CN101882665A - A kind of organic optoelectronic device and preparation method thereof - Google Patents

A kind of organic optoelectronic device and preparation method thereof Download PDF

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CN101882665A
CN101882665A CN 201010208521 CN201010208521A CN101882665A CN 101882665 A CN101882665 A CN 101882665A CN 201010208521 CN201010208521 CN 201010208521 CN 201010208521 A CN201010208521 A CN 201010208521A CN 101882665 A CN101882665 A CN 101882665A
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carbon nanotubes
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于军胜
陈苏杰
于欣格
蒋亚东
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University of Electronic Science and Technology of China
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Abstract

本发明公开了一种有机光电器件，包括衬底、阳极层、阴极层、设置在阳极层和阴极层之间的有机功能层，有机功能层包括空穴注入层、空穴传输层、发光层、电子传输层、电子注入层、阳极缓冲层、电子给体层、界面层、电子受体层和阴极缓冲层中的一种或多种，所述空穴传输层与电子给体层中掺杂磁性多壁碳纳米管，或电子传输层与电子受体层中掺杂磁性单壁碳纳米管，或空穴传输层与电子给体层中掺杂磁性多壁碳纳米管的同时电子传输层与电子受体层中掺杂磁性单壁碳纳米管，所述磁性多壁碳纳米管和磁性单壁碳纳米管长度方向垂直于阳极层表面。该器件降低了载流子传输层的电阻，提高了载流子的传输能力和载流子传输层的可见光透过率，提高了器件的光电性能。

Figure 201010208521

The invention discloses an organic photoelectric device, which comprises a substrate, an anode layer, a cathode layer, an organic functional layer arranged between the anode layer and the cathode layer, and the organic functional layer includes a hole injection layer, a hole transport layer, and a light emitting layer. , electron transport layer, electron injection layer, anode buffer layer, electron donor layer, interface layer, electron acceptor layer and cathode buffer layer, the hole transport layer is doped with the electron donor layer Heteromagnetic multi-walled carbon nanotubes, or magnetic single-walled carbon nanotubes doped in electron transport layer and electron acceptor layer, or simultaneous electron transport of magnetic multi-walled carbon nanotubes doped in hole transport layer and electron donor layer The layer and the electron acceptor layer are doped with magnetic single-wall carbon nanotubes, and the length direction of the magnetic multi-wall carbon nanotubes and the magnetic single-wall carbon nanotubes is perpendicular to the surface of the anode layer. The device reduces the resistance of the carrier transport layer, improves the transport capacity of the carrier and the visible light transmittance of the carrier transport layer, and improves the photoelectric performance of the device.

Figure 201010208521

Description

A kind of organic electro-optic device and preparation method thereof
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 organic electro-optic device and preparation method thereof.
Background technology
Organic electro-optic device is meant a kind of device that needs use hole and/or electronics to carry out energy exchange between electrode and organic material among the present invention.This organic electro-optic device can be divided into following two types substantially according to its operation principle: a class flows into from external light source for having that device forms exciton organic layer and this exciton is separated into electronics and hole, and the electronics of formation and hole are transferred to different electrodes respectively and as the photoelectric device of the configuration of power supply.Another kind of for having hole and/or electronics injection organic semiconducting materials, voltage or electric current arrive two or more electrodes and electrode forms the interface so that device relies on the photoelectric device of the configuration of injected electrons or hole operation by applying.
The example of organic electro-optic device includes organic electroluminescence devices and organic solar batteries.To be primarily aimed at organic solar batteries hereinafter explains detailedly.
Solar cell is that the transform light energy with solar radiation is the device of electric energy.Solar cell can be used to provide electric energy to load as electric light, computer etc.Traditional solar cell needs a large amount of high-quality inorganic semiconductor materials, as silicon, GaAs, makes cost very high.Although the application of polysilicon and unformed silicon is more much lower than monocrystalline silicon cost, efficient is not high can't large tracts of land be promoted with the high solar cell that still makes of cost.The research and development of organic solar batteries makes the solar cell cost degradation become possibility.The energy conversion efficiency of the best organic solar batteries of present report is the efficient of approaching business-like unformed solar cell.
The reason that the efficient of organic solar batteries is very low always for a long time is inseparable with its basic physical process.When solar irradiation is mapped on the inorganic semiconductor, can produce free carrier in the inorganic semiconductor, the effect of the internal electric field that these free carriers form between the doping content semiconductor different with doping type issue estranged from, in external circuit, form electric current.And when illumination is mapped on the organic semiconducting materials, can not form free carrier in the organic semiconductor usually, but form electron-hole pair (exciton) earlier.Utilize organic material to obtain photoelectric current these are opened by the exciton that optical excitation obtains, otherwise these excitons will be sent out by radiation or radiationless mode de excitation.Interface with two kinds of organic materials of different level structures is considered to split the place of exciton, and therefore the exciton that is produced by optical excitation must at first be diffused into the interface and could farthest split exciton.
The most typical organic solar batteries is by two kinds of double-deckers that organic semiconducting materials forms with different level structures, and is similar with the P/N junction structure in the inorganic solar cell.In this structure, internal electric field is considered to that the energy difference of the LUMO (minimum molecule is occupied orbital not) of the HOMO (the sub-occupied orbital of best result) of Donor (electron donor) and Acceptor (electron acceptor) forms.The great advantage of this bi-layer devices is the material that electronics and hole transport are provided simultaneously.When exciton after the D-A interface produces electric charge and shifts, electronics transmits in acceptor material, then transmit in donor material in the hole, so separation of charge efficient is higher, the compound again chance of free charge also reduces.But because the low characteristic of the self-conductance rate of organic material, the electric charge that causes producing at the D-A interface is difficult to be transferred to effectively electrode layer, has reduced the energy conversion efficiency of device.For organic electroluminescence device, the characteristic that the carrier transmission material conductivity is low also hampers the carrying out that electronics and hole effectively are transferred to the luminescent layer recombination luminescence, and therefore, the transmittability that improves carrier blocking layers is significant for the performance of boost device.
Summary of the invention
Problem to be solved by this invention is: how a kind of organic electro-optic device and preparation method thereof is provided, this device has reduced the resistance of carrier blocking layers, improve the transmittability of charge carrier, and improved the visible light transmissivity of carrier blocking layers, improved the photoelectric properties of device.
Technical problem proposed by the invention is to solve like this: a kind of organic electro-optic device is provided, comprise substrate, anode layer, cathode layer, be arranged on the organic function layer between anode layer and the cathode layer, organic function layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, anode buffer layer, the electron donor layer, boundary layer, in electron acceptor layer and the cathode buffer layer one or more, it is characterized in that: doped magnetic multi-walled carbon nano-tubes in described hole transmission layer and the electron donor layer, or doped magnetic Single Walled Carbon Nanotube in electron transfer layer and the electron acceptor layer, or doped magnetic Single Walled Carbon Nanotube in electron transfer layer and the electron acceptor layer doped magnetic multi-walled carbon nano-tubes time in hole transmission layer and the electron donor layer, described magnetic multi-walled carbon nano-tubes and magnetic Single Walled Carbon Nanotube length direction are perpendicular to the anode layer surface.
According to organic electro-optic device provided by the present invention, it is characterized in that described magnetic single wall and magnetic multi-wall carbon nano-tube length of tube are less than or equal to 100nm, and the surface evenly is attached with magnetic nanoparticle.
According to organic electro-optic device provided by the present invention, it is characterized in that the doping content of described magnetic Single Walled Carbon Nanotube and multi-walled carbon nano-tubes all is less than or equal to 45%.
According to organic electro-optic device provided by the present invention, it is characterized in that described organic electro-optic device is organic electroluminescence device and organic solar batteries.
