CN106187892B - 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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- CN106187892B CN106187892B CN201610548013.1A CN201610548013A CN106187892B CN 106187892 B CN106187892 B CN 106187892B CN 201610548013 A CN201610548013 A CN 201610548013A CN 106187892 B CN106187892 B CN 106187892B
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Classifications
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- C—CHEMISTRY; METALLURGY
- 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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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- 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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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention discloses a kind of organic blended type double-function devices and preparation method thereof, which is made of transparent substrates, anode layer, hole transmission layer, organic active doped layer, electron transfer layer and cathode layer.Wherein organic active doped layer is steamed method mixing vapor deposition using double source in the vaporization chamber of condition of high vacuum degree by material of main part and guest materials altogether or is prepared in spin coating instrument using mixed solution spin-coating method.Outside plus under the driving of forward voltage, which can be realized light-emitting function, and outside plus under the driving of backward voltage, which may be implemented ultraviolet detection function.Organic double-function device has the dual function of electroluminescent and ultraviolet detection simultaneously, not only device strong light, and detectivity is high, easy of integration, ultra-thin, and preparation process is simple, preparation time is short, at low cost.
Description
Technical field
The present invention relates to organic photoelectric subdomains, and in particular to a kind of organic blended type double-function device and its preparation side
Method.
Background technique
It is the high-precision tipping of device and equipment caused by the fast development of microelectronics and solid-state electronic techniques, 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 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 mature by huge market potential.Wherein, You Jizi
External detector is more with the incomparable function of inorganic UV detector that it is had based on small organic molecule or organic polymer
Sample and practicability, economy have obtained the extensive concern of researchers；In recent years as its film-forming process is horizontal and device
Preparation is horizontal to be significantly improved, and detectivity has reached 1015The superelevation of Jones is horizontal, thus track in life science element,
Medical treatment & health, environment fire hazard monitoring, military aerospace, weapon guidance etc. have more and more applications；Meanwhile organic electroluminescence
The series of advantages such as light emitting diode is energy-efficient with its, light portable, flexible rollable, healthy self-luminous and it is shown and shine
Researchers' extensive concern on bright boundary.
But some disadvantages of the sub- device of Traditional photovoltaic seriously constrain the development of its rapid businessization: 1, traditional organic photoelectric
Sub- device architecture is more complicated, have a single function and performance is lower, not can be achieved at the same time the device of multiple functions, not catching up with has
The development trend of machine photoelectron technology developed to flexible wearable；2, traditional organic optoelectronic device is common in the application
Substrate material includes glass, quartz, silicon and plastics.Wherein, glass substrate, quartz base plate and silicon substrate have hard, weight
Greatly, the disadvantages of inconvenient to carry, non-degradable, and it is frangible, do not have flexibility；Although and plastic base has quality light, soft
The features such as property, but the water oxygen barrier properties of most of plastics are general, and non-degradable or with certain toxicity, to natural life
State environment causes significantly to destroy, if large-scale application will generate a large amount of ecological rubbish, is unfavorable for alleviation and gets worse
Energy problem and environmental problem；3, the multi-functional organic optoelectronic device film thickness of tradition is larger, and preparation process is complicated, equipment
It is required that high, preparation process is cumbersome, at high cost, is extremely difficult to commercial requirement, it is difficult to industrialization.Therefore, research has electroluminescent
Its industrialization process is accelerated to the application range for widening organic optoelectronic technology with organic double-function device of ultraviolet detection performance
It is all of great significance with environmental protection.
Summary of the invention
For the prior art, the technical problem to be solved by the present invention is to how provide a kind of organic blended type double-function device
And preparation method thereof, it is therefore an objective to the generation for effectively inhibiting the organic double-function device efficiency roll-off phenomenon of tradition overcomes tradition organic
Opto-electronic device have a single function it is low with integrated level, the shortcomings that luminescent properties and ultraviolet detection degraded performance.
