TWI295902B - Electrode structure for electronic and opto-electronic devices - Google Patents

Description

1295902

Technical Field 曰本1: About an electrode design for an electronic device. More particularly, 疋' is related to the use of electronic and optoelectronic devices. Background / S and optoelectronic devices such as organic light-emitting diodes (0LED) are related to *α. Those QLEDs are also considered to be organic electroluminescent (EL) devices, typically comprising an organic electroluminescent material sandwiched between electrodes. The electroluminescent material is a multilayer structure comprising an electron transport layer, a precursor layer, and a hole transport layer. When applied - current, the material radiates light from the recombination of electrons and holes in the organic material. However, the electroluminescent material is sensitive to impurities, oxygen and humidity. In addition, in some, sub-photovoltaic devices, the electrodes affect the strength, radiation, and flexibility of the device. Organic electroluminescent devices (materials, structures) known in the art are described, for example, in U.S. Patent No. Μ%, No., U.S. Patent No. 5,593,788, and U.S. Patent No. As disclosed in 8,8, the disclosures are hereby incorporated by reference. The structure of the device is now well understood and widely used, and the residual performance of D is limited to the electrode. The primary figure of merit for the electrode material is the position of the electrode Fermi energy relative to the associated molecular energy level. In some ^, it is also known that the electrode assisted light extraction is expected. The electrode must also be non-chemically active relative to the material of the device to provide long-term stability of the electroluminescent device. ^Wood in the σ mid-day attention to the cathode, mostly because of the good electronic note -8 ϋ apply to the Chinese national standard ^ ^ ^ ¥ - X 297 public love) tender. Patent Application No. 166 Chinese Manual Replacement Page (March 1993)

Description of the invention (Is it necessary for the committee member to change the original substance to be a low work function metal after the revision of the case.) It is also a rapid chemical reaction at atmospheric pressure, limiting the reliability and life of the 0LED. Less attention is focused on & The optimization of the pole contacts is because the performance of the conventional tantalum anode is usually more inferior to that of the cathode: the hole that leads to the over-the-counter. Because of this, and the convenience and transparency of the indium tin oxide (ΙΤ0) V? Wenliang's anode has not been actively sought after as a modified cathode. The problem of sufficient hole injection and operational stability arises with the use of organic electro-optic devices. Some problems have been solved by the anode anti-treatment of the device. U.S. Patent No. 27, the number of which is incorporated herein by reference, discloses a method for forming an electroluminescent device comprising the steps of: providing a material having an anode comprising one of indium tin oxide (IT〇) Coating a substrate of one of the upper surfaces; and forming a non-crystalline conductive layer on the anode by providing the fluorocarbon gas in the base source The fluorocarbon gas is reduced to a pressure in the range of 0.1 to 20 m. In addition, an RF field is applied to the fluorocarbon gas of the basic source cavity to form a plasma having a CFx group and a CFx group is deposited on the anode. Forming an amorphous conductive 4 σ layer on the anode, and then forming a plurality of layers on the amorphous CFx conductive polymer layer and the layers including the at least one organic electroluminescent layer and the electroluminescent layer A cathode is formed. U.S. Patent No. 6,208,075 also relates to an organic electroluminescent device having a layer of a conductive fluorocarbon polymer deposited on an anode and the U.S. Patent No. Patent No. 208,077 shows the deposition of a thin layer of non-conductive fluorocarbon polymer on the anode. The fluorocarbon anti-polymer layer mentioned is used because of its transfer characteristics, so that it acts as a hole -9. -

