WO2013000162A1 - 顶发射有机电致发光器件及其制备方法 - Google Patents

顶发射有机电致发光器件及其制备方法 Download PDF

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WO2013000162A1
WO2013000162A1 PCT/CN2011/076704 CN2011076704W WO2013000162A1 WO 2013000162 A1 WO2013000162 A1 WO 2013000162A1 CN 2011076704 W CN2011076704 W CN 2011076704W WO 2013000162 A1 WO2013000162 A1 WO 2013000162A1
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layer
organic electroluminescent
electroluminescent device
top emission
emission organic
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French (fr)
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周明杰
王平
冯小明
黄辉
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Oceans King Lighting Science and Technology Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
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Priority to EP11868480.2A priority Critical patent/EP2728635A4/en
Priority to CN201180070970.3A priority patent/CN103548168A/zh
Priority to JP2014513028A priority patent/JP2014519206A/ja
Priority to US14/119,856 priority patent/US20140077202A1/en
Priority to PCT/CN2011/076704 priority patent/WO2013000162A1/zh
Publication of WO2013000162A1 publication Critical patent/WO2013000162A1/zh
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/818—Reflective anodes, e.g. ITO combined with thick metallic layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • H10K2102/3023—Direction of light emission
    • H10K2102/3026—Top emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • the present invention relates to the field of optoelectronic devices, and more particularly to a top emitting organic electroluminescent device.
  • the invention further relates to a method of preparing the top emission organic electroluminescent device.
  • OLED Organic Light Emission Diode
  • OLED has the characteristics of high brightness, wide material selection range, low driving voltage, full-curing active illumination, high-definition, wide viewing angle, fast response, etc., in line with the development trend of mobile communication and information display in the information age, and green
  • the requirements of lighting technology are the focus of many researchers at home and abroad.
  • an OLED device using a flexible material as a substrate an OLED than a glass substrate It has the advantages of being lighter and thinner and more resistant to impact. And the fabrication of flexible OLED devices can be produced in a roll-to-roll fashion, which significantly reduces manufacturing costs.
  • a polymer film is usually used as a substrate, an anode formed on the surface thereof is covered with a transparent conductive film such as ITO, IZO or the like by a sputtering process, but this is to prepare ITO.
  • the doping ratio composition of various elements such as indium (In) and (Sn) is difficult to control, which makes the morphology and carrier transport properties of ITO thin films difficult to control.
  • ITO is prepared on a flexible substrate.
  • a conductive film When a conductive film is used, a low-temperature sputtering technique is generally used, and the surface resistance of the prepared conductive film is high, and the bonding force between the film and the substrate is not strong, so that the flexible OLED is made. In the process of repeated bending, the conductive film is easily detached from the substrate, which affects the luminescent stability of the OLED light-emitting device.
  • Some metal materials such as aluminum (Al), silver (Ag), etc. can be formed on the polymer film by an evaporation process, while having good electrical conductivity and high reflectivity, after film formation on the polymer film,
  • the bonding strength with the substrate is superior to that of the ITO conductive film, and is suitable for the anode of the top-emitting OLED device.
  • the metal materials such as Al, Ag and other common hole transport materials (eg, NPB, TPD), resulting in poor hole injection capability of the anode, thus affecting organic electroluminescence.
  • the luminous efficiency of the device is a large barrier between the metal materials such as Al, Ag and other common hole transport materials (eg, NPB, TPD), resulting in poor hole injection capability of the anode, thus affecting organic electroluminescence.
  • the luminous efficiency of the device is a large barrier between the metal materials such as Al, Ag and other common hole transport materials (eg, NPB, TPD), resulting in poor hole injection capability of the anode,
  • a top-emitting organic electroluminescent device comprising a substrate, an anode layer, a self-assembled molecular modification layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer which are sequentially stacked.
  • the self-assembled molecular modification layer is a long molecular chain alkane thiol having a chemical formula of CH 3 (CH 2 ) n -SH , wherein 5 ⁇ n ⁇ 21 ,
  • the self-assembling molecular modification layer is bonded to the metal thin film by a sulfhydryl group on the thiol.
  • the top emission organic electroluminescent device of the present invention uses a substrate material which is a polymer film such as polyethylene terephthalate (PET), polyether sulfone (PES) or polyethylene naphthalate. Alcohol ester (PEN) or polycarbonate (PC).
  • PET polyethylene terephthalate
  • PES polyether sulfone
  • PEN Alcohol ester
  • PC polycarbonate
  • the cathode layer of the top emission organic electroluminescent device is a cathode monomer layer or two stacked cathode monomer layers; the cathode monomer layer is made of aluminum, silver, ruthenium or iridium.
  • each organic functional layer is selected from the following:
  • the material of the hole transport layer is N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl. -4,4'-diamine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'- Amine (TPD) or 1,1-bis(4'-bis(4'-tolyl)aminophenyl )cyclohexane (TAPC ) ;
  • the material of the light-emitting layer is doped with N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB).
  • NPB 2-methyl-diphenyl[f,h]quinoxaline) (acetylacetone) ( Ir(MDQ) 2 (acac) ), 4,4',4''-tris(carbazol-9-yl) - triphenylamine) (TCTA) doped tris(2-phenylpyridine) ruthenium (Ir(ppy) 3 ), 8-hydroxyquinoline aluminum (Alq 3 ) doped 4-4-dicyanomethylidene- 2-tert-Butyl-6-(1, 1, 7, 7-tetramethyl-julonidine-9-vinyl)-4H-pyran (DCJTB) or DPVBi; the material of the luminescent layer is NPB: Ir(MDQ) 2
  • the material of the electron transport layer is selected from (8-hydroxyquinoline)-aluminum (Alq 3 ), 4,7-diphenyl-phenanthroline (Bphen) or 1,3,5-tris(1-phenyl-1H).
  • - benzimidazol-2-yl)benzene (TPBi) 8-hydroxyquinoline-aluminum (Alq 3 ), 4,7-diphenyl-phenanthroline (Bphen) or 1,3,5-tris(1-phenyl-1H).
  • the material of the electron injecting layer is selected from LiF, CsF or Li 2 O;
  • the material of the anode is a metal such as Ag, Al or Au.
