CN101114699A - Novel electroluminescent device and method for producing the same - Google Patents
Novel electroluminescent device and method for producing the same Download PDFInfo
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- CN101114699A CN101114699A CNA2007100498801A CN200710049880A CN101114699A CN 101114699 A CN101114699 A CN 101114699A CN A2007100498801 A CNA2007100498801 A CN A2007100498801A CN 200710049880 A CN200710049880 A CN 200710049880A CN 101114699 A CN101114699 A CN 101114699A
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Abstract
The invention discloses a novel organic electroluminescent device, comprising a conducting base plate or a substrate, an anode layer and a cathode layer, an electrode on the surface of the substrate or the conducting base plate and an organic functional layer between the anode layer and the cathode layer which comprises at least a luminescent layer emitting light driven by an additional power, and is characterized in that the organic functional layer further comprises one or more type of a compound regulation layer, an electron transporting layer, a hole-transporting layer and a hole blocking layer, the compound regulation layer is a carrier compound regulation layer which is made by one or more materials of poly-N-vinylcarbazole, BCP, two(2-methyl-8-quinoline acid radical complex)three phenyl silanol aluminum(III), two (2-methyl-8-quinoline acid radical complex)4-phenol aluminum(III) and two(2-methyl-8-quinoline acid radical complex)4-phenyl-based phenol aluminum (III).
Description
Technical field
The present invention relates to technical field of organic electroluminescence in the electronic devices and components, relate to organic electroluminescence device of a kind of new structure and preparation method thereof.
Background technology
Display of organic electroluminescence has significant advantage: from main light emission, low-voltage DC driven, high-low temperature resistant, complete curings, wide visual angle, color enrich, do not need backlight, the visual angle is big, power is low, response speed can reach LCD 1000 times, and its manufacturing cost is lower than the LCD of equal performance, and it can provide technical support for little demonstration.Therefore, display of organic electroluminescence becomes the focus of people's research.
1987, people such as the C.W.Tang of Kodak were summing up the device of having invented sandwich structure on forefathers' the basis: they adopt, and fluorescence efficiency is very high, electronic transmission performance and the good organic small molecule material oxine aluminium (Alq of filming performance
3), with the aromatic diamine with hole transport characteristic (diamine) derivative make low driving voltage (＜10V), high-quantum efficiency (1%), high brightness (＞1000cd/m
2) organic EL device, this breakthrough has remotivated the enthusiasm of people for organic EL, makes people see the hope of organic electroluminescence device as flat-panel display device of new generation.From then on, organic electroluminescent has been gone on the road that develops rapidly, and people are synthetic at material, the device architecture design, and all many-sides such as carrier transport have been carried out deep research, make the performance of organic electroluminescence device move closer to the practicability level.
Organic elctroluminescent device is as a kind of novel photoconductive organic semiconductor information functional material and solid plate display device, and development in recent years is very fast.White light organic electroluminescent display device is the hot topic of OLED research and development in recent years especially, because white light is contained red, green, blue three kinds of primary colours of whole visible region, easily be converted to full color display device, this is one of best approach that obtains at present the full color demonstration, also will be OLED device practicability, a commercial cutting point.White light organic electroluminescent device life-span, problems such as colorimetric purity and stability are the stumbling-blocks of restriction its practicability and industrialization always.At present complex devices structure and manufacturing process have had a strong impact on its industrialization especially, high manufacturing cost and the device performance that is difficult to repetition all make its widely application be affected.
Although the OLED technology has obtained significant progress in recent years,, still there are a lot of problem demanding prompt solutions in present technology and technology in the organic electroluminescent field.No matter be that organic electroluminescence device is realized full-colorization demonstration, still use as single mains lighting supply, the preparation of devices that can send white light is vital, and the constructional simplicity of this kind device, high brightness, high efficiency, long-life all are the key factors that influences device practicability; Especially utilize known material, adopt structure to save the device of material simply, as far as possible as far as possible with good photoelectric properties, method as spin coating or inkjet printing, realize the luminous of high performance white, and obtain device aspect efficiently, need people to go continuous exploration especially.
