CN106187892A - A kind of organic blended type double-function device and preparation method thereof - Google Patents
A kind of organic blended type double-function device and preparation method thereof Download PDFInfo
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- CN106187892A CN106187892A CN201610548013.1A CN201610548013A CN106187892A CN 106187892 A CN106187892 A CN 106187892A CN 201610548013 A CN201610548013 A CN 201610548013A CN 106187892 A CN106187892 A CN 106187892A
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- 238000000034 method Methods 0.000 claims abstract description 15
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- 238000009834 vaporization Methods 0.000 claims abstract description 7
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Classifications
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
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- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract
The invention discloses a kind of organic blended type double-function device and preparation method thereof, this device is made up of transparent substrates, anode layer, hole transmission layer, organic active doped layer, electron transfer layer and cathode layer.Wherein organic active doped layer is used double source steam method mixing evaporation altogether or use mixed solution spin-coating method to be prepared in spin coating instrument by material of main part and guest materials in the vaporization chamber of condition of high vacuum degree.Under the driving of additional forward voltage, this organic double-function device is capable of lighting function, and under the driving of additional backward voltage, this device can realize ultraviolet detection function.This organic double-function device has the dual-use function of electroluminescent and ultraviolet detection simultaneously, and not only device is luminous strong, and detectivity is high, easy of integration, ultra-thin, and preparation technology is simple, preparation time is short, low cost.
Description
Technical field
The present invention relates to organic optoelectronic field, be specifically related to a kind of organic blended type double-function device and preparation side thereof
Method.
Background technology
Microelectronics tipping high-precision with the device and equipment that the fast development of solid-state electronic techniques causes, integrated and microcosmic turn to
The science and technology of large quantities of high-tech contents such as organic optoelectronic technology provides a new development platform.Simultaneously along with organic
The high speed development of photoelectron technology, with organic electroluminescence device, organic solar batteries, organic UV detector, organic field
Effect transistor is that the organic optoelectronic product of representative is fast-developing ripe by huge market potential.Wherein, You Jizi
External detector is many with the function that its inorganic UV detector having based on organic molecule or organic polymer is incomparable
Sample and practicality, economy have obtained the extensive concern of researchers；In recent years along with its film-forming process level and device
Significantly improving of preparation level, its detectivity has reached 1015The superelevation level of Jones, thus follow the tracks of at life sciences element,
The aspects such as medical treatment & health, environment fire hazard monitoring, military aerospace, weapon guidance have increasing application；Meanwhile, organic electroluminescence
The series of advantages such as light emitting diode is energy-efficient with it, light weight is portable, flexible rollable, healthy self-luminous and shown with shine
Researchers' extensive concern on bright boundary.
But some shortcomings of the sub-device of Traditional photovoltaic seriously constrain its rapid businessization to be developed: 1, tradition organic photoelectric
Sub-device architecture is more complicated, function singleness and performance relatively low, there is no to realize the device of several functions simultaneously, do not catch up with and have
The development trend to flexible wearable development of machine photoelectron technology；2, traditional organic optoelectronic device is commonly used in the application
Substrate material includes glass, quartz, silicon and plastics.Wherein, glass substrate, quartz base plate and silicon substrate have that quality is hard, weight
Greatly, carry the shortcoming such as inconvenience, non-degradable, and frangible, do not possess flexibility；And plastic base although to have quality light, soft
Property etc. feature, but the water oxygen barrier properties of most of plastics is general, and non-degradable or have certain toxicity, to natural life
State environment causes and destroys significantly, if large-scale application will produce substantial amounts of ecological rubbish, is unfavorable for alleviating the most serious
Energy problem and environmental problem；3, traditional multi-functional organic optoelectronic device film thickness is relatively big, complicated process of preparation, equipment
Requiring height, preparation process is loaded down with trivial details, and cost is high, is extremely difficult to commercial requirement, it is difficult to industrialization.Therefore, research has electroluminescent
With organic double-function device of ultraviolet detection performance, the range of application widening organic optoelectronic technology is accelerated its industrialization process
The most significant with environmental conservation.
Summary of the invention
For prior art, the technical problem to be solved in the present invention is how to provide a kind of organic blended type double-function device
And preparation method thereof, it is therefore an objective to effectively suppress the generation of traditional organic double-function device efficiency roll-off phenomenon, overcome tradition organic
Opto-electronic device function singleness and integrated level are low, luminescent properties and the shortcoming of ultraviolet detection degraded performance.
