CN101369630A - A kind of organic optoelectronic device with protective layer and preparation method thereof - Google Patents
A kind of organic optoelectronic device with protective layer and preparation method thereof Download PDFInfo
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- CN101369630A CN101369630A CN200810046173.1A CN200810046173A CN101369630A CN 101369630 A CN101369630 A CN 101369630A CN 200810046173 A CN200810046173 A CN 200810046173A CN 101369630 A CN101369630 A CN 101369630A
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Abstract
本发明公开了一种具有保护层的有机光电子器件，其特征在于，包括基板和有机光电子器件，还包括保护层，该保护层由n个组合层构成，n为整数且n＝1～100，所述组合层由三种方式构成：有机材料层/亲水材料层/有机材料层或者有机材料层/亲水材料层或亲水材料层/有机材料层；保护层中组合层的位置关系包括：设置在有机光电子器件的上层、下层、四周的一处或者几处；设置在基板和有机光电子器件之间或者设置在基板的一侧。该器件能克服现有技术中所存在的不足，结构新颖，提高了基板表面的平整度，保护层的粘结性解决了部件之间的联接度问题，能有效阻隔水氧进入器件内部。
The invention discloses an organic optoelectronic device with a protective layer, which is characterized in that it includes a substrate and an organic optoelectronic device, and also includes a protective layer, the protective layer is composed of n combined layers, n is an integer and n=1-100, The combined layer is composed of three ways: organic material layer/hydrophilic material layer/organic material layer or organic material layer/hydrophilic material layer or hydrophilic material layer/organic material layer; the positional relationship of the combined layer in the protective layer includes : arranged at one or several places on the upper layer, lower layer, or around the organic optoelectronic device; arranged between the substrate and the organic optoelectronic device or on one side of the substrate. The device can overcome the deficiencies in the prior art, has a novel structure, improves the flatness of the substrate surface, and the adhesiveness of the protective layer solves the problem of connection degree between components, and can effectively prevent water and oxygen from entering the device.
Description
Technical field
The present invention relates to the organic optoelectronic device technical field, be specifically related to a kind of organic optoelectronic device with protective layer.
Background technology
Now, along with the arriving of Development of Multimedia Technology and information-intensive society, more and more higher to the flat-panel monitor performance demands.Recently three kinds of Display Techniques newly occurred: plasma display, Field Emission Display and display of organic electroluminescence (OLED) have all remedied the deficiency of cathode ray tube and LCD to a certain extent.Wherein, a series of advantages such as display of organic electroluminescence has active illuminating, low-voltage DC driven, solidifies entirely, the visual angle is wide and color is abundant, compare with liquid crystal display device, organic electroluminescence device has broad application prospects, and is being seen one of following flat panel display that has competitiveness.
Realize that organic optoelectronic device comprises that the difficulty that volume production faced of OLED mainly contains the following aspects: stability and the life problems of (1) OLED; (2) technological process of production and quality management problem; (3) production cost problem.Wherein, the life-span is one of greatest problem that faces at present, has solved life problems, also just means on the industrialization road of OLED to have advanced a very important step.Studies show that in a large number, steam and oxygen are the main causes that causes the OLED component failure, particularly be the bendable musical form flexible organic electroluminescent device (FOLED) of substrate with the flexible polymer plastics, steam and oxygen are easy to be penetrated in the device and organic material or negative electrode generation chemical reaction by the pin hole on the polymer.Therefore, the life-span of OLED is depended on the quality of device package effect to a great extent.In fact, as long as it is 10% oxidized that the negative electrode of device has, the not light-emitting zone that forms is just very obviously (if the oxidation of negative electrode occurs in metal and at the interface organic, even ruined negative electrode only has 0.5nm also may cause the inefficacy of device), it has been generally acknowledged that, ignore the destruction to organic layer of water, oxygen, the encapsulated layer water vapor permeable rate that OLEDs requires should be less than 10
-5G/m
2Day.
In addition, being extensive use of of organic material effectively improves the encapsulation performance of film, and reduces the production cost of encapsulation, can be made into flexible device; Device is ultra-thin, and volume is little, and is in light weight, and the preparation method is rationally simple, easy operating.This technology is significant to the manufacture craft of organic optoelectronic device.