  • the invention also provides a method for fabricating the above-mentioned top emission organic electroluminescent device, which comprises the following steps:
  • S4 a method of vacuum coating, sequentially depositing a vapor transport hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer on the surface of the self-assembled molecular modification layer;
  • step S2 It also includes the following steps:
  • the prepared anode layer is placed in a plasma processor and evacuated to a 10-60 Pa state.
  • the high-frequency discharge is performed under an air atmosphere, and the surface of the anode layer is plasma-cleaned by a glow discharge treatment for 5-15 minutes under a radio frequency power of 60 W.
  • This plasma treatment improves the surface energy of the anode layer, thereby increasing the self-assembled molecules in the anode layer. Film formation uniformity and compactness of the surface.
  • step S3 also includes the steps:
  • the alkanethiol having the chemical formula CH 3 (CH 2 ) n -SH is dissolved in ethanol or diethyl ether, and is disposed as a solution, and the molar concentration of the solution may be between 0.1 and 10 mM;
  • the top-emitting organic electroluminescent device provided by the invention prepares a self-assembled molecular modification layer on the surface of the anode layer, the self-assembled molecular modification layer increases the work function of the anode layer, and reduces the anode layer and the hole transport layer. Inter-hole injection barrier, which lowers the startup voltage of the OLED device, thereby improving the OLED The luminous efficiency of the device.
  • FIG. 1 is a schematic structural view of a top emission organic electroluminescent device according to an embodiment
  • FIG. 2 is a flow chart showing a process of preparing a top emission organic electroluminescent device according to an embodiment
  • Example 3 is a comparison diagram of voltage-luminance curves of the top emission organic electroluminescence device fabricated in Example 2 and Comparative Example 1.
  • a top-emitting organic electroluminescent device includes a substrate 101 and an anode layer 102 which are sequentially stacked.
  • the self-assembled molecular modification layer 103 is a long molecular chain alkanethiol having a specific formula of CH 3 (CH 2 ) n -SH , wherein 5 ⁇ n ⁇ 21,
  • the assembled molecular modification layer is bonded to the metal thin film by a sulfhydryl group on the thiol;
  • the top emission organic electroluminescent device uses a substrate 101 made of a polymer film such as polyethylene terephthalate (PET). Polyethersulfone (PES), polyethylene naphthalate (PEN) or polycarbonate (PC); in view of the top-emitting organic electroluminescent device being a top-emitting OLED Therefore, the surface of the polymer film of the substrate material must be flat and hardened, and the surface hardness is as high as 2H-3H (pencil hardness).
  • PET polyethylene terephthalate
  • PES Polyethersulfone
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • the hole transport layer 104 of the top emission organic electroluminescent device, the light emitting layer 105, the electron transport layer 106, and the electron injection layer 107 The materials used are materials commonly used in the field, such as:
  • the material of the hole transport layer is N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl. -4,4'-diamine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'- Amine (TPD) or 1,1-bis(4'-bis(4'-tolyl)aminophenyl )cyclohexane (TAPC ) ;
  • the material of the light-emitting layer is doped with N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB).
  • NPB 2-methyl-diphenyl[f,h]quinoxaline) (acetylacetone) ( Ir(MDQ) 2 (acac) ), 4,4',4''-tris(carbazol-9-yl) - triphenylamine) (TCTA) doped tris(2-phenylpyridine) ruthenium (Ir(ppy) 3 ), 8-hydroxyquinoline aluminum (Alq 3 ) doped 4-4-dicyanomethylidene- 2-tert-Butyl-6-(1, 1, 7, 7-tetramethyl-julonidine-9-vinyl)-4H-pyran (DCJTB) or DPVBi; the material of the luminescent layer is NPB: Ir(MDQ) 2
  • the material of the electron transport layer is selected from (8-hydroxyquinoline)-aluminum (Alq 3 ), 4,7-diphenyl-phenanthroline (Bphen) or 1,3,5-tris(1-phenyl-1H).
  • - benzimidazol-2-yl)benzene (TPBi) 8-hydroxyquinoline-aluminum (Alq 3 ), 4,7-diphenyl-phenanthroline (Bphen) or 1,3,5-tris(1-phenyl-1H).
  • the material of the electron injecting layer is selected from LiF, CsF or Li 2 O;
  • the anode is made of metal Ag, Al or Au, and the anode layer has a thickness of 18-100 nm.
  • the cathode layer of the top emission organic electroluminescent device is one or two cathode monomer layers; the cathode monomer layer is made of aluminum (Al), silver (Ag), ⁇ (Sm) or ⁇ (Yb); The cathode layer is a translucent cathode with a total thickness of 18-30 nm; and the cathode layer has a transmittance of 55%-75% under visible light.
  • the present invention also provides a method for fabricating the above-described top emission organic electroluminescent device, as shown in FIG. 2, which comprises the following steps:
  • substrate eg, polymer film
  • Ultrasonic cleaning in deionized water containing detergent washing with deionized water, followed by isopropyl alcohol, acetone in ultrasonic treatment, and then drying with nitrogen, and standby;
  • the polymer film includes polyparaphenylene Ethylene glycol dicarboxylate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), or polycarbonate (PC);
  • a surface of the anode layer is prepared with a self-assembling molecular modification layer; wherein the self-assembled molecular modification layer is made of an alkanethiol having a chemical formula of CH 3 (CH 2 ) n -SH, and 5 ⁇ n ⁇ 21 ;
  • S4 a vacuum transporting method, sequentially depositing a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer on the surface of the anode layer; respectively, thicknesses of the hole transporting layer, the light emitting layer, the electron transporting layer, and the electron injecting layer 50 ⁇ 60nm , 15 ⁇ 20nm , 30 ⁇ 40nm and 1nm ;
  • step S2 It also includes the following steps:
  • the prepared anode layer is placed in a plasma processor, vacuum is drawn to 10-60 Pa, and high frequency discharge is performed in an air atmosphere. Glow discharge treatment for 5-15 minutes of plasma cleaning of the surface of the anode layer at 60W.
  • This plasma treatment improves the surface energy of the anode layer, thereby increasing the self-assembled molecules in the anode layer. Film formation uniformity and compactness of the surface.
