CN102005539A - White-light organic electroluminescent device and preparation method thereof - Google Patents
White-light organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN102005539A CN102005539A CN 201010293299 CN201010293299A CN102005539A CN 102005539 A CN102005539 A CN 102005539A CN 201010293299 CN201010293299 CN 201010293299 CN 201010293299 A CN201010293299 A CN 201010293299A CN 102005539 A CN102005539 A CN 102005539A
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Abstract
The invention discloses a white-light organic electroluminescent device with a supplementary color layer and a preparation method thereof. The organic electroluminescent device comprises a substrate, a first electrode layer positioned on the surface of the substrate, a function layer positioned on the surface of the first electrode layer, and a second electrode formed on the surface of the function layer, wherein the function layer comprises an electron injection layer, an electron transport layer, a luminous layer, a hole transport layer and a hole injection layer; the electroluminescent wavelength of the luminous layer ranges from 380 to 560nm; and the hole injection layer is a layer of organic film with supplementary color function, and comprises a hole injection material with the electroluminescent wavelength between 560 and 780nm. The illumination stability of the organic electroluminescent device effectively is improved effectively, and the preparation process for the device is simplified.
Description
Technical field
The present invention relates to the organic photoelectric technical field in the electronic devices and components, be specifically related to a kind of white light organic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescence device (Organic Light-Emitting Device, OLED) be a kind of photoelectric device that utilizes the organic solid-state semiconductor as luminescent material, its luminescence mechanism is electroluminescence (Electroluminescence, be called for short EL), the organic electroluminescence device so be otherwise known as (Organic Electroluminescence Device, OLED).Its structure comprises substrate 100 as shown in Figure 1, anode electrode 110, hole injection layer (Hole Injection Layer, HIL) 120, hole transmission layer (Hole Transport Layer, HTL) 130, luminescent layer (Emission Layer, EML) 140, electron transfer layer (Electron Transport Layer, ETL) 150, electron injecting layer (Electron Injection Layer, EIL) 160, cathode electrode 170.When applying a forward bias voltage at negative and positive the two poles of the earth, electronics and hole will transfer to luminescent layer by electron transfer layer and hole transmission layer, and compound in luminescent layer then (Recombination) is luminous.So organic electroluminescence device is a kind of photoelectric device that electric energy is converted into luminous energy.
Wherein, substrate can be nonbreakable glass substrate, ultra-thin glass, stainless steel substrates, plastic, and substrate for the back three white light organic electroluminescent device have flexible characteristic.In addition, it is luminous owing to the charge carrier that is made of electronics and hole only combines in electroluminescence layer, and this luminescent layer is extremely thin, thereby charge carrier is very fast in conjunction with speed, makes the response time that (Response Time) is very short, and panel size can be from several microns micro-display (Micro Display) to 100 inches large size panels, use very extensive, angle is wide, resolution height, ultra-thin, light weight.Therefore, organic electroluminescence device is the display device of high-quality of new generation and good area source.
Present white light organic electroluminescent device mainly is with crossing the luminous or luminous white light emission that realizes of complementary colours of realization RGB three primary colors, but variation along with voltage, the recombination region of device can be along with respective change, thereby the phenomenon of device chromaticity coordinates occur, thereby the stability of photoluminescence and the glow color of device have been influenced along with change in voltage.
In recent years, color stability problem and the simplification device preparation technology of scientific research personnel in order to solve white-light electroluminescence device proposes and developed the organic electroluminescence device with color conversion layer.For example in patent 200880006340.8, a kind of color conversion layer (FKS) with quantum dot is placed under the substrate, by color conversion layer to the absorption of prompt radiation and convert secondary radiation to, thereby produce white light; For example in patent 200910069451.X, with a kind of have organicly place under the glass substrate with inorganic composite color conversion membrane, thereby the glow color conversion of blue light-emitting is realized the white light of integral device by composite color conversion membrane.These have the organic electroluminescence device of color conversion layer, owing to life-span of color conversion layer causes device spectrum to change in time, and,, thereby influenced the luminous efficiency of device greatly owing to color conversion layer can impact the light extraction efficiency of device.
Summary of the invention
Problem to be solved by this invention is: how a kind of white light organic electroluminescent device and preparation method thereof is provided, this white light organic electroluminescent device has utilized the complementary color function of the luminescence generated by light of hole injection layer, improve the device stability of photoluminescence, improve device color color purity, improved the efficient and the life-span of device.