According to organic electro-optic device provided by the present invention, it is characterized in that, described hole injection layer material and anode buffer layer material comprise poly-(3 when device is organic electroluminescence device and organic solar batteries, the inferior second dioxy thiophene of 4-): polystyrene-based benzene sulfonic acid (PEDOT:PSS) or CuPc (CuPc) or 4,4 ', 4 " (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine (m-MTDATA) or molybdenum trioxide (MoO-three 3) or vanadic oxide (V 2O 5) or tungstic acid (WO 3) a class in the compound;
When device is organic electroluminescence device, described hole transport layer material is aromatic diamine compounds or aromatic triamine compounds or carbazole compound, wherein the aromatic diamine compounds comprises N, N '-two (naphthal-1-yl)-N, N '-two (phenyl)-benzidine (NPB) or N, N '-two (3-aminomethyl phenyl)-N, N '-two (phenyl)-benzidine (TPD) or N, N '-two (naphthal-1-yl)-N, N '-two (phenyl)-2,2 '-dimethylbenzidine (a-NPD), the aromatic triamine compounds comprises two-[4-(N, N-ditolyl-amino)-and phenyl] cyclohexane (TAPC), carbazole compound comprises polyvinylcarbazole (PVK);
When device is organic electroluminescence device and organic solar batteries, described electric transmission layer material and electron injecting layer material and cathode cushioning layer material are a kind of materials in metal organic complex, pyridines, o-phenanthroline class, 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 electron-like transferring 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 electron transport material is 1,3,5-three (N-phenyl-benzimidazolyl-2 radicals) benzene (TPBI);
When device is organic electroluminescence device and organic solar batteries, described luminescent layer material and boundary layer material are organic micromolecule compound or the high molecular polymers with high-quantum efficiency fluorescent characteristic, wherein, the enough vacuum deposition method film forming of organic micromolecule compound energy, as N, N '-two (3-naphthyl)-N, N '-diphenyl-[1,1 '-diphenyl]-4,4 '-diamines (NPB), 9,10-two-(2-naphthyl) anthracene (ADN), quinacridone (QA), the 2-{2-tert-butyl group-6-[2-(1,1,7,7,-tetramethyl)-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl]-vinyl }-pyrans-4-inner salt alkene }-malononitrile (DCJTB), oxine aluminium (Alq 3), rubrene (Rubrene), high molecular polymer can enough spin coatings and method film forming such as inkjet printing, as poly-phenylene vinylene (ppv) (PPV), polythiophene (PTV);
When device was organic solar batteries, described electron donor layer material was the thiophene-based material, p-phenylene vinylene (PPV) and derivative thereof, and aromatic amine material, condensed ring aromatic and phthalocyanine dye, thiophene-based material comprise 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 ,-two-(2-ethylhexyl)-4H-cyclopentene [and 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 " copolymer (PQTF8); 2] four polythiophenes)-alternately-(2; 7-fluorenes-9-ketone)]; gather (3-alkylthrophene) (P3AT); 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), the aromatic amine material comprises N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD), the condensed ring aromatic comprises aphthacene (Tetracene), pentacene (Pentacene), phthalocyanine dye comprise phthalocyanine hydrogen (H2Pc), inferior phthalocyanine (SubPc), CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine tin (SnPc);
When device is organic solar batteries, described electron acceptor layer material is C60 and derivative thereof, the thiophene-based material, the PPV derivative, the condensed ring aromatic, the C60 derivative comprises (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 organic electro-optic device provided by the present invention, it is characterized in that described magnetic nanoparticle is the nanometer Fe that diameter is less than or equal to 20nm 3O 4Particle, nanometer γ-Fe 2O 3The ferrite particle of particle, alkaline-earth metal ferrite particle or other nano-grade sizes, belong to the Al-Ni-Co system the AlNiCo alloying pellet, belong to the Sm-Co system alloying pellet, belong to the Pt-Co system alloying pellet, belong to alloying pellet of Nd-Fe-B system and composition thereof, and other magnetic nanoparticles such as cobalt particle, iron particle, nickel particles etc.
A kind of preparation method of organic electro-optic device is characterized in that, may further comprise the steps:
1. utilize acetone, ethanolic solution and deionized water that substrate is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen;
2. substrate is moved in the vacuum evaporation chamber, carry out the preparation of anode layer;
The substrate that 3. will prepare anode layer moves into vacuum chamber, carries out preliminary treatment under oxygen pressure ring border;
4. prepare organic function layer, described organic function layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, anode buffer layer, the electron donor layer, boundary layer, the electron acceptor layer, in the cathode buffer layer one or more, wherein be doped with the magnetic multi-walled carbon nano-tubes in hole transmission layer and the electron donor layer, or be doped with the magnetic Single Walled Carbon Nanotube in electron transfer layer and the electron acceptor layer, or be doped with the magnetic Single Walled Carbon Nanotube in electron transfer layer and the electron acceptor layer when being doped with the magnetic multi-walled carbon nano-tubes in hole transmission layer and the electron donor layer, be doped with the hole transmission layer of many walls of magnetic or Single Walled Carbon Nanotube, the electron donor layer, electron transfer layer or electron acceptor layer adopt the method preparation of spin coating, on direction, apply magnetic field during spin coating, make the magnetic carbon nano-tube length direction perpendicular to the anode layer surface perpendicular to substrate;
5. keep the pressure of above-mentioned vacuum chamber constant, finish cathode layer is carried out in the back in vacuum chamber preparation in the organic function layer preparation;
6. ready-made device is sent to glove box and encapsulates, glove box is a nitrogen atmosphere.
Preparation method according to organic electro-optic device provided by the present invention, it is characterized in that, the preparation method of organic function layer comprise the mode of taking evaporation in high vacuum chamber and in spin coater the mode of spin-coating film, or take to spray, self assembly, inkjet printing, silk screen printing, peel off, the mode of organic vapor phase deposition and being used in combination of above several preparation methods.
Many walls of doped magnetic or Single Walled Carbon Nanotube in the carrier blocking layers of organic electro-optic device provided by the present invention, and the length direction of this carbon nano-tube is perpendicular to the anode layer surface, because carbon nano-tube has the characteristics of high mobility, make electronics and cavity energy in the organic electroluminescence device more effectively are transferred to recombination luminescence in the luminescent layer, increased the luminescent properties of device, make electronics and hole in the organic solar batteries be drawn out to electrode layer effectively, and can suppress the compound again of electronics and hole, increased the energy conversion efficiency of device; Simultaneously, the introducing of magnetic carbon nano-tube has increased the visible light transmissivity of carrier blocking layers, has increased the external quantum efficiency of organic electroluminescence device, has increased the light absorption of organic solar batteries, helps the generation of exciton; In addition, introducing magnetic carbon nano-tube in organic solar batteries has increased in the device D-A internal electric field at the interface, helps the separation of exciton.
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 organic solar batteries provided by the present invention;
Fig. 3 is the structural representation of embodiment 1-3 provided by the present invention;
Fig. 4 is the structural representation of embodiment 4-6 provided by the present invention;
Fig. 5 is the structural representation of embodiment 7-8 provided by the present invention.
Fig. 6 is the structural representation of embodiment 9-10 provided by the present invention;
Fig. 7 is the structural representation of embodiment 11-13 provided by the present invention;
Fig. 8 is the structural representation of embodiment 14-16 provided by the present invention;
Fig. 9 is the performance comparison figure of two kinds of different components, and device A is the device of embodiment 1 provided by the present invention, and the structure of device B is glass substrate/ITO/NPB (50nm)/Alq 3(20nm)/BCP (40nm)/Mg:Ag (100nm).
