CN101373222A - Preparing method for reinforcing graphic luminous compound film by nano crystal - Google Patents
Preparing method for reinforcing graphic luminous compound film by nano crystal Download PDFInfo
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- CN101373222A CN101373222A CNA2008102006736A CN200810200673A CN101373222A CN 101373222 A CN101373222 A CN 101373222A CN A2008102006736 A CNA2008102006736 A CN A2008102006736A CN 200810200673 A CN200810200673 A CN 200810200673A CN 101373222 A CN101373222 A CN 101373222A
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Abstract
The invention belongs to the technical field of optoelectronic information, and particularly relates to a preparation technique of a nanometer crystal surface graph-strengthened light-emitting composite glass film. The preparation method comprises the following steps: sequentially preparing the glass film containing the light-emitting materials and the graphic film layer containing the metal materials, such as silver, gold or copper, on the glass, single-crystal or polymeric optical substrate surface; enabling the metal ions in the graphic film layer to directionally diffuse into the glass film containing the light-emitting materials and forming the metal (such as silver, gold or copper) nano-crystal in graphical distribution by employing the DC electric field induction thermal transfer printing technique; and improving the fluorescence efficiency of the light-emitting materials by adopting the surface plasma fluorescence enhancement effect of the metal nano-crystal, and further realizing the graphical light-emitting of the glass film. The nano-crystal enhanced graphical light-emitting film prepared based on the technique is applicable to the fields, such as optical information recording, displaying and processing.
Description
Technical field
The invention belongs to the opto-electronic information technology field, be specifically related to graphical fluorescent glass membraneous material of nanocrystalline enhancing and technology of preparing thereof on the optical base-substrate.
Background technology
The fluorescent glass membraneous material is by introducing all kinds of luminescent substances such as rare earth, semiconductor, metallic ion and nanocrystal thereof in the optical glass film matrix of Stability Analysis of Structures, excellent optical performance, thereby obtains the luminescent properties of various uniquenesses.Than some luminous organic materials, the fluorescent glass membraneous material has characteristics such as chemistry and Heat stability is good, long service life, obtains in fields such as information demonstration, storage, transmission, processing widely applying.The fluorescent glass membraneous material require glass matrix should have structural stability good, be easy to characteristics such as luminescent substance is introduced, the optical transmittance window meets the requirements, common glass film host material comprises silicate, borate, phosphate, tellurate etc. at present, wherein tellurate system glass material have that infrared transmission performance is good, phonon can be lower etc. advantage, be with a wide range of applications.In the fluorescent glass membraneous material, what play luminous effect mainly is luminescent substances such as some rare earths with effects such as photoluminescence, electroluminescence, cathode-ray luminescences, semiconductor, metallic ion and nanocrystal thereof.Common rare earth luminous material comprises yttrium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, holmium, thulium, ytterbium, lutetium, cerium plasma or its nanocrystal at present.Semiconductor material also is the common luminescent substance of a class, and its kind comprises materials such as gallium arsenide, gallium phosphide, indium phosphide, cadmium sulfide, cadmium selenide, cadmium sulfoselenide, cadmium telluride, silver chloride, zinc paste.In addition, also there are unique luminescent properties in transition metal ion such as gold, silver, copper, titanium, chromium, vanadium, manganese, molybdenum and nanocrystal thereof in glass basis.Common glass film preparation method comprises sol-gel process, spray pyrolysis, physical sputtering method, chemical vapour deposition technique, pulsed laser deposition etc.At present, improve the fluorescence radiation efficient of fluorescent glass membraneous material and the variety classes luminescent material is carried out the integrated design of functionalization become a vital task in advanced luminescent material and the luminescent device research and development.
Utilize the surface plasma body resonant vibration enhancement effect can effectively improve the fluorescence efficiency of luminescent material.Around luminescent substance, introduce metal nanocrystals such as some silver, gold, copper, when distance between metal nanocrystal and fluorescent material when very near, the free electron of metal nano-crystalline particle inside regular motion and surface plasma resonance of producing under the external electromagnetic field action of certain frequency can greatly strengthen the electromagnetic field around the nanocrystal; This surperficial local electromagnetic field strengthens the luminescent substance activation, the launching efficiency that make near grain surface and improves, thereby strengthen fluorescent emission intensity greatly.DE102004037882 has reported that promptly the glass substrate that utilizes the nanocrystalline rete of containing metal carries out the fluorescence enhancing analysis of dna molecular.But, have only when being present in the metallic nano crystal surface plasma resonance absorption peak position in the glass film and the excitation wavelength of luminescent substance is complementary on every side, could produce strong enhancement effect of fluorescence.
