CN101758014A - Method for preparation of patterning colloid photonic crystal by ink-jet printing - Google Patents
Method for preparation of patterning colloid photonic crystal by ink-jet printing Download PDFInfo
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Abstract
The invention belongs to the colloid photonic crystal preparation and application technical field, in particular to a method for preparation of high quality extensive patterning colloid photonic crystal by ink-jet printing. Under room temperature and by effective control of the substrate wetting quality and the surface tension of monodisperse emulsion particle emulsion ink for ink-jet printing, two or more types of monodisperse emulsion particle emulsion with the same particle diameter are respectively put into different ink boxes of an ink-jet printer and the concentration of the monodisperse emulsion particles in the emulsion in each ink box is 0.5-20 wt percent; and after monodisperse emulsion particle emulsion ink is used for the ink-jet printer to print patterns and then dried, a high-quality colloid photonic crystal with photon ban gaps in the ultraviolet light region and the visible light region is formed on the substrate surface. The highly-sequentially assembled colloid photonic crystals prepare by the invention has good optical property, realizes control effect of photon ban gaps to light and has wider application prospect in the fields of optical devices and optical integrated circuits.
Description
Technical field
The invention belongs to the preparation and the applied technical field of colloidal photon crystal, relate in particular to the method for preparing high-quality large area pattern colloidal photon crystal by inkjet printing methods.
Background technology
Because the patterning photonic crystal has a wide range of applications in fields such as optics, display and microfluids, the preparation of patterning photonic crystal has caused researcher's very big interest.The preparation of patterning photonic crystal generally obtains by the method with laser direct-writing or template assembling, laser direct-writing needs special expensive direct-writing device, though and the method for template assembling is simple, resulting pattern is limited by template, and the template preparation process is also very complicated.If can directly prepare the patterning photonic crystal by inkjet printing methods should be a kind of simple and easy method of operating.Inkjet printing is having a wide range of applications aspect the excellent device of processability as competitive pattern preparation method, for example: light emitting diode and photodetector.Yet the report for preparing photonic crystal about inkjet printing but seldom.Typical report is the colloidal crystal microarray that people such as Korea S scientist Moon utilizes the single injector printing ink to print to have prepared colloidal crystal and different size latex balloon to constitute, and has studied its pattern and optical property.This simple pattern photonic crystal construction method in conjunction with self assembly and direct writing technology is considered to be hopeful to be used for photon of future generation and display device.But what persons such as Moon used is expensive single shower nozzle printer, and has only carried out the research of single drop, does not prepare the photonic crystal of patterning.And select common printer for use, the photonic crystal of preparation patterning has great importance for the application, the especially application of patterning photonic crystal that develop the large area photon crystal.
In the patent application before the applicant (CN:200710179880.3,200810115540.9), the applicant has realized preparing the single band gap of patterning and the photonic crystal of compound single band gap by common commercially available ink-jet printer.But the optical property of preparation-obtained film is also relatively poor, can't satisfy real demands of applications fully.In the present invention, the applicant further regulates and control the wellability of print substrate, and ink-jet printing ink is formed to regulate and control, and has finally realized having prepared high-quality patterning photonic crystal by inkjet printing methods.
The present invention has used the patent No.: ZL200510011219.2, the monodisperse polymer emulsion particle that ZL 200510012021.6 obtains, and in conjunction with the method for number of patent application CN:200710179880.3 and 200810115540.9, further by effective regulation and control to print substrate wellability and single dispersed latex grain latex ink composition, realized single dispersed latex grain emulsion droplet effectively the sprawling and the three-dimensional assembling of the high-sequential of single dispersed latex grain of substrate surface, the final realization prepares the ultraviolet light zone by inkjet printing methods, the high-quality colloid photonic crystal film of visible region.
Patterning colloid photonic crystal film by the present invention prepares has the good optical performance, can realize the regulating and controlling effect to light, and at optics, integrated optical path and other fields has wide application prospect.
Summary of the invention
One of purpose of the present invention provides a kind of method for preparing high-quality large area pattern colloidal photon crystal by inkjet printing methods.
Two of purpose of the present invention provides a kind of by the combining of ink-jet printer and computer, can be in computer layout, realize the preparation method of first-rate quality pattern photonic crystal by inkjet printing methods.
