CN104300082A - Organic photoelectron integration device with electroluminescence and ultraviolet detection performance and preparation method thereof - Google Patents
Organic photoelectron integration device with electroluminescence and ultraviolet detection performance and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
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Abstract
The invention discloses an organic photoelectron integration device with the electroluminescence and ultraviolet detection performance and a preparation method of the organic photoelectron integration device. The organic photoelectron integration device is composed of a transparent substrate, an anode layer, a hole transport layer, an organic active layer, an electron transfer layer and a cathode layer. Under the drive of the applied forward voltage, the organic photoelectron integration device can achieve the luminous function, and under the drive of the applied backward voltage, the organic photoelectron integration device can achieve the ultraviolet detection function. The organic photoelectron integration device has the dual functions of electroluminescence and ultraviolet detection, and has the advantages of facilitating integration and being ultrathin, the preparation technology is simple, the manufacturing process is fast, and the cost is low.
Description
Technical field
The present invention relates to organic optoelectronic field, be specifically related to a kind of to there is electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance and preparation method thereof.
Background technology
Organic optoelectronic technology is the science that the scientific and technological content that develops rapidly after microelectric technique is very high.Along with the fast development of organic optoelectronic technology, the organic optoelectronic products such as organic electroluminescence device, organic solar batteries, organic UV detector are full-fledged all gradually.Wherein, energy-efficient organic electroluminescence device, with advantages such as its self-luminous, low-power consumption, high-low temperature resistant and flexibilities, attracts tremendous attention at information displaying and efficient illumination field; On the other hand, organic UV detector adopts organic/polymeric material and easy film-forming process to achieve detectivity more than 10
15the breakthrough of Jones, follows the tracks of in such as scientific observation and research, bioengineering, health care, environmental monitoring, military affairs, aviation and space flight and plays vital effect with the field such as control.
But traditional organic optoelectronic device has some shortcomings: the function singleness of 1, traditional organic optoelectronic device, be unfavorable for forming full stress-strain flexible integration circuit, such as traditional organic electroluminescence device does not have ultraviolet detection function; The integrated level of 2, traditional organic optoelectronic device is low, and thickness of detector is comparatively large, if large-scale application is by producing a large amount of electronic wastes, is unfavorable for alleviating day by day serious energy problem and environmental problem; 3, traditional multi-functional organic optoelectronic device complicated process of preparation, equipment requirement is high, and processing procedure is loaded down with trivial details, consuming time, and cost is high.It is significant to the range of application and environmental protection of widening organic optoelectronic technology that research has electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance.
Summary of the invention
For prior art, the technical problem to be solved in the present invention how to provide a kind of preparation method with electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, object overcomes traditional organic optoelectronic device function singleness and the low shortcoming of integrated level, prepare and can realize organic electroluminescence device electroluminescence function, the high-performance ultrathin organic optoelectronic integration device of organic UV detector ultraviolet detection function can be realized again.
Technical scheme of the present invention is: a kind of have electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, it comprises: transparent substrates, anode layer, hole transmission layer, organic active layer, electron transfer layer and cathode layer, and described organic active layer material used has following structural framework:
Wherein, R in structural framework
1group is selected from :-CH
3,-CH
2cH
3,-CH
2cH
2cH
3or-C (CH
3)
3;
R in structural framework
2group is selected from:
As preferably, the material used of transparent substrates described in the present invention be in glass, transparent polymer flexible material or biodegradable flexible material any one or multiple; Wherein, described transparent polymer flexible material be selected from polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid any one or multiple; Described biodegradable flexible material be selected from string, fibroin albumen, gelatin, PLA, glucose, viral fiber element, PLA, Poly(D,L-lactide-co-glycolide, polyvinyl alcohol, polyvinylpyrrolidone, pla-pcl, PHA, polysaccharide (such as shellac, shitosan and hyaluronic acid etc.), polyalcohols acid and copolymer thereof, collagen gel, in fibrin gel any one or multiple.