The technical scheme is that a kind of organic blended type double-function device, be followed successively by from top to bottom: transparent substrates,
Anode layer, hole transmission layer, organic active doped layer, electron transfer layer and cathode layer, described organic active doped layer is by main body
Material and guest materials mix, and guest materials shared mass percent in organic active doped layer is 2～21%, main body
Material shared mass percent in organic active doped layer is 98～79%, material of main part used and guest materials use with
A kind of or any of them in lower structural framework formula mixes:
Wherein, R in structural framework1Group is selected from :-CH3、-CH2CH3、-CH2CH2CH3Or-C (CH3)3；
R in structural framework2Group is selected from:
As preferably, the material used by heretofore described transparent substrates is glass, transparent polymer flexible material or life
Any one or more in the flexible material of Biodegradable；Wherein, described transparent polymer flexible material is selected from polyethylene, gathers
Any one in methyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid
Or it is multiple；Described biodegradable flexible material is selected from Plant fiber, fibroin albumen, gelatin, polylactic acid, glucose, virus
Cellulose, polylactic acid, Poly(D,L-lactide-co-glycolide, polyvinyl alcohol, polyvinylpyrrolidone, pla-pcl, poly-hydroxyl alkane
Acid esters, polysaccharide (such as Lac, chitosan and hyaluronic acid etc.), polyalcohols acid and copolymer, collagen gel, fibrin coagulate
Any one or more in glue.
As preferably, the material used by heretofore described anode layer is tin indium oxide (ITO), conductive polymer poly 3,4-
Ethylenedioxy thiophene/poly styrene sulfonate (PEDOT:PSS), Graphene (Graphene), CNT (Carbon
Nanotube), any one or more in metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire；Its
In, described metal simple-substance nano wire be Fe nanowire, copper nano-wire, nano silver wire, nanowires of gold, aluminum nano wire, nickel nano wire,
In 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, ferro-aluminum conjunction
Nanowires of gold, dilval nano wire, ferro-cobalt nano wire, manganeisen nano wire, cadmium ferroalloy nano wire, indium ferroalloy
Nano wire, stannum ferroalloy nano wire, ferro-tungsten nano wire, pt-fe alloy nano wire, yellow gold nano wire, gold copper are received
Rice noodle, aluminium copper nano wire, monel nano wire, cobalt-copper alloy nano wire, manganin nano wire, cadmium copper alloy nanometer
Line, yellow gold nano wire, gun-metal nano wire, tungsten-copper alloy nano wire, Mock gold nano wire, electrum nanometer
Line, aluminum silver alloy nanowires, bazar metal nano wire, cobalt silver alloy nanowires, manganese silver alloy nanowires, cadmium silver nanometer
Line, indium silver alloy nanowires, sn-ag alloy nano wire, tungsten silver alloy nanowires, platinum-silver alloys nano wire, aluminium gold alloy nano
Line, nickel billon nano wire, cobalt billon nano wire, manganese billon nano wire, cadmium billon nano wire, indium billon nanometer
Line, Sillim's alloy nano-wire, tungsten billon nano wire, cobalt-nickel alloy nano wire, manganese-nickel nano wire, cadmium-nickel alloy nanometer
Line, indium nickel alloy nano wire, tin-nickel alloy nano wire, tungsten nickel nano wire, platinum-nickel alloy nano wire, cadmium manganese alloy nanometer
Line, indium manganese alloy nano wire, stannum manganese alloy nano wire, tungsten manganese alloy nano wire, platinum manganese alloy nano wire, indium cadmium alloy nanometer
Line, stannum cadmium alloy nano wire, tungsten cadmium alloy nano wire, platinum cadmium alloy nano wire, tin-indium alloy nano wire, tungsten indium alloy nanometer
In line, platinum indium alloy nano wire, tungsten ashbury metal nano wire, platinum ashbury metal nano wire or platinum-tungsten alloys nano wire any one or
Multiple；Described metal hetero-junction nano wire is copper ferrum heterojunction nano-wire, silver ferrum heterojunction nano-wire, aufe hetero-junctions nanometer
Line, ferro-aluminum heterojunction nano-wire, ferronickel heterojunction nano-wire, ferro-cobalt heterojunction nano-wire, ferromanganese heterojunction nano-wire, cadmium ferrum are different
Matter junction nanowire, indium ferrum heterojunction nano-wire, stannum ferrum heterojunction nano-wire, ferrotungsten heterojunction nano-wire, platinum ferrum hetero-junctions nanometer
Line, silver-bearing copper heterojunction nano-wire, gold copper heterojunction nano-wire, aluminum copper dissimilar junction nanowire, ambrose alloy heterojunction nano-wire, cobalt copper are different
Matter junction nanowire, copper-manganese heterojunction nano-wire, cadmium copper heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, stannum copper hetero-junctions nanometer
Line, tungsten copper heterojunction nano-wire, platinoid heterojunction nano-wire, gold silver heterojunction nano-wire, aluminum silver heterojunction nano-wire, nickeline are different
