CN102201549B - Substrate for flexible light emitting device and fabrication method thereof - Google Patents
Substrate for flexible light emitting device and fabrication method thereof Download PDFInfo
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- CN102201549B CN102201549B CN 201110096762 CN201110096762A CN102201549B CN 102201549 B CN102201549 B CN 102201549B CN 201110096762 CN201110096762 CN 201110096762 CN 201110096762 A CN201110096762 A CN 201110096762A CN 102201549 B CN102201549 B CN 102201549B
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- silver wire
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Abstract
The invention discloses a substrate for a flexible light emitting device. The substrate comprises a flexible substrate and a conductive layer. The substrate is characterized in that the flexible substrate and the conductive layer are formed in the following two manners: (1) the flexible substrate is made of a transparent dielectric polymer material, the conductive layer is a silver nano-wire film, and the gap of the silver nano-wire film is filled with inorganic light-emitting nanoparticles; and (2) the flexible substrate is made of a transparent dielectric polymer material doped with inorganic light-emitting nanoparticles, the conductive layer is the silver nano-wire film, and the gap of the silver nano-wire film is filled with a transparent dielectric polymer material doped with the inorganic light-emitting nanoparticles. By the invention, the problems of large roughness of the silver nano-wire film and poor bonding force between the silver nano-wire film and the flexible substrate can be solved, the conductivity and the surface flatness of the silver nano-wire film can be improved and the bonding force between the silver nano-wire film and the flexible substrate can be enhanced.
Description
Technical field
The present invention relates to the organic optoelectronic technical field, be specifically related to a kind of flexible luminescent device substrate and preparation method thereof.
Background technology
Photoelectron technology is the very high industry of scientific and technological content that develops rapidly after microelectric technique.Along with the fast development of photoelectron technology, photoelectron products such as solar cell, optical image transducer, flat-panel screens, thin-film transistor are all full-fledged gradually, and they have improved people's life greatly.Simultaneously, opto-electronic information technology has also been created growing great market in the extensive use of social life every field.Developed country all the optoelectronic information industry as one of field of giving priority to, the competition of the field of opto-electronic information just launches at world wide.
Organic optoelectronic device mostly is that preparation is at rigid substrates (on glass or silicon chip), though they have good device performance, anti-vibration at present, shock proof ability a little less than, weight is heavier relatively, and it is very not convenient to carry, and is very restricted in the application of some occasion.People begin to attempt to be deposited on organic optoelectronic device on the flexible base, board rather than on the rigid substrates.
With flexible base, board replace the benefit of rigid substrates be product lighter, be difficult for broken, institute takes up space little and be more convenient for carrying.But, although these advantages are arranged, replace rigid substrates also to have many restrictions with flexible base, board, the preparation of flexible device still has many underlying issues to need to solve.For flexible substrate, because the profile pattern of flexible substrate is far away from rigid substrate, to handle equipment and the technology difficulty of wanting special bigger and flexible substrate is carried out surface smoothing, improved substrate production cost; The water of flexible substrate, oxygen permeability be much larger than rigid substrate, causes opto-electronic device to be subjected to the influence of the water oxygen that sees through from substrate, reduced the performance of device.
For electrode layer, conventional electrode layer material In
2O
3: SnO
2(ITO) there is following shortcoming in the electrode as flexible base, board: the indium among (1) ITO has severe toxicity, and is harmful in preparation and application; (2) In among the ITO
2O
3Expensive, cost is higher; (3) ito thin film is vulnerable to the reduction of hydrogen plasma, and effect reduces, and this phenomenon also can take place under low temperature, low plasma density; (4) phenomenon that conductivity descends can appear because of the bending of flexible substrate in the ito thin film on flexible substrate; (5) adopt thick ITO layer can reduce light transmittance, the light of 50-80% sponges at glass, ITO and organic layer, adopts thin ITO layer process difficulty bigger.In recent years, because the nano silver wire film has the electrode material that higher conductivity and visible light transmissivity have become potential replaced ITO, but there is the shortcoming of adhesion difference between surface roughness big and nano silver wire film and the flexible substrate in the nano silver wire film, has reduced the performance based on the opto-electronic device of nano silver wire membrane electrode.