Summary of the invention
Technical problem to be solved by this invention is how a kind of organic optoelectronic device with protective layer is provided; and preparation method thereof; this device can overcome existing deficiency in the prior art; novel structure; improved the evenness of substrate surface; the caking property of protective layer has solved the connection degree problem between the parts, can effectively intercept water oxygen and enter device inside.
Technical problem proposed by the invention is to solve like this: construct a kind of organic optoelectronic device with protective layer, it is characterized in that, comprise substrate and organic optoelectronic device, also comprise protective layer, this protective layer is made of n combination layer, n is integer and n=1～100, and described combination layer is made of three kinds of modes: organic material layer/water wetted material layer/organic material layer or organic material layer/water wetted material layer (and appearance one deck is an organic material layer) or water wetted material layer/organic material layer; The position of combination layer relation comprises in the protective layer: the upper strata, lower floor, a place all around or a few place that are arranged on organic optoelectronic device; Be arranged between substrate and the organic optoelectronic device or be arranged on a side of substrate.
According to the organic optoelectronic device with protective layer provided by the present invention; it is characterized in that; described water wetted material layer material is an alkali metal; alkaline-earth metal and metal oxide; zeolite; metal alcoholate with long-chain hydrocarbon; sulfate; halide; perchlorate; starch-acrylonitrile grafting polymerization hydrolysate; the Starch and Acrylic Acid copolymer; starch-acrylamide graft polymer; cellulose graft copolymer; the cellulose derivative cross-linking agent; polysaccharide (agarose; chitin); protein-based; the Sodium Polyacrylate cross-linking agent; acrylic acid-ethenol copolymer; acrylonitrile polymerization is saponified; polyvinyl alcohol crosslinked polymer; vinyl alcohol-hydrophilic monomer graft copolymer; poly(ethylene oxide) system; in butylene-copolymer-maleic anhydride one or several; alkali metal such as sodium; calcium; magnesium; barium etc., metal oxide such as calcium oxide barium monoxide or the like.
According to the organic optoelectronic device with protective layer provided by the present invention, it is characterized in that organic material layer is a ultra-violet curing glue, comprise free radical type ultraviolet photo-curing cementing agent, cation type ultraviolet photo-curing cementing agent and their mixed system.
According to the organic optoelectronic device with protective layer provided by the present invention, it is characterized in that described free radical type ultraviolet photo-curing cementing agent comprises base resin, monomer, light trigger and sensitising agent and auxiliary agent.
According to the organic optoelectronic device with protective layer provided by the present invention, it is characterized in that base resin comprises unsaturated polyester resin, acrylic resin and polythiol-polyenoid system.
According to the organic optoelectronic device with protective layer provided by the present invention, it is characterized in that described unsaturated polyester resin is to mix the linear polyesters that reacts and make with fractional saturation binary acid (or acid anhydrides) and dihydroxylic alcohols by undersaturated binary acid or acid anhydrides under action of evocating; Described acrylic resin comprises polyester-acrylate, epoxy-acrylate, carbamate-acrylate and polyethers-acrylate; Described polythiol-polyenoid system comprises following four kinds of materials:
According to the organic optoelectronic device with protective layer provided by the present invention, it is characterized in that monomer comprises styrene and derivative, simple function group or polyfunctional group (methyl) acrylate thereof; Light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and acetophenone derivative, sensitising agent comprises benzophenone, thia anthraquinone and Michler's keton, auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent, and light trigger comprises diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts and triaryl selenium salt.
According to the organic optoelectronic device with protective layer provided by the present invention; it is characterized in that; the organic material layer material of water wetted material layer both sides adopts same material or different materials, and the water wetted material layer material that is in the various combination layer adopts same material or different materials.
A kind of preparation method with organic optoelectronic device of protective layer is characterized in that, may further comprise the steps:
1, in upper strata, the lower floor of organic optoelectronic device or prepare organic material layer all around;
2, preparation one deck water wetted material layer on above-mentioned organic material layer;
3, deposition one deck organic material layer on above-mentioned water wetted material layer;
4, repeat above-mentioned steps 1,2,3 or repeating step 1,2, the combination layer in preparation (n-1) cycle replaces the thin layer of overlapping composition again.