Matter junction nanowire, cobalt silver heterojunction nano-wire, manganese silver heterojunction nano-wire, cadmium silver heterojunction nano-wire, indium silver hetero-junctions nanometer
Line, stannum silver heterojunction nano-wire, tungsten silver heterojunction nano-wire, platinum silver heterojunction nano-wire, aluminium gold heterojunction nano-wire, nickel gold are different
Matter junction nanowire, cobalt gold heterojunction nano-wire, manganese gold heterojunction nano-wire, cadmium gold heterojunction nano-wire, indium gold hetero-junctions nanometer
Line, Sillim's heterojunction nano-wire, tungsten gold heterojunction nano-wire, cobalt nickel heterojunction nano-wire, manganese nickel heterojunction nano-wire, cadmium nickel are different
Matter junction nanowire, indium nickel heterojunction nano-wire, stannum nickel heterojunction nano-wire, tungsten nickel heterojunction nano-wire, platinum nickel hetero-junctions nanometer
Line, cadmium manganese heterojunction nano-wire, indium manganese heterojunction nano-wire, stannum manganese heterojunction nano-wire, tungsten manganese heterojunction nano-wire, platinum manganese are different
Matter junction nanowire, indium cadmium heterojunction nano-wire, stannum cadmium heterojunction nano-wire, tungsten cadmium heterojunction nano-wire, platinum cadmium hetero-junctions nanometer
Line, stannum indium heterojunction nano-wire, tungsten indium heterojunction nano-wire, platinum indium heterojunction nano-wire, tungsten stannum heterojunction nano-wire, platinum stannum are different
Any one or more in matter junction nanowire or platinum tungsten heterojunction nano-wire.
As preferably, the material used by heretofore described hole transmission layer is 3,4-ethylene dioxythiophene mixing polyphenyl second
Alkene sulfonate, polyaniline compound organic conductive polymer, aromatic diamine compounds, star triphenyl amine compound, carbazole are birdsed of the same feather flock together
Compound, poly N-vinyl carbazole, 1,10-phenanthroline derivant, 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 aluminum (III) or two (conjunction of 2-methyl-8-quinoline acid group)-4-phenyl benzene
In phenol aluminum (III) any one or multiple.
As preferably, the material used by heretofore described electron transfer layer is 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane
Base)-1,3,4-diazole, diazoles electron transport material 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-two
In azoles 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 by heretofore described cathode layer is metallic film or alloy firm, this metallic film
For lithium or magnesium or calcium or strontium or aluminum or indium；Alloy firm is lithium, calcium, strontium, aluminum or indium and copper or the alloy of silver.
As preferably, heretofore described anode layer, hole transmission layer, organic active doped layer, electron transfer layer and the moon
Pole layer gross thickness is less than 185nm.
The preparation method of a kind of organic blended type double-function device in the present invention, comprises the following steps:
1. the substrate formed transparent substrates and transparent conductive anode ITO is carried out, and uses dry nitrogen air-blowing after cleaning
Dry；
2. it is sent to substrate be evaporated in vacuo the preparation carrying out electrode layer in room；
3. the substrate of the electrode layer prepared is moved into vacuum chamber, carry out plasma pretreatment；
4. the substrate after processing, in the vaporization chamber of condition of high vacuum degree, proceeds by the preparation of organic film, according to device
Structure is sequentially prepared hole transmission layer, organic active doped layer and electron transfer layer；
5. in vacuum evaporation room, carry out the preparation of cathode layer；
6. test device current-voltage characteristic curve under the conditions of ultraviolet light irradiates and irradiates without ultraviolet light, surveys simultaneously
The current-voltage-brightness characteristic curve of examination device and luminescent spectrum.
As preferably, step 4. in will process after substrate in spin coater, carry out hole biography successively according to device architecture
Defeated layer, organic active doped layer and the spin coating of electron transfer layer；Or the substrate after processing is deposited with in high vacuum chamber and revolves
The method that in painting machine, spin coating combines is sequentially prepared hole transmission layer, organic active doped layer and electronics according to device architecture and passes
Defeated layer, wherein organic active doped layer uses double source to steam method mixing evaporation altogether or at spin coater in the vaporization chamber of condition of high vacuum degree
Middle use mixed solution spin coating is prepared.