The technical solution of the present invention is as follows: a kind of organic blended type double-function device, from top to bottom successively are as follows: transparent substrates,
Anode layer, hole transmission layer, organic active doped layer, electron transfer layer and cathode layer, the 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
One of flowering structure skeleton general formula or their any mixing:
Wherein, R in structural framework1Group is selected from :-CH3、-CH2CH3、-CH2CH2CH3Or-C (CH3)3；
R in structural framework2Group is selected from:
Preferably, material used in heretofore described transparent substrates is glass, transparent polymer flexible material or life
Any one or more in the flexible material of Biodegradable；Wherein, the transparent polymer flexible material is selected from polyethylene, gathers
Any one in methyl methacrylate, polycarbonate, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid
Or it is a variety of；The biodegradable flexible material is selected from plant fiber, fibroin albumen, gelatin, polylactic acid, glucose, virus
Cellulose, polylactic acid, poly lactide-glycolide acid, polyvinyl alcohol, polyvinylpyrrolidone, pla-pcl, poly- hydroxyl alkane
Acid esters, polysaccharide (such as shellac, chitosan and hyaluronic acid etc.), polyalcohols acid and its copolymer, collagen gel, fibrin are solidifying
Any one or more in glue.
Preferably, material used in heretofore described anode layer is tin indium oxide (ITO), conductive polymer poly 3,4-
Ethylenedioxy thiophene/poly styrene sulfonate (PEDOT:PSS), graphene (Graphene), carbon nanotube (Carbon
Nanotube), metal simple-substance nano wire, metal alloy nanowires, any one or more in metal hetero-junction nano wire；Its
In, the metal simple-substance nano wire be Fe nanowire, copper nano-wire, silver nanowires, nanowires of gold, aluminium 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
It is a variety of；The metal alloy nanowires are copper-iron alloy nano wire, silver-colored 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, tin ferroalloy nano wire, ferro-tungsten nano wire, pt-fe alloy nano wire, yellow gold nano wire, gold copper are received
Rice noodles, 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, aluminium 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, tin manganese alloy nano wire, tungsten manganese alloy nano wire, platinum manganese alloy nano wire, indium cadmium alloy nanometer
Line, tin 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 tin alloy nano wire, platinum tin alloy nano wire or platinum-tungsten alloys nano wire any one or
It is a variety of；The metal hetero-junction nano wire is copper and iron heterojunction nano-wire, silver-colored iron heterojunction nano-wire, golden iron hetero-junctions nanometer
Line, ferro-aluminum heterojunction nano-wire, ferronickel heterojunction nano-wire, ferro-cobalt heterojunction nano-wire, manganese iron heterojunction nano-wire, cadmium iron are different
Matter junction nanowire, indium iron heterojunction nano-wire, tin iron heterojunction nano-wire, ferrotungsten heterojunction nano-wire, platinum iron hetero-junctions nanometer
Line, silver-bearing copper heterojunction nano-wire, golden 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, tin copper hetero-junctions nanometer
Line, tungsten copper heterojunction nano-wire, platinoid heterojunction nano-wire, gold and silver heterojunction nano-wire, aluminium 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, tin 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, tin 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, tin manganese heterojunction nano-wire, tungsten manganese heterojunction nano-wire, platinum manganese are different
Matter junction nanowire, indium cadmium heterojunction nano-wire, tin cadmium heterojunction nano-wire, tungsten cadmium heterojunction nano-wire, platinum cadmium hetero-junctions nanometer
Line, tin indium heterojunction nano-wire, tungsten indium heterojunction nano-wire, platinum indium heterojunction nano-wire, tungsten tin heterojunction nano-wire, platinum tin are different
Any one or more in matter junction nanowire or platinum tungsten heterojunction nano-wire.
Preferably, material used in heretofore described hole transmission layer is 3,4-ethylene dioxythiophene mixing polyphenyl second
Alkene sulfonate, polyaniline compound organic conductive polymer, aromatic diamines compound, star triphenyl amine compound, carbazole are birdsed of the same feather flock together
Close object, 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- phenyl benzene
In phenol aluminium (III) any one or it is a variety of.
Preferably, material used in heretofore described electron transfer layer is 2- (4- diphenyl) -5- (4- 2-methyl-2-phenylpropane
Base) -1,3,4- oxadiazoles, furodiazole electron transport material 2- (4- diphenyl) -5- (4- 2-methyl-2-phenylpropane base) -1,3,4- evil two
In azoles or imidazoles electron transport material 1,3,5- tri- (N- phenyl -2- benzimidazolyl-2 radicals) benzene any one or it is a variety of.
Preferably, material used in heretofore described cathode layer is metallic film or alloy firm, the metallic film
For lithium or magnesium or calcium or strontium or aluminium or indium；Alloy firm is the alloy of lithium, calcium, strontium, aluminium or indium and copper or silver.
Preferably, heretofore described anode layer, hole transmission layer, organic active doped layer, electron transfer layer and yin
Pole layer overall thickness is no more than 185nm.