Summary of the invention
Technical problem to be solved by this invention is how organic electroluminescence device that a kind of performance significantly improves and preparation method thereof is provided, purpose is to utilize the organic material of conventional function admirable, can be used as the functional material in the organic layer, the component of the 26S Proteasome Structure and Function layer by changing device prepares high performance organic luminescent device.
Technical problem proposed by the invention is to solve like this: construct a kind of novel electroluminescent device, comprise electrically-conductive backing plate or substrate, anode layer and cathode layer, wherein a kind of electrode is positioned at substrate or electrically-conductive backing plate surface, between described anode layer and the cathode layer organic function layer is set, which comprises at least luminescent layer, described luminescent layer is luminous under the driving of additional power source, it is characterized in that: described organic function layer also comprises compound regulation and control layer, electron transfer layer, in hole transmission layer and the hole blocking layer one or more, wherein compound regulation and control layer is the compound regulation and control layer of charge carrier, its thickness is at 0～20nm, the compound regulation and control layer material of described charge carrier can be the class material with electron transport ability and energy blocking hole, as the poly N-vinyl carbazole, BCP, two (2-methyl-8-quinoline acid group closes) tri-phenyl-silane aluminium alcoholates (III), in two (2-methyl-8-quinoline acid group closes) 4-phenol aluminium (III) and two (2-methyl-8-quinoline acid group closes) the 4-phenylphenol aluminium (III) one or more.
According to novel electroluminescent device provided by the present invention, it is characterized in that, described luminescent layer is to send the organic material layer of blue light or send the organic material layer of green glow or send the organic material layer of ruddiness, under the driving of described additional power source, send blue light, green glow or ruddiness that performance improves respectively.
According to novel electroluminescent device provided by the present invention, it is characterized in that, described luminescent layer is the combination layer that sends the organic material layer of blue light and send the organic material layer of green glow, described compound regulation and control layer is arranged between the two, under the driving of described additional power source, along with change in voltage is sent blue light, green glow or the blue or green light that performance improves.
According to novel electroluminescent device provided by the present invention, it is characterized in that, described luminescent layer is the combination layer that sends the organic material layer of ruddiness and send the organic material layer of green glow, described compound regulation and control layer is arranged between the two, under the driving of described additional power source, along with change in voltage is sent ruddiness, green glow or the gold-tinted that performance improves.
According to novel electroluminescent device provided by the present invention, it is characterized in that, described luminescent layer is the combination layer that sends the organic material layer of blue light and send the organic material layer of ruddiness, described compound regulation and control layer is arranged between the two, under the driving of described additional power source, along with change in voltage is sent ruddiness, blue light or the purple light that performance improves.
According to novel electroluminescent device provided by the present invention, it is characterized in that, described luminescent layer is the organic material layer that sends blue light, send the organic material layer of ruddiness and send the combination layer of the organic material layer of green glow, be provided with compound regulation and control layer between the adjacent layer, under the driving of described additional power source, along with change in voltage is sent the white light that performance improves.
According to novel electroluminescent device provided by the present invention, it is characterized in that, the described organic material layer that sends blue light is aromatic diamine compounds or star triphenyl amine compound, or carbazole polymer, or doping type blue fluorescent dyes or blue phosphorescent material, described aromatic diamine compounds is N, N '-two-(3-aminomethyl phenyl)-N, N '-diphenyl-[1,1 '-xenyl]-4,4 '-diamines or N, N '-two (3-naphthyl)-N, N '-diphenyl-[1,1 '-diphenyl]-4,4 '-diamines, described star triphenyl amine compound are three-[4-(5-phenyl-2-thienyl) benzene] amine or m-TDATA, and described carbazole polymer is a polyvinylcarbazole; The described organic material layer that sends green glow can be one or more in organic fluorescence materials, fluorescent dye, phosphor material and the metal complex material; The described organic material layer that sends redness is red fluorescence doping type layer or red phosphorescent doped layer or red fluorescence material, and the red fluorescence doped layer comprises material of main part and red fluorescence doping fuel, and this material of main part is Alq
3Perhaps ADN, described red fluorescence dopant dye and described red fluorescence material are DCJTB or DCM or DCM1 red dye, and the red phosphorescent doped layer comprises material of main part and red phosphorescence material, and this material of main part is CBP or NPB or TPBI or Alq
3Perhaps TAZ, red phosphorescence material is btp2Ir (acac) or (DPQ) Pt (acac) or (nazo)
2Ir (Fppz).