The beneficial effects of the present invention is:
1, the organic double-function device of this doping type utilize under electroluminescent pattern doping technique introduce absorption spectrum with
The guest materials that material of main part emission spectrum coincides so that the luminous energy that material of main part sends is absorbed again by guest materials again
Luminescence, improves efficiency, it is possible to increase energy utilization efficiency, improves luminous intensity；
2, the organic double-function device of this doping type utilizes doping process to introduce ultraviolet band absorption spectrum under detection mode
The guest materials coincided with material of main part absorption spectrum makes the device can significantly more efficient absorption ultraviolet under detection mode
Light, improves light utilization efficiency and energy conversion efficiency so that device photoelectric stream is greatly improved.
3, the organic double-function device of this doping type is for can realize organic electroluminescence device electroluminescent function, again can be real
The multifunction device of existing organic UV detector ultraviolet detection function；
4, this doping type organic double-function device integrated level is high, therefore device is ultra-thin, removes outside substrate thickness, device gross thickness
Less than 185nm；
5, this doping type organic double-function device preparation technology is simple, and processing procedure is short, time-consumingly few, low cost.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of organic blended type double-function device involved in the present invention；
Fig. 2 is that at ultraviolet light, (wavelength is 365nm to device described in embodiment 1 provided by the present invention, and intensity is 0.5mW/
cm2) irradiate and without the Current density-voltage characteristic curve under the conditions of ultraviolet light irradiation；
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, organic active doped layer, 5, electron transfer layer,
6, cathode layer, 7, test circuit.
Detailed description of the invention
The invention will be further described below in conjunction with the accompanying drawings:
A kind of organic blended type double-function device of offer is provided, as it is shown in figure 1, the structure bag of device
Include transparent substrates 1, anode layer 2, hole transmission layer 3, organic active doped layer 4, electron transfer layer 5, cathode layer 6.Device can
Under additional positive drive voltage, realize lighting function, ultraviolet detection function can be realized again under additional reverse drive voltages.
In the present invention, material of main part used by organic active doped layer and guest materials are respectively provided with following structural framework:
The material of main part used by organic active doped layer used and the example of guest materials are shown below:
In the present invention, transparent substrates 1 is the support of electrode and organic thin film layer, and it has at ultraviolet light and visible region
Good light transmission, has certain anti-steam and the ability of oxygen infiltration, has preferable profile pattern, and it can use glass
Any one or more in glass, transparent polymer flexible material or biodegradable flexible material；Wherein, described transparent poly-
Compound flexible material includes polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyimides, chlorine vinegar tree
Any one or more in fat or polyacrylic acid；Described biodegradable flexible material include Plant fiber, fibroin albumen,
Gelatin, polylactic acid, glucose, viral fiber element, polylactic acid, Poly(D,L-lactide-co-glycolide, polyvinyl alcohol, polyethylene pyrrole
Pyrrolidone, pla-pcl, PHA, polysaccharide (such as Lac, chitosan and hyaluronic acid etc.), polyalcohols are sour and are total to
Aggressiveness, collagen gel, fibrin gel etc. have any one or more in biological degradable material.Glass or flexibility
Substrate, flexible substrate uses a kind of material in polyesters, poly-phthalimide compound or relatively thin metal.
Anodic layer 2 of the present invention is as the articulamentum of device Yu applying bias, and it requires have preferable electric conductivity, ultraviolet
Light and visible transparent and higher work function.Generally use tin indium oxide (ITO), conductive polymer poly 3,4-ethylene two
Oxygen thiophene/poly styrene sulfonate (PEDOT:PSS), Graphene (Graphene), CNT (Carbon Nanotube),
Any one or more in metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire.
Hole-transporting layer 3 of the present invention is as the articulamentum of anode layer Yu organic active doped layer, and it requires have preferably
Cavity transmission ability.The material generally used has 3,4-ethylenedioxy thiophene mixing poly styrene sulfonate, polyaniline compound organic
Conducting polymer, aromatic diamine compounds, star triphenyl amine compound, carbazole polymer, poly N-vinyl carbazole, 1,
10-phenanthroline derivant, two (conjunction of 2-methyl-8-quinoline acid group) tri-phenyl-silane aluminium alcoholates (III), two (2-methyl-8-quinoline
Acid group closes) any one in-4-phenol aluminum (III) or two (conjunction of 2-methyl-8-quinoline acid group)-4-phenylphenol aluminum (III)
Or it is multiple.'-bis--(3-aminomethyl phenyl)-N, N '-diphenyl-[1,1 '-xenyl]-4,4 '-diamidogen (TPD), N such as N, N,
N '-bis-(3-naphthyl)-N, N '-diphenyl-[1,1 '-diphenyl]-4,4 '-diamidogen (NPB), polyvinylcarbazole (PVK), 4,4 '-
Cyclohexylidene-two (N, N-bis--4-aminomethyl phenyl) aniline (TAPC), 4,4', 4 "-three (N-3-methylphenyl-N-phenyl amino)
Triphenylamine (m-MTDATA).
