CN110534657A - A kind of top emitting device and preparation method thereof and full color display - Google Patents

A kind of top emitting device and preparation method thereof and full color display Download PDF

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Publication number
CN110534657A
CN110534657A CN201910695967.9A CN201910695967A CN110534657A CN 110534657 A CN110534657 A CN 110534657A CN 201910695967 A CN201910695967 A CN 201910695967A CN 110534657 A CN110534657 A CN 110534657A
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China
Prior art keywords
chamber
emitting device
regulating course
top emitting
layer
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CN201910695967.9A
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Inventor
彭俊彪
黄国辉
穆兰
曹丽娟
罗宇
李妙姿
李丹阳
郭标
王俊杰
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to CN201910695967.9A priority Critical patent/CN110534657A/en
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/85Arrangements for extracting light from the devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating

Abstract

The invention discloses a kind of top emitting device structure and preparation method thereof and full color display, the top emitting device includes the anode being arranged successively from bottom to up, the long regulating course of chamber, hole transmission layer, luminescent layer, electron transfer layer, cathode or the long regulating course of cathode, chamber, electron transfer layer, luminescent layer, hole transmission layer, anode.The long regulating course of chamber is PEDOT:PSS, NiOx, IGZO or graphene oxide.The long regulating course of chamber is prepared by spin-coating method or print process.Due to the good conductivity of the long regulating course of chamber and light transmittance, therefore when light regulating course long by chamber from emission of cathode, light loss is less, the injection of device carrier is had little influence on simultaneously, the external quantum efficiency of the top emitting device of preparation solves the problems, such as that blue light top emitting device color is partially white close to bottom emitting device.The material processing method of this low cost, while obtaining higher electric property, moreover it is possible to improve the excitation purity that shines, promote display colour gamut, obtain preferable display effect.

Description

A kind of top emitting device and preparation method thereof and full color display
Technical field
The invention belongs to the technical fields that semiconductor is shown, and in particular to a kind of top emitting device and preparation method thereof with it is complete Colour display screen display screen.
Background technique
With the development of display material of new generation, OLED/QLED comes into the visual field of people as high-performance display screen. Most of OLED/QLED/Pe-LED is bottom emitting device architecture at present, since bottom TFT and cabling occupy most of area, is made The lighting area very little of bottom emitting device is obtained, this is unfavorable for the development of sharpness screen.Therefore, it is based on top emitting device knot The OLED/QLED/Pe-LED of structure is at our finer selection.However, top emitting device due to microcavity effect, can make the face that shines Color changes, such as blue light is partially white, and different to different photochromic influences.Therefore, for top emitting device, Wo Menxu Want the chamber of adjusting means long;It the use of the long material of more extensive adjusting cavity is at present tin indium oxide (ITO), this is because ITO Material has good conductivity and light transmittance, and can form Ohmic contact with metal, but this material cost is higher, and right In the device of high-resolution pixel structure, sputter relatively difficult.Therefore need to develop solution processable, have good electrical conductivity And the long material that adjusts of chamber of light transmittance can be prepared in conjunction with techniques such as ink jet printings with sharpness screen.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the object of the present invention is to provide a kind of top emitting devices And preparation method thereof and full color display.
The purpose of the present invention is realized at least through one of following technical scheme.
A kind of top emitting device, including be arranged successively from bottom to up the long regulating course of anode, chamber, hole transmission layer, shine Layer, electron transfer layer, cathode or cathode, the long regulating course of chamber, electron transfer layer, luminescent layer, hole transmission layer, anode;The chamber The material of long regulating course is poly- 3,4-rthylene dioxythiophene: poly styrene sulfonate (PEDOT:PSS), nickel oxide (NiOx), oxygen Change indium gallium zinc (IGZO) or graphene oxide.
Further, the long regulating course of the chamber with a thickness of 1nm-160nm, preferably 20-100nm.
Further, the long regulating course of the chamber is prepared by spin-coating method or ink jet printing method.