Have the luminescent device exploitation of utility function, often need different types of luminescent material is carried out the integrated design of functionalization.The preparation of micro-nano graph is the important step of dwindling the optical information device size, improving device performance.Present existing graphical information device technology of preparing mainly comprises methods such as photoetching, ion beam etching, nano impression.Patent documents such as CN1035102, CN1593936, KR20040106999, JP2006038999, US2008138460 have reported that respectively technology such as employing laser scribing technology, laser pattern impression, hot press printing technology, ultraviolet etching prepare film pattern and nano graph on various substrates.These technologies of preparing generally only are used for the geometric preparation of various micro-nanos, and the difficult output that realizes fluorescent graphic.Chinese invention patent CN101261443A has reported that nanocrystalline figure electric field in a kind of glass or the monocrystal chip induces the technology of preparing of hot transfer printing, utilizes this technology metal nanocrystals such as silver, gold, copper graphically can be introduced as required in the glass basis to form the metallic nano crystal volume graphic.If this metallic nano crystal volume graphic technology of preparing and metallic nano crystal enhancement effect of fluorescence are combined, in containing the glass film of luminescent substance, introduce silver, gold, metallic nano crystal volume graphics such as copper, utilizing graphical distribution metal nanocrystal that luminescent substance is on every side carried out fluorescence strengthens, and then develop the fluorescent glass laminated film technology of preparing that a kind of metallic nano crystal strengthens, can simplify the optical information device preparing process, obtain excellent fluorescent graphic output function simultaneously, significant for the manufacturing and the practical application that promote nano material and nanometer optical information device.
Summary of the invention
It is the phenomenon that a kind of fluorescent emission intensity that is distributed near the fluorescent material of nanocrystals such as silver, gold, copper improves greatly that the surface strengthens fluorescent effect.The realization of the graphical luminescence technology of nanocrystalline enhancing at first requires metallic nano crystal physical efficiencys such as silver, gold, copper to realize graphical the distribution as required in containing luminescent substance optical glass film matrix; Have only simultaneously when the surface plasma resonance of introducing metal nanocrystal absorbs peak position and the excitation wavelength of luminescent substance is complementary on every side, could produce tangible fluorescence to luminescent substance at required local and strengthen, and then produce graphically luminous.For this reason, the objective of the invention is to propose a kind of graphical fluorescent glass composite membrane technology of preparing based on nanocrystalline figure heat-transmission transfer technique, utilize DC electric field to induce hot transfer technique transfer printing metallic nano crystal volume graphic in containing the luminescent substance glass film, the surface plasma resonance that metal nanocrystal is regulated in composition by glass film matrix design simultaneously absorbs peak position and makes it to be complementary with the excitation wavelength of corresponding luminescent substance, and then realizes the fluorescent graphic output of nanocrystalline enhancing; The stack-design of the graphical fluorescent glass film by having multiple emission wavelength, output when realizing multiple fluorescent graphic.
Its concrete method is, at first, also can adopt the synthetic glass film that contains required luminescent substance of methods such as spray pyrolysis, physical sputtering method, chemical vapour deposition technique, pulsed laser deposition can be anti-utilizing the sol-gel process preparation to contain the glass film of required various luminescent substances on the glass, monocrystalline, polymkeric substance optical base-substrate of 300 ℃ and above temperature; Then utilize serigraphy, exposure image, inkjet printing or etching figures technology of preparing to prepare one of them or several metallics figure rete of one deck argentiferous, gold, copper on the luminescent substance glass film again in containing of having applied; Utilize DC electric field to induce hot transfer technique again, with containing metal material pattern rete is anode, utilize metal electrode to apply DC electric field, place annealing device thermal treatment at a certain temperature simultaneously, the metallic ion under the guiding of DC electric field in the containing metal material pattern rete is that orientation diffuses into and contains the luminescent substance glass film; These metallic ions nucleation in follow-up heat treatment process is grown up, and forms the metal nanocrystal such as silver, gold, copper of required graphical distribution; By the chemical composition design that contains luminescent substance glass film matrix the surface plasma resonance absorption peak position of metal nanocrystal and the required excitation wavelength of luminescent substance on every side are complementary, thereby realize the fluorescent graphic output of nanocrystalline enhancing.For the fluorescent graphic of realizing multiple shape, multiple color is exported simultaneously, can be on optical base-substrate repeatedly alternately apply different form with figure contain luminescent substance glass-film and containing metal material pattern rete, launch different fluorescent graphics by the different glass rete.