Technical problem proposed by the invention is to solve like this: a kind of white light organic electroluminescent device is provided, comprise substrate, first electrode layer, functional layer and the second electrode lay, wherein first electrode layer is positioned at substrate surface, functional layer is positioned at first electrode layer surface, the second electrode lay is positioned at the functional layer surface, the formation of described functional layer comprises: electron injecting layer, electron transfer layer, luminescent layer, hole transmission layer and hole injection layer, it is characterized in that, described hole injection layer is the organic film that one deck has the complementary color function, hole injection layer is subjected to luminescent layer emergent light photoexcitation, light that hole injection layer sent and luminescent layer emergent light are mutually the white light complementary colours, and the electroluminescence wavelength of luminescent layer is less than the hole injection layer photoluminescence wavelength.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described luminescent layer electroluminescence wavelength is in the visible-range of 380nm～560nm.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described luminescent layer electroluminescence wavelength must be less than the hole injection layer photoluminescence wavelength.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described luminescent layer can be individual layer luminescent layer or illuminated in combination layer.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described illuminated in combination layer is meant by luminescent layer two-layer or that the multilayer organic film is formed.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that hole injection layer comprises a kind of luminescence generated by light peak position in the hole-injecting material of visible light long wave band 560nm～780nm.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, described hole injection layer material comprises the thiophene-based material, p-phenylene vinylene (PPV) and derivative thereof, aromatic amine material or condensed ring aromatic etc., wherein, the thiophene-based material is for gathering (3-alkylthrophene) (P3AT), 3-octyl group substituting polythiophene (P3OT), 3-hexyl substituting polythiophene (P3HT), the PPV derivative comprises poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-1, the support of 4-phenylene ethylene] (MEH-PPV), poly-[2-methoxyl group, 5-(3,7-dimethyl-octyloxy)-to the styrene support] (MDMO-PPV) etc.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described electron transport material/electronics injection material can be small molecule material or polymeric material.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, described organic molecule electron transport material/organic molecule electronics injection material comprises a kind of material in metal organic complex, pyridines, o-phenanthroline Lei, oxadiazole class or the glyoxaline compound material, and wherein metal organic complex comprises oxine aluminium (Alq
3) or two (2-methyl-8-quino)-4-(phenylphenol) aluminium (BAlq), pyridine compounds and their comprises three [2,4,6-trimethyl-3-(phenyl of pyridine-3-yl)]-borine (3TPYMB), the o-phenanthroline compounds comprises 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) or 4,7-biphenyl-1,10-phenanthrolene (BPhen) oxadiazole class material is 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-oxadiazole (PBD) or 1,3-two [(4-tertiary amine-butyl phenyl)-1,3,4-diazo acid-5-yl] benzene (OXD-7), the imidazoles material is 1,3,5-three (N-phenyl-benzimidazolyl-2 radicals) benzene (TPBi) etc.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, described organic polymer electron transport material/organic polymer electronics injection material comprises the C60 derivative, the thiophene-based material, PPV derivative or condensed ring aromatic, wherein, the C60 derivative is (6,6)-phenyl-C61-methyl butyrate (PCBM), (6,6)-phenyl-C61-butyl butyrate (PCBB), 1-(3-methoxycarbonyl group) propyl group-1-thienyl-[6,6]-methylene fullerene (ThCBM), the thiophene-based material comprises dicyano vinyl-three polythiophene (DCV3T), gather (3-cyano group-4-hexyl thiophene) (P3CN4HT), the PPV derivative comprises [oxa--1,4-phenylene-1,2-(1-cyano group)-ethenylidene-2,5-two hot oxygen-1,4-phenylene-1,2-(2-cyano group)-ethenylidene-1, the 4-phenylene] polymer (CN-Ether-PPV), poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-alpha-cyano-to the styrene support] (MEH-CN-PPV), condensed ring aromatic material comprises 3,4,9,10-perylene tetracarboxylic-bisbenzimidazole (PTCBI), 3,4,9,10-perylene tetracarboxylic acid dianhydride (PTCDA).
