TW201125431A - Organic light-emitting diode and method of fabricating the same - Google Patents

Abstract

An organic light-emitting diode (OLED) and a manufacturing method are provided. The OLED device includes more than one light emissive layer. The emissive zone is capable to emit a blue or a short wavelength emission near the cathode, and a red or a long wavelength emission near the anode. The device has a light output with a high color-temperature at low voltages, and has a light output with a low color-temperature at high operation voltages. By adjusting the input voltage, the device is capable to have a white emission or other emissions with desired color-temperature.

Description

201125431 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 6. Description of the invention: [Technical field to which the invention belongs] The invention is a secret-organic county diminishing device and a manufacturing method thereof; The layer structure is designed so that when the component is at a low voltage, the visible light of the higher color temperature 'at high voltage' can emit visible light of lower color temperature; by adjusting the input voltage, the component can emit white light of a specific color temperature or Other light colors. [Prior Art] Organic Electro-lumiueseeiiee Di_y5 Organic EL Display, also known as Organic Light Emitting Diode (OLED) is made in 1987 by Kodak Company's c. W.

Tang and SA VanSlyk et al. were first made using a vacuum steaming method. The hole transport material and the electron transfer material were respectively coated on a transparent indium tin oxide (ITO) glass. Evaporating a metal electrode to form a self-luminous OLED device's high brightness, fast response speed, light and thin, full color, no viewing angle difference, no need for liquid crystal display backlight, saving lamp and power consumption 'Therefore became a new generation of displays. Please refer to the first figure, which is a structural sectional view of the LED device according to one of the conventional ones. 201125431 The structure of the OLED device includes a transparent substrate η, a transparent % ΙΤΟ 12, a Hole Transporting Layer (iTTL), and an Organic Emitting Layer (EL) from bottom to top. , an electron transport layer 15 (Electron Transporting Layer, ETL), an electron injection layer 16 (Electr〇n

Injection Layer, EIL) and a metal cathode 17. When a forward bias voltage is applied, the hole 131 is injected from the anode 12, and the electron 151 is injected from the cathode 17, and the potential difference caused by the applied electric field causes the electron 151 and the hole 131 to move in the film, thereby In the organic light-emitting layer 14, a recombination is generated, and the energy released by the electron-hole bonding is excited, and the luminescent molecules of the organic luminescent layer 14 are excited to become an excited state, and when the luminescent molecules decay from an excited state to a ground state, A certain proportion of the energy is emitted in the form of photons, and the emitted light is organic electroluminescence. Please refer to the second figure, which is a structural cross-sectional view of another LED according to the conventional structure. This structure is made by Kodak. The OLED device is described in U. The anode 22, a hole injection layer 23, the light-emitting layer 24, and the metal cathode 25. When a forward bias voltage is applied, the hole is injected from the anode 22, and the electron is injected from the cathode 25, due to the applied electric field. Caused The potential difference causes the electrons and holes to move in the film, thereby forming a cladding in the light-emitting layer 24. Part of the energy released by the electron hole combination excites the light-emitting molecules of the light-emitting layer 24 to become an excited state, when the light-emitting molecules are When the excited state decays to the base H, the shape of the towel is determined to be different from that of the energy state, and the light emitted by 201125431 is organic electroluminescence. Please refer to the third figure, which is also a cross-sectional view of a conventional OLED device structure. U.S. Patent No. 4'720,432, issued to C. W. Tang of Kodak, Inc. in 1988. In this embodiment, the structure of the 〇LED device comprises a transparent substrate 31, transparent from bottom to top. The anode 32, a hole injection layer 33, an electron-transporting light-emitting layer 34, and a metal cathode 35. When a forward bias voltage k is applied, a hole is injected from the anode 32, and electrons are injected from the cathode 35. Due to the potential difference caused by the applied electric field, the electrons and the holes move in the film, and the cladding is formed in the light-emitting layer 34. The energy released by the electron-hole combination is partially excited by the light-emitting molecules of the light-emitting layer 34. When a luminescent molecule decays from an excited state to a ground state, a certain proportion of the energy is emitted in the form of photons, and the emitted light is organic electroluminescence. Please refer to the fourth figure 'C. W. Tang et al. Journal 〇f Applied physies