According to the preparation method with organic optoelectronic device of protective layer provided by the present invention; it is characterized in that water wetted material layer and organic material layer are by vacuum evaporation; ion cluster bundle deposition; ion plating; dc sputtering deposition; the RF sputter coating; ion beam sputtering deposition; ion beam assisted depositing; (wherein the plasma generator in the plasma reinforced chemical vapour deposition is a radio-frequency drive to plasma reinforced chemical vapour deposition; direct-current discharge; a kind of in microwave plasma and the electron cyclotron resonace); high density inductance coupling high formula plasma source chemical vapor deposition (HD-ICP-CVD); catalyst chemical vapour deposition (CVD) (Cat-CVD); magnetron sputtering; electroplate; spin coating; dip-coating; inkjet printing; one or several modes in roller coat and the LB film and forming.
Organic optoelectronic device with protective layer provided by the present invention, novel structure has improved the evenness of substrate polymers film surface, has improved its surface property; Protective layer caking property has solved the connection degree problem between organic-organic film, has improved the adhesive ability between polymer material layer and the absorbent material layer; Protective layer is carried out suitable cured, make it form compact texture, can more effectively intercept water oxygen and enter device inside, improve the performance and the life-span of device; Adopt the preparation method who provides among the present invention can effectively improve the encapsulation performance of film, and reduce the production cost of encapsulation, can be made into flexible device; Device is ultra-thin, and volume is little, and is in light weight, and the preparation method is rationally simple, easy operating.This technology is significant to the manufacture craft of organic optoelectronic device.
Description of drawings
Fig. 1 is the structural representation of a kind of embodiment of the organic optoelectronic device with protective layer provided by the present invention.
Fig. 2 is the structural representation of a kind of embodiment of the organic optoelectronic device with protective layer provided by the present invention.
Fig. 3 is the structural representation of a kind of embodiment of the organic optoelectronic device with protective layer provided by the present invention.
Fig. 4 is the structural representation with organic optoelectronic device of the protective layer of being made up of three layers of combination layer provided by the present invention.
1, substrate, 2, organic optoelectronic device, 31, organic material layer, 32, organic material layer, 33, organic material layer, 41, the water wetted material layer, 42, water wetted material layer, 43, water wetted material layer, 51, organic material layer, 52, organic material layer, 53, organic material layer, 61, combination layer, 62, combination layer, 63, combination layer.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and embodiment.
Technical scheme of the present invention provides a kind of organic optoelectronic device with protective layer; as shown in Figure 1, 2, 3; the structure of device comprises substrate 1; organic optoelectronic device 2, organic material layer 31,32 and 33, water wetted material layer 41,42 and 43; organic material layer 51,52 and 53; by organic material layer 31,32 and 33, the combination layer 61,62 and 63 that water wetted material layer 41,42 and 43, organic material layer 51,52 and 53 are formed respectively.
Organic optoelectronic device 2 is organic electroluminescence device, OTFT and organic solar batteries among the present invention.
Water wetted material layer 41 among the present invention, 42 and 43 is alkali metal, alkaline-earth metal and metal oxide, zeolite, metal alcoholate with long-chain hydrocarbon, sulfate, halide, perchlorate, starch-acrylonitrile grafting polymerization hydrolysate, the Starch and Acrylic Acid copolymer, starch-acrylamide graft polymer, cellulose graft copolymer, the cellulose derivative cross-linking agent, polysaccharide (agarose, chitin), protein-based, the Sodium Polyacrylate cross-linking agent, acrylic acid-ethenol copolymer, acrylonitrile polymerization is saponified, polyvinyl alcohol crosslinked polymer, vinyl alcohol-other hydrophilic monomer graft copolymer, poly(ethylene oxide) system, one or several of butylene-copolymer-maleic anhydride; Described water wetted material layer is one or several in sodium, calcium, magnesium, barium, calcium oxide, magnesium oxide, the barium monoxide.