The preparation of first-rate quality pattern colloidal photon crystal of the present invention, mainly be based on the infiltrating selection of print substrate and the regulation and control that single dispersed latex grain latex ink is formed, on this basis, to contain finite concentration and fixedly single dispersed latex grain emulsion of particle diameter pack in the print cartridge of ink-jet printer, wherein single dispersed latex grain can be more than one emulsion particle, through printing of inkjet printer, just can form periodic arrangement, pattern and the consistent colloidal photon crystal of software design; Can realize the high-sequential assembling of single dispersed latex grain by this method, the optical property of gained colloidal photon crystal is fine, thereby can realize the quick preparation of high-quality large tracts of land colloidal photon crystal.In conjunction with the design of computer, also can realize the preparation of first-rate quality pattern colloidal photon crystal simultaneously to print pattern.
The first-rate quality pattern photonic crystal of the present invention's preparation is significant to the application of development photonic crystal.
The method for preparing the first-rate quality pattern colloidal photon crystal by inkjet printing methods of the present invention is:
Under the room temperature, more than one the single dispersed latex grain emulsion that contains same particle size is loaded on respectively in the different print cartridge of ink-jet printer (particle diameter of the single dispersed latex grain in each print cartridge is identical), and the concentration of single dispersed latex grain in emulsion in each print cartridge is 0.5～20wt%; Through ink-jet printer is carrying out patterning printing and drying on the base material after, on substrate surface, obtain the colloid photonic crystal film of patterning.
The colloid photonic crystal film of described patterning has the pattern of computer design.
The concentration of the single dispersed latex grain in the single dispersed latex grain emulsion that contains same particle size of the present invention is 0.5～20wt%, and it is 10～60wt% that low surface tension is regulated auxiliary agent, and surplus is a water.
The described surface tension that contains single dispersed latex grain emulsion of same particle size is 25～60mN/m, and preferred surface tension force is 40～55mN/m; The capillary regulation and control of emulsion are to regulate auxiliary agent by the low surface tension in the emulsion to realize; The capillary regulation and control of emulsion can be adjusted drop effectively the sprawling at substrate surface of described emulsion.
Described low surface tension is regulated auxiliary agent and is selected from ethylene glycol, glycerine, at least a in the group that polyethylene glycol etc. are formed.
Described single dispersed latex grain is monodisperse polymer emulsion particle, single hard core-soft core structure triblock polymer emulsion particle, single inorganic oxide emulsion particle or their mixture of disperseing of disperseing.
Described single particle diameter of hard core-soft core structure triblock polymer emulsion particle that disperses is selected within 50～300nm scope, and the preparation of this triblock polymer emulsion particle is to adopt one step of batch method emulsifier-free emulsion polymerization to realize that the typical preparation method who is adopted is:
With the monomer 1 that hydrophily increases successively, monomer 2, monomer 3 mixing are dispersed in the aqueous solution that contains pH buffer and emulsifying agent; Is 300～800rpm with resulting emulsion polymerization systems at rotating speed, be preferably under the rotating speed of 500rpm and mix, and be heated to 65～85 ℃ (preferred temperature are 78 ℃), the initator that adds initator total amount 1/2 makes reaction begin to carry out, react the initator that adds initator total amount 1/4 after 2～4.5 hours again, remaining initator is continuing reaction adding after 2～4.5 hours, 0.2wt%～the 1wt% of the suitable monomer 1 of the total consumption of described initator, monomer 2 and monomer 3 sum gross weights is preferably 0.3wt%.Reaction continues end in 1～3 hour subsequently, obtains single dispersion index and is less than or equal to 0.005, and particle size range is single hard core-soft core structure triblock polymer emulsion particle that disperses of 50～300nm.
Wherein, monomer 1, monomer 2 and the total consumption of monomer 3 sums are that (consumption of monomer 1 is a monomer 1 in the emulsion polymerization systems for 11～17wt% of emulsion polymerization systems gross weight, 88～94wt% of monomer 2 and monomer 3 sum gross weights, monomer 2 is 3～6wt%, monomer 3 is 3～6wt%), the concentration of pH buffer in emulsion polymerization systems is 0.02～0.99wt%, the concentration of emulsifying agent in emulsion polymerization systems is that (monomer 1 in emulsifying agent consumption and the polymerization system for 0～0.097wt%, the weight rate 0～0.5wt%) of monomer 2 and monomer 3 sum total amounts, the concentration of initator in emulsion polymerization systems is 0.02～0.99wt%.