  • step S3 also includes the steps:
  • the alkanethiol having the chemical formula CH 3 (CH 2 ) n -SH is dissolved in ethanol or diethyl ether, and is disposed as a solution, and the molar concentration of the solution may be between 0.1 and 10 mM (ie, mmol/L);
  • the top-emitting organic electroluminescent device prepareds a self-assembled molecular modification layer of an alkanethiol of the chemical formula CH 3 (CH 2 ) n -SH on the surface of the anode layer, the self-assembled molecular modification layer
  • the work function of the anode layer is improved, the hole injection barrier between the anode layer and the hole transport layer is lowered, and the starting voltage of the OLED device is lowered, thereby improving the luminous efficiency of the OLED device.
  • the structure of the top emission organic electroluminescent device of the first embodiment is: PET/Al/CH 3 (CH 2 ) 5 -SH / ⁇ -NPD/NPB: Ir(MDQ) 2 (acac) / Alq 3 /LiF/ Ag .
  • the preparation process of the top emission organic electroluminescent device is as follows:
  • PET with a thickness of 0.175mm
  • the film was ultrasonically cleaned in deionized water containing detergent, then treated with isopropyl alcohol, acetone in ultrasonic, and then dried with nitrogen.
  • a thickness of 60 is formed by vacuum thermal evaporation.
  • the Al film of nm is prepared as a flexible anode.
  • the anode was placed in a plasma processor, evacuated to 10 Pa, and then subjected to high-frequency discharge, and glow discharge treatment was performed for 60 minutes under RF power of 60 W; 1-hexane thiol (CH 3 (CH 2 ) 5 - SH) Dissolved in ethanol at a concentration of 10 mM, then immersed the plasma-treated Al anode in the solution, soaked for 30 minutes, so that 1-hexanethiol was adsorbed on the surface of the Al film to form a self-assembled film, and then taken out. Dry with nitrogen.
  • 1-hexane thiol CH 3 (CH 2 ) 5 - SH
  • the hole transport layer NPB having a thickness of 50 nm and the light-emitting layer NPB: Ir(MDQ) 2 having a thickness of 20 nm are sequentially formed by vacuum thermal evaporation on the self-assembled monomolecular film-modified Al film.
  • (acac) (where NPB is the host material, Ir(MDQ) 2 (acac) is the guest material, the guest material is doped with 5% by mass), and the thickness is 40 nm.
  • the electron transport layer Alq 3 has a thickness of 1
  • the electron injection layer LiF of nm and the next layer are Ag layers with a thickness of 18 nm.
  • the structure of the top emission organic electroluminescent device of the second embodiment is: PES/Ag/CH 3 (CH 2 ) 11 -SH /NPB/ TCTA:Ir(ppy) 3 /Bphen/LiF/ (Al/Sm).
  • the preparation process of the top emission organic electroluminescent device is as follows:
  • the film was ultrasonically cleaned in deionized water containing detergent, then treated with isopropanol, acetone in ultrasonic, and then dried with nitrogen. On the surface of the flexible substrate, a thickness of 80 nm is formed by vacuum thermal evaporation.
  • the Ag film is prepared as a flexible anode.
  • the anode was placed in a plasma processor, evacuated to 40 Pa, and then subjected to high-frequency discharge, and glow discharge treatment was performed for 10 minutes under RF power of 60 W; n-dodecyl mercaptan (CH 3 (CH 2 ) 11 - SH) Dissolved in ethanol at a concentration of 1 mM, and then immersed the plasma-treated Ag anode in the solution for 15 minutes to form a self-assembled film. After completion, it was taken out and dried with nitrogen.
  • n-dodecyl mercaptan CH 3 (CH 2 ) 11 - SH
  • a hole transport layer NPB having a thickness of 60 nm and a light-emitting layer TCTA: Ir(ppy) 3 having a thickness of 15 nm are sequentially formed by vacuum thermal evaporation on the self-assembled monomolecular film-modified metal Ag film.
  • TCTA is the host material
  • Ir(ppy) 3 is the guest material
  • the guest material is doped with 3% by mass
  • the electron transport layer Bphen is 30 nm thick
  • the electron injection layer LiF is 1 nm thick.
  • the layer is a cathode layer of two monomer layers of Al (thickness 1 nm) / Sm (thickness 30 nm), which is a two-layer monomer layer.
  • the structure of the top emission organic electroluminescent device of the third embodiment is: PC/Au/CH 3 (CH 2 ) 17 -SH /TAPC/DPVBi/TPBi/CsF/Ag.
  • the preparation process of the top emission organic electroluminescent device is as follows:
  • PC with a thickness of 0.20mm
  • the film was ultrasonically cleaned in deionized water containing detergent, then treated with isopropyl alcohol, acetone in ultrasonic, and then dried with nitrogen.
  • Au is formed by vacuum thermal evaporation on the surface of the flexible substrate
  • the membrane was prepared as a flexible anode with an Au film thickness of 60 nm.
  • the anode was placed in a plasma processor, evacuated to 60 Pa, and then subjected to high-frequency discharge, and glow discharge treatment was performed for 10 minutes under RF power of 60 W; n-octadecyl mercaptan (CH 3 (CH 2 ) 17 ) -SH) Dissolved in ethanol at a concentration of 0.5 mM.
  • the plasma-treated Au anode was then immersed in the solution for 30 minutes to form a self-assembled film, which was then taken out and dried with nitrogen.
  • a hole transport layer having a thickness of 50 nm is sequentially formed on the Au film modified by the self-assembled monomolecular film by evaporation.
  • TAPC a light-emitting layer DPVBi with a thickness of 20 nm
  • the next layer is thickness 20 nm Ag layer.
  • the structure of the top emission organic electroluminescent device of the fourth embodiment is: PEN/Al/CH 3 (CH 2 ) 21 -SH /TPD/ Alq 3 : DCJTB / Alq 3 /Li 2 O/(Yb/Ag).
  • the preparation process of the top emission organic electroluminescent device is as follows:
  • PEN with a thickness of 0.18mm
  • the film was ultrasonically cleaned in deionized water containing detergent, then treated with isopropanol, acetone in ultrasonic, and then dried with nitrogen.
  • a thickness of 100 is formed by vacuum thermal evaporation.
  • the Al film of nm is made into an anode.