This paper scale is applicable to the National Standard for Towels (CNS) A4 specification (2lJ^ST L) is being replaced by the purchase of the Chinese version of the application in the patent No. 3.166. (In March, 1993) V. Invention description (3: - The mouse carbon polymer layer is preferably attached to an oxygen-containing anode, such as ΙΊΌ' (4), which causes the material to cause instability. The international application has the international publication number w〇99/39393. Presented: the assignee formerly assigned to the application, Department, about - organic light-emitting device: ;; sequentially an anode, a barrier layer, - anode correction layer, an organic region = Aiji correction layer directly with the organic Area contact. The == is configured to separate the anode correction layer from the anode 1 and this layer interferes with the injection because of the "non-blocking property.: The photovoltaic device can function as an upper emitter or a bottom emitter = (also considered Back emitting device. For the bottom emitting device, the positive sum must be almost transparent 'so that the emitted light can pass through the anode. Oxygen tin (ITO) has been widely used as an anode because it is almost transparent: iIT0 has its drawbacks as part of it It can react with the upper layer, for example, the hole-transporting organic material. This situation can lead to a shortened life of the device. For the case where the life of the device is shortened, a buffer layer, such as Cupc, is used for the anode and Between the organic materials, but on the other hand the buffer layer has a high electrical resistance and hinders the use of the injected 1 fluorocarbon polymer layer, as described above, allowing the buffer layer to be discarded. S For the upper emitter, the flip or molybdenum has been Application. These materials are not permeable to the moon and have a strong light absorption property. The platinum reflection index is not optimal. Silver (Ag) and Ming (4) have a high reflectivity but a lower work function' so it is not suitable as an anode material. In general, a material with a high work function will be implemented as the best suitable anode material. A material with a low work function, such as A, is usually highly chemically active, even with a buffer layer of -10- paper scale. Applicable towel a ® home fresh (CNS) A4 secret (21GX 297 public patent application Chinese manual replacement page (March 1993) V. Invention description (4 'for example (four) coverage, therefore those Unsuitable material: : This: the material and the group of the fluorine-blocking polymer layer: lead to the useless device. The effect of the crime b. Therefore, from the above description, the need for the related art of the good structure is::,; The electrode modification and high efficiency of the photovoltaic device. The improved structure of the electrode shows long-term stability. Therefore, one of the objects of the present invention is to improve the electrode structure of the organic device and the electronic device based on the electronic device. SUMMARY OF THE INVENTION The present invention provides an electronic device comprising a first electrode having substantially a conductive layer, a carbonaceous layer formed on the conductive layer other than the non-metal layer, and formed on the carbonaceous layer. a structure: and a second electrode formed on the structure. The electronic device may further include a buffer layer between the conductive layer and the non-metal layer. This buffer layer advantageously reduces the reaction between the other layers of the first electrode blood. In particular, oxidation procedures can be avoided. In a preferred embodiment, the conductive layer comprises aluminum (A1). Aluminum is usually highly reflective but also reactive. However, the electroluminescent device having a non-metallic layer or a buffer layer as described in combination with the non-metal layer on the conductive layer can be designed to have superior characteristics and characteristics. The non-metallic layer can include an oxide. The oxide may be used adequately or may be formed from a number of materials or compounds. The oxide may be based on a group selected from the group consisting of a 3d transition metal group, a ruthenium group, an IVa group, a rare earth metal group, or a combination thereof. 11 The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295902

2, the genus layer is and can be formed by the conductive layer _ potential oxide = ' 匕 日 丁 亦 is also considered as a heterogeneous oxide, then the hole of the electrode / light: 4 inch, such as injection and transparency can be The advantages of being modified. 1 If the conductive layer of the field f is formed of A1, it is formed by the conductive layer or the oxide is alumina. The fact is that the alumina has a higher resistance than, for example, oxygen: nickel (Ni〇x) resistance. Therefore, the use of Νί〇χ for the heterogeneous oxidation, 幵v j of the non-metallic layer shows better hole injection characteristics than alumina. The combination of the electrically conductive layer having an inter-reflectivity and the non-metallic layer supporting the hole injection additionally results in a reliable and significantly improved optical rounding improvement; a luminescent device. Depending on the characteristics of the provincial V-electrode layer, it is advantageous if the non-metallic layer has a thickness of 2 〇 nm for a single layer, since the electronic device then exhibits superior long-term stability and high efficiency. In electroluminescent devices, such as active drives, the thickness of the vehicle is often combined with higher drive values. The conductive layer may comprise a metal, a semiconductor or an organic conductor. In addition, the conductive layer may include a reflective material. The preferred material of the conductive layer, that is, the material of the electrode, is aluminum (A1) or silver (Ag). When an oxide or a heterogeneous oxide is used as the When the non-metallic layer on the conductive layer, those materials will become the focus. The conductive layer can form a mirror-like surface. The meaning is that the anode works as a mirror and reflects the emitted light to enhance the light output. This concept is for the upper emitter and the bottom. The transmitting device functions. The viewing function is an electrical-to-optical or optical-to-electrical converter -12-