A kind of preparation method of organic blended type double-function device in the present invention, comprising the following steps:
1. cleaning to substrate composed by transparent substrates and transparent conductive anode ITO, dry nitrogen air-blowing is used after cleaning
It is dry；
2. substrate to be sent to the preparation for being evaporated in vacuo and carrying out electrode layer in room；
3. the substrate of the electrode layer prepared is moved into vacuum chamber, plasma pretreatment is carried out；
4. starting the preparation for carrying out organic film, according to device by treated substrate in the vaporization chamber of condition of high vacuum degree
Structure is sequentially prepared hole transmission layer, organic active doped layer and electron transfer layer；
5. carrying out the preparation of cathode layer in being evaporated in vacuo room；
6. testing device in ultraviolet light and current-voltage characteristic curve under the conditions of without ultraviolet light, survey simultaneously
Try the current-voltage-brightness characteristic curve and luminescent spectrum of device.
Preferably, step 4. in will treated that substrate successively carries out hole biography according to device architecture in spin coater
The spin coating of defeated layer, organic active doped layer and electron transfer layer；Or substrate is deposited and revolves in high vacuum chamber by treated
The method that spin coating combines in painting machine passes to be sequentially prepared hole transmission layer, organic active doped layer and electronics according to device architecture
Defeated layer, wherein organic active doped layer steams method mixing vapor deposition using double source in the vaporization chamber of condition of high vacuum degree or altogether in spin coater
It is middle to be prepared using mixed solution spin coating.
The beneficial effects of the present invention are:
1, the organic double-function device of the doping type under electroluminescent mode using 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 issues is absorbed again by guest materials again
It shines, improves efficiency, can be improved energy utilization efficiency, improve luminous intensity；
2, the organic double-function device of the doping type introduces ultraviolet band absorption spectrum using doping process under detection mode
With the guest materials that material of main part absorption spectrum coincides device significantly more efficient can be absorbed under detection mode ultraviolet
Light improves light utilization efficiency and energy conversion efficiency, so that device photoelectric stream is greatly improved.
3, the organic double-function device of the doping type is not only to be able to achieve organic electroluminescence device electroluminescent function, but also energy is real
The multifunction device of existing organic UV detector ultraviolet detection function；
4, the organic double-function device integrated level of the doping type is high, therefore device is ultra-thin, removes outside substrate thickness, device overall thickness
No more than 185nm；
5, the organic double-function device preparation process of the doping type is simple, and processing procedure is short, and time-consuming is few, at low cost.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of organic blended type double-function device according to the present invention；
Fig. 2 is device described in embodiment 1 provided by the present invention in ultraviolet light (wavelength 365nm, intensity 0.5mW/
cm2) irradiate and without the Current density-voltage characteristic curve under the conditions of ultraviolet light；
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.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings:
The technical solution of the present invention is to provide a kind of organic blended type double-function devices, as shown in Figure 1, the structure packet 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
Light-emitting function is being realized outside plus under positive drive voltage, and can realize outside plus under reverse drive voltages ultraviolet detection function.
Material of main part used in organic active doped layer and guest materials all have following structural framework in the present invention:
The example of material of main part used in used organic active doped layer and guest materials is shown below:
Transparent substrates 1 are the support of electrode and organic thin film layer in the present invention, it has in ultraviolet light and visible light region
Good light transmission has the ability of certain anti-steam and oxygen infiltration, has preferable profile pattern, it can use glass
Any one or more in glass, transparent polymer flexible material or biodegradable flexible material；Wherein, described transparent poly-
Closing object flexible material includes polyethylene, polymethyl methacrylate, polycarbonate, polyurethanes, polyimides, chlorine vinegar tree
Any one or more in rouge or polyacrylic acid；The biodegradable flexible material include plant fiber, fibroin albumen,
Gelatin, polylactic acid, glucose, viral fiber element, polylactic acid, poly lactide-glycolide acid, polyvinyl alcohol, polyethylene pyrrole
Pyrrolidone, pla-pcl, polyhydroxyalkanoates, polysaccharide (such as shellac, chitosan and hyaluronic acid etc.), polyalcohols are sour and its total
Aggressiveness, collagen gel, fibrin gel etc. have any one or more in biological degradable material.Glass or flexibility
Substrate, flexible substrate use one of polyesters, poly- phthalimide compound material or relatively thin metal.
Articulamentum of the Anodic layer 2 of the present invention as device and applying bias, 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), carbon nanotube (Carbon Nanotube),
Metal simple-substance nano wire, metal alloy nanowires, any one or more in metal hetero-junction nano wire.