Some preferred embodiments according to the present invention, for the anode or cathode, there is no particular limitation, selects ability The common electrode material preparation in domain.In some specific embodiments, the reflective cathode is ITO/Ag/ITO.
Some preferred embodiments according to the present invention, for the electron transfer layer, there is no particular limitation, selects ability The common electron transport layer materials preparation in domain.In some specific embodiments, the electron transfer layer is zinc oxide nano Rice grain;Particularly, for blue light top emitting device, the electron transfer layer is doping polyethyleneimine or polyethoxy ethylene The Zinc oxide nanoparticle of imines or ethanol amine, wherein the doping of polyethyleneimine or polyethoxy aziridine or ethanol amine Mass percent is 0.1%-0.6%, and preferred mass percentage is 0.4%;For the top emitting device of feux rouges and green light, electronics Transport layer is Zinc oxide nanoparticle;For electron transfer layer, annealing temperature and time are preferably 100-150 DEG C, 10-20 Minute, preparation method is spin-coating method or ink jet printing method.
Some preferred embodiments according to the present invention, for the luminescent layer, there is no particular limitation, selects this field (amount Sub- point luminescent diode, perovskite light emitting diode, Organic Light Emitting Diode) commonly emitting layer material preparation.One In a little specific embodiments, in the luminescent layer, blue light material is poly- (alkoxyl phenyl substituted fluorene-S, S- dioxy-dibenzo thiophene Pheno), 2- methyl -9,10- two (2- naphthalene) anthracene: p- bis- (p- N, N- diphenylaminostyrene base) benzene and blue light quantum point.
Some preferred embodiments according to the present invention, for the hole transmission layer, there is no particular limitation, selects ability The common hole transport layer material preparation in domain.In some specific embodiments, the hole transmission layer preferably includes 4, (carbazole -9- base) triphenylamine (TCTA) of 4', 4''- tri- and molybdenum oxide, poly- (9- vinyl carbazole), poly- [(9,9- di-n-octyl fluorenyl - 2,7- diyl)-alt- (4,4'- (N- (4- normal-butyl) phenyl)-diphenylamines)] or N, N'- diphenyl-N, N'- (1- naphthalene)- At least one of 1,1'- biphenyl -4,4'- diamines.
Some preferred embodiments according to the present invention, for the cathode, there is no particular limitation, selects commonly used in the art Cathode material preparation.In some specific embodiments, the cathode is preferably magnesium/silver.
The preparation method of the top emitting device by the long adjusting layer material spin coating of chamber or is printed in the cathode or anode On, it is then annealed to obtain the long regulating course of chamber, is finally sequentially prepared other function layer and electrode evaporation again.
Further, when the material of the long regulating course of chamber is PEDOT:PSS, the temperature of annealing is 120-200 DEG C, is moved back The fiery time be 10-20min, preferably 170 DEG C, 10 minutes;When the material of the long regulating course of chamber is NiOx, the temperature of annealing It is 200-400 DEG C, time 20-60min, preferably 400 DEG C, 20 minutes;When the material of the long regulating course of chamber is graphene oxide When, the temperature of annealing is 100-250 DEG C, time 15-30min, preferably 120 DEG C, 20 minutes.
A kind of full color display is made of above-mentioned top emitting device, and the top emitting device is respectively by with insulating properties The pixel isolation layer of energy limits, and the long regulating course of the chamber of top emitting device is prepared by spin coating, ink-jet printing process.
The full color display forms three primary colors by red, green, blue, and the glow peak of blue light is in 450nm-470nm, the hair of green light Photopeak is in 510nm-530nm, and the glow peak of feux rouges is in 610nm-630nm.Thickness of the long regulating course of chamber in red, green, blue pixel hole Degree, material can be different.