Fresh Profit Application Chinese Manual Replacement Page (March 1993) ----- Invention Description

:) Positive replacement page Any device or optoelectronic device terminology that uses this device in its operation. Instrument belongs to

The two electronic devices may include one of the contacts with the conductive layer or the structure. The substrate may be any material containing glass (ie, one of the upper emitting materials), bismuth (Si) or plastic (ie, bottom emitting device). ^ An opaque material). The substrate can be used to form an electrical reference. The i Z Λ electronic device may be part of an electroluminescent device and a transistor bite. This shows that the electrode design can be widely used. However, it is not limited to the applications mentioned. It is not limited to the use of organic structures, 乂 〃 combined with the following structures: organic / inorganic, organic - inorganic mixed inorganic. In addition, the electrode design and the structure can be applied to a wide range of variations in optoelectronic applications. The invention is also directed to a method of forming the electronic device. The method comprises the steps of: providing a conductive layer to act as a first electrode and a non-metal layer on the first electrode; depositing a fluorocarbon layer on the non-onset; forming a plurality of layers on the fluorocarbon layer and forming a first On the structure. The knot, but the combination or the electron, the party: the shape of the metal, the second

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BRIEF DESCRIPTION OF THE DRAWINGS Preferred embodiments of the present invention will be described in detail below by way of example ' with reference to the following summary drawings. 1 shows a schematic explanation of one of the prior art organic electroluminescent devices; FIG. 2a shows a schematic explanation of a first embodiment of an organic electroluminescent device; -13- This paper scale applies to the standard of the towel sa (CNS) A4 specification (210 X 297 public) 1295902 A7 __ __ B7 V. Description of the invention (7) Figure 2b shows a schematic explanation of a second embodiment of an organic electroluminescent device; Figure 3a shows a A schematic diagram of a third embodiment of an organic transistor; FIG. 3b shows a schematic explanation of a fourth embodiment of an organic transistor; FIG. 4 shows a current-voltage of a first organic electroluminescent device. Figure 1 shows a graph of the relationship between the current-voltage and the brightness-voltage relationship of the organic electroluminescent device of the third test; FIG. A second graph of the efficiency-voltage relationship of the organic electroluminescent device of the second test; and FIG. 7 shows a normalized pattern of the lifetime of the organic electroluminescent device of a fourth test. The drawings are provided for illustrative purposes only and are not intended to be a DETAILED DESCRIPTION OF THE DRAWINGS While the present invention is applicable to a wide variety of electronic and optoelectronic application variations, it will focus on the application of an organic electroluminescent device, namely an organic light emitting device (OLED) and an organic transistor. . Prior to the description of specific embodiments of the present invention, prior art electroluminescent device construction will be presented. Fig. 1 shows an organic electroluminescent device 1A having a substrate 1〇2 on which an indium tin oxide (ITO) anode 1〇4 is deposited. The substrate 1〇2 and the ITO anode 104 are light transmissive. A polymer layer 1 8 is configured to be in direct contact with the IT crucible anode 104. An organic light-emitting structure η〇 is formed on the polymer layer-14 - the paper size applies to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm). The secret number patent application Chinese manual replacement page (March 1993) A7 B7 ^ IIII is a smear of the ninth aspect