As preferably, the material used of anode layer described in the present invention be in tin indium oxide (ITO), conductive polymer poly 3,4-ethylene dioxythiophene/poly styrene sulfonate (PEDOT:PSS), Graphene (Graphene), carbon nano-tube (Carbon Nanotube), metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire any one or multiple, wherein, described metal simple-substance nano wire be in Fe nanowire, copper nano-wire, nano silver wire, nanowires of gold, aluminium nano wire, nickel nano wire, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires any one or multiple, described metal alloy nanowires is copper-iron alloy nano wire, silver ferroalloy nano wire, bule gold nano wire, alfer nano wire, dilval nano wire, ferro-cobalt nano wire, manganeisen nano wire, cadmium ferroalloy nano wire, indium ferroalloy nano wire, tin ferroalloy nano wire, ferro-tungsten nano wire, pt-fe alloy nano wire, yellow gold nano wire, gold copper nano wire, aluminium copper nano wire, monel nano wire, cobalt-copper alloy nano wire, manganin nano wire, cadmium copper alloy nano wire, yellow gold nano wire, gun-metal nano wire, tungsten-copper alloy nano wire, Mock gold nano wire, electrum nano wire, aluminium silver alloy nanowires, bazar metal nano wire, cobalt silver alloy nanowires, manganese silver alloy nanowires, cadmium silver nano wire, indium silver alloy nanowires, sn-ag alloy nano wire, tungsten silver alloy nanowires, platinum-silver alloys nano wire, aluminium gold alloy nano-wire, nickel billon nano wire, cobalt billon nano wire, manganese billon nano wire, cadmium billon nano wire, indium billon nano wire, Sillim's alloy nano-wire, tungsten billon nano wire, cobalt-nickel alloy nano wire, manganese-nickel nano wire, cadmium-nickel alloy nano wire, indium nickel alloy nano wire, tin-nickel alloy nano wire, tungsten nickel nano wire, platinum-nickel alloy nano wire, cadmium manganese alloy nano wire, indium manganese alloy nano wire, tin manganese alloy nano wire, tungsten manganese alloy nano wire, platinum manganese alloy nano wire, indium cadmium alloy nano wire, tin cadmium alloy nano wire, tungsten cadmium alloy nano wire, platinum cadmium alloy nano wire, tin-indium alloy nano wire, tungsten indium alloy nano wire, platinum indium alloy nano wire, tungsten ashbury metal nano wire, in platinum ashbury metal nano wire or platinum-tungsten alloys nano wire any one or multiple, described metal hetero-junction nano wire is copper iron heterojunction nano-wire, silver iron heterojunction nano-wire, gold iron heterojunction nano-wire, ferro-aluminum heterojunction nano-wire, ferronickel heterojunction nano-wire, ferro-cobalt heterojunction nano-wire, ferromanganese heterojunction nano-wire, cadmium iron heterojunction nano-wire, indium iron heterojunction nano-wire, tin iron heterojunction nano-wire, ferrotungsten heterojunction nano-wire, platinum iron heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, gold copper heterojunction nano-wire, aluminum copper dissimilar junction nanowire, ambrose alloy heterojunction nano-wire, cobalt copper heterojunction nano-wire, copper-manganese heterojunction nano-wire, cadmium copper heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, tin copper heterojunction nano-wire, tungsten copper heterojunction nano-wire, platinoid heterojunction nano-wire, gold and silver heterojunction nano-wire, aluminium silver heterojunction nano-wire, nickeline heterojunction nano-wire, cobalt silver heterojunction nano-wire, manganese silver heterojunction nano-wire, cadmium silver heterojunction nano-wire, indium silver heterojunction nano-wire, tin silver heterojunction nano-wire, tungsten silver heterojunction nano-wire, platinum silver heterojunction nano-wire, aluminium gold heterojunction nano-wire, nickel gold heterojunction nano-wire, cobalt gold heterojunction nano-wire, manganese gold heterojunction nano-wire, cadmium gold heterojunction nano-wire, indium gold heterojunction nano-wire, Sillim's heterojunction nano-wire, tungsten gold heterojunction nano-wire, cobalt nickel heterojunction nano-wire, manganese nickel heterojunction nano-wire, cadmium nickel heterojunction nano-wire, indium nickel heterojunction nano-wire, tin nickel heterojunction nano-wire, tungsten nickel heterojunction nano-wire, platinum nickel heterojunction nano-wire, cadmium manganese heterojunction nano-wire, indium manganese heterojunction nano-wire, tin manganese heterojunction nano-wire, tungsten manganese heterojunction nano-wire, platinum manganese heterojunction nano-wire, indium cadmium heterojunction nano-wire, tin cadmium heterojunction nano-wire, tungsten cadmium heterojunction nano-wire, platinum cadmium heterojunction nano-wire, tin indium heterojunction nano-wire, tungsten indium heterojunction nano-wire, platinum indium heterojunction nano-wire, tungsten tin heterojunction nano-wire, in platinum tin heterojunction nano-wire or platinum tungsten heterojunction nano-wire any one or multiple.