The doped 〇LED device proposed in vol. 65, p. 3610 (1989), wherein the structure of the erbium LED is sequentially arranged from bottom to top, including a transparent substrate 41, a transparent anode 42, and a hole transport layer 43, A single component luminescent layer 44, a luminescent layer 45 containing a dye, a single component luminescent layer 46, and a metal cathode 47 can also produce organic electroluminescence. Please refer to the fifth figure, which is a doped 〇LED device proposed by CH Chen et al., Applied Physics Letters, Vol. 85, pp. 3301 (2004). The structure of the 〇LED device includes a transparent substrate from bottom to top. 51. A transparent anode 52, [S.1 11 201125431 - hole injection layer 53 - hole transport layer 54, - light-emitting layer % containing doping dye, - electron transport layer 56, - electron injection layer 57 And - the metal cathode %, can produce organic electroluminescence. According to the luminescent material OLED can emit a short light color, white light can be generated by mixing the complementary light colors, and the luminescent materials can be respectively located in different layers, or can be placed in the same layer luminescent layer; Please refer to the sixth figure, which is a single-light-emitting layer white OLED device published by the inventor in Applied Physics Letters, Vol. 88, No. 1935〇1 (2〇〇6). The structure of the OLED skirt is from bottom to top. The sequence includes a transparent substrate 61, a transparent anode 62, a hole transport layer 63, a push-type white light emitting layer 64, an electron transport layer 65, an electron injecting layer 66, and a metal cathode 67; The luminescent layer 64 may be mixed with a red light dye by a blue light main body, or further composed of a blue light main body mixed, a county and a red recording material, and the emitted white light is organic electroluminescence. In addition to the complementary light color produced by organic electroluminescence, white light can be generated, and organic electroluminescence and silk light can be used to generate self-light; see the seventh figure,

General Electric (GE), a. R. Duggal et al., in the US patent us 6,847,162 'published organic light layer and photoexcitation layer combined light source, the light source 包含 from bottom to top in sequence one can be issued a blue light-emitting LED element, a transparent substrate 73, and a photo-excited light layer 74; wherein the light-exciting light layer 74 absorbs blue light emitted by the ED element 72, and emits lower energy yellow light, the light source is The combination of blue light and yellow light produces white light. 12 201125431 White light mixed by monochromatic light such as light, green light or red light can change the color temperature of mixed white light by adjusting the intensity of each monochromatic light; see Figure 8 for