Wherein, 1, substrate, 2, anode layer, 3, organic function layer, 30, hole injection layer, 31, hole transmission layer, 32, luminescent layer, 33, electron transfer layer, 34, the luminescent layer electron transfer layer of holding concurrently, 4, cathode layer, 5, additional power source, 6, organic function layer, 60, anode buffer layer, 61, electron donor layer, 62, boundary layer, 63, the electron acceptor layer.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described:
Technical scheme of the present invention is organic electro-optic device that how to provide doped magnetic carbon nano-tube in a kind of carrier blocking layers and preparation method thereof, as shown in Figure 3, the structure of device comprises substrate 1, anode layer 2, organic function layer 3, cathode layer 4, wherein anode layer 2 is positioned at substrate 1 surface, and organic function layer 3 is between anode layer 2 and cathode layer 4, and organic function layer 3 comprises hole transmission layer 31, luminescent layer 32 and electron transfer layer 33, device device under the driving of additional power source 5 is luminous.
As shown in Figure 4, the structure of device comprises substrate 1, anode layer 2, organic function layer 3, cathode layer 4, wherein anode layer 2 is positioned at substrate 1 surface, organic function layer 3 is between anode layer 2 and cathode layer 4, and organic function layer 3 comprises hole injection layer 30, hole transmission layer 31, luminescent layer 32 and electron transfer layer 33, device device under the driving of additional power source 5 is luminous.
As shown in Figure 5, the structure of device comprises substrate 1, anode layer 2, organic function layer 3, cathode layer 4, wherein anode layer 2 is positioned at substrate 1 surface, organic function layer 3 is between anode layer 2 and cathode layer 4, organic function layer 3 comprises hole transmission layer 31, the luminescent layer electron transfer layer 34 of holding concurrently, and device device under the driving of additional power source 5 is luminous.
As shown in Figure 6, the structure of device comprises substrate 1, anode layer 2, organic function layer 6, cathode layer 4, wherein anode layer 2 is positioned at substrate 1 surface, and organic function layer 6 is between anode layer 2 and cathode layer 4, organic function layer 6 comprises anode buffer layer 60, electron donor layer 61, boundary layer 62 and electron acceptor layer 63, and device produces voltage at the illumination bottom electrode.
As shown in Figure 7, the structure of device comprises substrate 1, anode layer 2, organic function layer 6, cathode layer 4, wherein anode layer 2 is positioned at substrate 1 surface, and organic function layer 6 is between anode layer 2 and cathode layer 4, organic function layer 6 comprises anode buffer layer 60, electron donor layer 61 and electron acceptor layer 63, and device produces voltage at the illumination bottom electrode.
As shown in Figure 8, the structure of device comprises substrate 1, anode layer 2, organic function layer 6, cathode layer 4, wherein anode layer 2 is positioned at substrate 1 surface, and organic function layer 6 is between anode layer 2 and cathode layer 4, organic function layer 6 comprises electron donor layer 61 and electron acceptor layer 63, and device produces voltage at the illumination bottom electrode.
Substrate 1 is the support of electrode and organic thin film layer in organic electroluminescence device among the present invention and the organic solar batteries, 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, and flexible substrate adopts a kind of material or the thin metal in polyesters, the poly-phthalimide compound.
Anode layer 2 requires to have electric conductivity preferably in organic electroluminescence device of the present invention and the organic solar batteries, visible transparent and higher work function, comprise inorganic, metal oxide film or metallic film, wherein the inorganic, metal oxide film is tin indium oxide (ITO) film or zinc oxide (ZnO) film or zinc tin oxide film, and metallic film is the metallic film of gold, copper, silver; Described anode layer material also can be poly-(3, the inferior second dioxy thiophene of 4-): the organic conductive polymer of polystyrene-based benzene sulfonic acid (PEDOT:PSS) or polyaniline (PANI) class.
Cathode layer 4 requires to have electric conductivity and lower work function preferably in organic electroluminescence device of the present invention and the organic solar batteries, comprises metallic film that work functions such as lithium, magnesium, calcium, strontium, aluminium, indium, silver are lower or their alloy firm.
Hole injection layer 30 materials and anode buffer layer 60 materials comprise poly-(3 in organic electroluminescence device of the present invention and the organic solar batteries, the inferior second dioxy thiophene of 4-): polystyrene-based benzene sulfonic acid (PEDOT:PSS) or CuPc (CuPc) or 4,4 ', 4 " (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine (m-MTDATA) or MoO-three 3Or V 2O 5Or WO 3Deng the class in the compound.
Transmitting layer 31 material in hole is aromatic diamine compounds or aromatic triamine compounds or carbazole compound in the organic electroluminescence device of the present invention, wherein the aromatic diamine compounds is N, N '-two (naphthal-1-yl)-N, N '-two (phenyl)-benzidine (NPB) or N, N '-two (3-aminomethyl phenyl)-N, N '-two (phenyl)-benzidine (TPD) or 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)-and phenyl] cyclohexane (TAPC), carbazole compound comprises polyvinylcarbazole (PVK).
Luminescent layer material 32 and boundary layer 62 materials are organic micromolecule compound or the high molecular polymers with high-quantum efficiency fluorescent characteristic in organic electroluminescence device of the present invention and the organic solar batteries.The enough vacuum deposition method film forming of organic micromolecule compound energy, as N, N '-two (3-naphthyl)-N, N '-diphenyl-[1,1 '-diphenyl]-4,4 '-diamines (NPB), 9,10-two-(2-naphthyl) anthracene (ADN), quinacridone (QA), the 2-{2-tert-butyl group-6-[2-(1,1,7,7 ,-tetramethyl)-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl]-vinyl }-pyrans-4-inner salt alkene }-malononitrile (DCJTB), oxine aluminium (Alq 3), rubrene (Rubrene); Method film forming such as high molecular polymer enough spin coatings of energy and inkjet printing are as poly-phenylene vinylene (ppv) (PPV), polythiophene (PTV).
Electron transfer layer 33 materials are a kind of materials in metal organic complex, pyridines, o-phenanthroline Lei, oxadiazole class or the glyoxaline compound material in the organic electroluminescence device of the present invention, 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 electron-like transferring 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 electron transport material is 1,3,5-three (N-phenyl-benzimidazolyl-2 radicals) benzene (TPBI).
The luminescent layer existing luminescent properties preferably of electron transfer layer 34 material requirements of holding concurrently has the good electron transmittability again in the organic electroluminescence device of the present invention, is oxine aluminium (Alq 3) or two (2-methyl-8-quino)-4-(phenylphenol) aluminium (BAlq) etc.
Electron donor layer 61 material are the thiophene-based material in the organic solar batteries of the present invention, p-phenylene vinylene (PPV) and derivative thereof, aromatic amine material, condensed ring aromatic and phthalocyanine dye, 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 " copolymer (PQTF8); 2] four polythiophenes)-alternately-(2; 7-fluorenes-9-ketone)]; gather (3-alkylthrophene) (P3AT); 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), the aromatic amine material comprises N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD), comprise that the condensed ring aromatic is aphthacene (Tetracene), pentacene (Pentacene), phthalocyanine dye comprise phthalocyanine hydrogen (H2Pc), inferior phthalocyanine (SubPc), CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine tin (SnPc).
Electron acceptor layer 63 material are C60 and derivative thereof in the organic solar batteries of the present invention, the thiophene-based material, PPV derivative and condensed ring aromatic, wherein the C60 derivative comprises (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).