Therefore, if can solve above-mentioned these problems, will make opto-electronic device obtain using more widely and development more fast.
Summary of the invention
Problem to be solved by this invention is: how a kind of flexible luminescent device substrate and preparation method thereof is provided, this substrate has solved the problem of adhesion difference between nano silver wire film roughness big and nano silver wire film and the flexible substrate, has improved adhesion between the evenness of nano silver wire film surface and nano silver wire film and the flexible substrate.
Technical problem proposed by the invention is to solve like this: a kind of flexible luminescent device substrate is provided, comprise flexible substrate and conductive layer, it is characterized in that, described flexible substrate and conductive layer are made of a kind of in the following dual mode: 1. described flexible substrate is transparent dielectricity polymeric material, described conductive layer is the nano silver wire film, is filled with the inorganic light-emitting nano particle in the space of described nano silver wire film; 2. described flexible substrate is the transparent dielectricity polymeric material of doping inorganic light-emitting nano particle, and described conductive layer is the nano silver wire film, is filled with the transparent dielectricity polymeric material of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that described inorganic light-emitting nanoparticle size is 1～100nm, 2. in the kind mode doping mass ratio of inorganic light-emitting nano particle be less than or equal to 40%.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that, described inorganic light-emitting nano particle is to be luminous host with sulfide, oxide, fluoride, phosphate, vanadate, niobates, aluminate or molybdate etc., with the light-emitting particles of rare earth lanthanide as activator and co-activator.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that described sulfide comprises zinc sulphide, lanthanum sulfide, calcium sulfide, cerium sulphide, praseodymium sulfide, neodymium sulfide, samaric sulfide and gadolinium sulfide; Described oxide comprises zinc oxide, yittrium oxide, titanium oxide, gadolinium oxide and luteium oxide; Described fluoride comprises yttrium fluoride, gadolinium fluoride, lanthanum fluoride and cerium fluoride; Described phosphate comprises lanthanum orthophosphate, Gadolinium monophosphate, strontium phosphate, yttrium phosphate and barium phosphate; Described vanadate comprises vanadic acid gadolinium, vanadic acid yttrium, vanadic acid lanthanum, cerium vanadate, vanadic acid calcium, lead vanadate and vanadic acid strontium; Described niobates comprises calcium niobate, niobic acid yttrium, niobic acid gadolinium and niobic acid lutetium; Described aluminate comprises yttrium aluminate, barium aluminate, aluminic acid gadolinium, calcium aluminate and strontium aluminate; Described molybdate comprises lanthanum molybdate, strontium molybdate and barium molybdate; Described rare earth lanthanide comprises europium, samarium, erbium, neodymium, terbium, dysprosium, samarium, cerium, ytterbium and praseodymium.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that described transparent dielectricity polymeric material comprises polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin polyacrylic acid, PAEK, Kynoar, polyester, PEN, polyacrylate, poly-paraphenylene terephthalamide's trimethyl hexamethylene diamine, polybutene and polyvinyl alcohol.