A schematic diagram of the structure of a light color tunable organic electroluminescent light source disclosed by U.S. Patent No. 6,661,029, to A. R. Duggal et al., the entire disclosure of which is incorporated herein by reference. 82, red light 83 LED83, green light OLED 84, and blue light 〇 LED85, and the face monochrome light 〇 LED elements are electrically connected 'each composed - light-emitting element groups 86, 87, and 88 having a large hairline, and the device further includes A power source 89 is connected to the integrated controller 82 and the monochromatic light OLEDs 83' 84 and 85'. By integrating the controller 82, the intensity of each monochromatic light can be adjusted to change the color temperature of the mixed white light. The inventor is engaged in research and many practical experiences based on the year of the village. (4) Research and design and specialization, and in this issue, the second light and the law of the financial system, the components of the aeronautical layer structure, so that the components do not need additional circuits. Control, and only by daring, the navigational piece can correct the color temperature of the self-light or other light color, as the implementation and basis of the aforementioned expectations. SUMMARY OF THE INVENTION The subject, the purpose of the system is to supply a light-emitting diode with a sound ^=, the light-emitting diode element contains at least - above light = seen, near the cathode end, can be issued blue or shorter The wavelength can be 'b thing', Caifaling (4) This organic light-emitting diode, at low voltage, can emit a higher color temperature. 2 At 13 201125431 higher voltage, it can emit visible light with lower color temperature; By adjusting the input voltage, the component can emit white light or other light colors of a specific color temperature. The edge is an organic light-emitting diode device according to the present invention, which has a substrate, a -first conductive layer, a light-emitting layer and a second conductive layer, wherein the composition of the light-emitting layer is Close to the anode end, a red or longer wavelength visible light can be emitted near the cathode end to emit blue or shorter wavelength visible light. The method for manufacturing an organic light-emitting diode device of the present invention, comprising: a) providing a substrate; b) forming a first conductive layer above the substrate; c) forming a light-emitting layer is located above the first conductive layer; and a Φ-forming second conductive layer is located above the light-emitting layer; wherein the light-emitting layer is composed of a reddish or longer wavelength near the anode end Visible light; near the cathode end, emits visible or short-wavelength visible light. H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H τ 有 τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ . DETAILED DESCRIPTION OF THE INVENTION In order to make the above objects, features, and advantages of the present invention more comprehensible, the organic light-emitting diode device and the method of manufacturing the same according to the present invention are exemplified by the preferred embodiment of the present invention. A detailed description will be given below, and the components of the matriminal will be described by the same component symbols in m 14 201125431. . Referring to FIG. 9 , which is a cross-sectional view of a structure of a 〇led device according to a preferred embodiment of the present invention, the LED decorative structure includes a substrate 91, a first conductive layer 92 from bottom to top. - hole transport layer %, "first light emitting layer 94, a second light emitting layer 95, a first electron transport and hole barrier layer %, a second light emitting layer 97, a second electron transport and hole blocking layer 98. An electron injection layer 99 and a second conductive layer 910. Wherein the first conductive layer % is located above the substrate column, ♦ the hole transport layer 93 is located above the first conductive layer 92, the first light-emitting layer 94 is located above the hole transport layer 93, and the second light-emitting layer 95 is located at the first light-emitting layer 94. Above, the first electron transport and hole blocking layer 96 is located above the second light emitting layer 95, the third light emitting layer 97 is located above the first electron transport and hole blocking layer 96, and a second electron is disposed above the third light emitting layer 97. The transmission and hole blocking layer 98 is located above the second electron transporting and blocking layer 98, and the second conductive layer 91 is located above the electron injecting layer 99. The composition of the first luminescent layer can emit red visible light, the second luminescent layer can emit green visible light, and the third luminescent layer can emit blue visible light. Meanwhile, the luminescent layer further comprises: providing more than one fluorescent or phosphorescent luminescent material as the luminescent layer material, or providing a single or multiple combinations of organic materials as a host material 'mixing with the fluorescent or phosphorescent luminescent material' Early-or a combination of a carrier-transport material, a carrier-injecting material, a carrier-blocking material, or a functional auxiliary material to render the luminescent layer functional. The luminescent layer has a light source that emits a color ratio of 70 201125431 or more. The hole transport layer 93 can generally be poly(3,4-ethylene-dioxythiophene)-poly-(styrenesulfonate) (FEDOTiPSS) or N,N5-bis-(1-naphthy)-N,N, biphenyl-1, Γ Biphenyl-4,45-diamine (NPB) and other hole transport materials, electron transport and hole barriers 96 and 98 can generally be 1,3,5-tris (N-phenyl-benzimidazol-2-yl) benzene ( TPBi), tris (8-hydroxyquinoline) alumi-num (Alq3) and other electron transport and hole blocking function materials; electron injection layer 99 can generally be lithium fluoride (LiF) and other electron injection materials; second conductive layer 91〇 Generally, it may be a conductive material such as A1; the substrate 91 may generally be a glass substrate, a plastic substrate or a metal substrate; the first conductive layer 92 may generally be an indium tin oxide (ITO) layer or an indium zinc. Oxide, IZO) layer. Referring to the tenth figure, a flowchart of a method of fabricating an