65nA ion beam current for 8 minutes, developing for 60 seconds, hardening to obtain a patterned photoresist, and patterning the conductive substrate by patterning the photoresist on the surface.
(3) Preparing electrolyte: adjusting the pH value of 10mL of disodium ethylene diamine tetraacetate (EDTA-2Na) of a complexing agent solution with the concentration of 0.2mol/L to 7.0-9.0, respectively preparing a yttrium chloride or yttrium nitrate solution, a ytterbium chloride or ytterbium nitrate solution and a thulium chloride or thulium nitrate solution with the concentration of 0.1mol/L, preparing a rare earth ion mixed solution formed by yttrium ions, ytterbium ions and thulium ions with the molar ratio of 79.8:20:0.2 by taking the above rare earth nitrate or chloride as a precursor, adding 20mL of the rare earth ion mixed solution into the EDTA-2Na solution with the adjusted pH to form a stable complex solution, then adding 20mL of sodium ascorbate with the concentration of 0.5mol/L, adjusting the pH value of the complex solution to be alkalescent 7.0-8.0, and then adding 20-25 mL of ammonium fluoride (NH) with the concentration of 0.4mol/L4F) And adjusting the pH value of the solution to 5.0-7.0 to obtain transparent colloid electrolyte for later use.
(4) Electrochemical deposition: and forming a three-electrode system by using a conductive substrate with patterned photoresist as a working electrode and a platinum electrode as a counter electrode, and placing the three-electrode system in an electrolyte for electrodeposition, wherein an Ag/AgCl electrode is used as a reference electrode for electrodeposition, the deposition potential is 0.6V-1.2V relative to that of the Ag/AgCl electrode, the deposition time is 5-10 min, and the water bath deposition temperature is 20-80 ℃.
(5) Removing the photoresist: and immersing the patterned thin film subjected to electrochemical deposition in an acetone solution at normal temperature for 10 seconds, washing the patterned thin film for 3 times by using acetone, alcohol and deionized water in sequence, removing the photoresist on the surface of the substrate, and drying for later use.
(6) And (3) heat treatment: annealing the film prepared on the high-temperature resistant substrate (ITO or FTO) for 1-5 h in a tube furnace at the annealing temperature of 300-600 ℃ to obtain the NaYF4Yb, Tm up-conversion luminescence property. The PI-ITO flexible conductive substrate can adopt a 300 ℃ low-temperature near infrared sintering technology to realize extremely high energy density (up to 1000 kW/m) for a deposited film2) Rapidly sintering to obtain the NaYF4Yb, Tm (79.8:20:0.2) upconversion luminescence property。
As shown in FIG. 5, the film emits visible blue light with a wavelength of 450-510 nm under 980nm near-infrared light.
Example 4
A preparation method of the up-conversion fluorescent anti-counterfeiting label comprises the following implementation steps:
(1) the plasma is used for processing a conductive substrate (ITO or FTO or PI-ITO). , the conductive substrate (ITO or FTO or PI-ITO) is respectively cleaned by deionized water, glass cleaner, alcohol and acetone, and the surface of the conductive substrate (ITO or FTO or PI-ITO) is irradiated by ultraviolet radiation and ozone.
(2) Preparation of patterned photoresist conductive substrate (EBL electron beam exposure etching preparation of patterned photoresist on conductive substrate): firstly, setting a spin coater for 6 seconds at a low speed of 500rpm and 30 seconds at a high speed of 4000rpm, and uniformly spin-coating a polymethyl methacrylate (PMMA) electron beam resist on the conductive substrate obtained in the step S1. The Nanometer Pattern Generation System (NPGS) designs a pattern, generates an operation file, and aligns and carves the pattern. The film was developed and hardened using an accelerating voltage of 30keV, 2.5nA electron beam current for 1.5 hours, and finally 60 seconds.
(3) Preparing electrolyte: adjusting the pH value of 10mL of ethylene diamine tetraacetic acid (EDTA-2Na) solution with a complexing agent concentration of 0.003mol/L to 7.0-9.0, respectively preparing 0.1mol/L yttrium chloride or yttrium nitrate solution, ytterbium chloride or ytterbium nitrate solution and thulium chloride or thulium nitrate solution, preparing a rare earth ion mixed solution formed by yttrium ions, ytterbium ions and thulium ions with a molar ratio of 79.5:20:0.5 by using the above rare earth nitrate or chloride as a precursor, adding 20mL of the rare earth ion mixed solution into the pH-adjusted EDTA-2Na solution to form a stable complex solution, adding 20mL of 0.5mol/L sodium ascorbate, adjusting the pH of the complex solution to be alkalescent 7.0-8.0, and adding 20-25 mL of 0.4mol/L ammonium fluoride (NH)4F) And adjusting the pH value of the solution to 5.0-7.0 to obtain transparent colloid electrolyte for later use.