  • the anode was placed in a plasma processor, evacuated to 50 Pa, and then subjected to high-frequency discharge, and glow discharge treatment was performed for 15 minutes under RF power of 60 W; n-docosyl mercaptan (CH 3 (CH 2 )) 21 -SH) Dissolved in diethyl ether at a concentration of 0.1 mM, and then the plasma-treated Al anode was immersed in the solution for 5 minutes, and then taken out and dried with nitrogen.
  • n-docosyl mercaptan CH 3 (CH 2 )) 21 -SH
  • the hole transport layer TPD having a thickness of 50 nm and the light-emitting layer Alq 3 : DCJTB having a thickness of 20 nm are sequentially formed by vapor deposition on the self-assembled monomolecular film-modified metal Al film (wherein DCJTB is The guest material, Alq 3 is the host material, the guest material is doped with 2% by mass, the electron transport layer Alq 3 with a thickness of 35 nm, and the electron injection layer Li 2 O with a thickness of 1 nm.
  • the next layer is a cathode layer of a two-layer laminated monomer layer having a structure of Yb (thickness 10 nm) / Ag (thickness 12 nm).
  • the structure of the organic electroluminescent device of Comparative Example 1 was: PES/Ag/NPB/TCTA: Ir(ppy) 3 / Bphen/LiF/ (Al/Sm).
  • the preparation process of the organic electroluminescent device is as follows:
  • PES with a thickness of 0.15mm
  • the film was ultrasonically cleaned in deionized water containing detergent, then treated with isopropanol, acetone in ultrasonic, and then dried with nitrogen.
  • a thickness of 80 is formed by vacuum thermal evaporation.
  • the Ag film of nm is prepared as a flexible anode.
  • a hole transport layer NPB having a thickness of 60 nm and a light-emitting layer of TCTA: Ir(ppy) 3 having a thickness of 15 nm were sequentially formed by vacuum thermal evaporation (wherein TCTA is a host material, Ir(ppy) 3
  • TCTA is a host material, Ir(ppy) 3
  • the guest material is doped with 3% by mass
  • the electron injection layer LiF with a thickness of 1 nm and the next layer has a structure of Al (thickness 1 nm)/Sm ( A cathode layer of two monomer layers having a thickness of 30 nm).
  • the organic electroluminescent device fabricated by using the self-assembled molecular modification layer has a lower starting voltage than the organic electroluminescent device fabricated without the self-assembled molecular modification layer; this is because the anode metal film passes through After the modification of the self-assembled molecular modification layer, the hole injection barrier between the anode and the hole transporting material can be lowered, thereby lowering the starting voltage.