A kind of flexible luminescent device is characterized in that with the preparation method of substrate, may further comprise the steps:
1. the rigid substrates (as glass or silicon chip) of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
2. take the mode of spin coating or spraying or self assembly or inkjet printing or silk screen printing at the substrate preparation nano silver wire film of cleaning;
3. the transparent dielectricity polymer material layer of spin coating or spraying doping inorganic light-emitting nano particle on the nano silver wire film, or first spin coating or drip and to be coated with or to spray the solution that contains the inorganic light-emitting nano particle, spin coating or spray transparent dielectricity polymer material layer again, described transparent dielectricity polymeric material comprises polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyimides, the vinyl chloride-vinyl acetate resin polyacrylic acid, PAEK, Kynoar, polyester, PEN, polyacrylate, poly-paraphenylene terephthalamide's trimethyl hexamethylene diamine, polybutene and polyvinyl alcohol;
4. hot curing being carried out on the rigid substrates surface handles;
5. the transparent dielectricity polymer material layer after nano silver wire film and the curing or the transparent dielectricity polymer material layer of doping inorganic light-emitting nano particle are peeled off the rigid substrates surface, form the compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
Beneficial effect of the present invention: have the inorganic light-emitting nano particle in the conductive layer of the present invention, make conductive layer luminous under the exciting light irradiation, not only strengthened the luminous intensity based on the luminescent device of this substrate, and simplified based on the structure of the luminescent device of this substrate and required material, because the nano silver wire that conductive layer adopts can improve the luminous intensity of inorganic light-emitting nano particle, further increased the luminous intensity based on the luminescent device of this substrate simultaneously; Conductive layer of the present invention prepares at the little rigid substrates of roughness, be filled with the transparent dielectricity polymeric material of inorganic light-emitting nano particle or doping inorganic light-emitting nano particle in the conductive layer space, form the conductive layer of flexible base, board by the method peeled off, improved the evenness of conductive layer surface; Transparent dielectricity polymeric material in the flexible substrate of the present invention has the characteristics of high visible light transmissivity, has improved the visible light transmissivity of flexible base, board; The mode that adopts elder generation's preparation conductive layer to prepare flexible substrate again forms flexible base, board, has increased the adhesion between conductive layer and flexible substrate.
Description of drawings
Fig. 1 is the structural representation that the flexible luminescent device of embodiment of the invention 1-10 is used substrate;
Fig. 2 is the visible light transmissivity of the substrate in the embodiment of the invention 1.
Wherein, 1, flexible substrate, 2, conductive layer.
Embodiment
Be further described below in conjunction with accompanying drawing and the present invention of embodiment:
Technical scheme of the present invention provides a kind of flexible luminescent device substrate, and as shown in Figure 1, the structure of device comprises flexible substrate 1, conductive layer 2.
Below be specific embodiments of the invention:
Board structure as shown in Figure 1, flexible substrate 1 adopts polyethylene, and conductive layer 2 adopts the nano silver wire films, fills the inorganic light-emitting nano particle in the space of described nano silver wire film, and described inorganic light-emitting nanoparticle size is 1nm.
The preparation method is as follows:
1. the silicon substrate of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
2. nano silver wire is dispersed in the solvent, takes the spin coating mode at the silicon substrate preparation nano silver wire film of cleaning, rotating speed is 4000 revolutions per seconds during spin coating, duration 60 seconds, and thickness is about 80 nanometers;
3. contain the solution of inorganic light-emitting nano particle in the spraying of nano silver wire film, silicon substrate was placed 30 minutes in 80 ℃ environment, remove solvent remaining in the nano silver wire film, again spraying polyethylene on the nano silver wire film;
4. hot curing being carried out on the silicon substrate surface handles;
5. the polyethylene layer after nano silver wire film and the curing is peeled off the silicon substrate surface, form the compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
Board structure as shown in Figure 1, flexible substrate 1 adopts polymethyl methacrylate, and conductive layer 2 adopts the nano silver wire films, fills the inorganic light-emitting nano particle in the space of described nano silver wire film, and described inorganic light-emitting nanoparticle size is 5nm.
The preparation method is as follows:
1. the silicon substrate of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
2. nano silver wire is dispersed in the solvent, the mode of taking to spray prepares the nano silver wire film at the silicon substrate of cleaning;
3. contain the solution of inorganic light-emitting nano particle in the spraying of nano silver wire film, silicon substrate was placed 30 minutes in 80 ℃ environment, remove solvent remaining in the nano silver wire film, spray polymethyl methacrylate at the nano silver wire film again;
4. hot curing being carried out on the silicon substrate surface handles;
5. the polymethyl methacrylate layers after nano silver wire film and the curing is peeled off the silicon substrate surface, form the compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
Embodiment 3
Board structure as shown in Figure 1, flexible substrate 1 adopts Merlon, and conductive layer 2 adopts the nano silver wire films, fills the inorganic light-emitting nano particle in the space of described nano silver wire film, and described inorganic light-emitting nanoparticle size is 10nm.