(4) Electrochemical deposition: and forming a three-electrode system by using a conductive substrate with patterned photoresist as a working electrode and a platinum electrode as a counter electrode, and placing the three-electrode system in an electrolyte for electrodeposition, wherein an Ag/AgCl electrode is used as a reference electrode for electrodeposition, the deposition potential is 0.6V-1.2V relative to that of the Ag/AgCl electrode, the deposition time is 5-10 min, and the water bath deposition temperature is 20-80 ℃.
(5) Removing the photoresist: and immersing the patterned thin film subjected to electrochemical deposition in an acetone solution at normal temperature for 10 seconds, washing the patterned thin film for 3 times by using acetone, alcohol and deionized water in sequence, removing the photoresist on the surface of the substrate, and drying for later use.
(6) And (3) heat treatment: annealing the film prepared on the high-temperature resistant substrate (ITO or FTO) for 1-5 h in a tube furnace at the annealing temperature of 300-600 ℃ to obtain the NaYF4Yb, Tm up-conversion luminescence property. The PI-ITO flexible conductive substrate can adopt a 300 ℃ low-temperature near infrared sintering technology to realize extremely high energy density (up to 1000 kW/m) for a deposited film2) Rapidly sintering to obtain the NaYF4Yb, Tm (79.5:20:0.5) upconversion luminescence property.
As shown in fig. 8(a), the photoresist of the two-dimensional barcode pattern cannot be recognized under white light irradiation. As shown in FIG. 8(b), NaYF4Under the irradiation of near infrared light with the wavelength of 980nm, the Yb and Tm (79.5:20:0.5) patterned thin film emits blue visible fluorescence with the resolution of about 50 μm.
Example 5
A preparation method of the up-conversion fluorescent anti-counterfeiting label comprises the following implementation steps:
(1) the plasma is used for processing a conductive substrate (ITO or FTO or PI-ITO). , the conductive substrate (ITO or FTO or PI-ITO) is respectively cleaned by deionized water, glass cleaner, alcohol and acetone, and the surface of the conductive substrate (ITO or FTO or PI-ITO) is irradiated by ultraviolet radiation and ozone.
(2) Preparing a patterned photoresist conductive substrate: x-ray lithography (XRL) to prepare patterned photoresist on a conductive substrate: firstly, setting a spin coater for 6 seconds at a low speed of 500rpm and 30 seconds at a high speed of 4000rpm, and uniformly spin-coating a polymethyl methacrylate (PMMA) electron beam resist on the conductive substrate obtained in the step S1. And guiding the graph designed by the CAD into a system, regulating and controlling to obtain X photons with energy of 1-4kev to directly etch the photoresist on the surface of the conductive substrate for 2-5 minutes, finally developing for 60 seconds, hardening to obtain patterned photoresist, and realizing the patterning of the conductive substrate through the patterning of the photoresist on the surface.
(3) Preparing electrolyte: adjusting the pH value of 10mL of disodium ethylene diamine tetraacetate (EDTA-2Na) of a complexing agent solution with the concentration of 0.2mol/L to 7.0-9.0, respectively preparing a yttrium chloride or yttrium nitrate solution, a neodymium chloride or neodymium nitrate solution, a ytterbium chloride or ytterbium nitrate solution and a thulium chloride or thulium nitrate solution with the concentration of 0.1mol/L, preparing a rare earth ion mixed solution formed by yttrium ions, neodymium ions, ytterbium ions and thulium ions with the molar ratio of 92.8:3:4:0.2 by taking the rare earth nitrate or chloride as a precursor, adding 20mL of the rare earth ion mixed solution into the EDTA-2Na solution with the adjusted pH value to form a stable complex solution, then adding 20mL of sodium ascorbate with the concentration of 0.5mol/L, adjusting the pH value of the complex solution to be alkalescent 7.0, and then adding 20-25 mL of ammonium fluoride (NH) with the concentration of 0.4mol/L4F) And adjusting the pH value of the solution to 5.0-7.0 to obtain transparent colloid electrolyte for later use.