According to white light organic electroluminescent device provided by the present invention, it is characterized in that hole transport layer material comprises aromatic diamine compounds, aromatic triamine compounds, carbazole compound, thiophene-based material, p-phenylene vinylene (PPV) and derivative, aromatic amine material, condensed ring aromatic or phthalocyanine dye.Wherein the aromatic diamine compounds is N, N '-two (naphthal-1-yl)-N, N '-two (phenyl)-benzidine (NPB), N, N '-two (naphthal-2-yl)-N, N '-two (phenyl)-benzidine (β-NPB), N, N '-two (3-aminomethyl phenyl)-N, N '-two (phenyl)-benzidine (TPD), N, N '-two (naphthal-1-yl)-N, N '-two (phenyl)-2,2 '-dimethylbenzidine (a-NPD), the aromatic triamine compounds is two-[4-(N, N-ditolyl-amino)-phenyl] cyclohexanes (TAPC) etc.Wherein, the thiophene-based material comprises 5-vinyl-2-four polythiophene (V
4T), 5-vinyl-five polythiophene (V
5T), α, α-two (2,2-dicyano ethene)-five polythiophenes (DCV5T), [2,6-(4,4-two-(2-ethylhexyl)-4H-cyclopentene [2,1-b; 3,4-b ']-two thiophene)-replace-4,7-(2,1, the 3-diazosulfide)] copolymer (PCPDTBT), (5, the 5-dioctyl-[2,2 '; 5 ', 2 "; 5 "; 2] four polythiophenes)-alternately-(2; 7-fluorenes-9-ketone)] copolymer (PQTF8), poly-(3-alkylthrophene) (P3AT), 3-hexyl substituting polythiophene (P3HT); the PPV derivative comprises poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-1; 4-phenylene ethylene support] (MEH-PPV); poly-[2-methoxyl group, 5-(3,7-dimethyl-octyloxy)-to the styrene support] (MDMO-PPV) etc.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described luminescent layer comprises one or several luminous organic materials.Concrete can list: material of main part: 4,4 '-two (9-carbazole) biphenyl (CBP), 9,9 '-(1, the 3-phenyl) two-9H-carbazole (mCP), 4,4 ', 4 " three (carbazole-9-yl) triphenylamines (TcPa) etc.; Dopant: 3,5-two fluoro-2-(2-pyridine) phenyl-(2-carboxyl pyridine) closes iridium (FIrpic, glow peak: 472nm), three (2-phenylpyridines) close iridium (Ir (ppy)
3, glow peak: 514nm), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac), glow peak: 380nm and 524nm), 9, two [2,5-di-p-tolyl ammonia] anthracene (TTPA, the glow peaks: 560nm) etc. of 10-.
A kind of preparation method of white light organic electroluminescent device is characterized in that, may further comprise the steps:
1. utilize detergent solution, acetone, deionized water and ethanol that substrate is carried out ultrasonic cleaning, clean the back and dry up with high pressure nitrogen;
2. substrate is moved into the preparation of carrying out first electrode layer, functional layer and the second electrode lay in the vacuum film coating chamber successively, first electrode layer, functional layer and the second electrode lay directly are prepared on the substrate, perhaps are prepared on the substrate through behind the organic solvent diluting; Described first electrode layer, functional layer and the second electrode lay are by vacuum evaporation, ion cluster bundle deposition, ion plating, dc sputtering deposition, the RF sputter coating, ion beam sputtering deposition, ion beam assisted depositing, plasma reinforced chemical vapour deposition, high density inductance coupling high formula plasma source chemical vapor deposition, the catalyst chemical vapour deposition (CVD), magnetron sputtering, electroplate, spin coating, dip-coating, inkjet printing, roller coat, one or several modes in the LB film and forming, the formation of described functional layer comprises: electron injecting layer, electron transfer layer, luminescent layer, hole transmission layer and hole injection layer, described hole injection layer is the organic film that one deck has the complementary color function, hole injection layer is subjected to luminescent layer emergent light photoexcitation, light that hole injection layer sent and luminescent layer emergent light are mutually the white light complementary colours, and the electroluminescence wavelength of luminescent layer is less than the hole injection layer photoluminescence wavelength.
3. device is encapsulated at glove box, glove box is a nitrogen atmosphere.
The hole injection layer of white light organic electroluminescent device provided by the present invention has not only played hole injection effect, and has played the effect of luminescent layer complementary color layer.Because the complementary color effect of hole injection layer is to realize by the luminescence generated by light peak of hole injection layer, so the variation of voltage or electric current can not exert an influence to the luminescence generated by light peak of hole injection layer, i.e. the variation of voltage or electric current can only exert an influence to electroluminescent spectrum in the luminescent layer.Therefore, the more traditional white light organic electroluminescent device of the color stability of device is better.In addition, because white light organic electroluminescent device provided by the present invention is not introduced the factor that other have a negative impact to device performance, so the device performance excellence in the process that realizes white light.The present invention provides more choices for the design and the manufacturing of high-performance white-light electroluminescence device.