Adopt the organic electroluminescence device and the organic solar energy cell structure of the present invention's preparation to be exemplified below:
Glass/ITO/ luminescent layer/electron transfer layer/electron injecting layer/cathode layer
Glass/ITO/ hole injection layer/hole transmission layer/luminescent layer/cathode layer
Glass/ITO/ hole transmission layer/luminescent layer/electron transfer layer/cathode layer
Glass/ITO/ 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/conducting polymer/hole transmission layer/luminescent layer/cathode layer
Glass/conducting polymer/luminescent layer/electron transfer layer/electron injecting layer/cathode layer
Glass/conducting polymer/hole injection layer/hole transmission layer/luminescent layer/cathode layer
Glass/conducting polymer/hole transmission layer/luminescent layer/electron transfer layer/cathode layer
Glass/conducting polymer/hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/cathode layer
Flexible base, board/ITO/ hole transmission layer/luminescent layer/electron transfer layer/cathode layer
Flexible base, board/ITO/ 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 transmission layer/luminescent layer/electron transfer layer/electron injecting layer/cathode layer
Glass/ITO/ anode buffer layer/electron donor layer/electron acceptor layer/cathode layer
Glass/ITO/ anode buffer layer/electron donor layer/boundary layer/electron acceptor layer/cathode layer
Glass/ITO/ electron donor layer/electron acceptor layer/cathode layer
Flexible base, board/ITO/ anode buffer layer/electron donor layer/electron acceptor layer/cathode layer
Flexible base, board/ITO/ anode buffer layer/electron donor layer/boundary layer/electron acceptor layer/cathode layer
Flexible base, board/ITO/ electron donor layer/electron acceptor layer/cathode layer
Embodiment 1
As shown in Figure 3, the substrate 1 of device is a clear glass, and anode layer 2 is ITO, hole transmission layer 31 materials be doped with the surface evenly distribution diameter be the Fe of 10nm 3O 4The NPB of the multi-walled carbon nano-tubes of particle, luminescent layer 32 materials are Alq 3, electron transfer layer 33 materials are BCP, cathode layer 4 Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/NPB: the magnetic multi-walled carbon nano-tubes (15%, 50nm)/Alq 3(20nm)/BCP (40nm)/Mg:Ag (100nm)
The preparation method is as follows:
1. utilize acetone, ethanolic solution and deionized water that 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 15 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～20W;
3. adopt the method for spin coating to prepare the hole transmission layer NPB layer of doped magnetic multi-walled carbon nano-tubes, revolution is 3000 revolutions per seconds during spin coating, duration is 20S, thickness is 50nm, when the preparation hole transmission layer, apply the magnetic field of 200mT on the direction perpendicular to substrate surface, the length direction that makes magnetic carbon nano-tube is perpendicular to substrate surface;
4. with substrate in the vaporization chamber of condition of high vacuum degree, be 1 * 10 at air pressure -4Begin to carry out the evaporation of organic film under the condition of Pa.According to device architecture as mentioned above evaporation luminescent layer materials A lq successively 3Layer 20nm, electron transfer layer material B CP layer 40nm.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;
5. after organic layer preparation finishes, substrate moved into the preparation of carrying out metal electrode in the vacuum evaporation chamber.Its air pressure is 3 * 10 -3Pa, evaporation speed is～1nm/s, and Mg and Ag ratio are～10: 1 in the alloy, and thicknesses of layers is 100nm.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.
Table 1 is the various performance parameters of hole transmission layer in the NBP layer and the embodiment of the invention 1
Hole transmission layer Visible light transmissivity Hole mobility (cm 2/Vs)
??NPB(50nm) ??92.4％ ??5.1×10 -4
The even distribution diameter in 15% surface that mixes is the Fe of 10nm 3O 4The NPB of the multi-walled carbon nano-tubes of particle (50nm) ??93.2％ ??9.8×10 -4
Embodiment 2
As shown in Figure 3, the substrate 1 of device is a clear glass, and anode layer 2 is ITO, and hole transmission layer 31 materials are NPB, and luminescent layer 32 materials are Alq 3, electron transfer layer 33 materials be doped with the surface evenly distribution diameter be γ-Fe of 15nm 2O 3The BPhen of the Single Walled Carbon Nanotube of particle, cathode layer 4 Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/NPB (50nm)/Alq 3(20nm)/BPhen: the magnetic Single Walled Carbon Nanotube (10%, 50nm)/Mg:Ag (100nm)
The preparation method is as follows:
1. utilize acetone, ethanolic solution and deionized water that 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 15 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～20W;
3. substrate is placed under the nitrogen environment, adopt the method for spin coating to prepare organic film.According to device architecture as mentioned above spin coating hole transmission layer NPB layer successively, revolution is 3000 revolutions per seconds during spin coating, and duration is 20S, and thickness is 50nm; Spin coating luminescent layer Alq 3Layer, revolution is 4000 revolutions per seconds during spin coating, and duration is 20S, and thickness is 20nm; The electron transfer layer BPhen layer of spin coating doped magnetic Single Walled Carbon Nanotube, revolution is 3000 revolutions per seconds during spin coating, and duration is 20S, and thickness is 50nm, when spin coating BPhen layer, on direction, apply the magnetic field of 200mT, make magnetic carbon nanometer direction pipe perpendicular to substrate surface perpendicular to substrate surface;
4. after organic layer preparation finishes, substrate moved into the preparation of carrying out metal electrode in the vacuum evaporation chamber.Its air pressure is 3 * 10 -3Pa, evaporation speed is～1nm/s, and Mg and Ag ratio are～10: 1 in the alloy, and 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 sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
Embodiment 3
As shown in Figure 3, the substrate 1 of device is PETG (PET), anode layer 2 is ITO, hole transmission layer 31 materials are PVK, luminescent layer 32 materials are PPV, electron transfer layer 33 materials be doped with the surface evenly distribution diameter be the BPhen of Single Walled Carbon Nanotube of the cobalt particle of 15nm, cathode layer 4 Mg:Ag alloy.The entire device structrual description is:
PET/ITO/PVK (50nm)/PPV (20nm)/BPhen: the magnetic Single Walled Carbon Nanotube (15%, 50nm)/Mg:Ag (100nm)
The preparation method is as follows:
1. utilize acetone, ethanolic solution and deionized water that the PET substrate that is coated with ITO is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen.Wherein the ITO film above the PET substrate is as the anode layer of device, and the square resistance of ITO film is 15 Ω/, and thickness is 180nm;
2. dried substrate being moved into vacuum chamber, is under the oxygen pressure ring border of 20Pa ITO to be carried out low energy oxygen plasma preliminary treatment 10 minutes at air pressure, and sputtering power is～20W;
3. with under the substrate nitrogen environment, adopt the method preparation of self assembly to prepare hole transmission layer PVK layer 50nm, luminescent layer PPV layer 20nm successively.
4. adopt the method for spin coating or spraying to prepare the electron transfer layer BPhen layer of doped magnetic Single Walled Carbon Nanotube, on direction, apply the magnetic field of 200mT when spin coating or spraying perpendicular to substrate surface, make magnetic carbon nanometer direction pipe perpendicular to substrate surface, revolution is 3000 revolutions per seconds during spin coating, duration is 20S, and thickness is 50nm;
5. after organic layer preparation finishes, substrate moved into the preparation of carrying out metal electrode in the vacuum evaporation chamber.Its air pressure is 3 * 10 -3Pa, evaporation speed is～1nm/s, and Mg and Ag ratio are～10: 1 in the alloy, and thicknesses of layers is 100nm.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.