Since PEDOT:PSS, NiOx, indium gallium zinc (IGZO) or graphene oxide have good conductivity and light transmission Rate, therefore, when light regulating course long by chamber from emission of cathode, light loss is less, while having little influence on the carrier of device The external quantum efficiency of injection, the feux rouges of preparation, green light and blue light top emitting device is close or outer quantum better than bottom emitting device Efficiency, while the photochromic of blue light top emitting device is improved, and on the one hand shows and is able to solve top emitting device color not Pure problem makes device issue the blue light of standard, on the other hand shows that the spectrum of feux rouges, green light and blue light top emitting device is equal Narrow, this is conducive to the color saturation and colour gamut that improve display screen, keeps display effect more true to nature.
Compared with the existing technology, top emitting device structure and preparation method thereof of the invention has the following advantages that and beneficial to effect Fruit:
1, the present invention is for the first time using the poly- 3,4-rthylene dioxythiophene with good electrical conductivity and light transmittance: polystyrolsulfon acid The long regulating course of chamber of salt, nickel oxide, tin indium oxide, indium gallium zinc or graphene oxide as top emitting device, can pass through Spin-coating method and ink jet printing preparation, adjusting method is easy, at low cost, while obtaining higher device electric property, moreover it is possible to mention High illuminant colour purity promotes display colour gamut, obtains preferable display effect.
2, it is suitble to ink jet printing to prepare the colorful display screen based on top emitting device structure, is prepared by different colours personalization The long regulating course of the different chamber of thickness saves material and preparation cost;Meanwhile it can be made in sharpness screen dot structure The standby long regulating course of chamber, overcomes the problem of the long regulating course difficulty of the sputtering chamber in high-resolution display screen.
3, due to poly- 3,4-rthylene dioxythiophene: poly styrene sulfonate, nickel oxide, tin indium oxide, indium gallium zinc and Graphene oxide has good conductivity and light transmittance, therefore, when light regulating course long by chamber from emission of cathode, light loss It is less, while the carrier injection of device is had little influence on, the external quantum efficiency of the top emitting device of preparation is close or is better than bottom The external quantum efficiency of ballistic device, while it being able to solve the impure problem of top emitting device color, so that device is issued the light of saturation Color.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of top emitting device of the present invention;
Fig. 2 is the true color pixel arrangement schematic cross-section based on top emitting device structure of the present invention;
Fig. 3 is the electroluminescent light of the blue light top emitting device (with and without the long regulating course of chamber) based on spin-coating method preparation in embodiment 1 Spectrogram;
Fig. 4 is Current density-voltage-luminosity response of the blue light top emitting device based on spin-coating method preparation in embodiment 1 Figure;
Fig. 5 is the electroluminescent hair of the blue light top emitting device (with and without the long regulating course of chamber) based on ink jet printing method preparation in embodiment 2 Light spectrogram;
Fig. 6 is Current density-voltage-light characteristic of the blue light top emitting device based on ink jet printing method preparation in embodiment 2 Curve graph;
Wherein, 101- reflective cathode;The long regulating course of 102- chamber;103- electron transfer layer;104- luminescent layer;105- electron-transport Layer;106- anode.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited In this.
Embodiment 1
A kind of blue light top emitting device, the device architecture are upside-down mounting top emitting device, and cathode, electronics including stacking gradually pass Defeated layer, luminescent layer, hole transmission layer and anode;The cathode is ITO/Ag/ITO combination electrode;Electron transfer layer is that doping is poly- The Zinc oxide nanoparticle of aziridine;The luminescent layer is poly- (alkoxyl phenyl substituted fluorene-S, S- dioxy-dibenzo thiophene Pheno);The hole transmission layer is (carbazole -9- base) triphenylamine of 4,4', 4''- tri- and molybdenum oxide, and the cathode is silver, the chamber Long regulating course is PEDOT:PSS, and with a thickness of 100nm, device architecture is as shown in Figure 1.