According to novel electroluminescent device provided by the present invention, it is characterized in that, the used material of described hole blocking layer is the class material with electron transport ability and energy blocking hole, specifically is in poly N-vinyl carbazole, BCP, two (2-methyl-8-quinoline acid group closes) tri-phenyl-silane aluminium alcoholates (III), two (2-methyl-8-quinoline acid group closes) 4-phenol aluminium (III) and two (2-methyl-8-quinoline acid group closes) the 4-phenylphenol aluminium (III) one or more.
According to novel electroluminescent device provided by the present invention, it is characterized in that, described compound regulation and control layer, cathode layer and anode layer are respectively arranged with implanted layer, described electron transfer layer and implanted layer material are metal complex material Huo person oxadiazole electron-like transferring material, perhaps imidazoles electron transport material; Described hole transport layer material can be aromatic diamine compounds or star triphenyl amine compound, or carbazole polymer etc.
According to novel electroluminescent device provided by the present invention, it is characterized in that, described metal complex material is to have the compounds that central metal atom constitutes, as oxine aluminium or oxine gallium or two [2-(2-hydroxy phenyl-1)-pyridine] beryllium, Suo Shu oxadiazole electron-like transferring material is 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3, the 4-oxadiazole, described imidazoles electron transport material is 1,3,5-three (N-phenyl-2-benzimidazolyl-2 radicals) benzene; Described aromatic diamine compounds is N, N '-two-(3-aminomethyl phenyl)-N, N,-diphenyl-[1,1 '-xenyl]-4,4 '-diamines or N, N '-two (3-naphthyl)-N, N '-diphenyl-[1,1 ,-diphenyl]-4,4,-diamines and derivative thereof, described star triphenyl amine compound are three-[4-(5-phenyl-2-thienyl) benzene] amine or m-TDATA, and described carbazole polymer is polyvinylcarbazole or monomer whose etc.
According to novel electroluminescent device provided by the present invention, it is characterized in that described electrically-conductive backing plate is ito substrate or sheet metal or silicon substrate; Described substrate is glass or flexible substrate or sheet metal etc., and wherein flexible substrate is ultra-thin solid-state thin slice, polyesters or poly-phthalimide compounds etc.; Described anode layer can be metal-oxide film or metallic film, and this metal-oxide film is ito thin film or zinc-oxide film or zinc tin oxide film, and this metallic film is the higher metallic films of work function such as gold, copper, silver; Described anode layer can be PEDOT:PSS or PANI class organic conductive polymer; Described anode implanted layer and resilient coating can be the inorganic molecules compounds or have the organic compound of low the highest occupied energy level (HOMO) energy level, as phthalein cyanogen copper (CuPc) and silicon dioxide (SiO
2); Described cathode layer comprises resilient coating and metal level, described cushioning layer material can be the inorganic molecules compound or have the organic compound of high minimum unoccupied energy level (LUMO) energy level, for example LiF or CsF, described metal layer material can be metallic film or alloy firm, and this metallic film can be the alloy firm of the lower metallic film of lithium or work functions such as magnesium or calcium or strontium or aluminium or indium or they and copper or gold or silver etc.
The preparation method of this organic electroluminescence device may further comprise the steps:
1. utilize washing agent, ethanolic solution, acetone soln and deionized water that substrate or electrically-conductive backing plate are carried out ultrasonic cleaning, it is dry to clean the back;
2. substrate is sent to the preparation of carrying out electrode in the vacuum evaporation chamber, described electrode comprises anode layer or cathode layer, perhaps electrically-conductive backing plate is carried out array and handles;
The substrate that 3. will prepare electrode moves into vacuum chamber, under oxygen pressure ring border to carrying out the preliminary treatment of low energy oxygen plasma;
4. the substrate after will handling sets gradually organic functional layer according to device architecture, described organic function layer comprise luminescent layer, carrier blocking layers and (or) implanted layer and resilient coating;
5. finish to carry out in the vaporization chamber of back at condition of high vacuum degree the preparation of another electrode in the organic layer spin coating, described electrode comprises cathode layer or anode layer;
6. ready-made device is sent to glove box and encapsulates, glove box is an atmosphere of inert gases;
7. current-voltage-the light characteristic of test component, the luminescent spectrum parameter of test component simultaneously.