Embodiment 4
As shown in Figure 4, the substrate 1 of device is a clear glass, and anode layer 2 is ITO, and hole injection layer 30 materials are CuPc, hole transmission layer 31 materials be doped with the surface evenly distribution diameter be the Fe of 15nm 3O 4The TPD of the multi-walled carbon nano-tubes of particle, luminescent layer 32 materials are Alq 3, electron transfer layer 33 materials be doped with the surface evenly distribution diameter be the Fe of 20nm 3O 4The BPhen of the Single Walled Carbon Nanotube of particle, cathode layer 4 Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/CuPc (10nm)/TPD: the magnetic multi-walled carbon nano-tubes (20%, 80nm)/Alq 3(20nm)/BPhen: the magnetic Single Walled Carbon Nanotube (20%, 100nm)/Mg:Ag (100nm)
The preparation of devices method is as follows:
1. utilize acetone, ethanolic solution and deionized water that 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 15 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～20W;
3. substrate is moved under the nitrogen environment, adopt the method for spraying to prepare organic film.Spray hole injection layer CuPc layer 10nm successively, the hole transmission layer TPD layer 80nm of doped magnetic multi-walled carbon nano-tubes, luminescent layer Alq according to device architecture as mentioned above 3Layer 20nm, the electron transfer layer BPhen layer 100nm of doped magnetic Single Walled Carbon Nanotube when spraying TPD layer and BPhen layer, applies the magnetic field of 250mT on the direction perpendicular to substrate surface, make magnetic carbon nanometer direction pipe perpendicular to substrate surface;
4. after organic layer preparation finishes, substrate moved into the preparation of carrying out metal electrode in the vacuum evaporation chamber.Its air pressure is 3 * 10 -3Pa, evaporation speed is～1nm/s, and Mg and Ag ratio are～10: 1 in the alloy, and 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 sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
Embodiment 5
As shown in Figure 4, the substrate 1 of device is a clear glass, and anode layer 2 is ITO, and hole injection layer material 30 is PEDOT:PSS, hole transmission layer 31 materials be doped with the surface evenly distribution diameter be the Fe of 10nm 3O 4The NPB of the multi-walled carbon nano-tubes of particle, luminescent layer 32 materials are Alq 3, electron transfer layer 33 materials be doped with the surface evenly distribution diameter be γ-Fe of 20nm 2O 3The TPBI of the Single Walled Carbon Nanotube of particle, cathode layer 4 Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/PEDOT:PSS (20nm)/NPB: the magnetic multi-walled carbon nano-tubes (25%, 80nm)/Alq 3(20nm)/TPBI: the magnetic Single Walled Carbon Nanotube (30%, 100nm)/Mg:Ag (100nm)
The preparation of devices method is as follows:
1. utilize acetone, ethanolic solution and deionized water that 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 15 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～20W;
3. on different silicon base, adopt the method for spraying or spin coating to prepare hole injection layer PEDOT:PSS layer 20nm respectively, the hole transmission layer NPB layer 80nm of doped magnetic multi-walled carbon nano-tubes, luminescent layer Alq 3Layer 20nm, the electron transfer layer TPBI layer 100nm of doped magnetic Single Walled Carbon Nanotube when spraying or spin coating NPB layer and TPBI layer, applies the magnetic field of 300mT on the direction perpendicular to substrate surface, make magnetic carbon nanometer direction pipe perpendicular to substrate surface;
4. the organic function layer on the silicon base of above-mentioned preparation is peeled off from substrate, being added to preparation with the order stack of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer successively again has on the glass substrate of ITO;
5. the ITO substrate is moved into the preparation of carrying out metal electrode in the vacuum evaporation chamber.Its air pressure is 3 * 10 -3Pa, evaporation speed is～1nm/s, and Mg and Ag ratio are～10: 1 in the alloy, and thicknesses of layers is 100nm.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.
Embodiment 6
As shown in Figure 4, the substrate 1 of device is PET, and anode layer 2 is ITO, and hole injection layer material 30 is PEDOT:PSS, hole transmission layer 31 materials be doped with the surface evenly distribution diameter be the Fe of 20nm 3O 4The PVK of the multi-walled carbon nano-tubes of particle, luminescent layer 32 materials are PTV, electron transfer layer 33 materials be doped with the surface evenly distribution diameter be the TPBI of Single Walled Carbon Nanotube of the nickel particles of 15nm, cathode layer 4 Mg:Ag alloy.The entire device structrual description is:
PET/ITO/PEDOT:PSS (20nm)/PVK: the magnetic multi-walled carbon nano-tubes (35%, 80nm)/PTV (20nm)/TPBI: the magnetic Single Walled Carbon Nanotube (45%, 100nm)/Mg:Ag (100nm)
The preparation of devices method is as follows:
1. utilize acetone, ethanolic solution and deionized water that the PET substrate that plates by ITO is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen.Wherein the ITO film above the PET substrate is as the anode layer of device, and the square resistance of ITO film is 15 Ω/, and thickness is 180nm;
2. dried substrate being moved into vacuum chamber, is under the oxygen pressure ring border of 20Pa ITO to be carried out low energy oxygen plasma preliminary treatment 10 minutes at air pressure, and sputtering power is～20W;
3. under the environment of nitrogen, adopt inkjet printing or divide the method for child print to prepare hole injection layer PEDOT:PSS layer 20nm successively, the hole transmission layer PVK layer 80nm of doped magnetic multi-walled carbon nano-tubes, luminescent layer PTV layer 20nm, the electron transfer layer TPBI layer 100nm of doped magnetic Single Walled Carbon Nanotube, when inkjet printing or branch child print PVK layer and TPBI layer, on direction, apply the magnetic field of 350mT, make magnetic carbon nanometer direction pipe perpendicular to substrate surface perpendicular to substrate surface;
4. after organic layer preparation finishes, substrate moved into the preparation of carrying out metal electrode in the vacuum evaporation chamber.Its air pressure is 3 * 10 -3Pa, evaporation speed is～1nm/s, and Mg and Ag ratio are～10: 1 in the alloy, and 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 sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
Embodiment 7
As shown in Figure 5, the substrate 1 of device is a clear glass, and anode layer 2 is ITO, hole transmission layer 31 materials be doped with the surface evenly distribution diameter be γ-Fe of 15nm 2O 3The TPD of the multi-walled carbon nano-tubes of particle, luminescent layer electron transfer layer 34 materials of holding concurrently are Alq 3, cathode layer 4 Mg:Ag alloy.The entire device structrual description is:
Glass substrate/ITO/TPD: the magnetic multi-walled carbon nano-tubes (40%, 80nm)/Alq 3(60nm)/Mg:Ag (100nm)
The preparation of devices method is as follows:
1. utilize acetone, ethanolic solution and deionized water that 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 15 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～20W;
3. on different silicon base, adopt the method for spraying or spin coating to prepare the hole transmission layer TPD layer 80nm of doped magnetic multi-walled carbon nano-tubes respectively, the luminescent layer electron transfer layer Alq that holds concurrently 3Layer 60nm when spraying or spin coating TPD layer, applies the magnetic field of 300mT on the direction perpendicular to substrate surface, make magnetic carbon nanometer direction pipe perpendicular to substrate surface;
4. the organic function layer of above-mentioned preparation is peeled off from different substrates, be added to preparation and have on the glass substrate of ITO with the hold concurrently order stack of electron transfer layer of hole transmission layer, luminescent layer successively again;
5. the ITO substrate is moved into the preparation of carrying out metal electrode in the vacuum evaporation chamber.Its air pressure is 3 * 10 -3Pa, evaporation speed is～1nm/s, and Mg and Ag ratio are～10: 1 in the alloy, and thicknesses of layers is 100nm.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.