In the present invention, the glass film that contains luminescent substance at first must keep enough structural stabilities, can keep the stable of glass film matrix in luminescent substance or fluorescence strengthen with metal nanocrystal introducing process.Secondly, the glass film matrix also must keep lower phonon energy, makes the luminescent substance that mixes have good fluorescence efficiency.For this reason, glass film with the ethylate of tellurium, silicon, titanium, zirconium or aluminium, propylate, butylate, ethylene glycol salt, propylene glycol salt, chloride, nitrate, sulfate wherein one or more are raw material, adopt the sol-gel process preparation.Structure and crystallization stability characteristics according to glass film, can adopt dehydration, dealcoholysis respectively, take off ether, take off alkyl halide isosol-gel polymerisation mode synthesis oxide or oxygen halogen system gel film, obtain constitutionally stable oxide or oxygen halogen glass film by the thermal treatment means again; Also can adopt methods such as spray pyrolysis, physical sputtering method, chemical vapour deposition technique, pulsed laser deposition that above-mentioned raw materials is carried out thermal decomposition, deposition formation noncrystalline membrane.In order to obtain excellent enhancement effect of fluorescence, induce the surface plasma resonance absorption peak position of nanocrystals such as silver that hot transfer printing introduces, gold, copper to be complementary by electric field with the excitation wavelength of luminescent substance in the glass film.Therefore in the glass film building-up process, with have low phonon can tellurium oxide structure unit be the glass network main structure body or one of, and introducing silica, titanyl, zirconium oxygen, one of them of alumina or several network structure elements, add lithium simultaneously, sodium, potassium, silver, copper, gold, magnesium, calcium, strontium, barium, zinc, manganese, plumbous, iron, cobalt, nickel, niobium, vanadium, tungsten, the halogenide of boron, oxalates, acetate, nitrate, one of them of sulfate or several, regulate the plasma resonance absorption peak position of metal nanocrystal in glass film by glass network and ligand field structural adjustment, it is complementary with the excitation wavelength of various fluorescent materials in the 400-800nm scope.
In the present invention, containing the luminescent substance glass film is oxide glass or the oxygen halogen glass film that contains transition metal ions such as semiconducting compound, titanium, chromium, vanadium, manganese, molybdenum such as rare earth ions such as scandium, yttrium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, holmium, thulium, ytterbium, lutetium, cerium or its nanocrystal, gallium arsenide, gallium phosphide, indium phosphide, cadmium sulfide, cadmium selenide, cadmium sulfoselenide, cadmium telluride, silver chloride, zinc paste or its nanocrystal.Light emitting ionic such as rare earth, semiconductor, metal or its nanocrystal material can be introduced with ion, crystal grain form in the glass film building-up process alone or in combination, can form the nano luminescent crystal by the thermal treatment means again.
In the present invention, the effect of containing metal material pattern rete is to provide required metallic ion for graphical metal nanocrystal transfer printing.Its ethylate with silicon, titanium, zirconium, propylate, butylate, propylene glycol salt are raw material, introduce magnesium, calcium, strontium, barium, manganese, lead, niobium, vanadium, tungsten or boron halogenide, oxalates, acetate, nitrate, sulfate, ethylate, propylate, butylate wherein one or more, introduce simultaneously silver, gold, copper simple substance, halogenide, oxalates, carbonate, nitrate, sulfate wherein one or more, adopt dehydration, dealcoholysis polymerization methods to make colloidal sol; Also can directly adopt the metal paste, silver halide photographic emulsions etc. of silver, gold, copper to be raw material, adopt methods such as serigraphy, exposure image, inkjet printing, etching at the figure rete that is containing metallicses such as preparation one deck argentiferous, gold, copper on the luminescent substance glass film.