As preferably, the material used of hole transmission layer described in the present invention is 3, 4-ethylenedioxy thiophene mixing poly styrene sulfonate, polyaniline compound organic conductive polymer, aromatic diamine compounds, star triphenyl amine compound, carbazole polymer, poly N-vinyl carbazole, 1, 10-phenanthroline derivative, two (conjunction of 2-methyl-8-quinoline acid group) tri-phenyl-silane aluminium alcoholates (III), in two (conjunction of 2-methyl-8-quinoline acid group)-4-phenol aluminium (III) or two (conjunction of 2-methyl-8-quinoline acid group)-4-phenylphenol aluminium (III) any one or multiple.
As preferably, the material used of electron transfer layer described in the present invention is 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-oxadiazole, oxadiazole electron-like transferring material 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3, in 4-oxadiazole or imidazoles electron transport material 1,3,5-tri-(N-phenyl-2-benzimidazolyl-2 radicals) benzene any one or multiple.
As preferably, the material used of cathode layer described in the present invention is metallic film or alloy firm, and this metallic film can be golden or silver-colored etc. the alloy firm of lithium or magnesium or calcium or strontium or the metallic film such as aluminium or indium or they and copper.
As preferably, anode layer described in the present invention, hole transmission layer, organic active layer, electron transfer layer and cathode layer gross thickness are no more than 200nm.
A kind of preparation method with electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance in the present invention, comprises the following steps:
1. the substrate that transparent substrates and transparent conductive anode ITO form is cleaned, dry up with drying nitrogen after cleaning;
2. substrate is sent to the preparation carrying out electrode layer in vacuum evaporation room;
3. the substrate of the electrode layer prepared is moved into vacuum chamber, carry out plasma pretreatment;
4. by process after substrate in the vaporization chamber of condition of high vacuum degree, start the preparation carrying out organic film, prepare hole transmission layer, organic active layer and electron transfer layer successively according to device architecture;
5. in vacuum evaporation room, carry out the preparation of cathode layer;
6. test component is in UV-irradiation with without the current-voltage characteristic curve under UV-irradiation condition, simultaneously the current-voltage-brightness characteristic curve of test component and luminescent spectrum.
As preferably, step 4. in the substrate after process carried out in spin coater the spin coating of hole transmission layer, organic active layer and electron transfer layer successively according to device architecture; Or the substrate after process is prepared hole transmission layer, organic active layer and electron transfer layer according to device architecture successively adopting the method that in vapour deposition method and spin coater, spin-coating method combines in high vacuum chamber.