The preparation method is as follows:
1. the silicon substrate of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
2. nano silver wire is dispersed in the solvent, takes the mode of silk screen printing at the silicon substrate preparation nano silver wire film of cleaning;
3. contain the solution of inorganic light-emitting nano particle in the spraying of nano silver wire film, silicon substrate was placed 30 minutes in 80 ℃ environment, remove solvent remaining in the nano silver wire film, spray Merlon at the nano silver wire film again;
4. hot curing being carried out on the silicon substrate surface handles;
5. the layer of polycarbonate after nano silver wire film and the curing is peeled off the silicon substrate surface, form the compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
Embodiment 4
Board structure as shown in Figure 1, flexible substrate 1 adopts polyimides, and conductive layer 2 adopts the nano silver wire films, fills the inorganic light-emitting nano particle in the space of described nano silver wire film, and described inorganic light-emitting nanoparticle size is 20nm.
The preparation method is as follows:
1. the silicon substrate of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
2. nano silver wire is dispersed in the solvent, takes the mode of inkjet printing at the silicon substrate preparation nano silver wire film of cleaning;
3. contain the solution of inorganic light-emitting nano particle in the spraying of nano silver wire film, silicon substrate was placed 30 minutes in 80 ℃ environment, remove solvent remaining in the nano silver wire film, spray polyimides at the nano silver wire film again;
4. hot curing being carried out on the silicon substrate surface handles;
5. the polyimide layer after nano silver wire film and the curing is peeled off the silicon substrate surface, form the compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
Embodiment 5
Board structure as shown in Figure 1, flexible substrate 1 adopts the PAEK of doping inorganic light-emitting nano particle, conductive layer 2 nano silver wire films, fill the PAEK of doping inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 30nm, and the doping mass ratio of described inorganic light-emitting nano particle is 5%.
The preparation method is similar to embodiment 1.
Embodiment 6
Board structure as shown in Figure 1, flexible substrate 1 adopts the Kynoar of doping inorganic light-emitting nano particle, conductive layer 2 adopts the nano silver wire film, fill the Kynoar of doping inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 50nm, and the doping mass ratio of described inorganic light-emitting nano particle is 10%.
The preparation method is similar to embodiment 1.
Embodiment 7
Board structure as shown in Figure 1, flexible substrate 1 adopts the polyester of doping inorganic light-emitting nano particle, conductive layer 2 adopts the nano silver wire film, fill the polyester of doping inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 60nm, and the doping mass ratio of described inorganic light-emitting nano particle is 15%.
The preparation method is similar to embodiment 1.
Embodiment 8
Board structure as shown in Figure 1, flexible substrate 1 adopts the PEN of doping inorganic light-emitting nano particle, conductive layer 2 adopts the nano silver wire film, fill the PEN of doping inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 70nm, and the doping mass ratio of described inorganic light-emitting nano particle is 20%.
The preparation method is similar to embodiment 1.
Embodiment 9
Board structure as shown in Figure 1, flexible substrate 1 adopts the polyacrylate of doping inorganic light-emitting nano particle, conductive layer 2 adopts the nano silver wire film, fill the polyacrylate of doping inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 80nm, and the doping mass ratio of described inorganic light-emitting nano particle is 30%.
The preparation method is similar to embodiment 1.
Embodiment 10
Board structure as shown in Figure 1, flexible substrate 1 adopts the polybutene of doping inorganic light-emitting nano particle, conductive layer 2 adopts the nano silver wire film, fill the polybutene of doping inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 100nm, and the doping mass ratio of described inorganic light-emitting nano particle is 40%.
The preparation method is similar to embodiment 1.