Embodiment 8
As shown in Figure 5, the substrate 1 of device is PET, and anode layer 2 is ITO, hole transmission layer 31 materials be doped with the surface evenly distribution diameter be γ-Fe of 15nm 2O 3The NPB of the multi-walled carbon nano-tubes of particle, luminescent layer electron transfer layer 34 materials of holding concurrently are Alq 3, cathode layer 4 Mg:Ag alloy.The entire device structrual description is:
PET/ITO/NPB: the magnetic multi-walled carbon nano-tubes (45%, 80nm)/Alq 3(60nm)/Mg:Ag (100nm)
The preparation of devices method is as follows:
1. utilize acetone, ethanolic solution and deionized water that the PET substrate that is coated with ITO is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen.Wherein the ITO film above the PET substrate is as the anode layer of device, and the square resistance of ITO film is 15 Ω/, and thickness is 180nm;
2. dried substrate being moved into vacuum chamber, is under the oxygen pressure ring border of 20Pa ITO to be carried out low energy oxygen plasma preliminary treatment 10 minutes at air pressure, and sputtering power is～20W;
3. the hole transmission layer NPB layer 80nm that on different silicon base, adopts inkjet printing or divide the method for child print to prepare the doped magnetic multi-walled carbon nano-tubes respectively, the luminescent layer electron transfer layer Alq that holds concurrently 3Layer 60nm when spraying or spin coating NPB layer, applies the magnetic field of 400mT on the direction perpendicular to substrate surface, make magnetic carbon nanometer direction pipe perpendicular to substrate surface;
4. the organic function layer of above-mentioned preparation is peeled off from different substrates, be added to preparation and have on the glass substrate of ITO with the hold concurrently order stack of electron transfer layer of hole transmission layer, luminescent layer successively again;
5. the ITO substrate is moved into the preparation of carrying out metal electrode in the vacuum evaporation chamber.Its air pressure is 3 * 10 -3Pa, evaporation speed is～1nm/s, and Mg and Ag ratio are～10: 1 in the alloy, and thicknesses of layers is 100nm.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.
Embodiment 9
As shown in Figure 6, the substrate 1 of device is a clear glass, and anode layer 2 is ITO, and anode buffer layer 60 is MoO 3, electron donor layer 61 is γ-Fe of 15nm for being doped with the even distribution diameter in surface 2O 3The CuPc of the multi-walled carbon nano-tubes of particle, boundary layer 62 is DCJTB, and electron acceptor layer 63 is C60, and cathode layer 4 is used Ag.The entire device structrual description is:
Glass substrate/ITO/MoO 3(20nm)/CuPc: the magnetic multi-walled carbon nano-tubes (5%, 80nm)/DCJTB (1nm)/C60 (50nm)/Ag (100nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 10
As shown in Figure 6, the substrate 1 of device is a clear glass, and anode layer 2 is ITO, and anode buffer layer 60 is PEDOT:PSS, and electron donor layer 61 is MEH-PPV, and boundary layer 62 is DCJTB, and electron acceptor layer 63 is γ-Fe of 5nm for being doped with the even distribution diameter in surface 2O 3The C60 of the Single Walled Carbon Nanotube of particle, cathode layer 4 is used Ag.The entire device structrual description is:
Glass substrate/ITO/PEDOT:PSS (20nm)/MEH-PPV (50nm)/DCJTB (2nm)/C60: the magnetic Single Walled Carbon Nanotube (10%, 50nm)/Ag (100nm)
The preparation of devices flow process is similar to embodiment 2.
Embodiment 11
As shown in Figure 7, the substrate 1 of device is PET, and anode layer 2 is ITO, and anode buffer layer 60 is PEDOT:PSS, and electron donor layer 61 is MEH-PPV, and electron acceptor layer 63 is the Fe of 10nm for being doped with the even distribution diameter in surface 3O 4The C60 of the Single Walled Carbon Nanotube of particle, cathode layer 4 is used Ag.The entire device structrual description is:
PET/ITO/PEDOT:PSS (20nm)/MEH-PPV (50nm)/C60: the magnetic Single Walled Carbon Nanotube (15%, 50nm)/Ag (100nm)
The preparation of devices flow process is similar to embodiment 3.
Embodiment 12
As shown in Figure 7, the substrate 1 of device is a clear glass, and anode layer 2 is ITO, and anode buffer layer 60 is MoO 3, electron donor layer 61 is CuPc, electron acceptor layer 63 is the Fe of 20nm for being doped with the even distribution diameter in surface 3O 4The C60 of the Single Walled Carbon Nanotube of particle, cathode layer 4 is used Ag.The entire device structrual description is:
Glass substrate/ITO/MoO 3(20nm)/CuPc (60nm)/C60: the magnetic Single Walled Carbon Nanotube (20%, 80nm)/Ag (100nm)
The preparation of devices flow process is similar to embodiment 4.
Embodiment 13
As shown in Figure 7, the substrate 1 of device is a clear glass, and anode layer 2 is ITO, and anode buffer layer 60 is WO 3, electron donor layer 61 for be doped with the surface evenly distribution diameter be the P3HT of multi-walled carbon nano-tubes of the nickel particles of 10nm, electron acceptor layer 63 is C60, cathode layer 4 is used Ag.The entire device structrual description is:
Glass substrate/ITO/WO 3(20nm)/P3HT: the magnetic multi-walled carbon nano-tubes (25%, 50nm)/C60 (60nm)/Ag (100nm)
The preparation of devices flow process is similar to embodiment 5.
Embodiment 14
As shown in Figure 8, the electron donor layer 61 of device is P3HT, electron acceptor layer 63 for be doped with the surface evenly distribution diameter be the C60 of Single Walled Carbon Nanotube of the cobalt particle of 10nm, cathode layer 4 is used Ag.The entire device structrual description is:
Glass substrate/ITO/P3HT (40nm)/C60: the magnetic Single Walled Carbon Nanotube (30%, 60nm)/Ag (100nm)
The preparation of devices flow process is similar to embodiment 6.
Embodiment 15
As shown in Figure 8, the electron donor layer 61 of device is the Fe of 20nm for being doped with the even distribution diameter in surface 3O 4The P3HT of the multi-walled carbon nano-tubes of particle, electron acceptor layer 63 is the Fe of 10nm for being doped with the even distribution diameter in surface 3O 4The PCBM of the Single Walled Carbon Nanotube of particle, cathode layer 4 is used Ag.The entire device structrual description is:
Glass substrate/ITO/P3HT: the magnetic multi-walled carbon nano-tubes (35%, 80nm)/PCBM: the magnetic Single Walled Carbon Nanotube (35%, 100nm)/Ag (80nm)
The preparation of devices flow process is similar to embodiment 7.
Embodiment 16
As shown in Figure 8, the electron donor layer 61 of device is the Fe of 10nm for being doped with the even distribution diameter in surface 3O 4The MEH-PPV of the multi-walled carbon nano-tubes of particle, electron acceptor layer 63 is γ-Fe of 15nm for being doped with the even distribution diameter in surface 2O 3The PCBM of the Single Walled Carbon Nanotube of particle, cathode layer 4 is used Ag.The entire device structrual description is:
Glass substrate/ITO/MEH-PPV: the magnetic multi-walled carbon nano-tubes (45%, 60nm)/PCBM: the magnetic Single Walled Carbon Nanotube (45%, 80nm)/Ag (80nm)
The preparation of devices flow process is similar to embodiment 8.