LED device in accordance with a preferred embodiment of the present invention. The method includes the following steps: Step S101: providing a substrate; Step S102: forming a first conductive layer on the substrate; Step S103: forming a hole transport layer on the first conductive layer; Step S104: forming a first a light emitting layer is disposed above the hole transport layer; Step S105: forming a second light emitting layer above the first light emitting layer; Step S106: forming a first electron transport layer and a hole blocking layer, at a position m 16 201125431 Step S107. Form a third luminescent layer, located above the first electron transport layer and the hole blocking layer; Step S108. Form a second electron transport layer and a hole blocking layer, located in the third luminescent layer Above; • step S1〇9, forming an electron injection layer over the second electron transport layer and the hole barrier layer; and step S1010. forming a second conductive layer above the electron injection layer; wherein the first light The composition of the layer 'can emit visible light of a red or longer wavelength, and the composition of the second and third light-emitting layers can emit visible light of a blue or shorter wavelength than the first light-emitting layer. The luminescent layer further comprises a fluorescent material or a phosphorescent luminescent material, a material of the luminescent layer, or a single or multiple organic materials, and is combined with the fluorescent or phosphorescent luminescent material. Further, the first or a plurality of combinations of the carrier, the carrier material, the carrier blocking material or the Wei auxiliary material are included to make the light emitting layer functional. Its luminescent layer = ^ heart is clear. The touch wheel layer - two Γ Γ transmission material, electron transmission and hole blocking layer - generally can be moved, ^ sub-transmission (four) brewing m electron injection; the first: the input material material = S.1 17 201125431 can be glass a substrate, a plastic substrate or a metal substrate; the first conductive layer may generally be ITO or ΙΖ0. Please refer to FIG. 11 ' for the preferred embodiment of the present invention for the Luminance and Color Temperature as a function of voltage. Referring to Fig. 12, it is a graph showing changes in luminance and color temperature of an electric excitation light with electric waste according to another preferred embodiment of the present invention. [Embodiment 1] Embodiment 1 is an OLED device manufactured by applying the present invention. The device structure can be referred to the ninth figure. The manufacturing process is as follows: a glass substrate 91 having an ITO transparent conductive anode 92 is formed in one clock. In a sequential cleaning with detergent, deionized water, acetone and isopropanol, and placed in boiling hydrogen peroxide for surface treatment, then the surface is dried with a stream of nitrogen, and then sprayed in a nitrogen atmosphere. Cloth 35 nm pED〇T: pss electricity • hole transport layer 93, and then placed in a vacuum chamber, when the vacuum pressure reaches 10 ,, hot 瘵 plating, sequentially plated 10 奈The first light-emitting layer 94 of the rice, the first electron transport layer and the hole barrier layer (TPBi) of the nanometer 95, the second light-emitting layer of the nanometer 96, and the third light-emitting layer of the nanometer of the nanometer 97, 35 nm The first electron transport and hole barrier layer (TpBi) 98, the 0.7 nanometer UF electron injection layer 99, and the 15 () nanometer electrode 910. The first luminescent layer 94 is composed of a DPASN blue luminescent material doped with 0.8 wt% red dye DCJTB, and when electrically excited, 18 201125431 emits red visible light; the second luminescent layer 96 is composed of DPASN doped 0.05. The wt% green light dye BPTAPA emits green visible light when electrically excited, and the third light-emitting layer 97 is composed of a DPASN blue light-emitting material, which emits blue visible light when electrically excited. The OLED device emits a light color with a color temperature of 31,000 K at a voltage of 3 V. At a voltage of 9 V, the color of the emitted light has a color temperature of 9,000 K. The luminance and color temperature of the OLED device vary with voltage as shown in FIG. Shown. φ [Embodiment 2] S1 Embodiment 2 is another OLED device manufactured by applying the present invention. The device structure can also be referred to the ninth figure. The fabrication process is as follows: a plated transparent conductive anode 92 is used. The glass substrate 91 is ultrasonically oscillated and cleaned with detergent, deionized water, acetone and isopropyl alcohol, and placed in boiling hydrogen peroxide for surface treatment, and then dried on a nitrogen stream to rotate the surface in a nitrogen atmosphere. Apply 35 nm of PEDOT:PSS to the hole transport layer 93, and then place it into a vacuum chamber. When the vacuum pressure reaches 10-5 Torr, 10 nm is sequentially plated by thermal evaporation. First luminescent layer 94, 3 nm first electron transport layer and hole blocking layer (TPBi) 95, 2 nm second luminescent layer 96, 5 nm third luminescent layer 97, 35 nm A second electron transport and hole barrier layer (TPBi) 98, a 0.7 nm LiF electron injection layer 99, and a 150 nm aluminum electrode 910. The first luminescent layer 94 is composed of a DPASN blue luminescent material doped with 1.2 wt% red dye DCJTB. When the electric excitation light is emitted, 19 201125431 emits red visible light; the second luminescent layer 96 is composed of DPASN doped 0.05. The wt% green light dye BPTAPA emits green visible light when the light is electrically excited; the third light-emitting layer 97 is composed of a DPASN blue light-emitting material doped with 0.4 wt% red dye DJJTB, which can be used when the light is excited. Produces blue-white visible light. The OLED device emits a color of light at a voltage of 3V, and has a color temperature of 7,500K. At a voltage of 9V, the color of the emitted light has a color temperature of 3,000 Å; the luminance and color temperature of the OLED device vary with voltage as shown in Fig. 12. Show. The above is intended to be illustrative only and not limiting. Any changes or modifications to the spirit and scope of the present invention are intended to be included in the scope of the appended claims.