Claims (1)
1. a flexible luminescent device is with the preparation method of substrate, comprise flexible substrate and conductive layer, it is characterized in that, described flexible substrate and conductive layer are made of a kind of in the following dual mode: 1. described flexible substrate is transparent dielectricity polymeric material, described conductive layer is the nano silver wire film, is filled with the inorganic light-emitting nano particle in the space of described nano silver wire film; 2. described flexible substrate is the transparent dielectricity polymeric material of doping inorganic light-emitting nano particle, described conductive layer is the nano silver wire film, be filled with the transparent dielectricity polymeric material of the inorganic light-emitting nano particle that mixed in the space of described nano silver wire film, it is characterized in that, may further comprise the steps:
1. the rigid substrates of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
2. take the mode of spin coating or spraying or self assembly or inkjet printing or silk screen printing at the substrate preparation nano silver wire film of cleaning;
3. the transparent dielectricity polymer material layer of spin coating or spraying doping inorganic light-emitting nano particle on the nano silver wire film, or first spin coating or drip and to be coated with or to spray the solution that contains the inorganic light-emitting nano particle, spin coating or spray transparent dielectricity polymer material layer again, described transparent dielectricity polymeric material comprises polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyimides, the vinyl chloride-vinyl acetate resin polyacrylic acid, PAEK, Kynoar, PEN, polyacrylate, poly-paraphenylene terephthalamide's trimethyl hexamethylene diamine, polybutene or polyvinyl alcohol;
4. hot curing being carried out on the rigid substrates surface handles;
5. the transparent dielectricity polymer material layer after nano silver wire film and the curing or the transparent dielectricity polymer material layer of doping inorganic light-emitting nano particle are peeled off the rigid substrates surface, form the compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
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| CN104134484B (en) * | 2014-07-31 | 2017-09-19 | 中国电子科技集团公司第五十五研究所 | Flexible transparent conductive film and preparation method based on nano-silver thread |
| JP6727483B2 (en) | 2014-10-08 | 2020-07-22 | コンシューマー ライティング （ユー．エス．），エルエルシー | Materials and color components for lighting equipment color filters |
| CN107208868A (en) | 2015-01-06 | 2017-09-26 | 通用电气照明解决方案有限责任公司 | Material and light guide for the colour filter in lighting unit |
| CN107635911A (en) * | 2015-01-30 | 2018-01-26 | 南洋理工大学 | Method, nanometer line network and the transparent conductive electrode of interconnected nanowires |
| CN104766932A (en) * | 2015-04-22 | 2015-07-08 | 电子科技大学 | Biodegradable baseplate used for soft light electron device and manufacturing method thereof |
| CN106299160A (en) * | 2016-11-15 | 2017-01-04 | 吉林大学 | A kind of using plasma technical finesse nano silver wire the method preparing organic optoelectronic device flexible electrode by substrate transfer |
| CN109802035B (en) * | 2019-01-24 | 2023-04-28 | 北京印刷学院 | Memristor-based nerve synapse bionic device and preparation method thereof |
| CN112992424B (en) * | 2021-02-19 | 2021-11-12 | 中国科学院长春应用化学研究所 | Method for directly preparing silver nanowire/europium-doped calcium molybdate composite luminescent transparent conductive film |
| CN113054127B (en) * | 2021-03-16 | 2024-01-23 | 河北工业大学 | Low-voltage driven flexible light-emitting device and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101589473A (en) * | 2006-10-12 | 2009-11-25 | 凯博瑞奥斯技术公司 | Nanowire-based transparent conductors and applications thereof |
| CN101689568A (en) * | 2007-04-20 | 2010-03-31 | 凯博瑞奥斯技术公司 | Composite transparent conductors and methods of forming the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101589473A (en) * | 2006-10-12 | 2009-11-25 | 凯博瑞奥斯技术公司 | Nanowire-based transparent conductors and applications thereof |
| CN101689568A (en) * | 2007-04-20 | 2010-03-31 | 凯博瑞奥斯技术公司 | Composite transparent conductors and methods of forming the same |
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