In the present invention, adopt the method for DC electric field induced nano crystal graph transfer printing, with containing metal material pattern film surface is anode, to containing metal material pattern rete with contain the luminescent substance glass film and apply DC electric field, metallic ion in the guiding containing metal material pattern rete diffuses into along the line of electric force orientation and contains the luminescent substance glass film, forms the metallic ion figure in glass film.In follow-up heat treatment process, these graphical metallic ion nucleation that distribute, grow into required metallic nano crystal volume graphic, and fluorescent material is on every side carried out local fluorescence strengthen, and then realize the output of fluorescent graphic.After electric field was induced hot transfer printing, the form that the figure rete of being left over can mask prevented that each layer from containing the phase mutual interference between the luminescent substance glass film; Also can introduce some ray filtering materials in advance, control the characteristics of luminescence of film with the form of filter coating.
Preparation be can on optical base-substrate, alternately repeat in the present invention earlier and different luminescent substance glass films and containing metal material pattern rete contained, form multilayer overlapping distributed architecture, by the method for DC electric field induced nano crystal graph transfer printing, form multilayer luminous pattern rete again with different emission.Also can on optical base-substrate, prepare one deck earlier successively and contain luminescent substance glass film and containing metal material pattern rete, and after the method for utilizing DC electric field induced nano crystal graph transfer printing forms one deck and has the luminous pattern rete of single emission wavelength, change luminescent substance or glass film kind again, and the repetition above-mentioned steps, form multilayer luminous pattern rete with different emission.
In metal nanocrystal graph transfer printing process, metallics existence form and content in the containing metal material pattern rete, contain luminescent substance glass film composition and structure, heat treatment temperature, DC electric field intensity and processing time all can exert an influence to diffusion, the separating out of metal nanocrystal of metallic ion.Select suitable nanocrystalline graph transfer printing condition very necessary, cross low heat treatment temperature and electric field intensity and will be unfavorable for the diffusion of metallic ion, too high heat treatment temperature or long processing time will make nanocrystal too grow up and the nanometer crystal graph obfuscation, and too high electric field intensity also can cause the destruction of glass film.According to aspect requirements such as the size of transfer printing metal nanocrystal, content, electric field intensity when electric field is induced hot transfer printing is 10-1000V/mm, heat treatment temperature is 100-600 ℃, processing time is 1-1000min, and the selected heat treatment temperature of follow-up Technology for Heating Processing is 250-600 ℃, and the processing time is 5-1000min.
Nanocrystalline figure proposed by the invention strengthens graphic luminous compound film material and technology of preparing, collects rice optical information material preparation and device and is manufactured in one, can be used for the manufacturing field of nanometer information apparatus such as optical information demonstration, information record, information modulation.
Description of drawings
Structure of composite membrane synoptic diagram when Fig. 1 induces hot transfer printing for DC electric field.
Fig. 2 is the structure of composite membrane synoptic diagram after DC electric field is induced hot transfer printing and subsequent heat treatment.
Embodiment
As shown in Figure 1, wherein, 1 is second layer containing metal material pattern rete, 2 for the second layer contains the luminescent substance glass film, and 3 is ground floor containing metal material pattern rete, and 4 contain the luminescent substance glass film for ground floor, 5 is glass, monocrystalline or polymkeric substance optical base-substrate, and 6 is DC electric field.
At first utilize methods such as sol-gel process, spray pyrolysis, physical sputtering method, chemical vapour deposition technique, pulsed laser deposition on glass, monocrystalline or polymkeric substance optical base-substrate 5, to apply one deck and contain luminescent substance glass film 4, utilize methods such as serigraphy, exposure image, inkjet printing or etching on this film, to prepare one deck containing metal material pattern rete 3 again; Prepare multiple fluorescent graphic rhythmo structure composite membrane as need, can on figure rete 3, apply the second layer more successively and contain luminescent substance glass film 2, second layer containing metal material pattern rete 1, or luminescent substance glass film and the containing metal material pattern rete of containing more.Be anode with outermost metal material pattern rete then, the optical base-substrate side surface of not filming is that negative electrode applies DC electric field 6 and heating simultaneously, metallic ion in the guiding containing metal material pattern rete diffuses into along the line of electric force orientation and contains the luminescent substance glass film, contain at each layer by subsequent heat treatment again and form the graphical metal nanocrystal that distributes in the luminescent substance glass film, be used for that luminescent substance is on every side carried out graphical fluorescence and strengthen, the former containing metal material pattern rete of leaving over then can mask or the form of filter coating exist.