[si 20 201125431 々 [Simplified description of the drawings] The first figure is a structural sectional view of the conventional OLED device; the first figure is based on the conventional structure of the 0 LED device. The third figure is a conventional one. A cross-sectional view of the structure of the OLED device; the fourth figure is a cross-sectional view of the structure of the OLED device; the fifth figure is a structural cross-sectional view of another OLED device of the prior art;

The sixth figure is a schematic diagram of the structure of the conventional OLED device; the seventh figure of the light source is a cross-sectional view of a conventional combined structure of organic electroluminescence and photoexcitation; the eighth figure is a schematic diagram; The ninth embodiment of the OLED device of the preferred embodiment of the present invention is a cross-sectional view of the OLED device of the preferred embodiment of the present invention; FIG. 11 is a flow chart showing a method of manufacturing an OLED device according to a preferred embodiment of the present invention; and FIG. 12 is a diagram showing changes in luminance and color temperature of a OLED device according to a preferred embodiment of the present invention; And a twelfth figure which is a graph showing changes in luminance and color temperature of a OLED device according to another preferred embodiment of the present invention. f S.} 21 201125431 [Description of main component symbols] 11, 21, 31, 41, 51, 61, 91: substrate; 12, 62: anode; 13, 43, 54, 63, 93: hole transmission layer; 1301 : hole; 14: organic light-emitting layer; 15, 56, 65: electron transport layer; 1501: electron; 16, 33, 57, 66, 99: electron injection layer; 17, 67: cathode; 22, 32, 42, 52, 92: first conductive layer; 23, 33, 53: hole injection layer; 24: light-emitting layer; 25, 35, 47, 58, 910: second conductive layer; 34: light-emitting layer with electron transport function; 44, 46: single component luminescent layer; 45, 55: luminescent layer containing doping dye; 64: doped white light emitting layer; 71: organic electroluminescent and photoexcited light combined source; 72: organic electroluminescent device 73: transparent substrate; 74: photoexcited light layer; [S.1 81: light color tunable organic electroluminescent light source device; 22 201125431 82: integrated controller; 83: red organic light emitting diode; 84 : green organic light emitting diode; 85: blue organic light emitting diode; 86: first light emitting element group; 87: second light emitting element group; 88: third round Component group; 89: power supply; 94: first light-emitting layer; 95: second light-emitting layer; 96: first electron-transport layer and hole barrier layer; 97: third light-emitting layer; 98: second electron-transport layer and electricity Hole barrier layer; S101~S1010: process steps.