  • 3 is a comparison diagram of a voltage-luminance curve of a top-emitting organic electroluminescent device fabricated in Example 2 and Comparative Example 1; 3 It can be seen that the organic electroluminescent device modified by the self-assembled molecular modification layer over the anode layer has higher luminescence brightness than the organic electroluminescent device modified by the self-assembled molecular modification layer over the anode layer; The organic electroluminescent device in which the molecular modification layer is modified by the anode layer is also higher in current efficiency than the organic electroluminescent device in which the anode layer is not modified by the self-assembled molecular modification layer.

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Abstract

一种顶发射有机电致发光器件（OLED）及其制备方法，该顶发射有机电致发光器件包括依次层叠的衬底（101）、阳极层（102）、自组装分子修饰层（103）、空穴传输层(104）、发光层（105）、电子传输层（106）、电子注入层（107）和阴极层（108）。自组装分子修饰层（103）由化学通式为CH3(CH2)n-SH的垸烃硫醇形成。自组装分子修饰层（103）提高了阳极层（102）的功函数，降低了阳极层（102）和空穴传输层（104）之间的空穴注入势垒，使OLED器件的启动电压降低，并提高了OLED器件的发光效率。

Description

顶发射有机电致发光器件及其制备方法
技术领域
本发明涉及光电子器件领域，尤其涉及一种顶发射有机电致发光器件。本发明还涉及该顶发射有机电致发光器件的制备方法。
背景技术
有机电致发光 (Organic Light Emission Diode) ，简称 OLED ，具有亮度高、材料选择范围宽、驱动电压低、全固化主动发光等特性，同时拥有高清晰、广视角，以及响应速度快等优势，符合信息时代移动通信和信息显示的发展趋势，以及绿色照明技术的要求，是目前国内外众多研究者的关注重点。
在现有技术的 OLED 器件中，采用柔性材料作为衬底的 OLED 器件，比玻璃衬底的 OLED 具有更轻薄、更耐冲击的优点。并且柔性 OLED 器件的制备可以采用卷对卷方式生产，从而大幅地降低制造成本。 通常采用聚合物薄膜作为衬底时，在其表面制作的阳极，是通过溅射工艺覆盖一层透明导电薄膜如 ITO ， IZO 等材料，然而这在制备 ITO 薄膜的过程中，各种元素如铟 (In) ， (Sn) 的掺杂比例组成不易控制，导致 ITO 薄膜的形貌和载流子传输性能难以控制；其次，在柔性衬底上制备 ITO 等导电薄膜时，通常采用低温溅射技术，所制备的导电薄膜表面电阻高，薄膜与衬底的结合力不强，使得柔性 OLED 在反复弯曲的过程中容易发生导电薄膜从衬底脱落的情况，影响 OLED 发光装置的发光稳定性。
一些金属材料如铝(Al)，银(Ag)等可以通过蒸镀工艺在聚合物薄膜上成膜，同时其具有良好的导电性和较高的反射率，在聚合物薄膜上成膜后，与衬底的结合力优于ITO导电薄膜，适合制作顶发射OLED器件的阳极。但是Al，Ag等金属材料与常用的空穴传输材料(如，NPB，TPD)的HOMO轨道之间存在较大的势垒，导致阳极的空穴注入能力较差，因此，影响有机电致发光器件的发光效率。
发明内容
本发明的目的在于提供一种发光效率高的顶发射有机电致发光器件。
一种顶发射有机电致发光器件，包括依次层叠的衬底、阳极层、自组装分子修饰层、空穴传输层、发光层、电子传输层、电子注入层、阴极层。
在该顶发射有机电致发光器件中，自组装分子修饰层采用的是长分子链的烷烃硫醇，其化学通式为 CH3(CH2)n-SH ，其中， 5 ≦ n ≦ 21 ，自组装分子修饰层通过硫醇上的巯基与金属薄膜键合连接。
本发明的顶发射有机电致发光器件，其采用的衬底材料为聚合物薄膜，如，聚对苯二甲酸乙二醇酯(PET)、聚醚砜(PES)、聚萘二甲酸乙二醇酯(PEN)或聚碳酸酯(PC)。
该顶发射有机电致发光器件的阴极层为 一层阴极单体层或两层 层叠的 阴极单体层 ； 所述阴极单体层的材质为铝、银、钐或镱 。
该顶发射有机电致发光器件中，各有机功能层的材质选自如下：
空穴传输层的材料选用 N,N'- 二苯基 -N,N'- 二 (1- 萘基 )-1,1'- 联苯 -4,4'- 二胺 (NPB ) 、 N,N'- 二苯基 -N,N'- 二 (3- 甲基苯基 )-1,1'- 联苯 -4,4'- 二胺 (TPD) 或 1,1- 双 (4'- 双 (4'- 甲苯基 ) 氨基苯基 ) 环己烷 (TAPC) ；
发光层的材料选用 N,N'- 二苯基 -N,N'- 二 (1- 萘基 )-1,1'- 联苯 -4,4'- 二胺 (NPB ) 掺杂 ( 二 (2- 甲基 - 二苯基 [f,h] 喹喔啉 )( 乙酰丙酮 ) （ Ir(MDQ)2(acac) ）、 4,4',4''- 三 ( 咔唑 -9- 基 )- 三苯胺 ) （ TCTA ）掺杂三 (2- 苯基吡啶 ) 合铱 ( Ir(ppy)3) 、 8- 羟基喹啉铝 (Alq3) 掺杂 4-4- 二 氰基亚甲基 -2- 叔丁基 -6-(1, 1, 7, 7- 四甲基 - 久洛尼定 -9- 乙烯基 )-4H- 吡喃（ DCJTB ）或者 DPVBi ；即发光层的材料选用 NPB:Ir(MDQ)2(acac) （其中， NPB 为主体材料， Ir(MDQ)2(acac) 为客体材料，客体材料掺杂质量百分含量为 5%) 、 TCTA:Ir(ppy)3( 其中， TCTA 为主体材料， Ir(ppy)3 为客体材料，客体材料掺杂质量百分含量 3%) 、 Alq3: DCJTB ( 其中， Alq3 为主体材料， DCJTB 为客体材料，客体材料掺杂质量百分含量为 2%) 或者 DPVBi 。