Polynary allylic compound commonly used has CH
2=CHCH
2O (CH
2CH
2CH
2O)
nCH
2CH=CH
2, cyanacrylate
HS (CH
2CH
2O)
2CH
2CH
2One or more of SH, monomer comprises styrene and derivative, simple function group or polyfunctional group (methyl) acrylate thereof, as methyl methacrylate, ethyl acrylate, acrylic acid propylene glycol ester, n-butyl acrylate, light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and acetophenone derivative, sensitising agent has benzophenone, thia anthraquinone and Michler's keton, auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent, as silicone couplet CH
2=CHSi (OCH
2CH
2OCH
3)
3Cation type ultraviolet photo-curing cementing agent comprises monomer, as various epoxy resin or modified epoxy or fluorine-containing and not fluorine-containing hybrid resin or aliphat and bis-phenol D-type blending epoxy, various active epoxy diluent resins and various cyclic ethers, cyclic lactone, vinyl ether monomers are as the diluent of light-cured resin, and cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts, triaryl selenium salt; Their mixed system comprises the mixing of free radical type and cationic ultra-violet curing glue, as benzhydryl iodine hexafluorophosphate (DPI.PF
6) make light trigger, cause bisphenol A epoxide resin E
51Hybrid resin with acrylic ester prepolymer AE.
Adopt the OLED device architecture of the present invention's preparation to be exemplified below:
Substrate/organic electroluminescence device/protective layer
Protective layer/substrate/organic electroluminescence device
Substrate/protective layer/organic electroluminescence device
Protective layer/substrate/organic electroluminescence device/protective layer
Protective layer/substrate/protective layer/organic electroluminescence device
Substrate/protective layer/organic electroluminescence device/protective layer
Protective layer/substrate/protective layer/organic electroluminescence device/protective layer
Substrate/OTFT/protective layer
Protective layer/substrate/OTFT
Substrate/protective layer/OTFT
Protective layer/substrate/OTFT/protective layer
Protective layer/substrate/protective layer/OTFT
Substrate/protective layer/OTFT/protective layer
Protective layer/substrate/protective layer/OTFT/protective layer
Substrate/organic solar batteries/protective layer
Protective layer/substrate/organic solar batteries
Substrate/protective layer/organic solar batteries
Protective layer/substrate/organic solar batteries/protective layer
Protective layer/substrate/protective layer/organic solar batteries
Substrate/protective layer/organic solar batteries/protective layer
Protective layer/substrate/protective layer/organic solar batteries/be specific embodiments of the invention below the protective layer:
As shown in Figure 1, the substrate 1 in the structure of device, organic optoelectronic device 2 is an organic electroluminescence device, organic material layer 31, water wetted material layer 41, organic material layer 51, combination layer 61.
The substrate 1 of device is PET, and organic optoelectronic device 2 is an organic electroluminescence device, and organic material layer 31 is a UV glue, and water wetted material layer 41 is a calcium oxide, and organic material layer 51 is a UV glue.
The preparation method is as follows:
1. prepare organic material layer UV glue 300nm on the upper strata of organic electroluminescence device;
2. evaporation or spin coating one deck water wetted material layer calcium oxide 500nm on above-mentioned organic material layer UV glue;
3. on above-mentioned water wetted material layer calcium oxide, deposit one deck organic material layer UV glue 300nm;
4. repeat above-mentioned steps 1.～3., the combination layer in preparation (n-1) cycle replaces the thin layer of overlapping composition again.
As shown in Figure 2, the substrate 1 in the structure of device, organic optoelectronic device 2 is an organic electroluminescence device, organic material layer 32, water wetted material layer 42, organic material layer 52, combination layer 62.
The substrate 1 of device is PET, and organic optoelectronic device 2 is an organic electroluminescence device, and organic material layer 32 is a UV glue, and water wetted material layer 42 is a calcium oxide, and organic material layer 52 is a UV glue.
The preparation of devices flow process is as follows:
1. prepare organic material layer UV glue 300nm on the upper strata of substrate;
2. on above-mentioned organic material layer UV glue, prepare one deck water wetted material layer calcium oxide 500nm;
3. on above-mentioned water wetted material layer calcium oxide, deposit one deck organic material layer UV glue 300nm;
4. repeat above-mentioned steps 1.～3., the combination layer in preparation (n-1) cycle replaces the thin layer of overlapping composition again;
5. on above-mentioned thin layer, prepare organic electroluminescence device.