Wherein step spin coating method 4. also can replace with the method that vacuum evaporation or spin coating combine with vacuum evaporation according to the organic material difference that is adopted.
Organic electroluminescence device provided by the present invention, material therefor are organic substance/macromolecule, thereby range of choice is wide, can realize multicolor displaying; Related material is the organic semiconducting materials of the function admirable of routine, obtain device efficiently, synthetic and the device technical maturity of material therefor, cost are low, compare with the device that obtains function admirable by synthetic new material of cost plenty of time, this research has been opened up an approach that shows unique characteristics from the angle of technology, used compound all has stronger fluorescence among the present invention in liquid and solid film, has quite high heat, light, electricity and physical chemistry equistability simultaneously again.Driving voltage is low, and luminosity and luminous efficiency height can be made into flexible display device; Response speed is fast, and luminous visual angle is wide; Device is ultra-thin, and volume is little, and is in light weight; What is more important, luminous organic material are that material selects to provide broad scope with its intrinsic diversity, by to the design of organic molecular structure, assemble and cut out, can satisfy many-sided different needs and be easy to realize that large tracts of land shows.Also have the preparation method rationally simple, easy to operate.
Description of drawings
Fig. 1 is the structural representation of organic electroluminescence device provided by the present invention;
Fig. 2 is the structural representation of embodiment 1 provided by the present invention;
Fig. 3 is the structural representation of embodiment 2 provided by the present invention;
Fig. 4 is the structural representation of embodiment 3 provided by the present invention;
Fig. 5 is the structural representation of embodiment 4 provided by the present invention;
Fig. 6 is the brightness-voltage tester curve chart of device described in the embodiment 1 provided by the present invention;
Fig. 7 is the luminescent spectrum of device under the 10V forward voltage described in the embodiment 2 provided by the present invention.
Wherein, 1, substrate (perhaps electrically-conductive backing plate), 2, anode layer, 3, luminescent layer, 4, compound regulation and control layer, 5, cathode layer, 6, additional power source, 7, hole transmission layer, 31, green light emitting layer (sending the organic material layer of green glow), 32, blue light-emitting layer (sending the organic material layer of blue light), 33, green light emitting layer (sending the organic material layer of green glow), 34, blue light-emitting layer (sending the organic material layer of blue light), 35, red light emitting layer (sending the organic material layer of ruddiness), 36, red light emitting layer (sending the organic material layer of ruddiness), 37, green light emitting layer (sending the organic material layer of green glow).
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing.
Technical scheme of the present invention provides a kind of organic electroluminescence device that can send multiple color of light, as shown in Figure 1, and 1, substrate, 2, anode layer, 3, luminescent layer, 4, compound regulation and control layer, 5, cathode layer, 6, additional power source.
As shown in Figure 2, the structure of device comprises substrate 1, anode layer 2, and luminescent layer 3, compound regulation and control layer 4, cathode layer 5, additional power source 6, green light emitting layer 31, hole transmission layer 7, device is green light under the driving of additional power source 6.
As shown in Figure 3, the structure of device comprises substrate 1, anode layer 2, and luminescent layer 3, compound regulation and control layer 4, cathode layer 5, additional power source 6, blue light-emitting layer 32, green light emitting layer 33, device be blue light-emitting, green glow or blue or green light under the driving of additional power source 6.
As shown in Figure 4, the structure of device comprises substrate 1, anode layer 2, and luminescent layer 3, compound regulation and control layer 4, cathode layer 5, additional power source 6, red light emitting layer 35, blue light-emitting layer 34, device glows under the driving of additional power source 6, blue light or purple light.