Claims (8)

1.一种有机光电器件，包括衬底、阳极层、阴极层、设置在阳极层和阴极层之间的有机功能层，有机功能层包括空穴注入层、空穴传输层、发光层、电子传输层、电子注入层、阳极缓冲层、电子给体层、界面层、电子受体层和阴极缓冲层中的一种或多种，其特征在于：所述空穴传输层与电子给体层中掺杂磁性多壁碳纳米管，或电子传输层与电子受体层中掺杂磁性单壁碳纳米管，或空穴传输层与电子给体层中掺杂磁性多壁碳纳米管的同时电子传输层与电子受体层中掺杂磁性单壁碳纳米管，所述磁性多壁碳纳米管和磁性单壁碳纳米管长度方向垂直于阳极层表面。1. An organic photoelectric device, comprising a substrate, an anode layer, a cathode layer, an organic functional layer arranged between the anode layer and the cathode layer, the organic functional layer comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron One or more of transport layer, electron injection layer, anode buffer layer, electron donor layer, interface layer, electron acceptor layer and cathode buffer layer, characterized in that: the hole transport layer and the electron donor layer Doping magnetic multi-wall carbon nanotubes in the middle, or doping magnetic single-wall carbon nanotubes in the electron transport layer and the electron acceptor layer, or doping magnetic multi-wall carbon nanotubes in the hole transport layer and the electron donor layer The electron transport layer and the electron acceptor layer are doped with magnetic single-wall carbon nanotubes, and the length direction of the magnetic multi-wall carbon nanotubes and the magnetic single-wall carbon nanotubes is perpendicular to the surface of the anode layer. 2.根据权利要求1所述的有机光电器件，其特征在于，所述磁性单壁碳纳米管和磁性多壁碳纳米管长度小于或等于100nm，并且表面均匀附着有磁性纳米颗粒。2 . The organic optoelectronic device according to claim 1 , wherein the length of the magnetic single-wall carbon nanotubes and magnetic multi-wall carbon nanotubes is less than or equal to 100 nm, and magnetic nanoparticles are evenly attached to the surface. 3.根据权利要求1所述的有机光电器件，其特征在于，所述磁性单壁碳纳米管和多壁碳纳米管的掺杂浓度均小于或等于45％。3 . The organic photoelectric device according to claim 1 , wherein the doping concentrations of the magnetic single-wall carbon nanotubes and multi-wall carbon nanotubes are both less than or equal to 45%. 4.根据权利要求1所述的有机光电器件，其特征在于，所述有机光电器件为有机电致发光器件和有机太阳能电池。4. The organic optoelectronic device according to claim 1, characterized in that, the organic optoelectronic device is an organic electroluminescent device and an organic solar cell. 5.根据权利要求1所述的有机光电器件，其特征在于：5. The organic photoelectric device according to claim 1, characterized in that: 当器件为有机电致发光器件和有机太阳能电池时，所述空穴注入层材料和阳极缓冲层材料包括聚(3，4-亚乙二氧噻吩)：聚苯乙烯基苯磺酸或者酞菁铜或者4，4’，4”-三(N-3-甲基苯基-N-苯基-氨基)三苯胺或三氧化钼或五氧化二钒或三氧化钨；When the device is an organic electroluminescence device and an organic solar cell, the hole injection layer material and the anode buffer layer material include poly(3,4-ethylenedioxythiophene): polystyrene-based benzenesulfonic acid or phthalocyanine Copper or 4,4',4"-tris(N-3-methylphenyl-N-phenyl-amino)triphenylamine or molybdenum trioxide or vanadium pentoxide or tungsten trioxide; 当器件为有机电致发光器件时，所述空穴传输层材料是芳香族二胺类化合物或者芳香族三胺类化合物或咔唑类化合物，其中芳香族二胺类化合物是N，N’-二(萘亚甲基-1-yl)-N，N’-二(苯基)-联苯胺或者N，N’-二(3-甲基苯基)-N，N’-二(苯基)-联苯胺或者N，N’-二(萘亚甲基-1-yl)-N，N’-二(苯基)-2，2’-二甲基联苯胺，芳香族三胺类化合物是二-[4-(N，N-联甲苯-氨基)-苯基]环己烷，咔唑类化合物包括聚乙烯咔唑；When the device is an organic electroluminescent device, the hole transport layer material is an aromatic diamine compound or an aromatic triamine compound or a carbazole compound, wherein the aromatic diamine compound is N, N'- Bis(naphthylidene-1-yl)-N,N'-bis(phenyl)-benzidine or N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl )-benzidine or N,N'-bis(naphthylidene-1-yl)-N,N'-bis(phenyl)-2,2'-dimethylbenzidine, aromatic triamine compounds It is bis-[4-(N,N-bistolyl-amino)-phenyl]cyclohexane, and carbazole compounds include polyvinylcarbazole; 当器件为有机电致发光器件和有机太阳能电池时，所述电子传输层材料和电子注入层材料和阴极缓冲层材料是金属有机配合物、吡啶类、邻菲咯啉类、噁二唑类或咪唑类化合物材料中的一种，其中金属有机配合物包括8-羟基喹啉铝或者二(2-甲基-8-喹啉并)-4-(苯基苯酚)铝，吡啶类化合物包括三[2，4，6-三甲基-3-(吡啶-3-yl)苯基]-硼烷，邻菲咯啉类化合物包括2，9-二甲基-4，7-联苯-1，10-邻二氮杂菲(BCP)或者4，7-联苯-1，10-邻二氮杂菲，噁二唑类电子传输材料是2-(4-二苯基)-5-(4-叔丁苯基)-1，3，4-噁二唑或者1，3-二[(4-三元胺-丁基苯基)-1，3，4-重氮基酸-5-yl]苯，咪唑类电子传输材料是1，3，5-三(N-苯基-苯并咪唑-2)苯；When the device is an organic electroluminescence device and an organic solar cell, the electron transport layer material, the electron injection layer material and the cathode buffer layer material are metal-organic complexes, pyridines, phenanthrolines, oxadiazoles or One of the imidazole compound materials, wherein the metal-organic complex includes 8-hydroxyquinoline aluminum or bis(2-methyl-8-quinolino)-4-(phenylphenol)aluminum, and the pyridine compound includes tri [2,4,6-Trimethyl-3-(pyridine-3-yl)phenyl]-borane, o-phenanthroline compounds including 2,9-dimethyl-4,7-biphenyl-1 , 10-phenanthroline (BCP) or 4,7-biphenyl-1,10-phenanthrene, oxadiazole electron transport material is 2-(4-diphenyl)-5-( 4-tert-butylphenyl)-1,3,4-oxadiazole or 1,3-bis[(4-triamine-butylphenyl)-1,3,4-diazoic acid-5- yl] benzene, the imidazole electron transport material is 1,3,5-three (N-phenyl-benzimidazole-2) benzene; 当器件为有机电致发光器件和有机太阳能电池时，所述发光层材料和界面层材料是具有高量子效率荧光特性的有机小分子化合物或高分子聚合物；When the device is an organic electroluminescent device or an organic solar cell, the light-emitting layer material and the interface layer material are small organic molecular compounds or polymers with high quantum efficiency fluorescence characteristics; 当器件为有机太阳能电池时，所述电子给体层材料包括噻吩类材料、聚对苯乙炔及其衍生物、芳香胺类材料、稠环芳香化合物或酞菁染料，其中，噻吩类材料包括5-乙烯基-2-四聚噻吩、5-乙烯基-五聚噻吩、α，α-二(2，2-二氰基乙烯)-五聚噻吩、[2，6-(4，4-二-(2-乙基己基)-4H-环戊烯[2，1-b；3，4-b′]-二噻吩)-交替-4，7-(2，1，3-苯并噻二唑)]共聚物、(5，5-二辛基-[2，2′；5′，2”；5”，2]四聚噻吩)-交替-(2，7-芴-9-酮)]共聚物、聚(3-烷基噻吩)、3-己基取代聚噻吩，PPV衍生物包括聚[2-甲氧基-5-(2-乙基己氧基)-1，4-苯撑乙烯撑]，聚[2-甲氧基，5-(3，7-二甲基-辛氧基)-对苯乙烯撑]，芳香胺类材料包括N，N′-二苯基-N，N′-二(3-甲基苯基)-1，1′-联苯-4，4′-二胺，稠环芳香化合物包括并四苯、并五苯，酞菁染料包括酞菁氢、亚酞菁、酞菁铜、酞菁锌、酞菁锡；When the device is an organic solar cell, the electron donor layer material includes thiophene materials, polyphenylene