电子传输层的材料选用 ( 8- 羟基喹啉 )- 铝 (Alq3) 、 4,7- 二苯基 - 邻菲咯啉 (Bphen) 或者 1,3,5- 三 (1- 苯基 -1H- 苯并咪唑 -2- 基 ) 苯 (TPBi) ；
电子注入层的材料选用 LiF 、 CsF 或者 Li2O ；
所述阳极的材质为 Ag 、 Al 或者 Au 等金属。
本发明还提供一种上述顶发射有机电致发光器件的制作方法，其包括以下步骤：
S1 、清洗、干燥衬底，备用；
S2 、利用真空镀膜的方法，在所述衬底表面蒸镀一层阳极层；
S3 、在所述阳极层的表面制备一层自组装分子修饰层；
S4 、利用真空镀膜的方法，在所述自组装分子修饰层的表面依次层叠蒸镀空穴传输层、发光层、电子传输层、电子注入层；
S5 、在所述电子注入层的表面蒸镀阴极层；
上述制备工艺完成后，得到顶发射有机电致发光器件。
上述 顶发射有机电致发光器件的制作方法 中， 为了提高自组装分子在 阳极层 表面的吸附能力， 步骤 S2 中还包括如下步骤：
将制备好的阳极 层 置于等离子处理器中，真空抽至 10-60Pa 的状态 ，在空气气氛下进行高频放电，射频功率 60W 条件下， 辉光 放电 处理 5-15 分钟 的 等离子清洗阳极 层 表面 。
这种 通过等离子处理 方式 ，提高了阳极 层 的表面能，从而提高了自组装分子在阳极 层 表面的成膜均匀性和致密性。
上述步骤 S3 中还包括步骤：
S31 、 将化学通式为 CH3(CH2)n-SH 的烷烃硫醇溶解在乙醇或者乙醚中，配置成溶液，溶液 的摩尔 浓度可在 0.1 ~ 10 mM 之间 ；
S32 、将蒸镀有阳极层的衬底浸入到上述溶液中，浸泡 5~30mim 后取出，用氮气流进行干燥，随后在阳极层表面制得自组装分子修饰层。
本发明提供的顶发射有机电致发光器件，在阳极层的表面制备一层自组装分子修饰层，该自组装分子修饰层提高了阳极层的功函数，降低了阳极层与空穴传输层之间的空穴注入势垒，使OLED器件的启动电压降低，从而提高了OLED 器件的发光效率。
附图说明
图1为一实施方式的顶发射有机电致发光器件的结构示意图；其中，
101 衬底、 102 阳极层、 103 自组装分子修饰层 、 104 空穴传输层、 105 发光层、 106 电子传输层、 107 电子注入层、 108 阴极 ；
图2为一实施方式的顶发射有机电致发光器件的制备工艺流程图；
图3为实施例2制作的顶发射有机电致发光器件和对比例1的电压-亮度曲线对比图。
具体实施方式
一实施方式的顶发射有机电致发光器件，如图 1 所示，包括依次层叠的衬底 101 、阳极层 102 、自组装分子修饰层 103 、空穴传输层 104 、发光层 105 、电子传输层 106 、电子注入层 107 及阴极层 108 ；即：衬底 101/ 阳极层 102/ 自组装分子修饰层 103/ 空穴传输 104/ 发光层 105/ 电子传输层 106/ 电子注入层 107/ 阴极层 108 。
该顶发射有机电致发光器件中，自组装分子修饰层 103 采用的是长分子链的烷烃硫醇，其具体通式为 CH3(CH2)n-SH ，其中 5 ≦ n ≦ 21, 自组装分子修饰层通过硫醇上的巯基与金属薄膜键合连接；
该顶发射有机电致发光器件，其采用的衬底 101 的材料为聚合物薄膜，如，聚对苯二甲酸乙二醇酯 (PET) 、聚醚砜 (PES) 、聚萘二甲酸乙二醇酯 (PEN) 或聚碳酸酯 (PC) ；鉴于该顶发射有机电致发光器件为顶发射 OLED 器件，故其衬底材料的聚合物薄膜表面必须经过平整加硬处理，表面硬度高达 2H-3H( 铅笔硬度 ) 。
该顶发射有机电致发光器件的空穴传输层 104 、发光层 105 、电子传输层 106 、电子注入层 107 所用材料为本领域所常用的材质，比如：
空穴传输层的材料选用 N,N'- 二苯基 -N,N'- 二 (1- 萘基 )-1,1'- 联苯 -4,4'- 二胺 (NPB ) 、 N,N'- 二苯基 -N,N'- 二 (3- 甲基苯基 )-1,1'- 联苯 -4,4'- 二胺 (TPD) 或 1,1- 双 (4'- 双 (4'- 甲苯基 ) 氨基苯基 ) 环己烷 (TAPC) ；
发光层的材料选用 N,N'- 二苯基 -N,N'- 二 (1- 萘基 )-1,1'- 联苯 -4,4'- 二胺 (NPB ) 掺杂 ( 二 (2- 甲基 - 二苯基 [f,h] 喹喔啉 )( 乙酰丙酮 ) （ Ir(MDQ)2(acac) ）、 4,4',4''- 三 ( 咔唑 -9- 基 )- 三苯胺 ) （ TCTA ）掺杂三 (2- 苯基吡啶 ) 合铱 ( Ir(ppy)3) 、 8- 羟基喹啉铝 (Alq3) 掺杂 4-4- 二 氰基亚甲基 -2- 叔丁基 -6-(1, 1, 7, 7- 四甲基 - 久洛尼定 -9- 乙烯基 )-4H- 吡喃（ DCJTB ）或者 DPVBi ；即发光层的材料选用 NPB:Ir(MDQ)2(acac) （其中， NPB 为主体材料， Ir(MDQ)2(acac) 为客体材料，客体材料掺杂质量百分含量为 5%) 、 TCTA:Ir(ppy)3( 其中， TCTA 为主体材料， Ir(ppy)3 为客体材料，客体材料掺杂质量百分含量 3%) 、 Alq3: DCJTB ( 其中， Alq3 为主体材料， DCJTB 为客体材料，客体材料掺杂质量百分含量为 2%) 或者 DPVBi
电子传输层的材料选用 ( 8- 羟基喹啉 )- 铝 ( Alq3 ) 、 4,7- 二苯基 - 邻菲咯啉 (Bphen) 或者 1,3,5- 三 (1- 苯基 -1H- 苯并咪唑 -2- 基 ) 苯 (TPBi) ；
电子注入层的材料选用 LiF 、 CsF 或 Li2O ；
所述阳极的材质为金属 Ag 、 Al 或者 Au ，所述阳极层厚度为 18-100nm 。
该顶发射有机电致发光器件的阴极层为一层或两层阴极单体层；所述阴极单体层的材质为铝 (Al) 、银 (Ag) 、钐 (Sm) 或镱 (Yb); 该阴极层为半透明阴极，其总厚度为 18-30 nm ；阴极层在可见光下的透过率达到 55%-75% 之间。
本发明还提供一种上述顶发射有机电致发光器件的制作方法，如图 2 所示，其包括以下步骤：
S1 、将衬底 ( 如，聚合物薄膜 ) 放在含有洗涤剂的去离子水中进行超声清洗，用去离子水清洗干净后依次用异丙醇，丙酮在超声波中处理，然后在用氮气吹干，备用；其中，聚合物薄膜包括聚对苯二甲酸乙二醇酯 (PET) 、聚醚砜 (PES) 、聚萘二甲酸乙二醇酯 (PEN) 、或聚碳酸酯 (PC) ；