Description of drawings
Fig. 1 is the structural representation of embodiment 1, embodiment 2 and embodiment 3;
Fig. 2 is the electroluminescent spectrum of luminescent layer of embodiment 1 and the photoluminescence spectra of hole injection layer:
Fig. 3 is the spectrum property figure of embodiment 1 device;
Fig. 4 is embodiment 4, embodiment 5, embodiment 6 and embodiment 10 structural representations;
Fig. 5 is embodiment 7, embodiment 8 structural representations;
Fig. 6 is the structural representation of embodiment 9
Wherein, 100: substrate; 110: the first electrode layers (anode); 120: hole injection layer; 130: hole transmission layer; 140,143,144: luminescent layer; 150: electron transfer layer; 160: electron injecting layer; 170: the second electrode lay (negative electrode); 141: wall; 142: the dyestuff superthin layer.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described:
Technical scheme of the present invention provides a kind of novel white-light organic electroluminescence device that includes the hole injection layer of complementary color function.As shown in Figure 1, the structure of device comprises substrate 100, anode layer 110, hole injection layer 120, hole transmission layer 130, luminescent layer 140, electron transfer layer 150, electron injecting layer 160, negative electrode 170; Wherein anode layer 110 is positioned at substrate 100 surfaces, hole injection layer 120 is positioned at anode layer 110 surfaces, hole transmission layer 130 is positioned at hole injection layer 120 surfaces, luminescent layer 140 is positioned at hole transmission layer 130 surfaces, electron transfer layer 150 is positioned at luminescent layer 140 surfaces, electron injecting layer 160 is positioned at electron transfer layer 150 surfaces, and negative electrode 170 is positioned at electron injecting layer 160 surfaces.
What below list is the concrete example of common used material in the white light organic electroluminescent device of the present invention, but the present invention is not limited to these concrete examples.
In the white light organic electroluminescent device among the present invention, substrate 100 is the support of electrode and organic thin film layer, it has the good light transmittance energy in the visible region, the ability that the infiltration of certain anti-steam and oxygen is arranged, profile pattern is preferably arranged, it can be glass or flexible substrate or tinsel, and wherein flexible substrate can be ultra-thin glass, polyesters or poly-phthalimide compounds.
In the white light organic electroluminescent device among the present invention, anode layer 110 is as the articulamentum of white light organic electroluminescent device forward voltage, and it requires to have electric conductivity, visible transparent and higher work function preferably.Usually adopt inorganic, metal oxide (as tin indium oxide ITO, indium zinc oxide IZO etc.), organic conductive polymer (as PEDOT:PSS, PANI etc.) or high-work-function metal material (as gold, copper, silver, platinum etc.).
In the white light organic electroluminescent device among the present invention, cathode layer 170 is as the articulamentum of device negative voltage, its requires to have electric conductivity and lower work function preferably, and negative electrode is generally the alloy of the lower metal of work functions such as low workfunction metal material lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold, silver; Perhaps the buffer insulation layer that one deck is very thin is (as LiF, MgF
2Deng) and the metal or alloy that improves of front.
According to white light organic electroluminescent device provided by the present invention, described hole injection layer is the organic film that one deck has the complementary color function, comprises a kind of luminescence generated by light peak position in the visible light long wave band (hole-injecting material of 560nm～780nm).
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, described hole injection layer complementary color function is meant: hole injection layer is subjected to luminescent layer emergent light photoexcitation, and light that hole injection layer sent and luminescent layer emergent light are mutually the white light complementary colours.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described luminescent layer electroluminescence wavelength is in the visible-range of 380nm～560nm.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described luminescent layer electroluminescence wavelength must be less than the hole injection layer photoluminescence wavelength.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described luminescent layer can be individual layer luminescent layer or illuminated in combination layer.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that described illuminated in combination layer is meant by luminescent layer two-layer or that the multilayer organic film is formed.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that hole injection layer comprises a kind of luminescence generated by light peak position in the hole-injecting material of visible light long wave band 560nm～780nm.
In the white light organic electroluminescent device among the present invention, hole injection layer 120 is thiophene-based material, p-phenylene vinylene (PPV) and derivative thereof, aromatic amine material, condensed ring aromatic etc.Wherein, the thiophene-based material for poly-(3-alkylthrophene) (P3AT), 3-octyl group substituting polythiophene (P3OT), 3-hexyl substituting polythiophene (P3HT), the PPV derivative comprises poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-1, the support of 4-phenylene ethylene] (MEH-PPV), poly-[2-methoxyl group, 5-(3,7-dimethyl-octyloxy)-to the styrene support] (MDMO-PPV) etc.
In the white light organic electroluminescent device among the present invention, hole transmission layer 130 materials have the inorganic or organic compound of low the highest occupied energy level (HOMO).Described compound can be a phthalein cyanogen copper (CuPc), N, N '-two-(3-aminomethyl phenyl)-N, N '-diphenyl-[1,1 '-xenyl]-4,4 '-diamines (TPD) or N, N '-two (3-naphthyl)-N, N '-diphenyl-[1,1 '-diphenyl]-4,4 '-diamines (NPB), three-[4-(5-phenyl-2-thienyl) benzene] amine (PTDATA series), polyvinylcarbazole (PVK), poly-dioxoethyl thiophene: poly-p styrene sulfonic acid (PEDOT:PSS).