(4) Electrochemical deposition: and forming a three-electrode system by using a conductive substrate with patterned photoresist as a working electrode and a platinum electrode as a counter electrode, and placing the three-electrode system in an electrolyte for electrodeposition, wherein an Ag/AgCl electrode is used as a reference electrode for electrodeposition, the deposition potential is 0.6V-1.2V relative to that of the Ag/AgCl electrode, the deposition time is 5-10 min, and the water bath deposition temperature is 20-80 ℃.
(5) Removing the photoresist: and immersing the patterned thin film subjected to electrochemical deposition in an acetone solution at normal temperature for 10 seconds, washing the patterned thin film for 3 times by using acetone, alcohol and deionized water in sequence, removing the photoresist on the surface of the substrate, and drying for later use.
(6) And (3) heat treatment: annealing the film prepared on the high-temperature resistant substrate (ITO or FTO) for 1-5 h in a tube furnace at the annealing temperature of 300-600 ℃ to obtain the NaYF4Nd, Yb, Tm up-conversion luminescence property. The PI-ITO flexible conductive substrate can adopt a 300 ℃ low-temperature near infrared sintering technology to realize extremely high energy density (up to 1000 kW/m) for a deposited film2) Rapidly sintering to obtain the NaYF4Nd, Yb, Tm (92.8:3:4:0.2) up-conversion luminescenceAnd patterning the thin film.
As shown in FIG. 6, under the irradiation of near infrared light of 800nm, the film emits visible blue light with a wavelength of 460-500 nm, visible green light with a wavelength of 510-560 nm, visible yellow light with a wavelength of 560-610 nm, and the film appears green light with naked eyes.
Example 6
A preparation method of the up-conversion fluorescent anti-counterfeiting label comprises the following implementation steps:
(1) the plasma is used for processing a conductive substrate (ITO or FTO or PI-ITO or PET-ITO). , the conductive substrate (ITO or FTO or PI-ITO) is respectively cleaned by deionized water, glass cleaner, alcohol and acetone, and the surface of the conductive substrate (ITO or FTO or PI-ITO or PET-ITO) is irradiated by ultraviolet radiation and ozone.
(2) Preparing a patterned photoresist conductive substrate: firstly, a spin coater is arranged to spin at 600rpm for 6s at low speed and spin at 2000rpm for 30s at high speed, an AZ5214 photoresist (Suzhou Fuji film electronic materials Co., Ltd., positive photoresist) is spin-coated on a conductive substrate, and the conductive substrate is baked for 3min at 97 ℃. And then covering the mask plate in the step (b) in fig. 7 on the conductive substrate after the glue is homogenized, carrying out ultraviolet light exposure with the wavelength of 350-450 nm, setting the power of a mercury lamp to be 350W, setting the exposure time to be 10s, developing, taking down the photoetching mask plate, and finally baking at 110 ℃ for 80s to harden the film for later use.
(3) Preparing electrolyte: the pH value of 10mL of complexing agent solution EDTA-2Na with the concentration of 0.003-0.3 mol/L is adjusted to 7.0-9.0. Firstly, all the rare earth nitrates or chlorides are prepared into 0.1mol/L solution and bottled for later use. Mixing and stirring 20mL of rare earth nitrate solution according to the molar ratio of Y to Yb to Er to 38 to 60 to 2, adding the EDTA-2Na solution after pH adjustment into the mixed solution to form a stable complex solution, then adding 20mL of sodium ascorbate with the concentration of 0.5mol/L, adjusting the pH of the complex solution to be alkalescent 7.0-8.0, and then adding 20-25 mL of NH with the concentration of 0.4mol/L4And adjusting the pH value of the solution F to 5.0-7.0 to obtain transparent colloid electrolyte for later use.
(4) Electrochemical deposition: and (2) taking the conductive substrate with the patterned photoresist as a working electrode, the platinum electrode as a counter electrode, the Ag/AgCl electrode as a reference electrode, and putting the three electrodes into electrolyte for electrodeposition, wherein the deposition potential is 0.6-1.2V, the deposition time is 2-5 min, and the water bath deposition temperature is controlled within the range of 20-80 ℃.
(5) Removing the redundant photoresist: and immersing the patterned up-conversion fluorescent film prepared by electrochemical deposition in a normal-temperature acetone solution for 10 seconds, sequentially washing with acetone, alcohol and deionized water for 3 times, removing residual photoresist on the surface of the substrate, and drying for later use.
(6) And (5) repeating the step (2), and transferring the pattern of the mask plate in the step (c) to the conductive substrate obtained in the step (5).
