TW425346B - Organic light emitting devices and methods of fabricating the same - Google Patents

Abstract

Provided is a method of fabricating an organic light-emitting device, which method comprises the steps of: forming a first electrode for the device over a substrate; either forming by self-assembly at least one polymer layer over the first electrode and forming other than by self-assembly at least one layer of organic light emissive material over the at least one polymer layer; and forming a second electrode for the device over the at least one layer of organic light emissive material; or forming other than by self-assembly at least one layer of organic light emissive material over the first electrode and forming by self-assembly at least one polymer layer over the at least one layer of organic light emissive material; and forming a second electrode for the device over the at least one polymer layer. Also provided is an organic light emitting device, obtainable according to the method of the present invention.

Description

Forgive rir1, the ministry disappears in the fight ii 卬 y 425346 A7 " " ----------------------- B7 V. Description of the invention (1) The present invention relates to an improvement A method for manufacturing an organic light emitting device and a structure formed by the method. Organic light-emitting devices (OLEDs) are, for example, U.S. patents 5,247,190 or > ^ 11 ^^ "etc. issued to Cambridge Display Technology Corporation in the early days, and the contents thereof are described herein for reference and examples. It is likely to be used in a variety of display applications such as large-area flat panel displays. In principle, OLEDs include an anode that emits positively charged carriers, a cathode that emits negatively charged carriers, and at least one organic electroluminescent layer sandwiched between two electrodes. When When a positive bias is applied to the anode, the pore system is injected by the anode and the electron system is injected by the cathode. These carriers are recombined inside the organic electroluminescent layer to emit light. Typically, although not necessary, the anode is, for example, indium-tin-oxide ( ITO) thin film, which is a semi-transparent conductive oxide tablet, which has been deposited on glass or plastic substrates. The organic layer # type is a thin layer of residual polymer (100-1000 nm). Either spin coating, knife coating, dip coating, or crescent coating are deposited on the ITO coating substrate. The cathode layer is typically a low-work-function metal electrode on the organic layer. It is performed by thermal evaporation or sputtering of a suitable cathode metal. Aluminum, calcium, or magnesium: silver or town: an indium alloy or aluminum alloy layer is often used as a cathode material ^ One of the key advantages of OLED technology is that it can be operated at low drive voltages by cracking However, it is necessary to use an appropriate electroluminescent organic layer, and an electrode with good emission of positive and negative 4 carrier efficiency & 'The key performance parameter of polymer LED performance is quantum efficiency (photons emitted by each-charge carrier flowing in the circuit Volume), and drive the electric mill required to achieve a specific light output. Another important parameter is power efficiency (optical power output on the paper size of the paper in Shizhou 1 standard store (CNS) A4 size (2 （0 乂 297) ~] --------- '装-' 1-(诮 Read the precautions on the back before writing this page) Order i —ill -------- -4- 425346 A7 __ —______ __B7 V. Description of the invention (2) Ratio of electric power input). High power efficiency requires high quantum efficiency and low driving voltage. One. The main parameters of t-compound LED are to achieve maximum brightness, easy to manufacture and reproducible. , And the longest working life. In order to achieve the good performance of OLED, it is very important to All individual layers, including the anode, cathode, and organic layers, and the interfaces between the layers are optimized. A thin layer and a well-defined polymer layer is placed between any of the cathode or anode and the organic layer. The so-called interface layer can improve the device Performance. But in order to achieve improved performance, this layer must be manufactured under fairly thorough control conditions. In order to obtain the best placement performance, the thickness must be controlled in the nanometer range. Known as self-assembly technology can be used to deposit clearly defined polymer layers The polymer self-assembly technology involves stacking polymer films by adsorbing continuous multiple polymer layers in solution. This technology relies on attractive interactions between successive layers and requires that the layers formed be different from the previous layer formed. Typically, repeating polymer layers such as ABBA, ..., or ABCDABCD ... are used, where A, B, C and D represent individual different layers. Polymer light-emitting devices manufactured using self-assembly methods are described in A.C.