In the white light organic electroluminescent device among the present invention, luminescent layer 140 can comprise one or several luminous organic materials.Concrete can list: material of main part: 4,4 '-two (9-carbazole) biphenyl (CBP), 9,9 '-(1, the 3-phenyl) two-9H-carbazole (mCP), 4,4 ', 4 " three (carbazole-9-yl) triphenylamines (TcPa) etc.; Dopant: 3,5-two fluoro-2-(2-pyridine) phenyl-(2-carboxyl pyridine) closes iridium (FIrpic, glow peak: 472nm), three (2-phenylpyridines) close iridium (Ir (ppy)
3, glow peak: 514nm), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac), glow peak: 380nm and 524nm), 9, two [2,5-di-p-tolyl ammonia] anthracene (TTPA, the glow peaks: 560nm) etc. of 10-.
In the white light organic electroluminescent device among the present invention, electron transfer layer 150/ electron injecting layer 160 materials have the inorganic or organic compound of high minimum unoccupied track (LUMO).Described compound can be metal complex material 8-hydroxy quinoline aluminium (Alq
3) ， oxadiazole class material 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-oxadiazole 18 (PBD), imidazoles material 1,3,5-three (N-phenyl-2-benzimidazolyl-2 radicals) benzene 41 (TPBi) etc.
What list is white light organic electroluminescent device concrete example of the present invention herein, but the present invention is not limited to these concrete examples.
Adopt the white light organic electroluminescent device structure of the present invention's preparation to be exemplified below:
Glass/ITO/ hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/electron injecting layer/cathode layer
Glass/ITO/ hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/cathode layer
Glass/ITO/ hole injection layer/hole transmission layer/green light emitting layer/blue light-emitting layer/electron transfer layer/electron injecting layer/cathode layer
Glass/ITO/ hole injection layer/hole transmission layer/green light emitting layer/blue light-emitting layer/electron transfer layer/cathode layer
Glass/ITO/ hole injection layer/hole transmission layer/wall/dyestuff superthin layer/wall/electron transfer layer/electron injecting layer/cathode layer
Glass/ITO/ hole injection layer/hole transmission layer/wall/dyestuff superthin layer/wall/electron transfer layer/cathode layer
Glass/ITO/ hole injection layer/hole transmission layer/wall/green superthin layer/wall/blue superthin layer/wall/electron transfer layer/electron injecting layer/cathode layer
Glass/ITO/ hole injection layer/hole transmission layer/wall/green superthin layer/wall/blue superthin layer/wall/electron transfer layer/cathode layer
Flexible base, board/ITO/ hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/electron injecting layer/cathode layer
Flexible base, board/ITO/ hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/cathode layer
Flexible base, board/ITO/ hole injection layer/hole transmission layer/green light emitting layer/blue light-emitting layer/electron transfer layer/electron injecting layer/cathode layer
Flexible base, board/ITO/ hole injection layer/hole transmission layer/green light emitting layer/blue light-emitting layer/electron transfer layer/cathode layer
Flexible base, board/ITO/ hole injection layer/hole transmission layer/wall/dyestuff superthin layer/wall/electron transfer layer/electron injecting layer/cathode layer
Flexible base, board/ITO/ hole injection layer/hole transmission layer/wall/dyestuff superthin layer/wall/electron transfer layer/cathode layer
Flexible base, board/ITO/ hole injection layer/hole transmission layer/wall/green superthin layer/wall/blue superthin layer/wall/electron transfer layer/electron injecting layer/cathode layer
Flexible base, board/ITO/ hole injection layer/hole transmission layer/wall/green superthin layer/wall/blue superthin layer/wall/electron transfer layer/cathode layer
As shown in Figure 1, the substrate 100 of device is a glass substrate, and first electrode layer 110 is an anode, and 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 140, and electron transfer layer is 150, and electron injecting layer is 160, and cathode layer is 170.
The hole injection layer material of device is MEH-PPV, and hole transport layer material is NPB, and luminescent layer is selected blue phosphorescent material FIrpic doping mCP, electron transfer layer material selection TPBi, and the electronics injection material is chosen as Alq
3, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/MEH-PPV (100nm)/NPB (30nm)/mCP:FIrpic (20nm)/TPBi (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation method is as follows:
1. with washing agent, ethanolic solution and deionized water the transparent conduction base sheet 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/sq, 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 20W.
3. will in spin coater, carry out the spin coating of hole injection layer through pretreated substrate, and oven dry.
4. the substrate after will drying carries out the evaporation of organic film under high vacuum environment, according to hole transmission layer NPB, luminescent layer mCP:FIrpic, electron transfer layer TPBi and electron injecting layer Alq on the device architecture evaporation
3, evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
5. 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, and the Mg:Ag ratio is 10: 1 in the alloy, and evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
6. ready-made device is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
The luminescent spectrum parameter of the 7. current-voltage-light characteristic of test component, and test component.