As shown in Figure 5, the structure of device comprises substrate 1, anode layer 2, luminescent layer 3, compound regulation and control layer 4, cathode layer 5, additional power source 6, green light emitting layer 37, red light emitting layer 36.Device is green light, ruddiness or gold-tinted under the driving of additional power source 6.
Hole transmission layer 7 among the present invention is double, and to do blue light-emitting layer 32,34 materials can be aromatic diamine compounds or star triphenyl amine compound, or carbazole polymer mixes or be doping type blue fluorescent dyes or blue phosphorescent material.Described aromatic diamine compounds can be N, N '-two-(3-aminomethyl phenyl)-N, N '-diphenyl-[1,1 '-xenyl]-4,4 '-diamines or N, N '-two (3-naphthyl)-N, N '-diphenyl-[1,1 '-diphenyl]-4,4 '-diamines, described star triphenyl amine compound can be three-[4-(5-phenyl-2-thienyl) benzene] amine or m-TDATA, and described carbazole polymer can be a polyvinylcarbazole, described metal complex can be BAlq, and described other class blue light materials can be DPVBi, BCzVB, Perylene, BczVBi etc.
Green light emitting layer 31,33,37 among the present invention can be the green organic fluorescence materials with electron transport ability, and fluorescent dye or phosphor material or metal complex are as oxine aluminium (Alq
3).
Red light emitting layer 35,36 among the present invention can be Alq
3: doping type materials such as DCJTB, material of main part are Alq
3, perhaps the luminescent spectrum of the material that differs greatly of ADN or the like energy level and material of main part can with the absorption spectrum coupling of dopant dye, dopant dye is generally DCJTB or red dyes such as DCM or DCM1.
Compound regulation and control layer 4 material among the present invention can be the hole barrier materials with electron transport ability, as poly N-vinyl carbazole, BCP, two (2-methyl-8-quinoline acid group closes) tri-phenyl-silane alcohol (silanolate) aluminium (III), two (2-methyl-8-quinoline acid group closes) 4-phenol aluminium (III) or two (2-methyl-8-quinoline acid group closes) 4-phenylphenol aluminium (III).
Adopt the OLED device architecture of the present invention's preparation to be exemplified below:
1. the double blue light-emitting layer/compound regulation and control layer/green light emitting layer double as electron transfer layer/cathode layer of doing of glass/ITO/ hole transmission layer
2. the double blue light-emitting layer/compound regulation and control layer/red light emitting layer/electron transfer layer/cathode layer of doing of glass/ITO/ hole transmission layer
3. glass/ITO/ hole transmission layer/blue light-emitting layer/compound regulation and control layer/red light emitting layer/electron transfer layer/cathode layer
4. glass/ITO/ hole transmission layer/red light emitting layer/double electron transfer layer/cathode layer of doing of compound regulation and control layer/green light emitting layer
5. glass/ITO/ hole transmission layer/blue light-emitting layer/compound regulation and control layer/red light emitting layer/compound regulation and control layer/green light emitting layer/electron transfer layer/cathode layer
6. the double double electron transfer layer/cathode layer of doing of violet light layer/hole blocking layer of doing of glass/conducting polymer/hole transmission layer
7. glass/conducting polymer/hole transmission layer/blue light-emitting layer/double electron transfer layer/cathode layer of doing of compound regulation and control layer/green light emitting layer
8. the double blue light-emitting layer/hole blocking layer/green light emitting layer/electron transfer layer/cathode layer of doing of glass/conducting polymer/hole transmission layer
9. the double blue light-emitting layer/double electron transfer layer/cathode layer of doing of compound regulation and control layer/green light emitting layer of doing of flexible polymer substrate glass/ITO/ hole transmission layer
10. the double electron transfer layer/cathode layer of doing of flexible polymer substrate glass/ITO/ hole transmission layer/blue light-emitting layer/hole blocking layer/green light emitting layer
Below be specific embodiments of the invention:
As shown in Figure 2, the luminescent layer 3 in the structure of device comprises blue light-emitting layer 31, electron transfer layer 7, and compound regulation and control layer 4, the device that does not wherein comprise compound regulation and control layer 4 is a conventional device.