Articulamentum of the hole-transporting layer 3 of the present invention as anode layer and organic active doped layer, it requires to have preferable
Cavity transmission ability.The material generallyd use has 3,4- ethylenedioxy thiophene mixing poly styrene sulfonate, polyaniline compound organic
Conducting polymer, aromatic diamines compound, 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 (2- methyl -8- quinoline
Acid group closes) any one in -4- phenol aluminium (III) or two (conjunction of 2- methyl -8- quinoline acid group) -4- phenylphenol aluminium (III)
Or it is a variety of.Such as: N, N '-bis--(3- aminomethyl phenyl)-N, N '-diphenyl-[1,1 '-xenyl] -4,4 '-diamines (TPD), N,
Bis- (3- the naphthalene)-N of N ' -, N '-diphenyl-[1,1 '-diphenyl] -4,4 '-diamines (NPB), polyvinylcarbazole (PVK), 4,4 ' -
Cyclohexylidene-two (bis- -4- aminomethyl phenyl of N, N-) aniline (TAPC), 4,4', 4 "-three (N-3- methylphenyl-N-phenyl amino)
Triphenylamine (m-MTDATA).
Articulamentum of the electron transfer layer 5 as organic active doped layer and cathode layer in the present invention, it requires to have preferable
Electron transport ability.Material 2- (4- diphenyl) -5- (4- 2-methyl-2-phenylpropane the base) -1,3,4- oxadiazoles, furodiazole generallyd use
Electron transport material 2- (4- diphenyl) -5- (4- 2-methyl-2-phenylpropane base) -1,3,4- oxadiazoles or imidazoles electron transport material 1,3,
In 5- tri- (N- phenyl -2- benzimidazolyl-2 radicals) benzene any one or it is a variety of.Such as: 8-hydroxyquinoline aluminium (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).
Articulamentum of the cathode layer 6 as device and applying bias in the present invention, it require preferable electric conductivity and
Lower work function.Metallic film or alloy firm are generallyd use, which is lithium or magnesium or calcium or strontium or aluminium or indium；It closes
Gold thin film is the alloy of lithium, calcium, strontium, aluminium or indium and copper or silver.
It is as follows using a kind of organic blended type double-function device structure example prepared by the present invention:
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 specific embodiments of the present invention:
Embodiment 1
The hole transport layer material of device is NPB, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
The organic active doped layer includes following composition:
Material 2 100%
The preparation method is as follows:
1. being cleaned by ultrasonic with ethanol solution, acetone soln and deionized water to transparent conduction base sheet ito glass, clean
It is dried up afterwards with drying nitrogen.Wherein anode layer of the ito film above glass substrate as device, the square resistance of ito film are 10
Ω/, film thickness 155nm.
2. the substrate after drying is moved into vacuum chamber, ito glass is carried out in the case where air pressure is the oxygen pressure ring border of 20Pa low
Can be oxygen plasma pretreatment 5 minutes, sputtering power 20W.
3. treated substrate in the vaporization chamber of condition of high vacuum degree, starts to carry out the vapor deposition of organic film.According to institute as above
State device architecture successively evaporation material NPB layers of 20nm, 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 carries out the preparation of metal electrode after being deposited.Air pressure is 3 × 10-3Pa, evaporation rate 6nm/s,
Mg:Ag ratio is 10:1, thicknesses of layers 100nm in alloy.Evaporation rate and thickness are monitored by film thickness gauge.
5. testing device in ultraviolet light and current-voltage characteristic curve under the conditions of without ultraviolet light, survey simultaneously
Try the current-voltage-brightness characteristic curve and luminescent spectrum of device.
Device is bright in ultraviolet light and current-voltage characteristic curve, current-voltage-under the conditions of without ultraviolet light
Characteristic curve and device luminescent spectrum curve are spent respectively referring to attached drawing 2,3 and 4.
Embodiment 2
The hole transport layer material of device is NPB, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
The 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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
The 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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
The 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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
The 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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
The 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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
The 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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
Glass substrate/ITO/NPB (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
The 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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
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, electron transport material TPBI, cathode layer Mg:Ag alloy.Entirely
Device architecture description are as follows:
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, electron transport material Bphen, cathode layer Mg:Ag alloy.Entirely
Device architecture description are as follows:
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, electron transport material BCP, cathode layer Mg:Ag alloy.It is whole
A device architecture description are as follows:
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, electron transport material Alq3, cathode layer Mg:Ag alloy.Entire device
The description of part structure are as follows:
Glass substrate/ITO/PVK (20nm)/organic active doped layer (15nm)/Alq3(20nm)/Mg:Ag(100nm)
Material 14 79%
Material 4 21%
The preparation method is as follows:
1. being cleaned by ultrasonic with ethanol solution, acetone soln and deionized water to transparent conduction base sheet ito glass, clean
It is dried up afterwards with drying nitrogen.Wherein anode layer of the ito film above glass substrate as device, the square resistance of ito film are 10
Ω/, film thickness 155nm.