Structure of composite membrane after DC electric field is induced thermal diffusion and subsequent heat treatment as shown in Figure 2, wherein, 1 is second layer mask or filter coating, 2 is the graphical fluorescent glass film of the nanocrystalline enhancing of the second layer, 3 is ground floor mask or filter coating, 4 is the graphical fluorescent glass film of the nanocrystalline enhancing of ground floor, and 5 is glass, monocrystalline or polymkeric substance optical base-substrate.Utilize the graphical fluorescent glass film of the nanocrystalline enhancing of external light source irradiation, because metallic nano crystal figure in the different layers glass film and plasma resonance absorption peak position thereof, luminescent substance kind have nothing in common with each other, thereby strengthen at different wave length section metallic nano crystal and to inspire the fluorescent graphic that has nothing in common with each other.
With 1, the 2-propylene glycol is a solvent, successively add 0.8M1,2-propylene glycol tellurium, 0.2M niobium oxalate, 0.2M barium chloride, 0.01M europium nitrate, form colloidal sol 60 ℃ of ageings, utilize sol evenning machine to be coated on the silicon single crystal substrate, be heated to 130 ℃ of polymerizations and form the tellurate gel film, film is carried out 400 ℃ of thermal treatments obtain to contain europium tellurate system glass film.With the absolute ethyl alcohol is solvent, successively add 1M ethyl orthosilicate, 0.05M gold chloride, and adding 3M water is hydrolyzed, polymerization forms colloidal sol, utilizes ink-jet printing process containing europium tellurate system glass film surface formation figure rete, forms by ageing and 250 ℃ of thermal treatments to contain golden figure rete.To contain golden figure rete is anode, and silicon single crystal substrate not plated film side surface is a negative electrode, applies the DC electric field that intensity is 400V/mm, and to place temperature be after 300 ℃ heat-treatment furnace is handled 40min, to remove electric field and handle 120min down at 350 ℃ again.Containing gold ion in the golden figure rete and be orientation diffuses into and contains europium tellurate system glass film, form the gold nano-crystal of particle size at 15-25nm, and near wavelength 532nm, present tangible surface plasma resonance absorption, and then near this wavelength, the rare earth ion europium is carried out the enhancing of local fluorescence and forms fluorescent graphic.Residual formerly contain golden figure rete and promptly exist with the form of optical mask.
With the absolute ethyl alcohol is solvent, successively add 0.8M ethyl orthosilicate, 0.2M tellurium chloride, 0.2M caustic alcohol, 0.01M samaric nitrate, and adding 3M water is hydrolyzed under 60 ℃, polymerization forms colloidal sol, utilize sol evenning machine to be coated in the colloidal sol that makes on the optical glass substrate and ageing formation gel film, gel film is carried out 450 ℃ of thermal treatments obtain to contain samarium silicon tellurate system glass film.Silver halide photographic emulsions are coated in contain on the samarium silicon tellurate system glass film, adopt exposure method to form argent figure rete, and flush away imaging moiety not.With argent figure rete is anode, and optical glass substrate not plated film side surface is a negative electrode, applies the DC electric field that intensity is 200V/mm, and to place temperature be after 300 ℃ heat-treatment furnace is handled 60min, to remove electric field and handle 120min down at 450 ℃ again.Silver ion in the argent figure rete is that orientation diffuses into and contains samarium silicon tellurate glass film, form the silver-colored nanocrystal of particle size at 5-15nm, and near wavelength 404nm, present tangible surface plasma resonance absorption, and then near this wavelength, the rare earth ion samarium is carried out the enhancing of local fluorescence and forms fluorescent graphic.