(7) Preparing electrolyte: the pH value of 10mL of complexing agent solution EDTA-2Na with the concentration of 0.003-0.3 mol/L is adjusted to 7.0-9.0. Firstly, all the rare earth nitrates or chlorides are prepared into 0.1mol/L solution and bottled for later use. Mixing and stirring 20mL of rare earth nitrate solution according to the molar ratio of Y to Yb to Er of 78 to 20 to 2, adding the EDTA-2Na solution after pH adjustment into the mixed solution to form a stable complex solution, then adding 20mL of sodium ascorbate with the concentration of 0.5mol/L, adjusting the pH of the complex solution to be alkalescent 7.0-8.0, and then adding 20-25 mL of NH with the concentration of 0.4mol/L4And adjusting the pH value of the solution F to 5.0-7.0 to obtain transparent colloid electrolyte for later use.
(8) And (4) repeating the step (4) in the electrolyte of the step (7).
(9) And (5) repeating the step (5) to remove the redundant photoresist on the conductive substrate in the step (8).
(10) And (5) repeating the step (2), and transferring the pattern of the mask plate in the step (d) in the step (7) to the conductive substrate obtained in the step (9). .
(11) Preparing electrolyte: the pH value of 10mL of complexing agent solution EDTA-2Na with the concentration of 0.003-0.3 mol/L is adjusted to 7.0-9.0. Firstly, all the rare earth nitrates or chlorides are prepared into 0.1mol/L solution and bottled for later use. Mixing and stirring 20mL of rare earth nitrate solution according to the molar ratio of Y to Yb to Tm of 79.5 to 20 to 0.5, adding the mixed solution into the EDTA-2Na solution after pH adjustment to form a stable complex solution, then adding 20mL of sodium ascorbate with the concentration of 0.5mol/L, adjusting the pH of the complex solution to be alkalescent 7.0-8.0, and then adding 20-25 mL of NH with the concentration of 0.4mol/L4Adjusting the pH value of the solution F to 5.0-7.0 to obtain transparent colloidAnd (5) forming electrolyte for later use.
(12) And (4) repeating the step (4) in the electrolyte of the step (11).
(13) And (5) repeating the step (5) to remove the redundant photoresist on the conductive substrate in the step (12).
(13) And (3) heat treatment: annealing the film prepared on the high-temperature-resistant substrate (ITO, FTO) in a tube furnace for 1-5 h at 300-600 ℃, and realizing extremely high energy density (up to 1000 kW/m) of the deposited film by the flexible conductive substrate PI-ITO or PET-ITO by adopting a rapid 300 ℃ low-temperature near infrared sintering technology2) Rapidly sintering to obtain the NaYF4:Yb, Er(38:60:2)、NaYF4:Yb,Er(78:20:2)、NaYF4Yb, Tm (79.5:20:0.5) upconversion luminescence property.
As shown in fig. 8(e), rare earth doped NaYF4Under the irradiation of near infrared light with the wavelength of 980nm, the up-conversion fluorescence patterned film emits multicolor visible fluorescence in the coding region, and the resolution ratio reaches about 50 mu m.
Claims (10)
1, up-conversion fluorescent anti-counterfeiting label preparation method, characterized by, the step is as follows:
s1, sequentially carrying out ultrasonic cleaning on a conductive substrate by using deionized water, a glass cleaning agent, alcohol and acetone, and then carrying out wettability treatment on the surface of the conductive substrate by using plasma, or carrying out wettability treatment on the surface of the conductive substrate by using ultraviolet irradiation and ozone radiation;
s2, coating photoresist on the conductive substrate obtained in the step S1, baking for 3min at 97 ℃, and then exposing the patterned photoresist on the conductive substrate to expose the patterned conductive substrate for later use;
s3, preparing electrolyte; adding 0.1mol/L chloride/nitrate solution of a rare earth activator and 0.1mol/L chloride/nitrate solution of a rare earth sensitizer into 0.1mol/L yttrium nitrate or yttrium chloride solution to prepare a rare earth ion mixed solution; adjusting the pH value of 0.003-0.3 mol/L complexing agent solution to 7.0-9.0, adding the solution into a rare earth ion mixed solution, reacting the complexing agent and the rare earth ions to form a complex solution, adding a sodium ascorbate solution with the solubility of 0.5mol/L, and adjusting the pH value of the mixed solution to 7.0-8.0, wherein the volume ratio of the rare earth ion mixed solution to the complexing agent solution to the sodium ascorbate solution is 2: 1: and 2, adding ammonia fluoride or sodium fluoride solution to ensure that the molar ratio of fluorine ions to rare earth ions is 4-5: 1, adjusting the pH value to 5.0-7.0 to obtain transparent colloid electrolyte for later use;