The realization of the nucleocapsid structure of single dispersion hard core-soft core structure triblock polymer emulsion particle does not need special technical process, just hydrophilic different according to reaction monomers in the polymerization system (monomer 1, monomer 2 and monomer 3) and phase emergencing copolymer, hydrophilic radical progressively moves to the top layer in polymerization process, and lipophilic group partly moves to stratum nucleare, finally realizes hard core-soft core structure.
The reaction time of system is 5～12 hours, and the preferred reaction time is 10～11 hours.
Described reaction monomers is the compound that contains at least one ethylene linkage in the molecule, and its hydrophily increases successively, and monomer 1 is the relatively poor reaction monomers of hydrophily, as styrene, methyl styrene or their mixture etc.; And monomer 2 is a hydrophily monomer relatively preferably, and as esters of acrylic acid etc., described esters of acrylic acid is selected from least a etc. in the group that methyl methacrylate, butyl acrylate, isobutyl acrylate form; Monomer 3 is the very strong water-soluble reaction monomer of hydrophily, as acrylic acid, acrylamide or their mixture etc.The introducing of minor amount of water dissolubility reaction monomers 3 is in order to increase the stability of system.And selecting for use of the different successively reaction monomers of hydrophily is for spontaneous formation nucleocapsid structure in polymerization process.
Described initator is selected from alkali metal sulfates, ammonium persulfate or their mixture.Wherein initator is that form with the aqueous solution is incorporated in the polymerization system, and its solution concentration is 2～5wt%.
Described alkali metal is selected from potassium or sodium.
The emulsifying agent of the particle size of the final gained emulsion particle of described adjusting is selected from least a in the group that dodecyl sodium sulfate, lauryl sodium sulfate, neopelex etc. are formed.
Described pH buffer is selected from least a in the group that carbonic hydroammonium, sodium acid carbonate, dibastic sodium phosphate etc. are formed.
For guaranteeing effective realization of emulsion particle monodispersity, strict control stir speed (S.S.) is fed in raw material and heating schedule, to avoid the appearance of secondary nucleation in the polymerization process.
Described single hard core-soft core structure triblock polymer emulsion particle that disperses is selected from single hard polystyrene core-soft polymethacrylates-polyacrylic acid shell structure triblock polymer emulsion particle (list disperses poly-(styrene-methyl methacrylate-acrylic acid) emulsion particle) that disperses, single hard polymethylstyrene nuclear-soft polypropylene acid isobutyl ester-polyacrylamide shell structure triblock polymer emulsion particle (poly-(methyl styrene-isobutyl acrylate-acrylamide) emulsion particle of single dispersion) that disperses, single hard polymethylstyrene nuclear-soft polypropylene acid isobutyl ester-polyacrylamide shell structure triblock polymer emulsion particle (poly-(methyl styrene-isobutyl acrylate-acrylamide) emulsion particle of single dispersion) that disperses, single hard polymethylstyrene nuclear-soft polypropylene acid butyl ester-polyacrylamide shell structure triblock polymer emulsion particle (poly-(methyl styrene-butyl acrylate-acrylamide) emulsion particle of single dispersion) that disperses, at least a in the group that hard polymethylstyrene nuclear-soft polymethyl methacrylate-polyacrylic acid shell structure triblock polymer emulsion particle (single disperse to gather (methyl styrene-methyl methacrylate-acrylic acid) emulsion particle) etc. is formed.
Described monodisperse polymer emulsion particle is commercially available monodisperse polystyrene emulsion particle, single their mixture that disperses the polymethyl methacrylate emulsion particle or have same particle size; The particle diameter of above-mentioned monodisperse polymer emulsion particle is selected within 50～300nm scope.
Described single inorganic oxide emulsion particle that disperses is commercially available monodisperse titanium dioxide emulsion particle, monodisperse silica emulsion particle or their mixture with same particle size; Above-mentioned single particle diameter of inorganic oxide emulsion particle that disperses is selected within 50～300nm scope.
Need adopt the filter membrane of 1.2um to filter for above-mentioned single dispersed latex grain emulsion, to prevent the obstruction of print procedure.