The blue-light-emitting layer material of device is NPB, and the electric transmission layer material is Alq
3, compound regulation and control layer BCP, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/NPB (20nm)/BCP (0nm or 0.3nm)/Alq
3(50nm)/Mg:Ag (200nm)
The preparation method is as follows:
1. utilize washing agent, ethanolic solution, acetone soln and deionized water that the conductive substrate ito glass is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen.Wherein the ITO film above the glass substrate is as the anode layer of device, and the square resistance of ITO film is 10 Ω/, and thickness is 180nm.
2. dried substrate being moved into vacuum chamber, is under the oxygen pressure ring border of 20Pa ito glass to be carried out low energy oxygen plasma preliminary treatment 10 minutes at air pressure, and sputtering power is 0～20W.
3. the substrate after will handling is transferred to the organic vacuum vaporization chamber, treats that room pressure is 4 * 10
-4Pa begins to carry out the evaporation of organic film.According to the device architecture as mentioned above blue light material layer NPB of evaporation successively is 20nm, and the compound regulation and control layer of charge carrier BCP is 0.3nm, Alq
3Layer 10nm electron transfer layer.The evaporation speed 0.1nm/s of each organic layer, evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
4. finish the preparation of laggard row metal electrode at the organic layer evaporation.Its air pressure is 3 * 10
-3Pa, evaporation speed is～1nm/s, Mg in the alloy, the Ag ratio is～10: 1, thicknesses of layers is 100nm.Evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
5. ready-made device is encapsulated at glove box, glove box is 99.9% nitrogen atmosphere.
6. current-voltage-the light characteristic of test component, the luminescent spectrum parameter of test component simultaneously.
The brightness of described device-voltage tester curve such as Fig. 6;
As shown in Figure 3, the luminescent layer 3 in the structure of device comprises blue light-emitting layer 32, green light emitting layer 33, compound regulation and control layer 4.
The blue-light-emitting layer material of device is NPB, and the green emitting layer material is Alq
3, compound regulation and control layer BCP, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/NPB (20nm)/BCP (1.5nm)/Alq
3(50nm)/Mg:Ag (200nm)
The preparation of devices flow process is similar to embodiment 1.
Described device luminescent spectrum such as Fig. 7 under the 10V forward voltage.
Embodiment 3
As shown in Figure 4, the luminescent layer 3 in the structure of device comprises blue light-emitting layer 34, red light emitting layer 35, compound regulation and control layer 4.
The blue-light-emitting layer material of device is NPB, and the emitting red light layer material is Alq
3: DCJTB, compound regulation and control layer BCP, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/NPB (20nm)/BCP (0.3nm)/Alq
3: DCJTB (50nm)/Mg:Ag (200nm)
The preparation of devices flow process is similar to embodiment 1.
As shown in Figure 5, the luminescent layer 3 in the structure of device comprises red light emitting layer 36, green light emitting layer 37, compound regulation and control layer 4.
The green emitting layer material of device is Alq
3, the emitting red light layer material is Alq
3: DCJTB, compound regulation and control layer BCP, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/Alq
3: DCJTB (20nm)/BCP (0.3nm)/Alq
3(50nm)/Mg:Ag (200nm)
The preparation of devices flow process is similar to embodiment 1.
Luminescent layer in the structure of device comprises red light emitting layer, green light emitting layer, compound regulation and control layer, hole transmission layer.
The green emitting layer material of device is Alq
3, the emitting red light layer material is Alq
3: DCJTB, compound regulation and control layer BCP, hole transport layer material is NPB, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/NPB/Alq
3: DCJTB/BCP/Alq
3/ Mg:Ag (200nm)
The preparation of devices flow process is similar to embodiment 1.
Luminescent layer in the structure of white light parts comprises blue light-emitting layer, red light emitting layer, green light emitting layer, compound regulation and control layer.
The blue light-emitting layer of device is NPB, and the green emitting layer material is Alq
3, the emitting red light layer material is Alq
3: DCJTB, compound regulation and control layer BCP, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/NPB/BCP/Alq
3: DCJTB/BCP/Alq
3/ Mg:Ag
The preparation of devices flow process is similar to embodiment 1.