S2 、利用真空镀膜的方法，在洗净的衬底表面蒸镀一层阳极层，该阳极层的厚度为 18-100nm ；
S3 、所述阳极层的表面制备一层自组装分子修饰层；其中，所述自组装分子修饰层的材质是化学通式为 CH3(CH2)n-SH 的烷烃硫醇，且 5 ≦ n ≦ 21 ；
S4 、用真空镀膜的方法，在阳极层表面依次蒸镀空穴传输层、发光层、电子传输层、电子注入层；所述空穴传输层、发光层、电子传输层和电子注入层的厚度分别为 50~60nm 、 15~20nm 、 30~40nm 和 1nm ；
S5 、在所述电子注入层的表面蒸镀厚度为 18~30nm 的阴极层；
上述制备工艺完成后，得到顶发射有机电致发光器件。
上述 顶发射有机电致发光器件的制作方法 中， 为了提高自组装分子在 阳极层 表面的吸附能力， 步骤 S2 中还包括如下步骤：
将制备好的阳极 层 置于等离子处理器中，真空抽至 10-60Pa ，在空气气氛下进行高频放电，射频功率 60W 条件下， 辉光 放电 处理 5-15 分钟 的 等离子清洗阳极 层 表面 。
这种 通过等离子处理 方式 ，提高了阳极 层 的表面能，从而提高了自组装分子在阳极 层 表面的成膜均匀性和致密性。
上述步骤 S3 中还包括步骤：
S31 、 将化学通式为 CH3(CH2)n-SH 的烷烃硫醇溶解在乙醇或者乙醚中，配置成溶液，溶液 的摩尔 浓度可在 0.1 ~ 10 mM （即 mmol/L ） 之间 ；
S32 、 将蒸镀有阳极 层的衬底 浸入到上述溶液中，浸泡 5 ~ 30mim 后取出，用氮气流进行干燥 ，随后在阳极层表面制得 自组装分子修饰层 。
本发明提供的顶发射有机电致发光器件，在阳极层的表面制备一层化学通式为 CH3(CH2)n-SH 的烷烃硫醇的自组装分子修饰层，该自组装分子修饰层提高了阳极层的功函数，降低了阳极层与空穴传输层之间的空穴注入势垒，使 OLED 器件的启动电压降低，从而提高了 OLED 器件的发光效率。
下面结合附图，对本发明的较佳实施例作进一步详细说明。
实施例 1
本实施例 1 的顶发射有机电致发光器件结构为： PET/Al/ CH3(CH2)5-SH /α-NPD/NPB:Ir(MDQ)2(acac)/ Alq3/LiF/ Ag 。
该顶发射有机电致发光器件的制备工艺如下：
将厚度为 0.175mm 的 PET 薄膜放在含有洗涤剂的去离子水中进行超声清洗，然后依次用异丙醇，丙酮在超声波中处理，完毕后用氮气吹干。在 PET 薄膜表面，通过真空热蒸镀的方法形成厚度为 60 nm 的 Al 膜，制备成柔性阳极。
将阳极置于等离子处理器中，抽真空至 10 Pa ，然后进行高频放电，射频功率 60W 条件下产生辉光放电处理 30 分钟；将 1- 己烷硫醇 (CH3(CH2)5-SH) 溶解在乙醇中，浓度为 10mM ，然后将经过等离子处理的 Al 阳极浸泡在该溶液中，浸泡 30 分钟，使 1- 己烷硫醇吸附在 Al 膜表面，形成自组装薄膜，然后取出用氮气干燥。
干燥完毕后，在上述自组装单分子膜修饰的 Al 膜上通过真空热蒸镀的方法依次形成厚度为 50 nm 的空穴传输层 NPB ，厚度为 20 nm 的发光层 NPB:Ir(MDQ)2(acac)( 其中， NPB 为主体材料， Ir(MDQ)2(acac) 为客体材料，客体材料掺杂质量百分含量为 5%) ，厚度为 40 nm 的电子传输层 Alq3 ，厚度为 1 nm 的电子注入层 LiF ，下一层是厚度为 18 nm 的 Ag 层。
实施例 2
本实施例 2 的顶发射有机电致发光器件结构为： PES/Ag/ CH3(CH2)11-SH /NPB/ TCTA:Ir(ppy)3/ Bphen/LiF/ (Al/Sm) 。
该顶发射有机电致发光器件的制备工艺如下：
将厚度为 0.15mm 的 PES 薄膜放在含有洗涤剂的去离子水中进行超声清洗，然后依次用异丙醇，丙酮在超声波中处理，完毕后再用氮气吹干。在柔性衬底表面，通过真空热蒸镀的方法形成厚度为 80nm 的 Ag 膜，制备成柔性阳极。
将阳极置于等离子处理器中，抽真空至 40 Pa ，然后进行高频放电，射频功率 60W 条件下产生辉光放电处理 10 分钟；将正十二烷硫醇 (CH3(CH2)11-SH) 溶解在乙醇中，浓度为 1 mM ，然后将经过等离子处理的 Ag 阳极浸泡在该溶液中 15 分钟，形成自组装薄膜，完毕后取出用氮气干燥。
干燥完毕后，在上述自组装单分子膜修饰的金属 Ag 膜上通过真空热蒸镀依次形成厚度 60 nm 的空穴传输层 NPB ，厚度为 15 nm 的发光层 TCTA:Ir(ppy)3( 其中， TCTA 为主体材料， Ir(ppy)3 为客体材料，客体材料掺杂质量百分含量为 3% ) ，厚度为 30 nm 的电子传输层 Bphen ，厚度为 1 nm 的电子注入层 LiF ，下一层是结构为 Al( 厚度 1nm)/Sm( 厚度 30 nm) 的两层单体层的阴极层，该阴极层为两层单体层。
实施例 3
本实施例 3 的顶发射有机电致发光器件结构为： PC/Au/ CH3(CH2)17-SH /TAPC/DPVBi/ TPBi/CsF/ Ag 。
该顶发射有机电致发光器件的制备工艺如下：
将厚度为 0.20mm 的 PC 薄膜放在含有洗涤剂的去离子水中进行超声清洗，然后依次用异丙醇，丙酮在超声波中处理，完毕后用氮气吹干。在柔性衬底表面，通过真空热蒸镀的方法形成 Au 膜，制备成柔性阳极， Au 膜的厚度为 60 nm 。
将阳极置于等离子处理器中，抽真空至 60 Pa ，然后进行高频放电，射频功率 60W 条件下产生辉光放电处理 10 分钟；将正十八烷基硫醇 (CH3(CH2)17-SH) 溶解在乙醇中，浓度为 0.5 mM . 然后将经过等离子处理的 Au 阳极浸泡在该溶液中 30 分钟，形成自组装薄膜，然后取出用氮气干燥。
干燥完毕后，在上述自组装单分子膜修饰的 Au 膜上通过蒸镀依次形成厚度为 50 nm 的空穴传输层 TAPC ，厚度为 20 nm 的发光层 DPVBi ，厚度为 40 nm 的电子传输层 TPBi ，厚度为 1 nm 的电子注入层 CsF 。下一层是厚度为 20 nm 的 Ag 层。
实施例 4
本实施例 4 的顶发射有机电致发光器件结构为： PEN/Al/ CH3(CH2)21-SH /TPD/ Alq3: DCJTB / Alq3/Li2O/(Yb/Ag) 。