Fou '0. Onitsuka, M. Ferreira, and MF Rubner "Interlayer interactions in self-assembled poly (phenylene-phenylene-vinyl) multilayer non-homogeneous structures" means light-emitting and light-correcting diodes "Mat. Res. Soc, Symp. Proc. 'Vol. 369, pp. 575-580' 1995; and AC 'Fou, 0. Onitsuka, M. Ferreira' MF Rubner and BR Hsidh, "Based on the self Assembling multilayers to make light-emitting diodes and their properties "J. Appl. PHys., Vol. 79, pp. 7501-7509, 1996. These references make use of polymer cations and polymer anions from the paper size to the Chinese National Standard (CNS > A4 specification (210X297 mm) _ --------- 威 ------ ΐτ ------ ^ .J * f (Please read the notes on the back before filling in this I} 425346 A7 B7 Five 'invention description (3) Line assembly technology, described in G_ Decher, JD Hong and J. Schmitt, "Stacking ultra-thin multilayer films by self-assembly methods. 3. Successive changes in adsorption of anionic and cationic polyelectrolytes on charged surfaces", Thin Solid Film, Vol. 210 'ρρ · 831-835' 1992. In these structures, ρρν Precursors or their derivatives are used as polymeric cations, and various polymeric anions such as polystyrene sulfonic acid or sulfinated polyaniline are used. Poly (p-heridinyl vinylidene) and its derivatives have also been used in the manufacture of self Assemble the LED. The method of obtaining a working LED by self-assembling a film with sufficient thickness is extremely time-consuming because it involves too many dipping and cleaning steps. In the aforementioned work, the entire device was completed by self-assembly, so there was too much dipping Step problem. This method does not have Commercialization. Therefore, the object of the present invention is to provide a structure and manufacturing method in which a clearly defined thin polymer interface layer can be provided between the electrode of the LED and the electroluminescent material without unduly hindering standard commercial processes. According to an aspect of the present invention, a method for manufacturing an organic light-emitting device is provided, including the following steps: forming a first electrode of the device on a substrate by 'self-assembly to form at least one polymer layer on the first electrode; not by self-assembly Forming at least one organic light-emitting material on the at least one polymer layer; and forming a second electrode of the device on the at least one organic light-emitting material. A first aspect of the present invention also provides a method of manufacturing an organic light-emitting device, including the following steps: · • The first electrode of the device is formed on the substrate; at least one organic light-emitting material is not formed on the first electrode by self-assembly; at least one polymer layer is formed on the at least one organic light-emitting material by self-assembly State Chinese National Standard (CNS) Λ4 specification (210X297 mm) --------- wei ----- 1T ---- -^ *-(Please read the precautions on the back to fill out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs ^ Industry and Consumer Cooperatives 425346 A7

— \ M 5. Description of the invention (4) a 'and a second electrode forming the device on the at least one organic polymer layer. Thus, in the first aspect of the present invention, self-assembly is used to form at least one additional polymer. Layer on the electrode / luminescent material interface. The remaining equipment is then completed using standard techniques such as spin coating. The first aspect of the present invention has the advantages of fast processing speed and wide control effect in the polymer interface. In this way, the first aspect of the present invention can completely reduce the processing time and cost by using the prior art device manufactured by self-assembly. Compared to devices without an interface layer, quantum efficiency, driving voltage, power efficiency and / or maximum brightness are significantly improved and device life is improved. The thickness of the interface layer with a quantum efficiency in a certain range increases significantly, and the driving voltage increases with the thickness of the layer β, so the best power efficiency appears in the middle thickness. This thickness is less than is typically achievable using a spin-on interface layer. With this thickness method, thin and continuous well-defined films are obtained by self-assembly. This is an ideal technique for producing pinhole-free films in this thickness method. The at least one self-assembled polymer layer preferably includes one or more pairs of sublayers that cooperate together, and the at least one organic light-emitting layer includes a continuous layer having an overall uniform composition. The at least one self-assembled polymer layer may be any of an insulating polymer, a semiconductive polymer, or a conductive polymer. The device performance can be further optimized by depositing an insulating, semi-conductive or conductive polymer interface layer on the OLED by self-assembly. The cooperative sub-layers interact by attraction, and the sub-layers are different from each other. Preferably in a pair-the sublayer is positively charged, and the other sublayer in the pair is a paper ruler ship @ 国 2I〇xW 公 f) ^ 11τ ------ '^. T (Please (Please read the notes on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperative 425346 Λ7 ____ Η 7 1--.... ——. 