The following steps are included: PEDOT:PSS is spin-coated on anode, revolving speed and time is for the preparation method of the device 2000rpm and 30s, then the thermal station in glove box in 170 DEG C heats 15min;Then 0.4%wt polyethyleneimine will be adulterated Zinc oxide nanoparticle be spin-coated on PEDOT:PSS, as electron transfer layer, revolving speed and time are 4000rpm and 30s;It will Blue light material poly- (alkoxyl phenyl substituted fluorene-S, S- dioxo-dibenzothiophene) with revolving speed is 3000rpm, time 30s is spun on Luminescent layer is obtained on Zinc oxide nanoparticle layer;Then 50nm4,4', (carbazole -9- base) triphenylamine of 4''- tri- and 8nm oxygen is deposited Change molybdenum, obtains hole transmission layer;20nm silver electrode is finally deposited, the top emitting device is prepared.
The electroluminescent peak of obtained device is 456nm, and opening bright voltage is 3.4V, current efficiency 1.3cd/A, electroluminescent hair Light spectrum, Current density-voltage-luminosity response are shown in Fig. 3, Fig. 4;As seen from Figure 3, long without chamber when top emitting device When regulating course, the electroluminescent light spectrum width of device, color is partially white, and when adding the long regulating course of one layer of PEDOT:PSS chamber, device Electroluminescent spectrum narrows, and sending is the blue light being more saturated;Meanwhile from fig. 4, it can be seen that being added to one layer of PEDOT: The top emitting device current density plot of the long regulating course of PSS chamber is normal, without leakage current, and open it is bright normal, without because increasing One layer of PEDOT:PSS and open bright higher problem.
Fig. 2 is the true color pixel arrangement schematic cross-section based on the design of this top emitting device structure, wherein polyimides Red, green, blue luminescent device is separated as pixel limiting structure, wherein a length of 83 microns of pixel hole, it is 25 microns wide, it is high by 1.5 Micron, left and right adjacent pixel are divided into 10 microns, are divided into 22 microns between neighbouring pixel hole between cheating;Meanwhile for each A feux rouges top emitting device, Zinc oxide nanoparticle with a thickness of 35nm, red light quantum point is then deposited with a thickness of 15nm (carbazole -9- base) triphenylamine of 50nm 4,4', 4''- tri- and 8nm molybdenum oxide;For each green light top emitting device, PEDOT:PSS with a thickness of 40nm, Zinc oxide nanoparticle with a thickness of 35nm, green light quantum point with a thickness of 20nm, then 50nm 4,4', (carbazole -9- base) triphenylamine of 4''- tri- and 8nm molybdenum oxide is deposited;For each blue light top emitting device, PEDOT:PSS with a thickness of 100nm, adulterate the Zinc oxide nanoparticle of polyethyleneimine with a thickness of 40nm, poly- (alkoxy benzene Base substituted fluorene-S, S- dioxo-dibenzothiophene) with a thickness of 40nm, 50nm 4,4', 4''- tri- (carbazole -9- base) is then deposited Triphenylamine and 8nm molybdenum oxide.20nm silver electrode is finally deposited.
Embodiment 2
A kind of blue light top emitting device, the device architecture are upside-down mounting top emitting device, and cathode, electronics including stacking gradually pass Defeated layer, luminescent layer, hole transmission layer and anode;The cathode is ITO/Ag/ITO combination electrode;Electron transfer layer is that doping is poly- The Zinc oxide nanoparticle of aziridine;The luminescent layer is 2- methyl -9,10- two (2- naphthalene) anthracene: p- bis- (p- N, N- bis- Phenyl amino styryl) benzene;The hole transmission layer is 4,4', (carbazole -9- base) triphenylamine of 4''- tri- and molybdenum oxide;It is described Cathode is silver.The long regulating course of chamber is PEDOT:PSS, and with a thickness of 50nm, device architecture is as shown in Figure 1.