Photonic crystal print substrate used in the present invention comprises the base material of flexible parent metal, rigid substrate and various compound shapes, as polymer plastic, paper, glass, silicon chip, metal, pottery or timber etc.Being 20 °～95 ° for above-mentioned employed base material to the contact angle of single dispersed latex grain emulsion of containing same particle size wherein, is the best with 50 °～70 °.
Method of the present invention is by the wellability of regulation and control substrate surface, can effectively control drop effectively the sprawling of described emulsion at substrate surface, thereby obtaining above-mentioned base material is 20 °～95 ° to the contact angle of single dispersed latex grain emulsion of containing same particle size, is the best with 50 °～70 °; And capillary regulation and control can be controlled the rate of volatilization of drop on base material of described emulsion to described emulsion, guarantee that described emulsion prints and described single dispersed latex grain can be assembled in order carrying out patterning on the base material through ink-jet printer, realize the inkjet printing preparation of high-quality patterning colloid photonic crystal.
For the infiltrating regulate and control method of substrate surface be: the solution (concentration is 2wt%) of selecting the polymeric material of opposed polarity for use, method by spin coating or membrane applies thin film at substrate surface, and the wellability of substrate surface can be filmed by the polymeric material of opposed polarity and be obtained.
The polymeric material of selected opposed polarity is selected from least a in the group that polystyrene, Merlon, polymethyl methacrylate, polyvinyl alcohol, polyvinyl acetate etc. are formed.
That the present invention can obtain on substrate surface is high-quality, the high-sequential assembling have the colloidal photon crystal of photon band gap in ultraviolet light zone, visible region.Colloid photonic crystal film by the first-rate quality patternization for preparing by inkjet printing methods of the present invention has the good optical performance, at optics, integrated optical circuit, multicolour pattern, decorative coating prevents fields such as ultraviolet coating that wide application prospect is arranged.
The invention will be further described below in conjunction with accompanying drawing and by embodiment.
Description of drawings
The colloid photonic crystal film stereoscan photograph that Fig. 1 a prints in the pattern that obtains for embodiment 4, single as can be seen dispersed latex grain has been realized the assembling of high-sequential; Fig. 1 b is the digital photograph of colloid photonic crystal film.Fig. 1 c is the reflectance spectrum of colloid photonic crystal film, and photon band gap is narrower as can be seen, and the photon band gap symmetry is good;
The specific embodiment
Embodiment 1.
The preparation particle diameter is poly-(styrene-methyl methacrylate-acrylic acid) emulsion particle of single dispersion of 50nm, and concrete scheme is as follows:
With monomer mixture methyl methacrylate (1.2 gram), styrene (18 gram) and acrylic acid (1.2 gram), pH buffer (1.0 gram) and emulsifying agent dodecyl sodium sulfate (0.0786mg) are dissolved in the water (100mL), resulting mixed system is mixed at 600rpm, and be heated to 75 ℃.Potassium peroxydisulfate (0.8 gram is dissolved in the 20 ml waters) aqueous solution that adds 10 milliliters makes reaction begin to carry out, react the persulfate aqueous solution that adds 5 milliliters after 3.5 hours again, remaining persulfate aqueous solution is continuing reaction adding after 3 hours, and reaction continues to finish after 2 hours subsequently.Finally obtaining particle diameter is polystyrene-poly methyl methacrylate-polyacrylic acid three block monodisperse polymer emulsion particles (poly-(styrene-methyl methacrylate-acrylic acid) emulsion particle of single dispersion) of 50nm.
Under room temperature (20 ℃～30 ℃), 1 kind of emulsion that contains single dispersed latex grain is loaded in 1 print cartridge of ink-jet printer, and the single dispersed latex grain emulsion in the print cartridge is singly to disperse poly-(styrene-methyl methacrylate-acrylic acid) emulsion particle by what concentration was that the particle diameter of 0.5wt% is that 50nm above-mentioned obtains, the water as the polyethylene glycol of low surface tension auxiliary agent and 39.5wt% of 60wt% is formed, and surface tension that should list dispersed latex grain emulsion is 25mN/m; Through ink-jet printer be at contact angle to above-mentioned single dispersed latex grain latex ink carry out on 20 ° the glass baseplate that patterning is printed and drying after, poly-(styrene-methyl methacrylate-acrylic acid) emulsion particle of single dispersion forms the three-dimensional colloid photonic crystal film of periodic arrangement on the glass baseplate surface, this film disperses poly-(styrene-methyl methacrylate-acrylic acid) emulsion particle to pile up and form by single, has the computer designed pattern.