一一 5. Description of the Invention (5) — Negative Charge . Preferably, the positively-charged sublayers in pairs are formed by immersing the substrate in a polymeric cationic electrolyte solution, and the negatively-charged sublayers in pairs are formed by immersing the substrate in a polymeric anion solution. If the polymer is an insulating polymer, the polymeric anionic electrolyte solution preferably contains the structural formula of Figure 2 (a), and the polymeric cationic solution preferably contains the structural formula of Figure 2 (b). The right polymer is a semiconducting polymer ', and the polymerized anionic electrolyte solution preferably includes the structural formula of FIG. 2 (c), and the polymerized cationic solution preferably includes the structural formula of FIG. 2 (d). If the polymer is a conductive polymer, the polymeric anionic electrolyte solution preferably contains the non-protonated form of the structural formula of Figure 2 (e), and the polymeric cationic solution preferably contains the structural formula of Figure 2 (f). Alternative X 'Co-operative sub-layers can respond by recipient / giver interaction. The preferred recipient / donor interaction response is provided by hydrogen bonding. The general technology of hydrogen bonding is discussed in WB Stockton and MF Rubiner, "Molecular level processing of conjugated polymers. 4. Layer-by-layer operation of polyaniline through hydrogen bonding interaction", Macromolecule, 1997, 30, 2717 -2725 »It is preferred that the sub-layers of the paired sub-layers cooperating with each other have a thickness of 0.3 to 2 nm, preferably 1 nm. The at least one polymer layer preferably comprises a plurality of pairs of sublayers, such as two, four or ten pairs. This paper scale is applicable to the Chinese National Standard (CNS) A4 scale (2IOX297 public carboxylic acid) --------- ^ ------ II ------ ^ (Please read the notes on the back first (Refill this page) Λ7 425346 Description of the Five 'Inventions (6) At least one polymer layer may further include three or more sub-layers that cooperate together. Each sub-layer is different from each other. At least one polymer layer may include a plurality of three or more sublayers. The at least one polymer layer is preferably about 0.3 to 20 nanometers thick. The organic material is a conjugated polymer or a low molecular weight polymer. At least one layer of organic material includes a composite structure, including at least one layer of a conjugated polymer and at least one layer of a low molecular weight compound. If the at least one layer of organic material is a polymer, it is preferably a semiconductive conjugated polymer. The semiconductive conjugated polymer is preferably ρρν or a derivative thereof. The at least one organic light emitting material layer is formed by spin coating, doctor blade coating, crescent coating or dip coating. The at least one organic material layer preferably has a thickness in a range of about 30 nm to centimeters and more preferably about 90 nm. The method may further include a step of removing physically adsorbed water from the surface of the substrate before the step of forming at least one polymer layer. The step of removing the physically adsorbed water from the surface includes heating the substrate. The method further includes a step of forming a coupling layer before the step of forming at least one polymer layer. The step of forming the coupling layer preferably includes a silylated substrate. If the step of removing physically adsorbed water is performed, the step of forming a coupling layer is performed thereafter. The substrate has a surface charge associated with pH, and the method further comprises preparing the surface of the substrate by making the pH of the surface charge independent before self-assembly. The method further includes preparing a substrate surface before self-assembly, wherein the surface includes an amine group, and the method includes a step of quaternizing the amine group. The fourth version of the paper music scale is applicable to China Store Standard (CNS) A4 specifications (210X ^^ 11 ------ Xiang ------ ΐτ ------ Φ. •-'-(Please first Read the notes on the back and fill in this. 筲) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs.