Beneficial effect of the present invention is:
1, there is electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance for organic electroluminescence device electroluminescence function can be realized, the multifunction device of organic UV detector ultraviolet detection function can be realized again;
2, have electroluminescence device integration integrated with the organic optoelectronic of ultraviolet detection performance high, therefore device is ultra-thin, outside removing substrate thickness, device gross thickness is no more than 200nm;
3, have electroluminescence device preparation technology integrated with the organic optoelectronic of ultraviolet detection performance simple, equipment requirement is low, and processing procedure is short, and consuming time few, cost is low.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation with electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance involved in the present invention;
Fig. 2 is that at ultraviolet light, (wavelength is 350nm to device described in embodiment 1 provided by the present invention, and intensity is 0.6mW/cm
2) irradiate and without the Current density-voltage characteristic curve under UV-irradiation condition;
Fig. 3 is the current-voltage-brightness characteristic curve of device described in embodiment 1 provided by the present invention;
Fig. 4 is the test curve figure of the luminescent spectrum of device described in embodiment 1 provided by the present invention;
Wherein, 1, transparent substrates, 2, anode layer, 3, hole transmission layer, 4, there is the organic active layer of electroluminescence and ultraviolet detection double grading, 5, electron transfer layer, 6, cathode layer, 7, test circuit.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described:
Technical scheme of the present invention is to provide a kind ofly has electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, as shown in Figure 1, the structure of device comprises transparent substrates 1, anode layer 2, hole transmission layer 3, organic active layer 4, electron transfer layer 5, cathode layer 6.Device can realize lighting function under additional positive drive voltage, can realize ultraviolet detection function again under additional reverse drive voltages.
The material that in the present invention, organic active layer is used has following structural framework:
The example of the material that the organic active layer used is used is as shown below:
In the present invention, transparent substrates 1 is the support of electrode and organic thin film layer, it has good light transmission at ultraviolet light and visible region, there is the ability of certain anti-steam and oxygen infiltration, have good profile pattern, it can adopt in glass, transparent polymer flexible material or biodegradable flexible material any one or multiple; Wherein, described transparent polymer flexible material comprise in polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid any one or multiple; Described biodegradable flexible material comprise string, fibroin albumen, gelatin, PLA, glucose, viral fiber element, PLA, Poly(D,L-lactide-co-glycolide, polyvinyl alcohol, polyvinylpyrrolidone, pla-pcl, PHA, polysaccharide (such as shellac, shitosan and hyaluronic acid etc.), polyalcohols acid and copolymer, collagen gel, fibrin gel etc. have in biological degradable material any one or multiple.Glass or flexible substrate, a kind of material in flexible substrate employing polyesters, poly-phthalimide compound or thinner metal.
Anodic layer 2 of the present invention is as the articulamentum of device and applying bias, and it requires good electric conductivity, ultraviolet light and visible transparent and higher work function.In usual employing tin indium oxide (ITO), conductive polymer poly 3,4-ethylene dioxythiophene/poly styrene sulfonate (PEDOT:PSS), Graphene (Graphene), carbon nano-tube (Carbon Nanotube), metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire any one or multiple.
Hole-transporting layer 3 of the present invention is as the articulamentum of anode layer and organic active layer, and it requires good cavity transmission ability.The material of usual employing has 3, in 4-ethylenedioxy thiophene mixing poly styrene sulfonate, polyaniline compound organic conductive polymer, aromatic diamine compounds, star triphenyl amine compound, carbazole polymer, poly N-vinyl carbazole, 1,10-phenanthroline derivative, two (conjunction of 2-methyl-8-quinoline acid group) tri-phenyl-silane aluminium alcoholates (III), two (conjunction of 2-methyl-8-quinoline acid group)-4-phenol aluminium (III) or two (conjunction of 2-methyl-8-quinoline acid group)-4-phenylphenol aluminium (III) any one or multiple.As: N, N '-bis--(3-aminomethyl phenyl)-N, N '-diphenyl-[1,1 '-xenyl]-4,4 '-diamines (TPD), N, N '-bis-(3-naphthyl)-N, N '-diphenyl-[1,1 '-diphenyl]-4,4 '-diamines (NPB), polyvinylcarbazole (PVK), 4,4 '-cyclohexylidene-two (N, N-bis--4-aminomethyl phenyl) aniline (TAPC), 4,4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamines (m-MTDATA).