vinylene and its derivatives, aromatic amine materials, condensed ring aromatic compounds or phthalocyanine dyes, wherein the thiophene materials include 5 -Vinyl-2-tetrathiophene, 5-vinyl-pentathiophene, α,α-bis(2,2-dicyanoethylene)-pentathiophene, [2,6-(4,4-di -(2-Ethylhexyl)-4H-cyclopentene[2,1-b; 3,4-b']-dithiophene)-alternate-4,7-(2,1,3-benzothiabis oxazole)] copolymer, (5,5-dioctyl-[2,2′;5′,2″;5″,2]tetrathiophene)-alternate-(2,7-fluoren-9-one) ] copolymers, poly(3-alkylthiophene), 3-hexyl-substituted polythiophene, PPV derivatives including poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy, 5-(3,7-dimethyl-octyloxy)-p-phenylene], aromatic amine materials including N, N'-diphenyl-N, N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, fused ring aromatic compounds include tetracene and pentacene, phthalocyanine dyes include hydrogen phthalocyanine, Subphthalocyanine, copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine; 当器件为有机太阳能电池时，所述电子受体层材料包括C60及其衍生物、噻吩类材料、PPV衍生物或稠环芳香化合物，其中C60衍生物为(6，6)-苯基-C61-丁酸甲酯、(6，6)-苯基-C61-丁酸丁酯、1-(3-甲氧羰基)丙基-1-噻吩基-[6，6]-亚甲基富勒烯，噻吩类材料包括二氰基乙烯基-三聚噻吩、聚(3-氰基-4-己基噻吩)，PPV衍生物包括[氧杂-1，4-亚苯基-1，2-(1-氰基)-亚乙烯基-2，5-二辛氧-1，4-亚苯基-1，2-(2-氰基)-亚乙烯基-1，4-亚苯基]聚合物、聚[2-甲氧基-5-(2-乙基己氧基)-α-氰基-对苯乙烯撑]，稠环芳香化合物材料包括3，4，9，10-苝四羧基-双苯并咪唑、3，4，9，10-苝四甲酸二酐。When the device is an organic solar cell, the electron acceptor layer material includes C60 and its derivatives, thiophene materials, PPV derivatives or fused ring aromatic compounds, wherein the C60 derivative is (6,6)-phenyl-C61 -methyl butyrate, (6,6)-phenyl-C61-butyl butyrate, 1-(3-methoxycarbonyl)propyl-1-thienyl-[6,6]-methylenefuller Alkenes, thiophene materials include dicyanovinyl-trithiophene, poly(3-cyano-4-hexylthiophene), PPV derivatives include [oxa-1,4-phenylene-1,2-( 1-cyano)-vinylidene-2,5-dioctyloxy-1,4-phenylene-1,2-(2-cyano)-vinylidene-1,4-phenylene] polymerization compounds, poly[2-methoxy-5-(2-ethylhexyloxy)-α-cyano-p-phenylene], fused ring aromatic compound materials including 3,4,9,10-perylenetetracarboxy - bisbenzimidazole, 3,4,9,10-perylenetetracarboxylic dianhydride. 6.根据权利要求2所述的有机光电器件，其特征在于，所述磁性纳米颗粒直径小于或等于20nm，包括纳米Fe3O4粒子、纳米γ-Fe2O3粒子、碱土金属铁氧体颗粒、属于Al-Ni-Co体系的AlNiCo合金颗粒、属于Sm-Co体系的合金颗粒、属于Pt-Co体系的合金颗粒或属于Nd-Fe-B体系的合金颗粒及其混合物。6. The organic optoelectronic device according to claim 2, characterized in that the diameter of the magnetic nanoparticles is less than or equal to 20nm, comprising nano-Fe 3 O 4 particles, nano-γ-Fe 2 O 3 particles, alkaline earth metal ferrite Particles, AlNiCo alloy particles belonging to the Al-Ni-Co system, alloy particles belonging to the Sm-Co system, alloy particles belonging to the Pt-Co system or alloy particles belonging to the Nd-Fe-B system and mixtures thereof. 7.一种有机光电器件的制备方法，其特征在于，包括以下步骤：7. A method for preparing an organic photoelectric device, comprising the following steps: ①利用丙酮、乙醇溶液和去离子水对衬底进行超声清洗，清洗后用干燥氮气吹干；①Use acetone, ethanol solution and deionized water to ultrasonically clean the substrate, and dry it with dry nitrogen after cleaning; ②将衬底移入真空蒸发室中，进行阳极层的制备；② Move the substrate into the vacuum evaporation chamber to prepare the anode layer; ③将制备好阳极层的衬底移入真空室，在氧气压环境下进行预处理；③ Move the substrate with the prepared anode layer into the vacuum chamber, and perform pretreatment under the oxygen pressure environment; ④制备有机功能层，所述有机功能层包括空穴注入层、空穴传输层、发光层、电子传输层、电子注入层、阳极缓冲层、电子给体层、界面层、电子受体层、阴极缓冲层中的一种或多种，其中空穴传输层和电子给体层中掺杂有磁性多壁碳纳米管，或电子传输层和电子受体层中掺杂有磁性单壁碳纳米管，或空穴传输层和电子给体层中掺杂有磁性多壁碳纳米管的同时电子传输层和电子受体层中掺杂有磁性单壁碳纳米管，掺杂有磁性多壁或单壁碳纳米管的空穴传输层、电子给体层、电子传输层或电子受体层采用旋涂的方法制备，旋涂时在垂直于衬底的方向上施加磁场，使磁性碳纳米管长度方向垂直于阳极层表面；4. Prepare an organic functional layer, the organic functional layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an anode buffer layer, an electron donor layer, an interface layer, an electron acceptor layer, One or more of the cathode buffer layers, wherein the hole transport layer and the electron donor layer are doped with magnetic multi-walled carbon nanotubes, or the electron transport layer and the electron acceptor layer are doped with magnetic single-walled carbon nanotubes tubes, or the hole transport layer and the electron donor layer are doped with magnetic multi-wall carbon nanotubes while the electron transport layer and the electron acceptor layer are doped with magnetic single-wall carbon nanotubes, doped with magnetic multi-wall or The hole transport layer, electron donor layer, electron transport layer or electron acceptor layer of single-walled carbon nanotubes are prepared by spin coating, and a magnetic field is applied in a direction perpendicular to the substrate during spin coating to make the magnetic carbon nanotubes The length direction is perpendicular to the surface of the anode layer; ⑤保持上述真空室的压力不变，在有机功能层制备结束后在真空室中进行阴极层的制备；5. Keep the pressure of the above-mentioned vacuum chamber constant, and prepare the cathode layer in the vacuum chamber after the preparation of the organic functional layer is completed; ⑥将做好的器件传送到手套箱进行封装，手套箱为氮气氛围。⑥Transfer the finished device to the glove box for packaging, and the glove box is a nitrogen atmosphere. 8.根据权利要求7所述的有机光电器件的制备方法，其特征在于，有机功能层的制备方法包括采取在高真空室中蒸镀的方式和在旋涂机中旋涂成膜的方式，或采取喷涂、自组装、喷墨打印、丝网印刷、剥离、有机气相沉积的方式及以上几种制备方式的组合使用。8. the preparation method of organic photoelectric device according to claim 7, it is characterized in that, the preparation method of organic functional layer comprises the mode that adopts evaporation in high-vacuum chamber and the mode of spin-coating film-forming in spin coater, Or use spraying, self-assembly, inkjet printing, screen printing, stripping, organic vapor deposition and a combination of the above preparation methods.
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