Embodiment 2
As shown in Figure 1, the substrate 100 of device is a flexible substrate, and first electrode layer 110 is an anode, and 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 140, and electron transfer layer is 150, and electron injecting layer is 160, and cathode layer is 170.
The flexible substrate of device is PET, and the hole injection layer material is MEH-PPV, and hole transport layer material is NPB, and luminescent layer is selected blue phosphorescent material FIrpic doping mCP, electron transfer layer material selection TPBi, and the electronics injection material is chosen as Alq
3, cathode layer Mg:Ag alloy.The entire device structrual description is:
Flexible substrate/ITO/MEH-PPV (100nm)/NPB (30nm)/mCP:FIrpic (20nm)/TPBi (20nm)/Alq
3(30am)/Mg:Ag (100nm)
The preparation method is as follows:
1. utilize acetone, ethanolic solution and deionized water that transparent PET substrate is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen.
2. dried PET substrate is moved into vacuum chamber, sputtering ITO film on the PET substrate, thickness are 180nm.
3. substrate is carried out the spin coating of hole injection layer in spin coater, and oven dry.
4. the substrate after will drying carries out the evaporation of organic film under high vacuum environment, according to hole transmission layer NPB, luminescent layer mCP:FIrpic, electron transfer layer TPBi and electron injecting layer Alq on the device architecture evaporation
3, evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
5. 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, and the Mg:Ag ratio is 10: 1 in the alloy, and evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
6. ready-made device is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
The luminescent spectrum parameter of the 7. current-voltage-light characteristic of test component, and test component.
Embodiment 3
As shown in Figure 1, the substrate 100 of device is a flexible substrate, and first electrode layer 110 is the conducting polymer anode, 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 140, electron transfer layer is 150, and electron injecting layer is 160, and cathode layer is 170.
The conducting polymer anode of device is PANI, and the hole injection layer material is MEH-PPV, and hole transport layer material is NPB, and luminescent layer is selected blue phosphorescent material FIrpic doping mCP, electron transfer layer material selection TPBi, and the electronics injection material is chosen as Alq
3, cathode layer Mg:Ag alloy.The entire device structrual description is:
Flexible substrate/PANI/MEH-PPV (100nm)/NPB (30nm)/mCP:FIrpic (20nm)/TPBi (20nm)/Alq
3(30nm)/Mg:Ag (100nm)
The preparation method is as follows:
1. utilize acetone, ethanolic solution and deionized water that transparent PET substrate is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen;
2. the PET substrate of cleaning is put into nitrogen environment, adopt inkjet printing or divide the method for child print to prepare the first electrode layer PANI, oven dry then.
3. substrate is carried out the spin coating of hole injection layer in spin coater, and oven dry.
4. the substrate after will drying carries out the evaporation of organic film under high vacuum environment, according to hole transmission layer NPB, luminescent layer mCP:FIrpic, electron transfer layer TPBi and electron injecting layer Alq on the device architecture evaporation
3, evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
5. 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, and the Mg:Ag ratio is 10: 1 in the alloy, and evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
6. ready-made device is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
The luminescent spectrum parameter of the 7. current-voltage-light characteristic of test component, and test component.
Embodiment 4
As shown in Figure 4, the substrate 100 of device is a glass substrate, and first electrode layer 110 is the conducting polymer anode, and 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 140, and electron transfer layer is 150, and cathode layer is 170.
The hole injection layer material of device is MDMO-PPV, and hole transport layer material is NPB, and luminescent layer is selected blue phosphorescent material FIrpic doping mCP, electron transfer layer material selection TPBi, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/MDMO-PPV (100nm)/NPB (30nm)/mCP:FIrpic (20nm)/TPBi (30nm)/Mg:Ag (100nm)
The preparation method is as follows:
1. with washing agent, ethanolic solution and deionized water the transparent conduction base sheet 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/sq, 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 20W.
3. will in spin coater, carry out the spin coating of hole injection layer through pretreated substrate, and oven dry.
4. the substrate after will drying carries out the evaporation of organic film under high vacuum environment, according to hole transmission layer NPB, luminescent layer mCP:FIrpic, electron transfer layer TPBi on the device architecture evaporation, evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
5. 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, and the Mg:Ag ratio is 10: 1 in the alloy, and evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
6. ready-made device is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
The luminescent spectrum parameter of the 7. current-voltage-light characteristic of test component, and test component.
Embodiment 5
As shown in Figure 4, the substrate 100 of device is a glass substrate, and first electrode layer 110 is the conducting polymer anode, and 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 140, and electron transfer layer is 150, and cathode layer is 170.