2. the substrate after drying is moved into vacuum chamber, ito glass is carried out in the case where air pressure is the oxygen pressure ring border of 20Pa low
Can be oxygen plasma pretreatment 5 minutes, sputtering power 20W.
3. compound concentration is the PVK solution of 10mg/ml, solvent uses chloroform；It is then spin coated by cleaning treatment
On tin indium oxide (ITO) electro-conductive glass substrate afterwards, in low vacuum chamber after ten minutes with 60 DEG C of drying, it is 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 carries out the preparation of metal electrode after being deposited.Air pressure is 3 × 10-3Pa, evaporation rate 6nm/s,
Mg:Ag ratio is 10:1, thicknesses of layers 100nm in alloy.Evaporation rate and thickness are monitored by film thickness gauge.
5. testing device in ultraviolet light and current-voltage characteristic curve under the conditions of without ultraviolet light, survey simultaneously
Try the current-voltage-brightness characteristic curve and luminescent spectrum of device.
Wherein embodiment 1, embodiment 2, embodiment 3, embodiment 4 are the undoped device as reference.
Table 1: the electroluminescent properties and ultraviolet detection the performance test results of Examples 1 to 20
Claims (9)
1. a kind of organic blended type double-function device, which is characterized in that from top to bottom successively are as follows: transparent substrates, anode layer, hole
Transport layer, organic active doped layer, electron transfer layer and cathode layer, the 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 are led to using following structural framework
One of formula or their any mixing:
Wherein, R in structural framework1Group is selected from :-CH3、-CH2CH3、-CH2CH2CH3Or-C (CH3)3；
R in structural framework2Group is selected from:
2. a kind of organic blended type double-function device according to claim 1, which is characterized in that used in the transparent substrates
Material be glass, transparent polymer flexible material or biodegradable flexible material in any one or more；Wherein,
The transparent polymer flexible material is selected from polyethylene, polymethyl methacrylate, polycarbonate, polyurethanes, polyamides
Any one or more in imines, vinyl chloride-vinyl acetate resin or polyacrylic acid；It is fine that the biodegradable flexible material is selected from plant
Dimension, fibroin albumen, gelatin, polylactic acid, glucose, viral fiber element, polylactic acid, poly lactide-glycolide acid, polyethylene
Alcohol, polyvinylpyrrolidone, pla-pcl, polyhydroxyalkanoates, polysaccharide (such as shellac, chitosan and hyaluronic acid etc.),
Polyalcohols acid and its copolymer, collagen gel, any one or more in fibrin gel.
3. a kind of organic blended type double-function device according to claim 1, which is characterized in that used in the anode layer
Material is tin indium oxide (ITO), conductive polymer poly 3,4- ethylenedioxy thiophene/poly styrene sulfonate (PEDOT:PSS), stone
Black alkene (Graphene), carbon nanotube (Carbon Nanotube), metal simple-substance nano wire, metal alloy nanowires, metal are different
Any one or more in matter junction nanowire；Wherein, the metal simple-substance nano wire is Fe nanowire, copper nano-wire, Yin Na
Rice noodles, nanowires of gold, aluminium nano wire, nickel nano wire, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire,
Any one or more in tungsten nanowires or Pt nanowires；The metal alloy nanowires are copper-iron alloy nano wire, silver-colored iron
Alloy nano-wire, bule gold nano wire, alfer nano wire, dilval nano wire, ferro-cobalt nano wire, manganese iron close
Nanowires of gold, 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 are received
Rice noodles, 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, aluminium 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, tin manganese alloy nano wire, tungsten manganese alloy nanometer
Line, platinum manganese alloy nano wire, indium cadmium alloy nano wire, tin 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 tin alloy nano wire, platinum tin alloy nano wire
Or any one or more in platinum-tungsten alloys nano wire；The metal hetero-junction nano wire is copper and iron heterojunction nano-wire, silver
Iron heterojunction nano-wire, golden iron heterojunction nano-wire, ferro-aluminum heterojunction nano-wire, ferronickel heterojunction nano-wire, ferro-cobalt hetero-junctions
Nano wire, manganese iron heterojunction nano-wire, cadmium iron heterojunction nano-wire, indium iron heterojunction nano-wire, tin iron heterojunction nano-wire, tungsten
Iron heterojunction nano-wire, platinum iron heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, golden 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, tin copper heterojunction nano-wire, tungsten copper heterojunction nano-wire, platinoid heterojunction nano-wire, gold and silver hetero-junctions
Nano wire, aluminium silver heterojunction nano-wire, nickeline heterojunction nano-wire, cobalt silver heterojunction nano-wire, manganese silver heterojunction nano-wire, cadmium
Silver-colored heterojunction nano-wire, indium silver heterojunction nano-wire, tin 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
Golden 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, 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 hetero-junctions
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 hetero-junctions
Any one or more in nano wire, tungsten tin heterojunction nano-wire, platinum tin heterojunction nano-wire or platinum tungsten heterojunction nano-wire.