In the present invention, electron transfer layer 5 is as the articulamentum of organic active doped layer Yu cathode layer, and it requires have preferably
Electron transport ability.Generally material 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane the base)-1,3,4-diazole of employing, diazoles
Electron transport material 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-diazole or imidazoles electron transport material 1,3,
In 5-tri-(N-phenyl-2-benzimidazolyl-2 radicals) benzene any one or multiple.As: 8-hydroxyquinoline aluminum (Alq3)、1,3,5-
Three (N-phenyl-2-benzimidazolyl-2 radicals) benzene (TPBI), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,10-phenanthroline spread out
Biological (BCP).
In the present invention, cathode layer 6 is as the articulamentum of device Yu applying bias, it require have preferable electric conductivity and
Relatively low work function.Generally using metallic film or alloy firm, this metallic film is lithium or magnesium or calcium or strontium or aluminum or indium；Close
Gold thin film is lithium, calcium, strontium, aluminum or indium and copper or the alloy of silver.
The one organic blended type double-function device structure example using the present invention to prepare is as follows:
1. glass/ITO/ hole transmission layer/organic active doped layer/electron transfer layer/cathode layer
2. glass/conducting polymer/hole transmission layer/organic active doped layer/electron transfer layer/cathode layer
3. flexible polymer substrate/ITO/ hole transmission layer/organic active doped layer/electron transfer layer/cathode layer
The following is the specific embodiment of the present invention:
Embodiment 1
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
This organic active doped layer includes following composition:
Material 2 100%
Preparation method is as follows:
1. with ethanol solution, acetone soln and deionized water, transparent conduction base sheet ito glass is carried out ultrasonic cleaning, clean
Dry up with drying nitrogen afterwards.Wherein the ito film above glass substrate is as the anode layer of device, and the square resistance of ito film is 10
Ω/, thickness is 155nm.
2. dried substrate is moved into vacuum chamber, under the oxygen pressure ring border that air pressure is 20Pa, ito glass is carried out low
Energy oxygen plasma pretreatment 5 minutes, sputtering power is 20W.
3. the substrate after processing, in the vaporization chamber of condition of high vacuum degree, proceeds by the evaporation of organic film.According to as above institute
State device architecture deposition material NPB layer 20nm successively, organic active doped layer 15nm, materials A lq3Layer 20nm.Each organic layer
Evaporation rate 0.6nm/s, evaporation rate and thickness are monitored by film thickness gauge.
4. organic layer evaporation terminates the preparation of laggard row metal electrode.Air pressure is 3 × 10-3Pa, evaporation rate is 6nm/s,
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 device current-voltage characteristic curve under the conditions of ultraviolet light irradiates and irradiates without ultraviolet light, surveys simultaneously
The current-voltage-brightness characteristic curve of examination device and luminescent spectrum.
Device irradiates and without the current-voltage characteristic curve under the conditions of ultraviolet light irradiation, current-voltage-bright at ultraviolet light
Degree characteristic curve and device luminescent spectrum curve see accompanying drawing 2,3 and 4 respectively.
Embodiment 2
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
This organic active doped layer includes following composition:
Material 6 100%
The preparation flow of device is similar to Example 1.
Embodiment 3
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
This organic active doped layer includes following composition:
Material 10 100%
The preparation flow of device is similar to Example 1.
Embodiment 4
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
This organic active doped layer includes following composition:
Material 14 100%
The preparation flow of device is similar to Example 1.
Embodiment 5
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
This organic active doped layer includes following composition:
Material 2 98%
Material 9 2%
The preparation flow of device is similar to Example 1.
Embodiment 6
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
This organic active doped layer includes following composition:
Material 2 97%
Material 6 3%
The preparation flow of device is similar to Example 1.
Embodiment 7
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
This organic active doped layer includes following composition:
Material 2 93%
Material 15 7%
The preparation flow of device is similar to Example 1.
Embodiment 8
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
This organic active doped layer includes following composition:
Material 2 95%
Material 4 5%
The preparation flow of device is similar to Example 1.
Embodiment 9
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 6 97%
Material 13 3%
The preparation flow of device is similar to Example 1.
Embodiment 10
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 6 96%
Material 10 4%
The preparation flow of device is similar to Example 1.