--------] V V. Description of the invention (7) ~~~~ '一 — The surface is positively charged. The method further includes preparing a surface of the substrate before self-assembly, wherein the surface includes a thiol group, and the method includes a step of oxidizing the thiol group. The oxidized surface is negatively charged. Before forming the first electrode, the substrate includes any one of glass or plastic material. The substrate may include any one of polyester, polycarbonate, polyimide, or polyetherimine. The method further includes a step of forming a conductive material layer on the second electrode. The conductive material preferably contains aluminum or an alloy thereof. Conductive materials can be deposited by sputtering, preferably by DC magnetron or 1 ^ sputter deposition, or by vapor deposition, preferably by resistance or electron beam thermal evaporation. The first electrode may be a cathode and the second electrode may be an anode, or the first electrode may be an anode and the second electrode may be a cathode. The cathode contains a light-emitting conductive oxide, preferably indium tin oxide, tin oxide or zinc oxide. The cathode can be obtained by sputtering deposition or evaporation. The anode contains a light-emitting conductive oxide, preferably indium tin oxide, tin oxide or zinc oxide. The anode can be obtained by sputtering deposition or evaporation. A first aspect of the present invention also provides an organic light-emitting device including: at least one organic light-emitting material layer interposed between the first electrode and the second electrode, the at least one organic light-emitting material is formed by not self-assembly; and at least one polymer layer Between at least one of the first and second electrodes and at least one organic light emitting material layer, the at least one polymer layer is formed by self-assembly. Preferably, at least one polymer layer includes at least one pair of sublayers that cooperate together, and the at least one organic material layer is a continuous layer, which has an overall consistent composition. The paper size is applicable to the Chinese National Standard (CNS). 297 mm) -10- ---------- ¾ ------ II ------. ^-„-. (Read the precautions on the back before filling in; (5 pages) Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 425346 Λ7 ________H7 V. Description of the invention (8) '~ + 〇 At least one polymer layer preferably includes multiple pairs of common cooperation layers. A preferred embodiment of the present invention t. The self-assembly technology of polyelectrolyte is used to deposit a thin and clearly defined insulating, semi-conductive or conductive polymer layer between the electrode of a polymer LED (preferably an ITO electrode) and a light-emitting polymer. In this technology, one The substrate is immersed in the polymer cation and polymer anion solution alternately, and the alternating layer is deposited by electrostatic attraction. The self-assembly technology only deposits a thin interface layer, and the rest of the device is preferably deposited by spin coating. Self-assembled devices can significantly shorten manufacturing processes Time. Since the thickness of each self-assembled layer is thin and continuous, according to this aspect of the present invention, it is possible to pile up a structure defined by vocals, while controlling the thickness of the interface layer in the nanometer range. The present invention also provides the best material and thickness of the interface layer. The best quantum and power efficiency of the polymer LED is obtained. By using the present invention, it is possible to achieve significantly improved power efficiency and significantly increased maximum brightness. Self-assembly methods preferably require a clearly defined surface charge on the starting surface. Typical This is achieved by forming a coupling layer with the surface before self-assembly, typically using a silylating agent to treat the surface. A second object of the present invention is to provide an improved starting surface for a self-assembly method for manufacturing organic LEDs or parts thereof. According to a second aspect, a method for manufacturing an organic light-emitting device includes the following steps: forming a first electrode of the device on a substrate; removing physically adsorbed water from the surface of the first electrode; forming a coupling layer; and forming at least one polymer layer by self-assembly On the first electrode; forming at least one organic light emitting material layer on the at least one polymer layer On the physical layer; and the second electrode forming the device applies the Chinese national standard {CNS) A4 specification (2 丨 〇 X 297 public dream) to the paper rule --------- meal -------- 1T ------ ^ (Please read the notes on the back of Vg before filling in the "sir page") Λ7 425346 V. Description of the invention (9) The at least one light-emitting material layer. The steps for forming such a coupling layer are better A silylated substrate is included. A second aspect of the present invention also provides a method for manufacturing an organic light emitting device, including the following steps: forming a first electrode of the device on the substrate; forming at least one organic light emitting material layer on the first electrode; Removing physically adsorbed water from the surface of the at least one organic light emitting material layer; forming a coupling layer; forming at least one polymer layer on the at least one organic light emitting material layer by self-assembly; and forming a second electrode of the device on the at least one polymer On the floor. Before the surface silylation reaction and LED production, physically adsorbed water is removed from the surface, preferably by vacuum heating to remove the ITO substrate, which can result in a well-defined surface before self-assembly, resulting in improved interface layer quality control. A second aspect of the present invention also provides a method for reducing device degradation by removing water close to the interface layer. If the physically adsorbed water is not removed, the coupling layer may form a gel and float on the surface during deposition. Thus, the second aspect of the present invention provides an improvement in coupling of the coupling layer to the electrode. A third object of the present invention is to provide an improved starting surface for a self-assembly method, thereby diversifying the practice of the self-assembly method. According to a third aspect of the present invention, there is provided a method for preparing a surface having a pH-related surface charge before self-assembly, comprising a step of making the surface charge independent of pH. The surface is preferably a substrate of a light emitting device & the light emitting device is preferably an organic light emitting device. The third aspect of the present invention also provides a method for preparing a surface containing an amine group before self-grading, which comprises a step of quaternizing the amine group. The surface is preferably the surface of a light-emitting device substrate. The light emitting device is preferably an organic light emitting device. This paper size applies to the Chinese National Standard (CNS) A4 specification (2! 0X297) 苈 ΤΪΤ7 ------ ^ ------ 1T ------. ^ '.-(Please first The French and Italian matters on the back of the occasional reading are really filled in.) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs.