The following steps are included: PEDOT:PSS is spin-coated on anode, revolving speed and time is for the preparation method of the device 2000rpm and 30s, then the thermal station in glove box in 170 DEG C heats 15min;Then 0.4%wt polyethyleneimine will be adulterated ZnO be spin-coated on PEDOT:PSS, revolving speed and time are 7000rpm and 30s;Then methyl -9 blue light material 2- are deposited altogether, 10- bis- (2- naphthalene) anthracene: p- bis- (p- N, N- diphenylaminostyrene base) benzene, with a thickness of 25nm;Then it is deposited 20nmTCTA, 8nm molybdenum oxide;20nm silver electrode is finally deposited.
The peak EL of obtained device is 466nm, and opening bright voltage is 3.2V, current efficiency 0.38cd/A, electroluminescent light Spectrum, Current density-voltage-luminosity response are shown in Fig. 5, Fig. 6.It is seen from fig 5 that when top emitting device is adjusted that chamber is not long When layer, due to microcavity effect, the electroluminescent light spectrum width of device, color is partially white, and adds one layer of long regulating course of PEDOT:PSS chamber When, the electroluminescent spectrum of device narrows, and sending is the blue light being more saturated;Meanwhile from fig. 6, it can be seen that being added to one The top emitting device of the layer long regulating course of PEDOT:PSS chamber open it is bright normal, being opened because one layer of PEDOT:PSS is increased Bright higher problem.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (9)

1. a kind of top emitting device, which is characterized in that including be arranged successively from bottom to up the long regulating course of anode, chamber, hole pass Defeated layer, luminescent layer, electron transfer layer, cathode or cathode, the long regulating course of chamber, electron transfer layer, luminescent layer, hole transmission layer, sun Pole;The material of the long regulating course of chamber is PEDOT:PSS, nickel oxide, indium gallium zinc or graphene oxide.
2. top emitting device structure according to claim 1, which is characterized in that the long regulating course of chamber with a thickness of 1nm- 160nm。
3. top emitting device according to claim 1, which is characterized in that the long regulating course of chamber passes through spin-coating method or ink-jet Print process is prepared.
4. top emitting device according to claim 1, which is characterized in that the electron transfer layer is doping polyethyleneimine The Zinc oxide nanoparticle of amine, polyethoxy aziridine or ethanol amine, or the Zinc oxide nanoparticle to undope.
5. top emitting device according to claim 1, which is characterized in that the luminescent layer is poly- (alkoxyl phenyl substitution Fluorenes-S, S- dioxo-dibenzothiophene), 2- methyl -9,10- two (2- naphthalene) anthracene: p- bis- (p- N, N- diphenyl amino benzene second Alkenyl) benzene or blue light quantum point.
6. top emitting device according to claim 1, which is characterized in that the hole transmission layer is 4,4', 4''-, tri- (click Azoles -9- base) triphenylamine (TCTA) and molybdenum oxide, poly- (9- vinyl carbazole), poly- [(9,9- di-n-octyl fluorenyl -2,7- diyl) - Alt- (4,4'- (N- (4- normal-butyl) phenyl)-diphenylamines)] or N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl - 4,4'- diamines.
7. the preparation method of top emitting device described in a kind of any one of claim 1-6, which is characterized in that by the long tune of chamber The spin coating of ganglionic layer material is printed on the cathode or anode, is then annealed to obtain the long regulating course of chamber, finally again successively Prepare other function layer and electrode evaporation.
8. preparation method according to claim 7, which is characterized in that when the material of the long regulating course of chamber is PEDOT:PSS, The temperature of annealing is 120-200 DEG C, time 10-20min;When the material of the long regulating course of chamber is NiOx, annealing Temperature be 200-400 DEG C, time 20-60min;When the material of the long regulating course of chamber is graphene oxide, annealing Temperature is 100-250 DEG C, time 15-30min.
9. a kind of full color display, which is characterized in that it is made of multiple top emitting devices described in any one of claims 1-6, And the top emitting device is limited by the pixel isolation layer with insulation performance respectively, the long regulating course of the chamber of top emitting device is logical Cross spin coating, ink-jet printing process preparation.
CN201910695967.9A 2019-07-30 2019-07-30 A kind of top emitting device and preparation method thereof and full color display Pending CN110534657A (en)

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