Claims (13)
1. novel electroluminescent device, comprise electrically-conductive backing plate or substrate, anode layer, cathode layer, wherein a kind of electrode is positioned at substrate or electrically-conductive backing plate surface, between described anode layer and the cathode layer organic function layer is set, which comprises at least luminescent layer, described luminescent layer is luminous under the driving of additional power source, it is characterized in that: described organic function layer also comprises compound regulation and control layer, electron transfer layer, in hole transmission layer and the hole blocking layer one or more, wherein compound regulation and control layer is the compound regulation and control layer of charge carrier, the compound regulation and control layer material of described charge carrier poly N-vinyl carbazole, BCP, two (2-methyl-8-quinoline acid group closes) tri-phenyl-silane aluminium alcoholates (III), in two (2-methyl-8-quinoline acid group closes) 4-phenol aluminium (III) and two (2-methyl-8-quinoline acid group closes) the 4-phenylphenol aluminium (III) one or more.
2. novel electroluminescent device according to claim 1, it is characterized in that, described luminescent layer is to send the organic material layer of blue light or send the organic material layer of green glow or send the organic material layer of ruddiness, under the driving of described additional power source, send blue light, green glow or ruddiness respectively.
3. novel electroluminescent device according to claim 1, it is characterized in that, described luminescent layer is the combination layer that sends the organic material layer of blue light and send the organic material layer of green glow, described compound regulation and control layer is arranged between the two, under the driving of described additional power source, along with change in voltage is sent blue light, green glow or blue or green light.
4. novel electroluminescent device according to claim 1, it is characterized in that, described luminescent layer is the combination layer that sends the organic material layer of ruddiness and send the organic material layer of green glow, described compound regulation and control layer is arranged between the two, under the driving of described additional power source, along with change in voltage is sent ruddiness, green glow or gold-tinted.
5. novel electroluminescent device according to claim 1, it is characterized in that, described luminescent layer is the combination layer that sends the organic material layer of blue light and send the organic material layer of ruddiness, described compound regulation and control layer is arranged between the two, under the driving of described additional power source, along with change in voltage is sent ruddiness, blue light or purple light.
6. novel electroluminescent device according to claim 1, it is characterized in that, described luminescent layer is the organic material layer that sends blue light, send the organic material layer of ruddiness and send the combination layer of the organic material layer of green glow, be provided with compound regulation and control layer between the adjacent layer, under the driving of described additional power source, along with change in voltage is sent white light.
7. according to the arbitrary described novel electroluminescent device of claim 2～6, it is characterized in that, the described organic material layer that sends blue light is aromatic diamine compounds or star triphenyl amine compound, or carbazole polymer, or doping type blue fluorescent dyes or blue phosphorescent material, described aromatic diamine compounds is N, N '-two-(3-aminomethyl phenyl)-N, N '-diphenyl-[1,1 '-xenyl]-4,4 '-diamines or N, N '-two (3-naphthyl)-N, N '-diphenyl-[1,1 '-diphenyl]-4,4 '-diamines, described star triphenyl amine compound are three-[4-(5-phenyl-2-thienyl) benzene] amine or m-TDATA, and described carbazole polymer is a polyvinylcarbazole; The described organic material layer that sends green glow is one or more in organic fluorescence materials, fluorescent dye, phosphor material and the metal complex material; The described organic material layer that sends redness is red fluorescence doping type layer or red phosphorescent doped layer or red fluorescence material, and the red fluorescence doped layer comprises material of main part and red fluorescence doping fuel, and this material of main part is Alq
3Perhaps ADN, described red fluorescence dopant dye and described red fluorescence material are DCJTB or DCM or DCM1 red dye, and the red phosphorescent doped layer comprises material of main part and red phosphorescence material, and this material of main part is CBP or NPB or TPBI or Alq
3Perhaps TAZ, red phosphorescence material is btp2Ir (acac) or (DPQ) Pt (acac) or (nazo)
2Ir (Fppz).