of the invention. The replacement of the fifth page of the invention (8 108 between the ITO anode 1 〇 4 and a cathode 12 涂布. The organic light-emitting structure 110 includes, in order, one has An electromechanical hole transfer layer 12, an organic light emitting layer 114, and an organic electron transport layer 116. When a potential difference is applied between the anode 104 and the cathode 12?, the anode 4 is positive with respect to the cathode 120. When electrically, the cathode ι2 〇 will inject electrons into the organic electron transport layer ,6, and the electrons will traverse the electron transport layer 116 and the luminescent layer 112. At the same time, the hole will be injected from the anode 丨〇4 The hole transport layer 1 1 2 'and the holes will migrate across the layer 112 and eventually recombine with the interface between the hole transfer layer 112 and the light-emitting layer 14 . The generated electrons and the holes generated by the valence band radiate In the group, photons can be emitted through the light-transmissive anode 1〇4 and the substrate 1〇2 as indicated by the arrows for viewing by an observer. The polymer layer 108 can be made of fluorocarbon of RF plasma. Preparation of a plasma polymerization of a gas. The fluorocarbon polymer is a polymer such as a Teflon and is substantially formed of carbon and fluorine. It may also contain hydrogen and/or a small amount of impurities such as nitrogen, oxygen, and the like. The thickness of the layer is chosen such that it will have full coverage on the underlying conductive layer, and its low conductivity does not have a negative impact on device performance. Figure 2a shows the first specificity of an organic electroluminescent device 2 (10) Embodiment j is a schematic explanation. The organic electroluminescent device 2 is an upper portion, and a substrate 202 is disposed on the substrate, and a first electrode 2 is deposited on the substrate, and is also regarded as an anode 204. The anode 204 includes a layer of conductive and height (four) material, indicated by Μ, to provide a mirror-like surface. A non-metallic layer 206 comprising substantially an oxide is formed on the anode 2 〇 4. Further, 1

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123⁄4办2〇 Patent Application No. 166 Chinese Manual Replacement Page (March 1993) A7 B7

V. Description of the Invention (9 A polymer layer 208 comprising a fluorocarbon is formed on the non-metal layer 206. An organic light-emitting structure 210 is formed on the non-metal layer 206 coated with the fluorocarbon layer 208 The organic light emitting structure 2 10 includes, in order, an organic hole transport layer 2 12, an organic light emitting layer 2 14 and an organic electron transport layer 2 16 . The structure of the description is compared with that of FIG. 1 . The prior art structure is characterized in that the non-metal layer 206 is disposed between the anode 204 and the polymer layer 208. The polymer layer 208 is prepared by plasma polymerization of a fluorine plasma of RF plasma. It is possible to apply chemical vapor deposition (CVD). The anode 204 comprises a layer of electrically conductive and highly reflective material, preferably A1 or Ag' to provide a mirror-like surface. The non-metallic layer 2〇6 comprises an oxide, and The conductive and highly reflective materials are in contact with oxygen or the oxides formed therein are different from the oxides herein, such as ITO, NiOx2. Some deposition methods of the non-metal layer 206 are listed below: - Chemical gas Phase deposition (CVD) Contains plasma enhanced chemical vapor deposition (PECVD); - Sputter deposition or reflective (eg, in an oxygen environment) sputter deposition; - Hot steaming; - Electron beam evaporation; - Oxygen electricity (electropolymerization) Auxiliary oxidation); - Annealing of oxidizing environment; -UV-ozone treatment; - Wet chemical oxidation; - Electrochemical oxidation. -16-