Embodiment 3
As shown in Figure 3, the substrate 1 in the structure of device, organic optoelectronic device 2 is an OTFT, organic material layer 33, water wetted material layer 43, organic material layer 53, combination layer 63.
The substrate 1 of device is PET, and organic optoelectronic device 2 is an OTFT, and organic material layer 33 is a UV glue, and water wetted material layer 43 is a calcium oxide, and organic material layer 53 is a UV glue.
The preparation of devices flow process is similar to embodiment 2.
Embodiment 4
As shown in Figure 4, the substrate 1 in the structure of device, organic optoelectronic device 2 organic solar batteries; organic material layer 31, water wetted material layer 41, organic material layer 51; combination layer 61, organic material layer 32, water wetted material layer 42; organic material layer 52, combination layer 62, organic material layer 33; water wetted material layer 43; organic material layer 53, combination layer 63, combination layer 61,62,63 is formed protective layer.
The substrate 1 of device is PET, organic solar batteries, organic material layer 31 is a UV glue, and water wetted material layer 41 is a calcium oxide, and organic material layer 51 is a UV glue, organic material layer 32 is a UV glue, water wetted material layer 42 is a calcium oxide, and organic material layer 52 is a UV glue, and organic material layer 33 is a UV glue, water wetted material layer 43 is a calcium oxide, and organic material layer 53 is a UV glue.
The preparation of devices flow process is similar with 2 to embodiment 1.
Claims (10)
1. organic optoelectronic device with protective layer, it is characterized in that, comprise substrate and organic optoelectronic device, also comprise protective layer, this protective layer is made of n combination layer, n is integer and n=1～100, and described combination layer is made of three kinds of modes: organic material layer/water wetted material layer/organic material layer or organic material layer/water wetted material layer or water wetted material layer/organic material layer; The position of combination layer relation comprises in the protective layer: the upper strata, lower floor, a place all around or a few place that are arranged on organic optoelectronic device; Be arranged between substrate and the organic optoelectronic device or be arranged on a side of substrate.
2. the organic optoelectronic device with protective layer according to claim 1; it is characterized in that described water wetted material layer material is an alkali metal; alkaline-earth metal and metal oxide; zeolite; metal alcoholate with long-chain hydrocarbon; sulfate; halide; perchlorate; starch-acrylonitrile grafting polymerization hydrolysate; the Starch and Acrylic Acid copolymer; starch-acrylamide graft polymer; cellulose graft copolymer; the cellulose derivative cross-linking agent; polysaccharide; protein-based; the Sodium Polyacrylate cross-linking agent; acrylic acid-ethenol copolymer; acrylonitrile polymerization is saponified; polyvinyl alcohol crosslinked polymer; vinyl alcohol-hydrophilic monomer graft copolymer; poly(ethylene oxide) system; in butylene-copolymer-maleic anhydride one or several.
3. the organic optoelectronic device with protective layer according to claim 1 is characterized in that organic material layer is a ultra-violet curing glue, comprises free radical type ultraviolet photo-curing cementing agent, cation type ultraviolet photo-curing cementing agent and their mixed system.
4. the organic optoelectronic device with protective layer according to claim 3 is characterized in that, described free radical type ultraviolet photo-curing cementing agent comprises base resin, monomer, light trigger and sensitising agent and auxiliary agent.
5. the organic optoelectronic device with protective layer according to claim 4 is characterized in that, base resin comprises unsaturated polyester resin, acrylic resin and polythiol-polyenoid system.
6. the organic optoelectronic device with protective layer according to claim 5, it is characterized in that described unsaturated polyester resin is to mix the linear polyesters that reacts and make with fractional saturation binary acid and dihydroxylic alcohols by undersaturated binary acid or acid anhydrides under action of evocating; Described acrylic resin comprises polyester-acrylate, epoxy-acrylate, carbamate-acrylate and polyethers-acrylate; Described polythiol-polyenoid system comprises following four kinds of materials:
7. the organic optoelectronic device with protective layer according to claim 4 is characterized in that, monomer comprises styrene and derivative, simple function group or multi-functional acrylate; Light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and acetophenone derivative, sensitising agent comprises benzophenone, thia anthraquinone and Michler's keton, auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent, and light trigger comprises diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts and triaryl selenium salt.