The hole injection layer material of device is MDMO-PPV, and hole transport layer material is TATC, and luminescent layer is selected green phosphorescent material Ir (ppy)
3Doping mCP, electron transfer layer material selection Alq
3, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/MDMO-PPV (100nm)/TATC (30nm)/mCP:Ir (ppy)
3(20nm)/Alq
3(30nm)/Mg:Ag (100nm)
Preparation method such as embodiment 4.
Embodiment 6
As shown in Figure 4, the substrate 100 of device is a flexible substrate, and first electrode layer 110 is the conducting polymer anode, and 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 140, and electron transfer layer is 150, and cathode layer is 170.
The hole injection layer material of device is P3AT, and hole transport layer material is NPB, and luminescent layer is selected green phosphorescent material Ir (ppy)
3Doping mCP, electron transfer layer material selection BPhen, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/P3AT (100nm)/NPB (30nm)/mCP:Ir (ppy)
2(acac) (20nm)/BPhen (30nm)/Mg:Ag (100nm)
Preparation method such as embodiment 4.
Embodiment 7
As shown in Figure 5, the substrate 100 of device is a glass substrate, first electrode layer 110 is the ITO conductive anode, 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 141 and 142 composite bed, 141 walls of forming for material of main part wherein, 142 superthin layers for the dyestuff composition, electron transfer layer is 150, cathode layer is 170.
The hole injection layer material of device is P3AT, and hole transport layer material is TATC, and it is superthin layer that luminescent layer is selected blue phosphorescent material Fir6, and mCP is a wall, electron transfer layer material selection BPhen, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/P3AT (100nm)/TATC (30nm)/mCP (10nm)/Fir6 (1nm)/mCP (10nm)/BPhen (30nm)/Mg:Ag (100nm)
Preparation method such as embodiment 4.
Embodiment 8
As shown in Figure 5, the substrate 100 of device is a glass substrate, first electrode layer 110 is the ITO conductive anode, 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 141 and 142 composite bed, 141 walls of forming for material of main part wherein, 142 superthin layers for the dyestuff composition, electron transfer layer is 150, cathode layer is 170.
The hole injection layer material of device is P3HT, and hole transport layer material is TATC, and it is superthin layer that luminescent layer is selected blue phosphorescent material Fir6, and CBP is a wall, electron transfer layer material selection BPhen, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/P3HT (100nm)/TATC (30nm)/CBP (10nm)/Fir6 (1nm)/CBP (10nm)/BPhen (30nm)/Mg:Ag (100nm)
Preparation method such as embodiment 4.
Embodiment 9
As shown in Figure 6, the substrate 100 of device is a flexible substrate, first electrode layer 110 is the conducting polymer anode, 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 143 and 144 composite bed, wherein 143 is blue light-emitting layer, 144 is green light emitting layer, and electron transfer layer is 150, and cathode layer is 170.
The hole injection layer material of device is P3HT, and hole transport layer material is TATC, and selection mCP:Fir6 is a blue light-emitting layer, selects mCP:Ir (PPy)
3Be green light emitting layer, electron transfer layer material selection BPhen, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/P3HT (100nm)/TATC (30nm)/mCP:Fir6 (10nm)/mCP:Ir (ppy)
3(10nm)/BPhen (30nm)/Mg:Ag (100nm)
Preparation method such as embodiment 4.
Embodiment 10
As shown in Figure 4, the substrate 100 of device is a glass substrate, and first electrode layer 110 is the conducting polymer anode, and 120 is hole injection layer, and 130 is hole transmission layer, and the luminescent layer in the structure of device is 140, and electron transfer layer is 150, and cathode layer is 170.
The hole injection layer material of device is P3OT, and hole transport layer material is TATC, and luminescent layer is selected blue phosphorescent material Fir6 doping mCP, electron transfer layer material selection BPhen, cathode layer Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/P3OT (100nm)/TATC (30nm)/mCP:TTPA (20nm)/BPhen (30nm)/Mg:Ag (100nm)
The preparation method is as follows:
1. with washing agent, ethanolic solution and deionized water the transparent conduction base sheet 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/sq, 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 20W.
3. adopt the method for self assembly to be prepared as follows film successively: hole injection layer P3OT, hole transmission layer TATC, luminescent layer mCP:Fir6 mixes, electron transfer layer BPhen.
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, and the Mg:Ag ratio is 10: 1 in the alloy, and evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
5. ready-made device is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
The luminescent spectrum parameter of the 6. current-voltage-light characteristic of test component, and test component.