[S1 23

Claims (1)

201125431 VII. Patent application scope: 1. An organic light emitting diode device comprising: a substrate, a first conductive layer disposed above the substrate; a light emitting layer disposed above the first conductive layer; a first conductive layer is disposed above the light-emitting layer; wherein the light-emitting layer is configured to emit visible light having a reddish or longer wavelength near the anode end; and a blue or shorter wavelength near the cathode end Visible light. 2. The organic light-emitting diode device according to the above-mentioned patent application, wherein the light-emitting layer is composed of a single-layer light-emitting layer, a double-layer light-emitting layer or a multi-layer light-emitting layer 3. The organic light-emitting diode device of claim 1, wherein the light-emitting layer further comprises a single or multiple combinations of doped i-transport materials, carrier-injecting materials, carrier-supporting materials, or a functional auxiliary material. In order to make the light-emitting layer B functional. 4. The organic light emitting diode device of claim j, wherein the first conductive layer and the light emitting layer further comprise at least a functional auxiliary layer. 5. The organic light emitting diode device of claim 1, wherein the light emitting layer and the second conductive layer further comprise at least one functional auxiliary layer. 6. The organic light-emitting diode device of claim 4, wherein the power-assisted auxiliary layer comprises - carrier injection, carrier transport, carrier blocking or - functionality Single or multiple combinations of auxiliary materials. The organic light-emitting diode device of claim 5, wherein the functional auxiliary layer comprises a carrier injection, a carrier transport, a carrier block or a functional auxiliary material. Single or multiple combinations. 8. The organic light-emitting diode device of claim 2, wherein the double-layer light-emitting layer structure or the layer of the fresh light-emitting layer structure further comprises at least one functional auxiliary layer. 9. For the organic hair-emitting diode device described in item g of the patent scope, • the energy-assisted layer system includes a carrier injection, a carrier carrier, a carrier resistance or a functional aid. Single or multiple combinations of materials. 10. For the application of the organic light-emitting diode device of the item i, wherein the light-emitting layer has a light source having a color rendering index of 70 or more. 11. If the application of the paste is omitted, the organic light emitting diode, wherein the light color emitted by the light emitting layer can change from a high color temperature to a low color temperature when the voltage is increased. 12. A method of fabricating an organic light emitting diode device, comprising: • providing a substrate; forming a first conductive layer over the substrate; forming a light emitting layer over the first conductive layer; Forming a first conductive layer, located above the light-emitting layer; wherein the light-emitting layer is composed of visible light near the anode end and light having a longer wavelength; and near the cathode end, emitting a blue or wavelength Shorter visible light. [S] 25 201125431 13. For the application method of the organic light-emitting diode described in Item 12 of the special design, the composition of the light-emitting layer is a single-layer light-emitting layer, a double-layer light-emitting layer or more Layer light-emitting layer structure. 14. The method of fabricating an organic light-emitting diode device according to claim 12, wherein the light-emitting layer further comprises a carrier-carrying material, a carrier-injecting material, a carrier-blocking material or A single or multiple groups of functional auxiliary materials to render the luminescent layer functional. 15. The method of fabricating an organic light-emitting diode device according to claim 12, wherein the first conductive layer and the light-emitting layer further comprise at least one functional auxiliary layer. The method of manufacturing an organic light-emitting diode device according to claim 12, wherein the light-emitting layer and the second conductive layer further comprise at least one functional auxiliary layer. The method of manufacturing an organic light-emitting diode device according to claim 15, wherein the functional auxiliary layer comprises a carrier injection, a carrier transmission, a barrier or a functional auxiliary. Single or multiple combinations of materials. 15. The method of fabricating an organic light-emitting diode device according to claim 1, wherein the functional auxiliary layer comprises a carrier injection, a carrier transport, a barrier or a functional auxiliary material. Single or multiple combinations. The method of manufacturing an organic light-emitting diode according to claim 12, wherein the double-layer light-emitting layer structure or the layer and the layer of the multi-layer light-emitting layer structure further comprise at least one functional auxiliary Floor. The method of manufacturing the organic light-emitting diode device according to the invention of claim 19, wherein the functional auxiliary layer comprises a carrier injection, a carrier transmission, a carrier blocking or a functional auxiliary Single or multiple combinations of materials. The method of manufacturing an organic light-emitting diode device according to the invention, wherein the light-emitting layer has a light source having a color rendering index of 7 〇 or more. 22. The method of fabricating an organic light-emitting diode device according to claim 12, wherein the light color emitted by the light-emitting layer changes from a high color temperature to a low color temperature when the electric house is increased. [S.1 27