In the present invention, electron transfer layer 5 is as the articulamentum of organic active layer and cathode layer, and it requires good electron transport ability.Material 2-(4-the diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1 of usual employing, 3,4-oxadiazole, oxadiazole electron-like transferring material 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-oxadiazole or imidazoles electron transport material 1, in 3,5-tri-(N-phenyl-2-benzimidazolyl-2 radicals) benzene any one or multiple.As: oxine aluminium (Alq
3), 1,3,5-tri-(N-phenyl-2-benzimidazolyl-2 radicals) benzene (TPBI), 4,7-diphenyl-1,10-phenanthrolines (Bphen), 1,10-phenanthroline derivative (BCP).
In the present invention, cathode layer 6 is as the articulamentum of device and applying bias, and its requires to have good electric conductivity and lower work function.Usual employing metallic film or alloy firm, this metallic film can be golden or silver-colored etc. the alloy firm of lithium or magnesium or calcium or strontium or the metallic film such as aluminium or indium or they and copper.
The electroluminescence device architecture integrated with the organic optoelectronic of ultraviolet detection performance that have adopting the present invention to prepare is exemplified below:
1. glass/ITO/ hole transmission layer/organic active layer/electron transfer layer/cathode layer
2. glass/conducting polymer/hole transmission layer/organic active layer/electron transfer layer/cathode layer
3. flexible polymer substrate/ITO/ hole transmission layer/organic active layer/electron transfer layer/cathode layer
Below specific embodiments of the invention:
Embodiment 1
The hole transport layer material of device is NPB, and organic active layer material is material 1, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 1 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
Preparation method is as follows:
1. with ethanolic solution, acetone soln and deionized water, ultrasonic cleaning is carried out to transparent conduction base sheet ito glass, dry up with drying nitrogen after cleaning.Ito film wherein above glass substrate is as the anode layer of device, and the square resistance of ito film is 10 Ω/, and thickness is 180nm.
2. dried substrate is moved into vacuum chamber, under the oxygen pressure ring border that air pressure is 20Pa, carry out low energy oxygen plasma preliminary treatment 5 minutes to ito glass, sputtering power is 20W.
2. the substrate after process, in the vaporization chamber of condition of high vacuum degree, starts the evaporation carrying out organic film.According to device architecture described above successively deposition material NPB layer 20nm, material 1 layer of 20nm, materials A lq
3layer 30nm.The evaporation rate 0.1nm/s of each organic layer, evaporation rate and thickness are monitored by film thickness gauge.
3. organic layer evaporation terminates the preparation of laggard row metal electrode.Air pressure is 3 × 10
-3pa, evaporation rate is 1nm/s, and in alloy, Mg:Ag ratio is 10:1, and thicknesses of layers is 100nm.Evaporation rate and thickness are monitored by film thickness gauge.
5. test component is in UV-irradiation with without the current-voltage characteristic curve under UV-irradiation condition, simultaneously the current-voltage-brightness characteristic curve of test component and luminescent spectrum.
Device UV-irradiation and without the current-voltage characteristic curve under UV-irradiation condition, current-voltage-brightness characteristic curve and device luminescent spectrum curve respectively see accompanying drawing 3 and 4.