Embodiment 3
With the absolute ethyl alcohol is solvent, successively add 0.7M ethyl orthosilicate, 0.2M butyl titanate, 0.1M zirconium iso-propoxide, 0.2M potassium nitrate, 0.01M erbium nitrate, and adding 3M water is hydrolyzed under 60 ℃, polymerization forms colloidal sol, utilize sol evenning machine to be coated in the colloidal sol that makes on the optical glass substrate and ageing formation gel film, gel film is carried out 500 ℃ of thermal treatments acquisition ground floors contain erbium silicon titanium zirconium system glass film.With the absolute ethyl alcohol is solvent, successively add 1M ethyl orthosilicate, 0.05M silver nitrate, and adding 3M water is hydrolyzed, polymerization forms colloidal sol, utilize silk screen print method that colloidal sol is coated in and contain erbium silicon titanium zirconium system glass film surface and ageing formation argentiferous gel film figure, form ground floor argentiferous figure retes by 250 ℃ of thermal treatments.With 1, the 2-propylene glycol is a solvent, successively add 0.6M1,2-propylene glycol tellurium, 0.2M niobium oxalate, 0.2M barium chloride, 0.01M praseodymium nitrate, form colloidal sol 60 ℃ of ageings, utilize sol evenning machine to be coated on the ground floor argentiferous figure rete, be heated to 130 ℃ of polymerizations and form the tellurate gel film, film is carried out 450 ℃ of thermal treatments acquisition second layers contain praseodymium tellurate system glass film.Utilization contains preparation second layer argentiferous figure rete on the luminescent substance glass film with quadrat method at the second layer, and be anode with it, optical glass substrate not plated film side surface is a negative electrode, apply the DC electric field that intensity is 450V/mm, and to place temperature be after 300 ℃ heat-treatment furnace is handled 50min, to remove electric field and handle 120min down at 400 ℃ again.Silver ion in the argentiferous figure rete is that orientation diffuses into and contains in the luminescent substance glass film and form silver-colored nanocrystal, near 488nm and 443nm, present tangible surface plasma resonance respectively and absorb, and then respectively rare earth ion erbium, praseodymium are carried out the enhancing of local fluorescence and form fluorescent graphic.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (12)
1. reinforcing graphic luminous compound film by nano crystal preparation method, its step comprises:
(a) preparation contains rare earth or semiconductor or metal luminescent substance glass film on optical base-substrate; (b) prepare argentiferous, gold or copper metallics figure rete on the luminescent substance glass film in containing of (a) step acquisition; (c) adopt DC electric field to induce that the metallic ion orientation diffuses into glass film in the hot transfer technique guiding containing metal material pattern rete, and in containing the luminescent substance glass film, forms silver, gold or the copper metal nanocrystal of graphical distribution by subsequent heat treatment.
2. method according to claim 1 is characterized in that: described optical base-substrate be can be anti-glass or the monocrystalline or the polymkeric substance optical base-substrate of 300 ℃ and above temperature.
3. method according to claim 1, it is characterized in that: it is consistent with the fluorescence exciting wavelength of luminescent substance that described silver, gold or the copper metal nanocrystal surface plasma resonance in containing the luminescent substance glass film absorbs peak position, utilize the graphical silver that distributes, gold, copper nanocrystal and then the fluorescence efficiency of luminescent substance is strengthened, realize the output of nanocrystalline enhancing luminous pattern.
4. method according to claim 1, it is characterized in that: in the described step (a) contain luminescent substance glass film matrix with the ethylate of tellurium, silicon, titanium, zirconium or aluminium, propylate, butylate, ethylene glycol salt, propylene glycol salt, chloride, nitrate, sulfate wherein one or more are raw material, wherein the molar content of tellurium compound is less than or equal to 90%, the molar content of silicon compound, titanium compound, zirconium compounds or aluminium compound is less than or equal to 80%, and the total molar content of these compounds is more than or equal to 60%; Introduce simultaneously lithium, sodium, potassium, silver, copper, gold, magnesium, calcium, strontium, barium, zinc, manganese, lead, iron, cobalt, nickel, niobium, vanadium, tungsten or boron halogenide, oxalates, acetate, nitrate, sulfate, ethylate, propylate, butylate wherein one or more, its molar content is for being less than or equal to 40%.
5. method according to claim 1, it is characterized in that: on optical base-substrate, prepare oxide or oxygen halogen gel and glass film, and adjusting silver, gold or the copper nanocrystal surface plasma resonance absorption peak position in glass film is adjustable continuously in the 400-800nm scope with sol-gel process.
6. method according to claim 1 is characterized in that: the method for synthetic described glass film also comprises spray pyrolysis, physical sputtering method, chemical vapour deposition technique or pulsed laser deposition.
7. method according to claim 1 is characterized in that: the thickness of described glass film is 100-10000nm.