8. novel electroluminescent device according to claim 1, it is characterized in that the used material of described hole blocking layer is one or more in poly N-vinyl carbazole, BCP, two (2-methyl-8-quinoline acid group closes) tri-phenyl-silane aluminium alcoholates (III), two (2-methyl-8-quinoline acid group closes) 4-phenol aluminium (III) and two (2-methyl-8-quinoline acid group closes) the 4-phenylphenol aluminium (III).
9. novel electroluminescent device according to claim 1, it is characterized in that, described compound regulation and control layer, cathode layer and anode layer are respectively arranged with implanted layer, described electron transfer layer and implanted layer material are metal complex material Huo person oxadiazole electron-like transferring material, perhaps imidazoles electron transport material; Described hole transport layer material is aromatic diamine compounds or star triphenyl amine compound, or carbazole polymer.
10. novel electroluminescent device according to claim 9, it is characterized in that, described metal complex material is that oxine aluminium or oxine gallium or two [2-(2-hydroxy phenyl-1)-pyridine] beryllium Suo Shu oxadiazole electron-like transferring material are 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3, the 4-oxadiazole, described imidazoles electron transport material is 1,3,5-three (N-phenyl-2-benzimidazolyl-2 radicals) benzene; Described aromatic diamine compounds is N, N '-two-(3-aminomethyl phenyl)-N, N '-diphenyl-[1,1 '-xenyl]-4,4 '-diamines or N, N '-two (3-naphthyl)-N, N '-diphenyl-[1,1 '-diphenyl]-4,4 '-diamines and derivative thereof, described star triphenyl amine compound is three-[4-(5-phenyl-2-thienyl) benzene] amine or m-TDATA, and described carbazole polymer is polyvinylcarbazole or monomer whose.
11. the organic electroluminescence device that can send white light according to claim 1 is characterized in that, described electrically-conductive backing plate is ito substrate or sheet metal or silicon substrate; Described substrate is glass or flexible substrate or sheet metal, and wherein flexible substrate is ultra-thin solid-state thin slice, polyesters or poly-phthalimide compounds; Described anode layer is metal-oxide film or metallic film, and this metal-oxide film is ito thin film or zinc-oxide film or zinc tin oxide film, and this metallic film is the metallic film of gold, copper or silver; Described anode layer is PEDOT:PSS or PANI class organic conductive polymer; Described metal layer material is metallic film or alloy firm, and this metallic film is the lower metallic film of lithium or work functions such as magnesium or calcium or strontium or aluminium or indium or they and the golden or silver-colored alloy firm of copper.
12. the preparation method of a novel electroluminescent device is characterized in that, may further comprise the steps:
1. utilize washing agent, ethanolic solution, acetone soln and deionized water that substrate or electrically-conductive backing plate are carried out ultrasonic cleaning, it is dry to clean the back;
2. substrate is sent to the preparation of carrying out electrode in the vacuum evaporation chamber, described electrode comprises anode layer or cathode layer, perhaps electrically-conductive backing plate is carried out array and handles;
The substrate that 3. will prepare electrode moves into vacuum chamber, under oxygen pressure ring border to carrying out the preliminary treatment of low energy oxygen plasma;
4. the substrate after will handling carries out the spin coating of organic film in spin coater, set gradually organic functional layer according to device architecture, and described organic function layer comprises one or more in luminescent layer, carrier blocking layers, implanted layer and the resilient coating;
5. finish to carry out in the vaporization chamber of back at condition of high vacuum degree the preparation of another electrode in the organic layer spin coating, described electrode comprises cathode layer or anode layer;
6. ready-made device is sent to glove box and encapsulates, glove box is an atmosphere of inert gases;
7. electric current-the voltage of test component-light characteristic, the luminescent spectrum parameter of test component simultaneously.
13. novel organic electroluminescence preparation of devices method according to claim 12 is characterized in that, step organic function layer 4. the method that adopts vacuum deposition method or spin coating method or spin coating to combine with vacuum evaporation is set.
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| CN101728491B (en) * | 2009-12-21 | 2012-09-05 | 中国科学院长春应用化学研究所 | White organic luminescent element and preparation method thereof |
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