8. the organic optoelectronic device with protective layer according to claim 1; it is characterized in that; the organic material layer material of water wetted material layer both sides adopts same material or different materials, and the water wetted material layer material that is in the various combination layer adopts same material or different materials.
9. the preparation method with organic optoelectronic device of protective layer is characterized in that, may further comprise the steps:
1. in upper strata, the lower floor of organic optoelectronic device or prepare organic material layer all around;
2. on above-mentioned organic material layer, prepare one deck water wetted material layer;
3. on above-mentioned water wetted material layer, deposit one deck organic material layer;
4. repeat above-mentioned steps 1., 2., 3. or repeating step 1., 2., the combination layer in preparation (n-1) cycle replaces the thin layer of overlapping composition again.
10. the preparation method with organic optoelectronic device of protective layer according to claim 9; it is characterized in that water wetted material layer and organic material layer are to form by one or several modes in vacuum evaporation, ion cluster bundle deposition, ion plating, dc sputtering deposition, RF sputter coating, ion beam sputtering deposition, ion beam assisted depositing, plasma reinforced chemical vapour deposition, high density inductance coupling high formula plasma source chemical vapor deposition, catalyst chemical vapour deposition (CVD), magnetron sputtering, plating, spin coating, dip-coating, inkjet printing, roller coat and the LB film.
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| CN103700782A (en) * | 2013-12-26 | 2014-04-02 | 合肥京东方光电科技有限公司 | OLED (organic light emitting diode) display panel and preparing method thereof |
| CN105051929A (en) * | 2012-11-22 | 2015-11-11 | 密歇根大学董事会 | Hybrid planar-mixed heterojunction for organic photovoltaics |
| CN105389049A (en) * | 2015-11-11 | 2016-03-09 | 京东方科技集团股份有限公司 | Touch OLED display device and method for manufacturing same |
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| CN105051929A (en) * | 2012-11-22 | 2015-11-11 | 密歇根大学董事会 | Hybrid planar-mixed heterojunction for organic photovoltaics |
| US11121336B2 (en) | 2012-11-22 | 2021-09-14 | The Regents Of The University Of Michigan | Hybrid planar-mixed heterojunction for organic photovoltaics |
| TWI568003B (en) * | 2012-12-19 | 2017-01-21 | 茂迪股份有限公司 | Solar battery, manufacturing method thereof and solar battery module |
| US10003043B2 (en) | 2013-12-26 | 2018-06-19 | Boe Technology Group Co., Ltd. | OLED display panel and production process thereof |
| CN103700782B (en) * | 2013-12-26 | 2015-12-09 | 合肥京东方光电科技有限公司 | A kind of OLED display panel and preparation method thereof |
| CN103700782A (en) * | 2013-12-26 | 2014-04-02 | 合肥京东方光电科技有限公司 | OLED (organic light emitting diode) display panel and preparing method thereof |
| CN105389049A (en) * | 2015-11-11 | 2016-03-09 | 京东方科技集团股份有限公司 | Touch OLED display device and method for manufacturing same |
| CN106654039A (en) * | 2016-09-27 | 2017-05-10 | 上海天马微电子有限公司 | Display panel, display device and manufacturing method of display panel |
| CN106935720A (en) * | 2017-03-13 | 2017-07-07 | 京东方科技集团股份有限公司 | Display base plate, display panel, display device and the method for manufacturing it |
| CN108183178A (en) * | 2017-12-28 | 2018-06-19 | 深圳市华星光电技术有限公司 | OLED display panel and preparation method thereof |
| CN111092159A (en) * | 2019-12-13 | 2020-05-01 | 固安翌光科技有限公司 | Organic semiconductor device and connection structure thereof |
| CN111092159B (en) * | 2019-12-13 | 2023-08-11 | 固安翌光科技有限公司 | Organic semiconductor device and connection structure thereof |
| CN112359270A (en) * | 2020-11-03 | 2021-02-12 | 广东新兴铸管有限公司 | Internal-spraying PE coating ductile iron pipe and preparation method thereof |
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