Embodiment 2
The hole transport layer material of device is NPB, and organic active layer material is material 2, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 2 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 3
The hole transport layer material of device is NPB, and organic active layer material is material 3, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 3 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 4
The hole transport layer material of device is NPB, and organic active layer material is material 4, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 4 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 5
The hole transport layer material of device is NPB, and organic active layer material is material 5, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 5 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 6
The hole transport layer material of device is NPB, and organic active layer material is material 6, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 6 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 7
The hole transport layer material of device is NPB, and organic active layer material is material 7, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 7 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 8
The hole transport layer material of device is NPB, and organic active layer material is material 8, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 8 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 9
The hole transport layer material of device is NPB, and organic active layer material is material 9, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 9 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 10
The hole transport layer material of device is NPB, and organic active layer material is material 10, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 10 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 11
The hole transport layer material of device is NPB, and organic active layer material is material 11, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 11 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 12
The hole transport layer material of device is NPB, and organic active layer material is material 12, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 12 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 13
The hole transport layer material of device is NPB, and organic active layer material is material 13, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 13 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 14
The hole transport layer material of device is NPB, and organic active layer material is material 14, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 14 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 15
The hole transport layer material of device is NPB, and organic active layer material is for being material 15, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 15 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 16
The hole transport layer material of device is NPB, and organic active layer material is material 16, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/NPB (20nm)/material 16 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 17
The hole transport layer material of device is TAPC, and organic active layer material is material 1, and electron transport material is TPBI, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/TAPC (20nm)/material 1 (20nm)/TPBI (30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 18
The hole transport layer material of device is TPD, and organic active layer material is material 2, and electron transport material is Bphen, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/TPD (20nm)/material 2 (20nm)/Bphen (30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 19
The hole transport layer material of device is m-MTDATA, and organic active layer material is material 3, and electron transport material is BCP, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/m-MTDATA (20nm)/material 3 (20nm)/BCP (30nm)/Mg:Ag (100nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 20
The hole transport layer material of device is PVK, and organic active layer material is material 4, and electron transport material is Alq
3, cathode layer Mg:Ag alloy.Whole device architecture is described as:
Glass substrate/ITO/PVK (20nm)/material 4 (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
Preparation method is as follows:
1. utilize ethanolic solution, acetone soln and deionized water to carry out ultrasonic cleaning to transparent conduction base sheet ito glass, dry up with drying nitrogen after cleaning.Ito film wherein above glass substrate is as the anode layer of device, and the square resistance of ito film is 10 Ω/, and thickness is 180nm.
2. dried substrate is moved into vacuum chamber, under the oxygen pressure ring border that air pressure is 20Pa, carry out low energy oxygen plasma preliminary treatment 5 minutes to ito glass, sputtering power is 20W.
4. compound concentration is the PVK solution of 10mg/ml, and solvent adopts chloroform; Then be spin-coated on the tin indium oxide after clean (ITO) electro-conductive glass substrate, dry 10 minutes with 60 DEG C in low vacuum chamber after, be placed in the vaporization chamber of condition of high vacuum degree, deposition material 4 is 20nm, electron transport material Alq
3for 30nm.The evaporation rate 0.1nm/s of organic layer, evaporation rate and thickness are monitored by film thickness gauge.
5. organic layer evaporation terminates the preparation of laggard row metal electrode.Air pressure is 3 × 10
-3pa, evaporation rate is 1nm/s, and in alloy, Mg:Ag ratio is 10:1, and thicknesses of layers is 100nm.Evaporation rate and thickness are monitored by film thickness gauge.
5. test component is in UV-irradiation with without the current-voltage characteristic curve under UV-irradiation condition, simultaneously the current-voltage-brightness characteristic curve of test component and luminescent spectrum.
Claims (9)
1. one kind has electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, it comprises: transparent substrates, anode layer, hole transmission layer, organic active layer, electron transfer layer and cathode layer, and described organic active layer material used has following structural framework:
Wherein, R in structural framework
1group is selected from :-CH
3,-CH
2cH
3,-CH
2cH
2cH
3or-C (CH
3)
3;
R in structural framework
2group is selected from:
2. according to claim 1 have electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, it is characterized in that, described transparent substrates material used be in glass, transparent polymer flexible material or biodegradable flexible material any one or multiple; Wherein said transparent polymer flexible material be selected from polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid any one or multiple; Described biodegradable flexible material be selected from string, fibroin albumen, gelatin, PLA, glucose, viral fiber element, PLA, Poly(D,L-lactide-co-glycolide, polyvinyl alcohol, polyvinylpyrrolidone, pla-pcl, PHA, polysaccharide, polyalcohols acid and copolymer thereof, collagen gel, in fibrin gel any one or multiple.