Claims (9)
1. white light organic electroluminescent device, comprise substrate, first electrode layer, functional layer and the second electrode lay, wherein first electrode layer is positioned at substrate surface, functional layer is positioned at first electrode layer surface, the second electrode lay is positioned at the functional layer surface, the formation of described functional layer comprises: electron injecting layer, electron transfer layer, luminescent layer, hole transmission layer and hole injection layer, it is characterized in that, described hole injection layer is the organic film that one deck has the complementary color function, hole injection layer is subjected to luminescent layer emergent light photoexcitation, the emergent light of hole injection layer and the emergent light of luminescent layer are mutually the white light complementary colours, and the electroluminescence wavelength of luminescent layer is less than the hole injection layer photoluminescence wavelength.
2. white light organic electroluminescent device according to claim 1 is characterized in that, described luminescent layer electroluminescence wavelength is in the visible-range of 380nm～560nm; Described luminescent layer is individual layer luminescent layer or illuminated in combination layer.
3. white light organic electroluminescent device according to claim 2 is characterized in that, described illuminated in combination layer is meant by luminescent layer two-layer or that the multilayer organic film is formed.
4. white light organic electroluminescent device according to claim 1 is characterized in that, hole injection layer comprises a kind of luminescence generated by light peak position in the hole-injecting material of visible light long wave band 560nm～780nm.
5. white light organic electroluminescent device according to claim 1, it is characterized in that hole transport layer material comprises aromatic diamine compounds, aromatic triamine compounds, carbazole compound, thiophene-based material, p-phenylene vinylene and derivative thereof, aromatic amine material, condensed ring aromatic or phthalocyanine dye.
6. white light organic electroluminescent device according to claim 1, it is characterized in that, described hole injection layer material comprises thiophene-based material, p-phenylene vinylene and derivative thereof, aromatic amine material or condensed ring aromatic, wherein, the thiophene-based material is poly-(3-alkylthrophene), 3-octyl group substituting polythiophene, 3-hexyl substituting polythiophene, the PPV derivative comprises poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-1,4-phenylene ethylene support], poly-[2-methoxyl group, 5-(3,7-dimethyl-octyloxy)-to the styrene support].
7. white light organic electroluminescent device according to claim 1 is characterized in that, electron injecting layer and electron transfer layer are organic small molecule material or organic polymer material.
8. white light organic electroluminescent device according to claim 7, it is characterized in that, described organic small molecule material comprises metal organic complex, pyridines, o-phenanthroline Lei, oxadiazole class or glyoxaline compound, and described organic polymer material comprises C60 derivative, thiophene-based material, PPV derivative or condensed ring aromatic.
9. the preparation method of a white light organic electroluminescent device is characterized in that, may further comprise the steps:
1. utilize detergent solution, acetone, deionized water and ethanol that substrate is carried out ultrasonic cleaning, clean the back and dry up with high pressure nitrogen;
2. substrate is moved into the preparation of carrying out first electrode layer, functional layer and the second electrode lay in the vacuum film coating chamber successively, first electrode layer, functional layer and the second electrode lay directly are prepared on the substrate, perhaps are prepared on the substrate through behind the organic solvent diluting; Described first electrode layer, functional layer and the second electrode lay are by vacuum evaporation, ion cluster bundle deposition, ion plating, dc sputtering deposition, the RF sputter coating, ion beam sputtering deposition, ion beam assisted depositing, plasma reinforced chemical vapour deposition, high density inductance coupling high formula plasma source chemical vapor deposition, the catalyst chemical vapour deposition (CVD), magnetron sputtering, electroplate, spin coating, dip-coating, inkjet printing, roller coat, one or several modes in the LB film and forming, the formation of described functional layer comprises: electron injecting layer, electron transfer layer, luminescent layer, hole transmission layer and hole injection layer, described hole injection layer is the organic film that one deck has the complementary color function, hole injection layer is subjected to luminescent layer emergent light photoexcitation, light that hole injection layer sent and luminescent layer emergent light are mutually the white light complementary colours, and the electroluminescence wavelength of luminescent layer is less than the hole injection layer photoluminescence wavelength;
3. device is encapsulated at glove box, glove box is a nitrogen atmosphere.
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| CN102214797A (en) * | 2011-05-20 | 2011-10-12 | 电子科技大学 | WOLED (white organic light-emitting device) and manufacturing method thereof |
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| CN102675352A (en) * | 2011-10-20 | 2012-09-19 | 京东方科技集团股份有限公司 | Lithium pyridine formate complex, preparation method thereof and organic electroluminescent device |
| CN102675352B (en) * | 2011-10-20 | 2014-11-12 | 京东方科技集团股份有限公司 | Lithium pyridine formate complex, preparation method thereof and organic electroluminescent device |
| CN103682170A (en) * | 2013-12-25 | 2014-03-26 | 电子科技大学 | Organic electroluminescent device with color complementing layer and manufacturing method thereof |
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Application publication date: 20110406 |