Embodiment 11
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 6 95%
Material 3 5%
The preparation flow of device is similar to Example 1.
Embodiment 12
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 6 94%
Material 8 6%
The preparation flow of device is similar to Example 1.
Embodiment 13
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 10 92%
Material 1 8%
The preparation flow of device is similar to Example 1.
Embodiment 14
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 10 90%
Material 14 10%
The preparation flow of device is similar to Example 1.
Embodiment 15
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 10 88%
Material 7 12%
The preparation flow of device is similar to Example 1.
Embodiment 16
The hole transport layer material of device is NPB, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 10 86%
Material 16 14%
The preparation flow of device is similar to Example 1.
Embodiment 17
The hole transport layer material of device is TAPC, and electron transport material is TPBI, cathode layer Mg:Ag alloy.Whole
Device architecture is described as:
Glass substrate/ITO/TAPC (20nm)/organic active doped layer (15nm)/TPBI (20nm)/Mg:Ag (100nm)
Material 14 84%
Material 5 16%
The preparation flow of device is similar to Example 1.
Embodiment 18
The hole transport layer material of device is TPD, and electron transport material is Bphen, cathode layer Mg:Ag alloy.Whole
Device architecture is described as:
Glass substrate/ITO/TPD (20nm)/organic active doped layer (15nm)/Bphen (20nm)/Mg:Ag (100nm)
Material 14 82%
Material 2 18%
The preparation flow of device is similar to Example 1.
Embodiment 19
The hole transport layer material of device is m-MTDATA, and electron transport material is BCP, cathode layer Mg:Ag alloy.Whole
Individual device architecture is described as:
Glass substrate/ITO/m-MTDATA (20nm)/organic active doped layer (15nm)/BCP (20nm)/Mg:Ag
(100nm)
Material 14 80%
Material 11 20%
The preparation flow of device is similar to Example 1.
Embodiment 20
The hole transport layer material of device is PVK, and electron transport material is Alq3, cathode layer Mg:Ag alloy.Whole device
Part structure is described as:
Glass substrate/ITO/PVK (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 14 79%
Material 4 21%
Preparation method is as follows:
1. with ethanol solution, acetone soln and deionized water, transparent conduction base sheet ito glass is carried out ultrasonic cleaning, clean
Dry up with drying nitrogen afterwards.Wherein the ito film above glass substrate is as the anode layer of device, and the square resistance of ito film is 10
Ω/, thickness is 155nm.
2. dried substrate is moved into vacuum chamber, under the oxygen pressure ring border that air pressure is 20Pa, ito glass is carried out low
Energy oxygen plasma pretreatment 5 minutes, sputtering power is 20W.
3. compound concentration is the PVK solution of 10mg/ml, and solvent uses chloroform；It is then spin coated onto processing through cleaning
After tin indium oxide (ITO) electro-conductive glass substrate on, dry after 10 minutes with 60 DEG C in coarse vacuum chamber, be placed in condition of high vacuum degree
In vaporization chamber, organic active doped layer is 15nm, electron transport material Alq3For 20nm.The evaporation rate 0.6nm/s of organic layer,
Evaporation rate and thickness are monitored by film thickness gauge.
4. organic layer evaporation terminates the preparation of laggard row metal electrode.Air pressure is 3 × 10-3Pa, evaporation rate is 6nm/s,
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 device current-voltage characteristic curve under the conditions of ultraviolet light irradiates and irradiates without ultraviolet light, surveys simultaneously
The current-voltage-brightness characteristic curve of examination device and luminescent spectrum.
Wherein embodiment 1, embodiment 2, embodiment 3, embodiment 4 is the undoped device as reference.
Table 1: the electroluminescent properties of embodiment 1～20 and ultraviolet detection the performance test results
Claims (9)
1. an organic blended type double-function device, it is characterised in that be followed successively by from top to bottom: transparent substrates, anode layer, hole
Transport layer, organic active doped layer, electron transfer layer and cathode layer, described organic active doped layer is by material of main part and object material
Material mixes, and guest materials shared mass percent in organic active doped layer is 2～21%, and material of main part is in organic work
Property doped layer in shared mass percent be 98～79%, material of main part used and guest materials use following structural framework to lead to
A kind of or any of them in formula mixes:
Wherein, R in structural framework1Group is selected from :-CH3、-CH2CH3、-CH2CH2CH3Or-C (CH3)3；
R in structural framework2Group is selected from:
One the most according to claim 1 organic blended type double-function device, it is characterised in that used by described transparent substrates
Material be any one or more in glass, transparent polymer flexible material or biodegradable flexible material；Wherein
Described transparent polymer flexible material is selected from polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyamides
Any one or more in imines, vinyl chloride-vinyl acetate resin or polyacrylic acid；Described biodegradable flexible material is fine selected from plant
Dimension, fibroin albumen, gelatin, polylactic acid, glucose, viral fiber element, polylactic acid, Poly(D,L-lactide-co-glycolide, polyethylene
The acid of alcohol, polyvinylpyrrolidone, pla-pcl, PHA, polysaccharide, polyalcohols and copolymer, collagen gel, fiber
Any one or more in protein gel.