1295902 A7

The tongue substrate 2 0 2 uses inflammation _ now F is the reference and must be electrically insulated. Because the object is set as an upper smoke device, that is, the generated light reflects the surface of the anode 2〇4 and penetrates the cathode 220, as indicated by the arrow, the storm The board can be used for day and day. . In this case, the cathode 220 must be light transmissive. The invention is not limited to being applied to the bottom emission sign. 4 service device' so all its advantages can of course be installed. Then, the anode 204 must have a penetrating property and the structure of the substrate 2G2 must be light penetrating. In this case, the anode ^(10) also includes a translucent material or a metal (four). These may include - transparent conductive oxides such as indium tin oxide, doped tin oxide or aluminum doped zinc oxide. These materials must be suitably deposited on the transparent substrate 2, such as glass quartz or a polymer substrate such as polyethylene terephthalate or polyvinyl acetate. Various different compositions of the organic light-emitting structure 210 can be utilized. Hole transfer layer and hole injection layer: The following materials are suitable for the hole injection layer and the organic hole transfer layer 2 12 . A material containing an aromatic amine group, similar to tetra-based diaminodiphenyl (TPD-1, TPD-2 or TAD) and NPB (see C. Tang, SID Conference in Chicago in 1996 and Appliced in 1995) Physics Letters 66, page 2679 C. Adachi et al.), TPA, NIPC, TPM, DEH (for abbreviations, see for example: AD 1993)\^1^1〇61^1^1*?: 6〇1^1^〇1^61: and 〇.8

Weiss's Photoreceptors for Imaging Systems). These aromatic amines - 17 - This paper scale applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1295902 A7 _ __B7 V. Description of invention (n) Groups can also be combined in polymers, starbursts (eg TCTA) , m-MTDATA 'Please refer to the article by Y. Kuwabara et al., Advanced Materials, Volume 6, page 677, 1974, Applied Physics Letters, vol. 65, p. 807, Y. Shirota et al., and spiral compounds. . Other examples are: copper g-cyanine (CuPc), (N,N,-diphenyl-N,Nf-bis-(4-phenylphenyl)-1, fluorene-biphenyl-4,4f-di Amine), distyryl arylene derivatives (DSA), anthraquinone, anthraquinone derivatives (eg NSD), quinacridone (QA), poly(3-methylthiophene) (P3MT) and derivatives thereof , hydrazine and anthracene derivatives, polythiophene (PT), 3,4,9,10-decane tetracarboxylic dianhydride (ptcda), PPV and some PPV derivatives, such as MEH-PPV, poly(9-vinyl Carbazole) (PVK), discotic liquid crystal material (HPT). The electron transport/emissive material is: Alq3, Gaq3, Inq3, Scq3, (q reference 8-hydroxyquinolinate or a derivative thereof) and other 8-hydroxyquinoline metal complexes such as Znq2, Beq2, Mgq2. ZnMq2, BeMq2, BAlq, and AlPrqs. These materials can be used as the organic electron transport layer 216 or the organic light-emitting layer 214. Other classes of electron-transporting materials are electron-deficient nitrogen-containing systems, such as oxygen-dosing similar to PBD (and many derivatives) and triazoles such as taz (1,2,4-triazole). These functional groups can also be incorporated into polymers, starbursts, and spiral compounds. Other classes are materials containing the functions of pyridine, pyrimidine, pyridin, and 1,2-diazatriene. Finally, it contains quinoline, quinoxaline, σ octyl phenyl, hydrazine and quinazoline functions "18" This paper scale applies to China National Standard (CNS) Α4 specifications (21〇X 297 public) _ 1295902 A7 B7 5. The material of the invention (12) is well known for its electron transport capabilities. Other materials are dimercaptohexaphene (DPS6T), bis-triisopropyldecyl hexazone (2D6T), quinone imine-zinc complex, pyridin (eg BNVP), styryl E derivative (eg BSA-1, BSA-2), non-planar distyryl arylene derivatives such as DPVBi (see C. Hosokawa and T. Kusumoto, BC 1994, Hamamatsu, 42 International Inorganic and Organic Electroluminescence Monographs published papers, cyano-substituted polymers such as cyano-PPV (PPV means poly(p-phenylene extended ethylene)) and cyano-PPV derivatives. The following materials are particularly suitable for the emissive layer as well as impurities: hydrazine, pyridine derivatives (eg ATP), imine-zinc complexes, sorghum (eg BNVP), styryl hydrazine derivatives (eg BSA-1, BSA-) 2), hydrazine, coumarin, DCM compound (DCM1, DCM2), distyryl arylene derivative (DSA), alkyl substituted stilbene benzene derivative (DSB), benzimidazole derivative ( For example, NBI), anthracycline derivatives (eg NSD), oxadiazole derivatives (eg OXD, OXD-1, OXD-7), N, N, N, Nf-tetra (m-methylbenzene) , 1,3-diaminobenzene (PDA), hydrazine and anthracene derivatives, phenyl substituted cyclopentadiene derivatives, anthranilone, hexa-4 (6T), polythiophene, quinacridine Ketone (QA) (see T. Wakimoto et al., 1994, Hamamatsu, 77, International Symposium on Inorganic and Organic Electroluminescence) and substituted quinacridone (MQA), red fluorene, DCJT (See for example: C. Tang, SID Conference, San Diego; Proceedings, 1996, 181), a total of non-common and non-common polymers, such as PPV and PPV derivatives, trialkoxy and Trialkyl -19- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)