Embodiment 2.
Particle diameter is that single preparation method of poly-(methyl styrene-methyl methacrylate-acrylic acid) emulsion particle that disperses of 300nm is as follows: with monomer mixture methyl methacrylate (1.2 gram), methyl styrene (18 gram) and acrylic acid (1.2 gram), pH buffer (1.0 gram) is dissolved in the water (100mL), resulting mixed system is mixed at 600rpm, and be heated to 75 ℃.Potassium peroxydisulfate (0.8 gram is dissolved in the 20 ml waters) aqueous solution that adds 10 milliliters makes reaction begin to carry out, react the persulfate aqueous solution that adds 5 milliliters after 3.5 hours again, remaining persulfate aqueous solution is continuing reaction adding after 3 hours, and reaction continues to finish after 2 hours subsequently.Finally obtain polymethylstyrene-polymethyl methacrylate that particle diameter is 300nm-polyacrylic acid three block monodisperse polymer emulsion particles (poly-(methyl styrene-methyl methacrylate-acrylic acid) emulsion particle of single dispersion).
Under room temperature (20 ℃～30 ℃), to contain same particle diameter and be loaded in the same print cartridge of ink-jet printer for the emulsion of single dispersed latex grain of different materials, and the single dispersed latex grain emulsion in the print cartridge is to be that the particle diameter of 20wt% is that above-mentioned single poly-(methyl styrene-methylacrylic acid methyl esters-acrylic acid) emulsion particle and the particle diameter of disperseing that obtains of 300nm is the mixture (volume respectively accounts for 50%) of the monodisperse polystyrene emulsion particle (luxuriant nanometer laboratory is bought from Zhejiang) of 300nm by concentration, the water as the ethylene glycol of low surface tension auxiliary agent and 70wt% of 10wt% is formed, and surface tension that should list dispersed latex grain emulsion is 60mN/m; Is 95 ° polystyrene plastics plate substrate (contact angle that the polystyrene plastics base material itself has with described single dispersed latex grain latex ink is 95 °) or the silicon chip that is applied by polystyrene through ink-jet printer at the contact angle to above-mentioned single dispersed latex grain latex ink, potsherd, after carrying out patterning printing and drying on wooden sheet or the sheet metal base material, single poly-(methyl styrene-methyl methacrylate-acrylic acid) emulsion particle and monodisperse polystyrene emulsion particle of disperseing is at polystyrene plastics substrate sheets or the silicon chip that applies at polystyrene, potsherd, form the three-dimensional colloid photonic crystal film of periodic arrangement on the surface of wooden sheet or sheet metal base material, this film is piled up by poly-(methyl styrene-methyl methacrylate-acrylic acid) emulsion particle of single dispersion and monodisperse polystyrene emulsion particle and is formed, and has the computer designed pattern.
Described polystyrene coating is the method by spin coating, with concentration is the surface that the polystyrene of 2wt% is spin-coated on described silicon chip, potsherd, wooden sheet or sheet metal base material, coating thickness is 20～30 microns all, and making the polystyrene-coated surface is 95 ° to the contact angle of above-mentioned single dispersed latex grain latex ink.
Embodiment 3.
Under room temperature (20 ℃～30 ℃), what dispose a kind of surface tension respectively and be 60mN/m is that the particle diameter of 10wt% is the monodisperse silica emulsion particle (available from Fujian good fortune sodium Materials Co., Ltd) of 215nm by concentration, the emulsion of single dispersed latex grain that the glycerine of 10wt% and the water of 80wt% are formed; And another kind of surface tension be 45mN/m be that the particle diameter of 10wt% is the monodisperse polystyrene emulsion particle (purchases of luxuriant nanometer laboratory, Zhejiang) of 300nm by concentration, the emulsion of single dispersed latex grain of the glycerine of 10wt% and the water of 80wt% composition.The above-mentioned two kinds emulsions that contain single dispersed latex grain are loaded on respectively in 2 print cartridges of ink-jet printer; Through ink-jet printer the contact angle to above-mentioned two kinds of single dispersed latex grain latex inks all be carry out on the aluminium sheet that applies of 70 ° Merlon or the potsherd base material that patterning is printed and drying after, monodisperse silica emulsion particle and monodisperse polystyrene emulsion particle form the three-dimensional colloid photonic crystal film of periodic arrangement on aluminium sheet that Merlon applies or potsherd substrate surface, this film is piled up by monodisperse silica emulsion particle and monodisperse polystyrene emulsion particle and is formed, and has the computer designed pattern.