3. according to claim 1 have electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, it is characterized in that, described anode layer material used be in tin indium oxide (ITO), conductive polymer poly 3,4-ethylene dioxythiophene/poly styrene sulfonate (PEDOT:PSS), Graphene (Graphene), carbon nano-tube (Carbon Nanotube), metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire any one or multiple, wherein said metal simple-substance nano wire be in Fe nanowire, copper nano-wire, nano silver wire, nanowires of gold, aluminium nano wire, nickel nano wire, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires any one or multiple, described metal alloy nanowires is copper-iron alloy nano wire, silver ferroalloy nano wire, bule gold nano wire, alfer nano wire, dilval nano wire, ferro-cobalt nano wire, manganeisen nano wire, cadmium ferroalloy nano wire, indium ferroalloy nano wire, tin ferroalloy nano wire, ferro-tungsten nano wire, pt-fe alloy nano wire, yellow gold nano wire, gold copper nano wire, aluminium copper nano wire, monel nano wire, cobalt-copper alloy nano wire, manganin nano wire, cadmium copper alloy nano wire, yellow gold nano wire, gun-metal nano wire, tungsten-copper alloy nano wire, Mock gold nano wire, electrum nano wire, aluminium silver alloy nanowires, bazar metal nano wire, cobalt silver alloy nanowires, manganese silver alloy nanowires, cadmium silver nano wire, indium silver alloy nanowires, sn-ag alloy nano wire, tungsten silver alloy nanowires, platinum-silver alloys nano wire, aluminium gold alloy nano-wire, nickel billon nano wire, cobalt billon nano wire, manganese billon nano wire, cadmium billon nano wire, indium billon nano wire, Sillim's alloy nano-wire, tungsten billon nano wire, cobalt-nickel alloy nano wire, manganese-nickel nano wire, cadmium-nickel alloy nano wire, indium nickel alloy nano wire, tin-nickel alloy nano wire, tungsten nickel nano wire, platinum-nickel alloy nano wire, cadmium manganese alloy nano wire, indium manganese alloy nano wire, tin manganese alloy nano wire, tungsten manganese alloy nano wire, platinum manganese alloy nano wire, indium cadmium alloy nano wire, tin cadmium alloy nano wire, tungsten cadmium alloy nano wire, platinum cadmium alloy nano wire, tin-indium alloy nano wire, tungsten indium alloy nano wire, platinum indium alloy nano wire, tungsten ashbury metal nano wire, in platinum ashbury metal nano wire or platinum-tungsten alloys nano wire any one or multiple, described metal hetero-junction nano wire is copper iron heterojunction nano-wire, silver iron heterojunction nano-wire, gold iron heterojunction nano-wire, ferro-aluminum heterojunction nano-wire, ferronickel heterojunction nano-wire, ferro-cobalt heterojunction nano-wire, ferromanganese heterojunction nano-wire, cadmium iron heterojunction nano-wire, indium iron heterojunction nano-wire, tin iron heterojunction nano-wire, ferrotungsten heterojunction nano-wire, platinum iron heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, gold copper heterojunction nano-wire, aluminum copper dissimilar junction nanowire, ambrose alloy heterojunction nano-wire, cobalt copper heterojunction nano-wire, copper-manganese heterojunction nano-wire, cadmium copper heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, tin copper heterojunction nano-wire, tungsten copper heterojunction nano-wire, platinoid heterojunction nano-wire, gold and silver heterojunction nano-wire, aluminium silver heterojunction nano-wire, nickeline heterojunction nano-wire, cobalt silver heterojunction nano-wire, manganese silver heterojunction nano-wire, cadmium silver heterojunction nano-wire, indium silver heterojunction nano-wire, tin silver heterojunction nano-wire, tungsten silver heterojunction nano-wire, platinum silver heterojunction nano-wire, aluminium gold heterojunction nano-wire, nickel gold heterojunction nano-wire, cobalt gold heterojunction nano-wire, manganese gold heterojunction nano-wire, cadmium gold heterojunction nano-wire, indium gold heterojunction nano-wire, Sillim's heterojunction nano-wire, tungsten gold heterojunction nano-wire, cobalt nickel heterojunction nano-wire, manganese nickel heterojunction nano-wire, cadmium nickel heterojunction nano-wire, indium nickel heterojunction nano-wire, tin nickel heterojunction nano-wire, tungsten nickel heterojunction nano-wire, platinum nickel heterojunction nano-wire, cadmium manganese heterojunction nano-wire, indium manganese heterojunction nano-wire, tin manganese heterojunction nano-wire, tungsten manganese heterojunction nano-wire, platinum manganese heterojunction nano-wire, indium cadmium heterojunction nano-wire, tin cadmium heterojunction nano-wire, tungsten cadmium heterojunction nano-wire, platinum cadmium heterojunction nano-wire, tin indium heterojunction nano-wire, tungsten indium heterojunction nano-wire, platinum indium heterojunction nano-wire, tungsten tin heterojunction nano-wire, in platinum tin heterojunction nano-wire or platinum tungsten heterojunction nano-wire any one or multiple.