One the most according to claim 1 organic blended type double-function device, it is characterised in that used by described anode layer
Material is tin indium oxide (ITO), conductive polymer poly 3,4-ethylenedioxy thiophene/poly styrene sulfonate (PEDOT:PSS), stone
Ink alkene (Graphene), CNT (Carbon Nanotube), metal simple-substance nano wire, metal alloy nanowires, metal are different
Any one or more in matter junction nanowire；Wherein said metal simple-substance nano wire is Fe nanowire, copper nano-wire, silver nanoparticle
Line, nanowires of gold, aluminum nano wire, nickel nano wire, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten
Any one or more in nano wire or Pt nanowires；Described metal alloy nanowires is copper-iron alloy nano wire, silver ferrum conjunction
Nanowires of gold, 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, stannum ferroalloy nano wire, ferro-tungsten nano wire, pt-fe alloy are received
Rice noodle, yellow gold nano wire, gold copper nano wire, aluminium copper nano wire, monel nano wire, cobalt-copper alloy nanometer
Line, manganin nano wire, cadmium copper alloy nano wire, yellow gold nano wire, gun-metal nano wire, tungsten-copper alloy nanometer
Line, Mock gold nano wire, electrum nano wire, aluminum silver alloy nanowires, bazar metal nano wire, cobalt silver alloy nanometer
Line, manganese silver alloy nanowires, cadmium silver nano wire, indium silver alloy nanowires, sn-ag alloy nano wire, tungsten silver alloy nanometer
Line, platinum-silver alloys nano wire, aluminium gold alloy nano-wire, nickel billon nano wire, cobalt billon nano wire, manganese billon nanometer
Line, cadmium billon nano wire, indium billon nano wire, Sillim's alloy nano-wire, tungsten billon nano wire, cobalt-nickel alloy nanometer
Line, manganese-nickel nano wire, cadmium-nickel alloy nano wire, indium nickel alloy nano wire, tin-nickel alloy nano wire, tungsten nickel nanometer
Line, platinum-nickel alloy nano wire, cadmium manganese alloy nano wire, indium manganese alloy nano wire, stannum manganese alloy nano wire, tungsten manganese alloy nanometer
Line, platinum manganese alloy nano wire, indium cadmium alloy nano wire, stannum cadmium alloy nano wire, tungsten cadmium alloy nano wire, platinum cadmium alloy nanometer
Line, tin-indium alloy nano wire, tungsten indium alloy nano wire, platinum indium alloy nano wire, tungsten ashbury metal nano wire, platinum ashbury metal nano wire
Or any one or more in platinum-tungsten alloys nano wire；Described metal hetero-junction nano wire is copper ferrum heterojunction nano-wire, silver
Ferrum heterojunction nano-wire, aufe heterojunction nano-wire, ferro-aluminum heterojunction nano-wire, ferronickel heterojunction nano-wire, ferro-cobalt hetero-junctions
Nano wire, ferromanganese heterojunction nano-wire, cadmium ferrum heterojunction nano-wire, indium ferrum heterojunction nano-wire, stannum ferrum heterojunction nano-wire, tungsten
Ferrum heterojunction nano-wire, platinum ferrum heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, gold copper heterojunction nano-wire, aluminum copper dissimilar knot
Nano wire, ambrose alloy heterojunction nano-wire, cobalt copper heterojunction nano-wire, copper-manganese heterojunction nano-wire, cadmium copper heterojunction nano-wire, silver
Copper heterojunction nano-wire, stannum copper heterojunction nano-wire, tungsten copper heterojunction nano-wire, platinoid heterojunction nano-wire, gold silver hetero-junctions
Nano wire, aluminum 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, stannum silver heterojunction nano-wire, tungsten silver heterojunction nano-wire, platinum silver hetero-junctions
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 hetero-junctions
Nano wire, manganese nickel heterojunction nano-wire, cadmium nickel heterojunction nano-wire, indium nickel heterojunction nano-wire, stannum nickel heterojunction nano-wire, tungsten
Nickel heterojunction nano-wire, platinum nickel heterojunction nano-wire, cadmium manganese heterojunction nano-wire, indium manganese heterojunction nano-wire, stannum manganese hetero-junctions
Nano wire, tungsten manganese heterojunction nano-wire, platinum manganese heterojunction nano-wire, indium cadmium heterojunction nano-wire, stannum cadmium heterojunction nano-wire, tungsten
Cadmium heterojunction nano-wire, platinum cadmium heterojunction nano-wire, stannum indium heterojunction nano-wire, tungsten indium heterojunction nano-wire, platinum indium hetero-junctions
Any one or more in nano wire, tungsten stannum heterojunction nano-wire, platinum stannum heterojunction nano-wire or platinum tungsten heterojunction nano-wire.