s4, taking the patterned conductive substrate in the step S2 as a working electrode, a platinum electrode as a counter electrode and an Ag/AgCl electrode as a reference electrode, and carrying out electrodeposition in the electrolyte in the step S3, wherein the deposition potential of the electrolyte is 0.6-1.2V relative to that of the Ag/AgCl electrode, the deposition time is 5-10 min, the water bath deposition temperature is 20-80 ℃, and the rare earth doped up-conversion fluorescent nano-crystals are deposited and grown on the exposed conductive substrate to prepare an up-conversion fluorescent film;
s5, placing the patterned conductive substrate in an acetone solution for 10 minutes at room temperature, and dissolving to remove the residual photoresist on the surface of the conductive substrate;
s6, placing the patterned conductive substrate processed in the step S5 in a tube furnace for annealing for 1-5 hours at the annealing temperature of 300-600 ℃, or selectively and rapidly heat-treating the film on the conductive substrate by using a 100-300 ℃ low-temperature near infrared sintering method by utilizing the absorption difference of the upconversion fluorescent film and the conductive layer substrate to near infrared band light to obtain the patterned upconversion fluorescent film with the upconversion luminescence characteristic.
2. The method for preparing according to claim 1, wherein the conductive substrate is made of ITO, FTO conductive glass, or flexible conductive glass: PET-ITO, PI-ITO.
3. The method of claim 1, wherein the plasma is nitrogen or argon activated by a plasma generator.
4. The method for preparing a composite material according to claim 1, wherein the method further comprises the steps between steps S2 and S3: the conductive substrate was baked at 110 ℃ for 80s to harden.
5. The method according to claim 1, wherein the rare earth-doped upconversion fluorescent film is a sodium yttrium fluoride film co-doped with a rare earth activator and a rare earth sensitizer, the rare earth activator is erbium and thulium, and the rare earth sensitizer is ytterbium and neodymium.
6. The preparation method of claim 1, wherein the rare earth doped upconversion fluorescent film is a ytterbium and erbium co-doped sodium yttrium fluoride film, the molar content of ytterbium is 20%, the molar content of erbium is 2%, and the film emits green fluorescence under laser irradiation with a wavelength of 980 nm;
the rare earth doped up-conversion fluorescent nanoparticle is an ytterbium and thulium co-doped sodium yttrium fluoride film, the molar content of ytterbium is 20%, the molar content of thulium is 0.2-2%, and the nanoparticle emits blue fluorescence under the irradiation of laser with the wavelength of 980 nm;
the rare earth doped upconversion fluorescent nanoparticle is a ytterbium and erbium co-doped sodium yttrium fluoride film, the molar content of ytterbium is 60%, the molar content of erbium is 2%, and the nanoparticle emits red fluorescence under the irradiation of laser with the wavelength of 980 nm;
the rare earth doped up-conversion fluorescent nanoparticle is a ytterbium-neodymium-thulium-codoped sodium yttrium fluoride film, the molar content of ytterbium is 2-20%, the molar content of neodymium is 3%, the molar content of erbium is 0.2-2%, and green fluorescence is emitted under laser irradiation with wavelength of 808 nm.
7. The method according to claim 1, wherein the mixed solution in step S3 includes the following ions in molar content:
Y3+38～88％
Yb3+10～60％
Er3+2％；
or
Y3+78～79.8％
Yb3+20％
Tm3+0.2～2％。
Or
8. The method of claim 1, wherein the complex is disodium edetate or ethylenediaminetetraacetic acid.
9. The method of claim 1, wherein the photoresist patterning in step S2 is performed by any of methods including exposing the patterned photoresist by UV exposure on the homogenized conductive substrate using a mask, developing, and baking the hardened film to obtain a patterned conductive substrate with the patterned photoresist attached thereon, or by directly patterning the exposed photoresist using Electron Beam Lithography (EBL), X-ray lithography (XRL), and Laser Direct Writing (LDW), developing to dissolve the photoresist in the exposed region, baking the hardened film, and patterning the conductive substrate by patterning the photoresist on the surface.
10. The method of any one of claims 1 to 9 to , wherein the method further comprises a step of repeating the steps S2 to S5 a plurality of times in sequence between the steps S5 and S6.
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