Described Merlon coating is the method by spin coating, with concentration is that the Merlon of 2wt% is spin-coated on described aluminium sheet or potsherd substrate surface, coating thickness is 20～30 microns, makes the Merlon coating surface all be 70 ° to the contact angle of above-mentioned two kinds of single dispersed latex grain latex inks.
Embodiment 4.
The single method of poly-(methyl styrene-butyl acrylate-acrylamide) emulsion particle of disperseing for preparing particle diameter and be 280nm is as follows: with monomer mixture butyl acrylate (1.2 gram), methyl styrene (18 gram) and acrylamide (1.2 gram), pH buffer (1.0 gram), and emulsifying agent dodecyl sodium sulfate (0.001mg) is dissolved in the water (100mL), resulting mixed system is mixed at 600rpm, and be heated to 75 ℃.Potassium peroxydisulfate (0.8 gram is dissolved in the 20 ml waters) aqueous solution that adds 10 milliliters makes reaction begin to carry out, react the persulfate aqueous solution that adds 5 milliliters after 3.5 hours again, remaining persulfate aqueous solution is continuing reaction adding after 3 hours, and reaction continues to finish after 2 hours subsequently.Finally obtain polymethylstyrene-butyl polyacrylate that particle diameter is 280nm-polyacrylamide three block monodisperse polymer emulsion particles (poly-(methyl styrene-butyl acrylate-acrylamide) emulsion particle of single dispersion).
The preparation particle diameter is that single method of poly-(methyl styrene-methyl methacrylate-acrylamide) emulsion particle of disperseing of 220nm is as follows: with monomer mixture methyl methacrylate (1.2 gram), methyl styrene (18 gram) and acrylamide (1.2 gram), pH buffer (1.0 gram), and emulsifying agent dodecyl sodium sulfate (0.007mg) is dissolved in the water (100mL), resulting mixed system is mixed at 600rpm, and be heated to 75 ℃.Potassium peroxydisulfate (0.8 gram is dissolved in the 20 ml waters) aqueous solution that adds 10 milliliters makes reaction begin to carry out, react the persulfate aqueous solution that adds 5 milliliters after 3.5 hours again, remaining persulfate aqueous solution is continuing reaction adding after 3 hours, and reaction continues to finish after 2 hours subsequently.Finally obtain polymethylstyrene-polymethyl methacrylate that particle diameter is 220nm-polyacrylamide three block monodisperse polymer emulsion particles (poly-(methyl styrene-methyl methacrylate-acrylamide) emulsion particle of single dispersion).
The preparation particle diameter is that single method of poly-(methyl styrene-isobutyl acrylate-acrylamide) emulsion particle of disperseing of 180nm is as follows: with monomer mixture isobutyl acrylate (1.2 gram), methyl styrene (18 gram) and acrylamide (1.2 gram), pH buffer (1.0 gram), and emulsifying agent dodecyl sodium sulfate (0.013mg) is dissolved in the water (100mL), resulting mixed system is mixed at 600rpm, and be heated to 75 ℃.Potassium peroxydisulfate (0.8 gram is dissolved in the 20 ml waters) aqueous solution that adds 10 milliliters makes reaction begin to carry out, react the persulfate aqueous solution that adds 5 milliliters after 3.5 hours again, remaining persulfate aqueous solution is continuing reaction adding after 3 hours, and reaction continues to finish after 2 hours subsequently.Finally obtain polymethylstyrene-polyisobutyl acrylate that particle diameter is 180nm-poly-polyacrylamide three block monodisperse polymer emulsion particles (poly-(methyl styrene-isobutyl acrylate-acrylamide) emulsion particle of single dispersion).