425346 a7 ----- B7

V. Description of the invention (Y Sihua surface is positively charged. {Please read the notes on the back before filling this page) The third aspect of the present invention further provides a method for preparing a surface containing mercapto groups before self-assembly, which includes In the step of oxidizing the M group, the surface is preferably the surface of the substrate of the light emitting device. The light emitting device is preferably an organic light emitting device. The surface of the oxygen year is negatively charged. After oxidation, the surface is preferably deprotonated. A variety of polymer ions are stable only at certain pH values, so the fourth and oxidation steps are respectively compared with the range that may previously allow a wider range of polymer ions to be deposited on the LED structure without changing the coupling agent. This allows a certain range of polymerized cations and polymerized anions (which are ionic stable to the solution and require different pH values). They can be assembled by themselves using the same coupling agent. Fourth-generation and oxidation technologies are described, for example, in J. March, "Advanced Organic Chemistry · Reactions, Mechanisms, and Structures", 3rd Edition, ‘About Willie & Sons, New York, Chapters 10 and 19 of 1985. According to the third aspect of the present invention, the coupling agent obtained as a result of the fourth chemical process or the oxidation process is preferably greatly reduced in sensitivity to oxidation, and the oxidation process may cause device problems. The present invention will now be described with reference to the accompanying drawings, with attached drawings: Brief description of the first diagram Illustrates the OLED manufactured according to the present invention; Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy; Composition example; Figure 3 illustrates the efficiency obtained through the device example according to the present invention. Figure 4 illustrates the power efficiency obtained through the device example according to the present invention. Figure 5 illustrates the power efficiency obtained through the device example according to the present invention. Brightness This paper size is applicable to the National Solid Standard (CNS) A4 specification (210x297 mm) 425346 Λ7 H? Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) The 6th item contains 5BTF8 (F8) 5 % F8BT) Unexpected cross-sectional view of the device as a luminescent material; Figure 7 shows poly (styrene sulfonic acid) doped poly (ethylene dioxophenone) (PEDOT-PSS), poly (2,7- (9, Chemical structures of 9-di-n-octyl) (F8) and poly (2,7 · (9,9_-di-n-octyl)) _ 3,6-benzoxadiazole (F8BT); Figure 8 The chemical structural formula of the silane-based coupling layer is shown. Figure 9 shows the assembly solution of the device. Measurement of external light _ visible light absorption spectrum; Figure HM4 shows current and light output performance efficiency vs. voltage of device J_v; Figure 15 shows power efficiency vs. brightness of device; Examples of Figures 16a and 16b Describe the energy levels of two example devices; Figure Π is a plot of the current density through the device versus the applied voltage; Figure 18 is a plot of the drive voltage vs. brightness of device iv; Figure 19 shows the representativeness of device X Performance; Figure 20 shows the typical performance of device γ; and Figure 21 shows the typical performance of device z. In the first example, the device is a commercial 1x1 cm2 ίτ〇 (indium tin oxide) -glass substrate ( Balzers). With reference to Figure 1, a sample substrate is shown in which the ITO layer 4 is formed on a glass substrate 2. For all the chemical treatment steps of this first example, the substrate is fixed to the substrate holder in a vertical configuration. Unless otherwise noted, the solvent used in this example is Ηριχ grade or this paper size ϋ Chinese national standard CNS) A4 size (210X 297 km) ~~~ ^ ------ ίτ ------ ^ (Please read the notes on the back first Write this page) 425346 Λ7 Η 7 V. description of the invention (12) is better. The reactants used are of AR grade or better. In the first step, the ITO layer is patterned and cleaned. The ITO surface was selectively coated with a commercial photoresist and then baked in an oven at 45 ° C for 10 minutes. The exposed area was removed by etching at 200-5% 5% hydrochloric acid at 60-65 ° C for 45 minutes. The photoresist was then stripped off in 2x100 ml of acetone. After the pattern is made, the ITO substrate is cleaned with RCA formula (10: 2: 