8. method according to claim 1, it is characterized in that: the containing metal material pattern rete in the described step (b) with the ethylate of silicon, titanium or zirconium, propylate, butylate, ethylene glycol salt, propylene glycol salt wherein one or more are raw material, its total molar content is more than or equal to 60%; Introduce magnesium, calcium, strontium, barium, manganese, lead, niobium, vanadium, tungsten or boron halogenide, oxalates, acetate, nitrate, sulfate, ethylate, propylate, butylate wherein one or more, its total molar content is for being less than or equal to 40%; Introduce simultaneously silver, gold or copper simple substance, halogenide, oxalates, carbonate, nitrate, sulfate wherein one or more, its molar content is for being less than or equal to 10%; Prepare colloidal sol and be coated in to contain on the luminescent substance glass film and form figure gel and glass rete, after electric field is induced hot transfer printing, exist with forms such as mask, filter coatings.
9. method according to claim 1 is characterized in that: the metal paste, silver halide photographic emulsions of selecting silver, gold or copper in the described step (b) for use are as figure rete raw material.
10. method according to claim 1, it is characterized in that: described step (c) is to induce down in DC electric field, with argentiferous, gold or copper metallics graphic films laminar surface are anode, glass, the side surface of not filming of monocrystalline or polymkeric substance optical base-substrate is a negative electrode, to containing metal material pattern rete with contain the heat treated DC electric field that applies simultaneously of luminescent substance glass film, metallic ion orientation in the guiding figure rete diffuses into and contains the luminescent substance glass film, its electric field intensity is 10-1000V/mm, heat treatment temperature is 100-600 ℃, and the processing time is 1-1000min; Its follow-up heat treatment temperature is 250-600 ℃, and processing time 5-1000min induces to diffuse into metallic ion gathering formation silver, gold or the copper nanocrystal that contains in the luminescent substance glass film under air or reducing atmosphere.
11. method according to claim 1, it is characterized in that: by once carry out (a) and (b) step obtain individual layer and contain luminescent substance glass film and containing metal material pattern rete, perhaps by alternately repeat (a) and (b) step obtain that multilayer overlaps distribution contain luminescent substance glass film and containing metal material pattern rete, induce hot transfer technique that metallic ion orientation in each containing metal material pattern rete is diffused into by the DC electric field of (c) step again and contain the luminescent substance glass film, form luminous pattern layer through subsequent heat treatment with single emission wavelength, the multilayer luminous pattern that perhaps has different emission.
12. method according to claim 1 is characterized in that: by alternately repeating (a) and (b) and (c) step preparation multilayer luminous pattern with different emission.
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| CN102439113B (en) * | 2009-06-26 | 2014-04-30 | 海洋王照明科技股份有限公司 | Luminescent glass element, manufacturing method and luminescence method thereof |
| WO2011113208A1 (en) * | 2010-03-19 | 2011-09-22 | 海洋王照明科技股份有限公司 | Glass substrate light emitting element and methods for manufacturing and luminescence thereof |
| CN102714120A (en) * | 2010-03-19 | 2012-10-03 | 海洋王照明科技股份有限公司 | Glass substrate light emitting element and methods for manufacturing and luminescence thereof |
| CN102714120B (en) * | 2010-03-19 | 2014-08-06 | 海洋王照明科技股份有限公司 | Glass substrate light emitting element and methods for manufacturing and luminescence thereof |
| CN102268254A (en) * | 2010-06-02 | 2011-12-07 | 海洋王照明科技股份有限公司 | Yttria light-emitting element and preparation method thereof |
| CN102268254B (en) * | 2010-06-02 | 2013-10-23 | 海洋王照明科技股份有限公司 | Yttria light-emitting element and preparation method thereof |
| CN104593891A (en) * | 2015-01-25 | 2015-05-06 | 北京化工大学 | Preparation method for fluorescence-enhanced sheath-core structure nano fiber |
| CN108699701A (en) * | 2015-12-17 | 2018-10-23 | 保尔·萨巴梯埃—图卢兹第三大学 | The method for manufacturing component by laser irradiation metal oxalate layer or supporting micro-structure |
| CN110342457A (en) * | 2018-04-02 | 2019-10-18 | 中国科学院物理研究所 | A kind of metal nanoparticle dot matrix and its preparation method and application |
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| CN101373222B (en) | 2010-12-08 |
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