One the most according to claim 1 organic blended type double-function device, it is characterised in that described hole transmission layer institute
Material be 3,4-ethylenedioxy thiophene mixing poly styrene sulfonate, polyaniline compound organic conductive polymer, aromatic series two
Aminated compounds, star triphenyl amine compound, carbazole polymer, poly N-vinyl carbazole, 1,10-phenanthroline derivant,
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 aluminum
(III) in or two (conjunction of 2-methyl-8-quinoline acid group)-4-phenylphenol aluminum (III) any one or multiple.
One the most according to claim 1 organic blended type double-function device, it is characterised in that described electron transfer layer institute
Material be 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-diazole, diazoles electron transport material 2-(4-
Diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-diazole or imidazoles electron transport material 1,3,5-tri-(N-phenyl-2-benzene
And imidazoles-2) in benzene any one or multiple.
One the most according to claim 1 organic blended type double-function device, it is characterised in that used by described cathode layer
Material is metallic film or alloy firm, and this metallic film is lithium or magnesium or calcium or strontium or aluminum or indium；Alloy firm be lithium, calcium,
Strontium, aluminum or indium and copper or the alloy of silver.
One the most according to claim 1 organic blended type double-function device, it is characterised in that described anode layer, hole
Transport layer, organic active doped layer, electron transfer layer and cathode layer gross thickness are less than 185nm.
8., according to the preparation method of a kind of organic blended type double-function device described in any one of claim 1-7, its feature exists
In, comprise the following steps:
1. the substrate formed transparent substrates and transparent conductive anode ITO is carried out, and dries up with drying nitrogen after cleaning；
2. the substrate preparing electrode layer is moved into vacuum chamber, carry out plasma pretreatment；
3. the substrate after processing, in the vaporization chamber of condition of high vacuum degree, proceeds by the preparation of organic film, according to device architecture
It is sequentially prepared hole transmission layer, organic active doped layer and electron transfer layer；
4. in vacuum evaporation room, carry out the preparation of cathode layer；
5. test device current-voltage characteristic curve under the conditions of ultraviolet light irradiates and irradiates without ultraviolet light, tester simultaneously
The current-voltage-brightness characteristic curve of part and luminescent spectrum.
The preparation method of a kind of organic blended type double-function device the most according to claim 8, it is characterised in that in step
3. the substrate after processing in carries out hole transmission layer, organic active doped layer and electricity in spin coater successively according to device architecture
The spin coating of sub-transport layer；Or the method that substrate is deposited with in high vacuum chamber and in spin coater, spin coating combines after processing is come
It is sequentially prepared hole transmission layer, organic active doped layer and electron transfer layer, wherein organic active doped layer according to device architecture
Double source is used to steam method mixing evaporation altogether or use mixed solution spin coating to carry out in spin coater in the vaporization chamber of condition of high vacuum degree
Preparation.
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| CN107154462A (en) * | 2017-05-08 | 2017-09-12 | 武汉华星光电技术有限公司 | A kind of preparation method of OLED and OLED |
| US10163580B2 (en) | 2017-05-08 | 2018-12-25 | Wuhan China Star Optoelectronics Technology Co., Ltd. | OLED device and method for manufacturing the same |
| CN107565026A (en) * | 2017-08-30 | 2018-01-09 | 电子科技大学 | A kind of double-function device based on perovskite material and preparation method thereof |
| CN110246907A (en) * | 2019-07-12 | 2019-09-17 | 通威太阳能（成都）有限公司 | A kind of battery structure with promotion heterojunction solar battery photoelectric conversion efficiency |
| CN110739399A (en) * | 2019-10-24 | 2020-01-31 | 昆明物理研究所 | NPB/nitrogen-doped graphene nano heterojunction ultraviolet detector with flexible vertical structure and preparation method thereof |
| CN111139527A (en) * | 2020-04-07 | 2020-05-12 | 季华实验室 | Method for producing organic crystalline material, and light-emitting element |
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