4. a kind of organic blended type double-function device according to claim 1, which is characterized in that the hole transmission layer institute
Material is 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 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 in two (conjunction of 2- methyl -8- quinoline acid group) -4- phenylphenol aluminium (III) any one or it is a variety of.
5. a kind of organic blended type double-function device according to claim 1, which is characterized in that the electron transfer layer institute
Material is 2- (4- diphenyl) -5- (4- 2-methyl-2-phenylpropane base) -1,3,4- oxadiazoles, furodiazole electron transport material 2- (4-
Diphenyl) -5- (4- 2-methyl-2-phenylpropane base) -1,3,4- oxadiazoles or the (N- phenyl -2- benzene of imidazoles electron transport material 1,3,5- tri-
And imidazoles -2) in benzene any one or it is a variety of.
6. a kind of organic blended type double-function device according to claim 1, which is characterized in that used in the cathode layer
Material is metallic film or alloy firm, which is lithium or magnesium or calcium or strontium or aluminium or indium；Alloy firm be lithium, calcium,
The alloy of strontium, aluminium or indium and copper or silver.
7. a kind of organic blended type double-function device according to claim 1, which is characterized in that the anode layer, hole
Transport layer, organic active doped layer, electron transfer layer and cathode layer overall thickness are no more than 185nm.
8. a kind of preparation method of organic blended type double-function device according to claim 1-7, feature exist
In, comprising the following steps:
1. being cleaned to substrate composed by transparent substrates and transparent conductive anode ITO, dried up after cleaning with drying nitrogen；
2. substrate to be sent to the preparation for being evaporated in vacuo and carrying out electrode layer in room；
3. the substrate of the electrode layer prepared is moved into vacuum chamber, plasma pretreatment is carried out；
4. starting the preparation for carrying out organic film, according to device architecture by treated substrate in the vaporization chamber of condition of high vacuum degree
It is sequentially prepared hole transmission layer, organic active doped layer and electron transfer layer；
5. carrying out the preparation of cathode layer in being evaporated in vacuo room；
6. testing device in ultraviolet light and current-voltage characteristic curve under the conditions of without ultraviolet light, while tester
The current-voltage-brightness characteristic curve and luminescent spectrum of part.
9. a kind of preparation method of organic blended type double-function device according to claim 8, which is characterized in that in step
By treated, substrate successively carries out hole transmission layer, organic active doped layer and electricity in spin coater according to device architecture in 4.
The spin coating of sub- transport layer；Or the method combined with spin coating in spin coater is deposited in substrate in high vacuum chamber by treated
It is sequentially prepared hole transmission layer, organic active doped layer and electron transfer layer according to device architecture, wherein organic active doped layer
In the vaporization chamber of condition of high vacuum degree method mixing vapor deposition is steamed using double source altogether or is carried out in spin coater using mixed solution spin coating
Preparation.
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| US10163580B2 (en) | 2017-05-08 | 2018-12-25 | Wuhan China Star Optoelectronics Technology Co., Ltd. | OLED device and method for manufacturing the same |
| CN107565026B (en) * | 2017-08-30 | 2019-04-23 | 电子科技大学 | A kind of double-function device and preparation method thereof based on perovskite material |
| 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 |
| CN110739399B (en) * | 2019-10-24 | 2023-04-07 | 昆明物理研究所 | NPB/nitrogen-doped graphene nano heterojunction ultraviolet detector with flexible vertical structure and preparation method thereof |
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