该顶发射有机电致发光器件的制备工艺如下：
将厚度为 0.18mm 的 PEN 薄膜放在含有洗涤剂的去离子水中进行超声清洗，然后依次用异丙醇，丙酮在超声波中处理，完毕后再用氮气吹干。在柔性衬底表面，通过真空热蒸镀的方法形成厚度为 100 nm 的 Al 膜，制作成阳极。
将阳极置于等离子处理器中，抽真空至 50 Pa ，然后进行高频放电，射频功率 60W 条件下产生辉光放电处理 15 分钟；将正二十二烷基硫醇 (CH3(CH2)21-SH) 溶解在乙醚中，浓度为 0.1mM ，然后将经过等离子处理的 Al 阳极浸泡在该溶液中 5 分钟，然后取出用氮气干燥。
干燥完毕后，在上述自组装单分子膜修饰的金属 Al 膜上通过蒸镀依次形成厚度厚度为 50 nm 的空穴传输层 TPD ，厚度为 20 nm 的发光层 Alq3: DCJTB ( 其中， DCJTB 为客体材料， Alq3 为主体材料，客体材料掺杂质量百分含量为 2%) ，厚度为 35 nm 的电子传输层 Alq3 ，厚度为 1 nm 的电子注入层 Li2O 。下一层是结构为 Yb( 厚度 10nm)/Ag( 厚度 12 nm) 结构的两层层叠单体层的阴极层。
对比例 1
本对比例 1 的有机电致发光器件结构为： PES/Ag/NPB/ TCTA:Ir(ppy)3/ Bphen/LiF/ (Al/Sm) 。
该有机电致发光器件的制备工艺如下：
将厚度为 0.15mm 的 PES 薄膜放在含有洗涤剂的去离子水中进行超声清洗，然后依次用异丙醇，丙酮在超声波中处理，完毕后再用氮气吹干。在柔性衬底表面，通过真空热蒸镀的方法形成厚度为 80 nm 的 Ag 膜，制备成柔性阳极。
在上述金属 Ag 膜上通过真空热蒸镀依次形成厚度 60 nm 的空穴传输层 NPB ，厚度为 15 nm 的发光层 TCTA:Ir(ppy)3( 其中， TCTA 为主体材料， Ir(ppy)3 为客体材料，客体材料掺杂质量百分含量 3% ) ，厚度为 30 nm 的电子传输层 Bphen ，厚度为 1 nm 的电子注入层 LiF ，下一层是结构为 Al( 厚度 1nm)/Sm( 厚度 30 nm) 的两层单体层的阴极层。
将实施例 1 ， 2 ， 3 ， 4 和对比例 1 制作的器件进行发光性能测试，测试结果如表 1 所示。
表 1
启动电压 (V) 9V 时亮度 (cd/cm2) 电流效率 (cd/A)
实施例 1 3.8 2551 12.5
实施例 2 3.3 3258 18.7
实施例 3 3.1 2214 13.9
实施例 4 3. 5 3112 14.5
对比例 1 4.4 1947 10.4
结果表明，采用了自组装分子修饰层的阳极制作的有机电致发光器件，其启动电压明显低于未进行自组装分子修饰层的阳极制作的有机电致发光器件；这是由于阳极金属薄膜经过自组装分子修饰层的修饰后，可以降低阳极与空穴传输材料之间的空穴注入势垒，因此降低了启动电压。
图 3 为 实施例 2 制作的 顶发射有机电致发光器件 和对比例 1 的 电压 - 亮度曲线对比图；由图 3 可以看出，采用了自组装分子修饰层修饰过阳极层的有机电致发光器件，其发光亮度要高于未经自组装分子修饰层修饰过阳极层的有机电致发光器件；且采用了自组装分子修饰层修饰过阳极层的有机电致发光器件，其电流效率也要高于未经自组装分子修饰层修饰过阳极层的有机电致发光器件。
应当理解的是，上述针对本发明较佳实施例的表述较为详细，并不能因此而认为是对本发明专利保护范围的限制，本发明的专利保护范围应以所附权利要求为准。

Claims (10)

  1. 一种顶发射有机电致发光器件，其特征在于，该顶发射有机电致发光器件包括依次层叠的衬底、阳极层、自组装分子修饰层、空穴传输层、发光层、电子传输层、电子注入层及阴极层。
  2. 根据权利要求1所述的顶发射有机电致发光器件，其特征在于，所述自组装分子修饰层的材质是化学通式为CH3(CH2)n-SH的烷烃硫醇；其中，5≦n≦21。
  3. 根据权利要求1所述的顶发射有机电致发光器件，其特征在于，所述阴极层为单一材质的一层阴极单体层或者材质相异的两层层叠的阴极单体层；所述阴极单体层的材质为铝、银、钐或镱。
  4. 根据权利要求1所述的顶发射有机电致发光器件，其特征在于，所述衬底的材质为聚对苯二甲酸乙二醇酯、聚醚砜、聚萘二甲酸乙二醇酯或者聚碳酸酯；所述阳极层的材质为银、铝或者金。
  5. 一种顶发射有机电致发光器件的制备方法，包括如下步骤：
    S1 ，清洗、干燥衬底；
    S2 ，在所述衬底的表面蒸镀阳极层；
    S3 ，在所述阳极层的表面制备自组装分子修饰层；
    S4 ，在所述自组装分子修饰层的表面依次蒸镀层叠的空穴传输层、发光层、电子传输层、电子注入层；
    S5 ，在所述电子注入层的表面蒸镀阴极层，制得所述顶发射有机电致发光器件。
  6. 根据权利要求 5 所述的顶发射有机电致发光器件的制备方法，其特征在于，所述步骤 S2 中还包括如下步骤：
    将制备好的阳极层置于等离子处理器中，真空状态、空气气氛下进行高频放电等离子清洗阳极层表面。
  7. 根据权利要求5所述的顶发射有机电致发光器件的制备方法，其特征在于，所述自组装分子修饰层的材质是化学通式为CH3(CH2)n-SH的烷烃硫醇；其中，5≦n≦21。
  8. 根据权利要求 7 所述的顶发射有机电致发光器件的制备方法，其特征在于，所述步骤 S3 还包括如下步骤：
    S31 、 将化学通式为 CH3(CH2)n-SH 的烷烃硫醇溶解在乙醇或者乙醚中，配置成 摩尔 浓度 为 0.1 ~ 10 mM 的溶液；
    S32、将蒸镀有阳极层的衬底浸入到上述溶液中，浸泡5~30mim后取出，用氮气流进行干燥，随后在阳极层表面制得自组装分子修饰层。
  9. 根据权利要求5所述的顶发射有机电致发光器件的制备方法，其特征在于，所述阴极层为单一材质的一层阴极单体层或材质相异的两层层叠的阴极单体层；所述阴极单体层的材质为铝、银、钐或镱。
  10. 根据权利要求5所述的顶发射有机电致发光器件的制备方法，其特征在于，所述衬底的材质为聚对苯二甲酸乙二醇酯、聚醚砜、聚萘二甲酸乙二醇酯或者聚碳酸酯；所述阳极层的材质为银、铝或者金。
PCT/CN2011/076704 2011-06-30 2011-06-30 顶发射有机电致发光器件及其制备方法 Ceased WO2013000162A1 (zh)

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