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Claims (1)

Ι295^Θ2ΐ20166 ttt# - ί文Application for the replacement of patent scope (September 96) ABC 96·year 9· if 4 day repair (^) original six, application for patent garden] · An electronic device, including ·· An electrode substantially having a conductive layer (2〇4, 3〇4); a non-metal layer (206, 306) formed on the conductive layer (2〇4, 304); formed on the non-metal layer (206) , 306) a fluorocarbon layer (208, 308); a structure (210, 310) formed on the fluorocarbon layer (208, 308); and opening/forming on the structure (21〇, 310) a second electrode (220, 311, 330) 〇2. The device of claim 1, further comprising a buffer layer between the conductive layer (2〇4) and the non-metal layer (206) 205). A device according to any one of the preceding claims, wherein the non-metallic layer (2〇6, 306) comprises an _oxide. 4. The device of claim 3, wherein the oxide is selected from the group consisting of: a 3d transition metal group, a jIIA group, a VA group, and a rare earth metal group or Is one of the combinations. 5. The device of claim 3, wherein the oxide of the non-metallic layer (206, 306) is different from the latent oxide formed by the conductive layer 10(10), 3〇4). 3〇6) A device having a thickness from a single layer to a range of 20 nm in the range of 6's, and wherein the non-metallic layer (206, the device of claim 5, wherein the conductive layer (204) , 3〇4) includes a light reflective material. 80471-960914.doc X 297 mm) 1295902, the scope of the patent application A B c D 8 The device of claim 5, wherein the conductive layer (2〇4, 3〇4) forms a mirror-like surface. 9. The device of claim 5, wherein the conductive layer (204, 304) comprises aluminum (A1). 1. The device of claim 5, further comprising a substrate (202) that is in contact with the conductive layer (204) or the structure (2 1〇). 11. A device as claimed in claim 5, which is part of an electroluminescent device (OLED), a transistor or a sensor. 12. A method for forming a device according to any of the preceding claims, comprising the steps of: providing a conductive layer (204, 304) to function as a first electrode; forming a non-metallic layer (206) On the conductive layer (2〇4, 304); depositing a layer of fluorocarbon (208, 308) on the non-metal layer (206, 306); 幵 y into a plurality of layers of the fluorocarbon layer (2 〇 8, 3) 0 8 ) structure (2 1 0, 310); and forming a second electrode (22〇, 311, 330) on the structure (210, 310) 〇 80471-960914.doc This paper scale applies to Chinese national standards (CNS) A4 size (210 X 297 mm)