4. according to claim 1 have electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, it is characterized in that, described hole transmission layer material used is 3, 4-ethylenedioxy thiophene mixing poly styrene sulfonate, polyaniline compound organic conductive polymer, aromatic diamine compounds, star triphenyl amine compound, carbazole polymer, poly N-vinyl carbazole, 1, 10-phenanthroline derivative, two (conjunction of 2-methyl-8-quinoline acid group) tri-phenyl-silane aluminium alcoholates (III), in two (conjunction of 2-methyl-8-quinoline acid group)-4-phenol aluminium (III) or two (conjunction of 2-methyl-8-quinoline acid group)-4-phenylphenol aluminium (III) any one or multiple.
5. according to claim 1 have electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, it is characterized in that, described electron transfer layer material used is 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-oxadiazole, oxadiazole electron-like transferring material 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-oxadiazole or imidazoles electron transport material 1, in 3,5-tri-(N-phenyl-2-benzimidazolyl-2 radicals) benzene any one or multiple.
6. according to claim 1 have electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, it is characterized in that, described cathode layer material used is metallic film or alloy firm, and this metallic film can be the golden or silver-colored alloy firm of lithium or magnesium or calcium or strontium or the metallic film such as aluminium or indium or they and copper.
7. according to claim 1 have electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, and it is characterized in that, described anode layer, hole transmission layer, organic active layer, electron transfer layer and cathode layer gross thickness are no more than 200nm.
8. prepare the method with electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance described in any one of claim 1-7, it is characterized in that, comprise the following steps:
1. the substrate that transparent substrates and transparent conductive anode ITO form is cleaned, dry up with drying nitrogen after cleaning;
2. substrate is sent to the preparation carrying out electrode layer in vacuum evaporation room;
3. the substrate of the electrode layer prepared is moved into vacuum chamber, carry out plasma pretreatment;
4. by process after substrate in the vaporization chamber of condition of high vacuum degree, start the preparation carrying out organic film, prepare hole transmission layer, organic active layer and electron transfer layer successively according to device architecture;
5. in vacuum evaporation room, carry out the preparation of cathode layer;
6. test component is in UV-irradiation with without the current-voltage characteristic curve under UV-irradiation condition, simultaneously the current-voltage-brightness characteristic curve of test component and luminescent spectrum.
9. preparation according to claim 8 has the method for electroluminescence device integrated with the organic optoelectronic of ultraviolet detection performance, it is characterized in that, step 4. in the substrate after process is carried out the spin coating of hole transmission layer, organic active layer and electron transfer layer successively in spin coater according to device architecture; Or the substrate after process is prepared hole transmission layer, organic active layer and electron transfer layer according to device architecture successively adopting the method that in vapour deposition method and spin coater, spin-coating method combines in high vacuum chamber.
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