Under room temperature (20 ℃～30 ℃), what dispose three kinds of surface tension respectively and all be 55mN/m all is single single single poly-(methyl styrene-butyl acrylate-acrylamide) emulsion particle, emulsion of single dispersed latex grain that the polyethylene glycol of 40wt% and the water of 45wt% are formed of disperseing of disperseing poly-(methyl styrene-methyl methacrylate-acrylamide) emulsion particle, 280nm of disperseing poly-(methyl styrene-isobutyl acrylate-acrylamide) emulsion particle, 220nm that the particle diameter of 15wt% is respectively 180nm by concentration.The above-mentioned three kinds emulsions that contain single dispersed latex grain are loaded on respectively in 3 print cartridges of ink-jet printer; Through ink-jet printer all be at contact angle to above-mentioned three kinds of single dispersed latex grain latex inks carry out on 50 ° the poly methyl methacrylate plastic plate substrate that patterning is printed and drying after, above-mentioned three kinds of different-grain diameters, the emulsion particle of different materials forms the three-dimensional colloid photonic crystal film of periodic arrangement on poly methyl methacrylate plastic plate substrate surface, this film is by poly-(methyl styrene-isobutyl acrylate-acrylamide) emulsion particle of single dispersion, single disperse poly-(methyl styrene-methyl methacrylate-acrylamide) emulsion particle and singly disperse poly-(methyl styrene-butyl acrylate-acrylamide) emulsion particle to pile up to form, have the computer designed pattern.
Fig. 1 a is that particle diameter is single stereoscan photograph that disperses the colloid photonic crystal film of poly-(methyl styrene-methyl methacrylate-acrylamide) emulsion particle print area of 220nm.As can be seen, inkjet printing methods can prepare the colloidal photon crystal that high-sequential is arranged from Fig. 1 a, and Fig. 1 b is corresponding colloid photonic crystal film reflectance spectrum.Fig. 1 c is the digital photograph of corresponding colloid photonic crystal film.
Embodiment 5.
Under room temperature (20 ℃～30 ℃), respectively configuration surface tension force be 40mN/m be that the particle diameter of 10wt% is monodisperse polystyrene (purchase of luxuriant nanometer laboratory, the Zhejiang) emulsion particle of 100nm by concentration, the glycerine of 30wt%, single dispersed latex grain emulsion that the water of 60wt% is formed; And surface tension be 48mN/m be that the particle diameter of 10wt% is single polymethyl methacrylate emulsion particle that disperses of 210nm by concentration, the glycerine of 30wt%, single dispersed latex grain emulsion that the water of 60wt% is formed; And surface tension be 55mN/m be that the particle diameter of 10wt% is monodisperse silica (available from the Fujian good fortune sodium Materials Co., Ltd) emulsion particle of 300nm by concentration, the glycerine of 30wt%, single dispersed latex grain emulsion that the water of 60wt% is formed.The above-mentioned three kinds emulsions that contain single dispersed latex grain are loaded on respectively in 3 print cartridges of ink-jet printer;
Through ink-jet printer to contain particle diameter be the contact angle of single dispersed latex grain latex ink of 100nm be carry out on the paper base material that applies of 45 ° polyvinyl acetate that patterning is printed and drying after, the monodisperse polystyrene emulsion particle forms the three-dimensional colloid photonic crystal film of periodic arrangement on substrate surface, this film is piled up by the monodisperse polystyrene emulsion particle and is formed, and has the computer designed pattern;
Through ink-jet printer to contain particle diameter be the contact angle of single dispersed latex grain latex ink of 210nm be carry out on the silicon wafer substrate that applies of 56 ° polyvinyl alcohol that patterning is printed and drying after, polymethyl methacrylate forms the three-dimensional colloid photonic crystal film of periodic arrangement on substrate surface, this film is piled up by single dispersion polymethyl methacrylate emulsion particle and is formed, and has the computer designed pattern;
Through ink-jet printer to contain particle diameter be the contact angle of single dispersed latex grain latex ink of 300nm be carry out on 63 ° the poly methyl methacrylate plastic base material (contact angle that the poly methyl methacrylate plastic base material itself has with described single dispersed latex grain latex ink is 63 °) that patterning is printed and drying after, the monodisperse silica emulsion particle forms the three-dimensional colloid photonic crystal film of periodic arrangement on substrate surface, this film is piled up by the monodisperse silica emulsion particle and is formed, and has the computer designed pattern.
The silicon wafer substrate that paper base material that described polyvinyl acetate applies and polyvinyl alcohol apply all is that the method by spin coating or membrane is that the polyvinyl acetate of 2wt% is coated in described paper or silicon wafer substrate surface with concentration, coating thickness is 20～30 microns all, and making the polyvinyl acetate coating surface is that the contact angle of single dispersed latex grain latex ink of 100nm is 45 ° to the above-mentioned particle diameter that contains; Making the polyethylene coating surface is that the contact angle of single dispersed latex grain latex ink of 210nm is 56 ° to the above-mentioned particle diameter that contains.
Claims (10)
1. the method for a preparation of patterning colloid photonic crystal by ink-jet printing, it is characterized in that: under the room temperature, more than one the single dispersed latex grain emulsion that contains same particle size is loaded on respectively in the different print cartridge of ink-jet printer, through ink-jet printer is carrying out patterning printing and drying on the base material after, on substrate surface, obtain the colloid photonic crystal film of patterning;
The concentration of the single dispersed latex grain in the described single dispersed latex grain emulsion that contains same particle size is 0.5～20wt%, and it is 10～60wt% that low surface tension is regulated auxiliary agent, and surplus is a water;
Described single dispersed latex grain is monodisperse polymer emulsion particle, single hard core-soft core structure triblock polymer emulsion particle, single inorganic oxide emulsion particle or their mixture of disperseing of disperseing;
Described low surface tension is regulated auxiliary agent and is selected from ethylene glycol, glycerine, at least a in the group that polyethylene glycol is formed.
2. method according to claim 1 is characterized in that: the colloid photonic crystal film of described patterning has the pattern of computer design.
3. method according to claim 1 is characterized in that: described substrate surface has polymer material membrane;
Described base material is polymer plastic, paper, glass, silicon chip, metal, pottery or timber.
4. method according to claim 3 is characterized in that: described polymeric material is selected from least a in the group that polystyrene, Merlon, polymethyl methacrylate, polyvinyl alcohol, polyvinyl acetate form.
5. according to claim 1 or 3 described methods, it is characterized in that: described base material is 20 °～95 ° to the contact angle of single dispersed latex grain emulsion of containing same particle size.
6. method according to claim 5 is characterized in that: described base material is 50 °～70 ° to the contact angle of single dispersed latex grain emulsion of containing same particle size.
7. according to claim 1 or 6 described methods, it is characterized in that: the described surface tension that contains single dispersed latex grain emulsion of same particle size is 25～60mN/m.
8. method according to claim 5 is characterized in that: the described surface tension that contains single dispersed latex grain emulsion of same particle size is 25～60mN/m.
9. method according to claim 7 is characterized in that: the described surface tension that contains single dispersed latex grain emulsion of same particle size is 40～55mN/m.
10. method according to claim 1, it is characterized in that: described single particle diameter of hard core-soft core structure triblock polymer emulsion particle that disperses is selected from 50～300nm, and this list disperses hard core-soft core structure triblock polymer emulsion particle to be selected from single hard polystyrene core-soft polymethacrylates-polyacrylic acid shell structure triblock polymer emulsion particle that disperses, single hard polymethylstyrene nuclear-soft polypropylene acid isobutyl ester-polyacrylamide shell structure triblock polymer emulsion particle that disperses, single hard polymethylstyrene nuclear-soft polypropylene acid isobutyl ester-polyacrylamide shell structure triblock polymer emulsion particle that disperses, single hard polymethylstyrene nuclear-soft polypropylene acid butyl ester-polyacrylamide shell structure triblock polymer emulsion particle that disperses, at least a in the hard group that polymethylstyrene nuclear-soft polymethyl methacrylate-polyacrylic acid shell structure triblock polymer emulsion particle is formed;
The particle diameter of described monodisperse polymer emulsion particle is selected from 50～300nm, and this monodisperse polymer emulsion particle is monodisperse polystyrene emulsion particle, single polymethyl methacrylate emulsion particle or their mixture of disperseing;
Described single particle diameter of inorganic oxide emulsion particle that disperses is selected from 50～300nm, and it is monodisperse titanium dioxide emulsion particle, monodisperse silica emulsion particle or their mixture that this list disperses the inorganic oxide emulsion particle.
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