0.6 H20_H202-NH3, 200 ml) and gently stirred at 55-60 ° C for 75 minutes. In the second step *, Figure 1 shows that the coupling layer of layer 6 is ready for self-assembly layer by layer. It is better and simpler. The substrate is heated in a dynamic oven at 165-170 ° C to 165-170 ° C for 2-3 hours. Before the surface silylation reaction, the physically adsorbed water is removed in a vacuum oven. The substrate was then briefly cooled to 100 ° C in air, and then immersed in 200 ml of a toluene bath containing 5 vol% 3-aminopropyltrimethoxysilane. The reaction bath was warmed to 95-97 ° C for 2 hours, carefully removing water vapor. It was obtained that the surface of tingo was functionalized with an amine (-NH2) group, and the amine group was connected to the end of the short c3 alkyl chain. The silylated substrate was washed in 2x100 ml of benzyl and lx methanol in this order and dehydrated under a nitrogen spray. "Visual inspection of the specular reflection of the surface at this point shows the optically clear and uniform surface. 'Few spattered particles appear in the needle-free Hole in the ITO film. Then the amine group is preferably converted into a pH-insensitive trimethylammonium (· NMe3 +) portion. In order to achieve this, the substrate is immersed in 200 ml containing 5 vol% methyl iodide and 0-6 vol% triethylamine. Of n, N-dimethylformamide for 3 hours. The reaction bath is maintained at room temperature (24.0) in the dark. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 public goods) ---------------- 1T-- -----. ^ (Please read the back. '5' precautions before filling out this page} Central Standards Bureau of the Ministry of Economic Affairs: Printed by the Industrial and Consumer Cooperatives -15- Λ7 B? 425346 V. Description of the Invention (13) The substrate after the quaternization was washed with 2 × 100 ml of methanol, 1 × 100 μl of 45 μm water, and then filtered with 1 × 100 mL of 0.45 μm IPA in this order and dried under a nitrogen spray. Visual inspection The display surface remains optically clear and uniform. In the second step, the first icon shown as layer 8 is composed of layers that are self-assembled layer by layer. The self-assembly manufacturing steps can be performed by any number of self-assembly techniques. An alternative way_, The attractiveness of the sub-layer interactions of pairwise co-operation is provided by the recipient / donor interaction, especially by hydrogen bonding. It is provided by the opposite charge layer of each sublayer in each pair. The third step is performed on the derived ITO substrate in a laminar flow box at room temperature. Each assembly cycle assembles two layers, that is, a pair of cooperating sublayers and includes the following steps: ⑴ Immersion in a polymer anion electrolyte bath ( Static) for 14 minutes; (Π) bath (mild agitation) in fresh water (MiUipore) for 10 seconds; (iii) immersion in polymer cation bath (static) for 14 minutes; (iv) in fresh water (Millipore) Bath (gentle agitation) lasts 10 seconds. The assembled film is preferably not dried between successive steps. The solution is carried to the next step and the contamination is minimized through careful handling and cleaning. The interface layer of the example is an insulating polymer. The polymer anion electrolyte bath contains 20 ml of water (Millipore), 21 mg of poly (benzyl sulfonic acid, sodium salt) (Aldrich, MW 70k), 30 mg of gasified sodium and aqueous hydrochloric acid. The paper scale for pH adjustment is in accordance with Chinese National Standards (CNS) to specifications {2 丨 OX297g t) --------- Meal ------ iT ------ Φ (Please read first (Please fill in this page with the notes of VI41) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -16-Liji Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Education 425346 Λ7 H7 --- ---------------------------- 5. Description of the Invention (14) '' Round to about 3. The polymer cation bath (in this case, the insulating polymer) contains 20 ml of water (Millipore) '8 mg poly (allylamine hydrochloride) (Aldrich, MW 50-65k), The pH was adjusted to about 3 with 30 mg of sodium vaporization and aqueous hydrochloric acid. After the self-assembly steps (i) to (iv), the 'double layer' contains a sublayer of the structure of Fig. 2 (a) and a sublayer of the structure of Fig. 2 (b). In the first example of this first example, steps ii to (iv) are performed twice to assemble a double-layered structural formula or two pairs of sub-layers. The substrate was then washed in 2 X 40 ml of water (Millipore) for 2 minutes. The substrate was then dehydrated under dynamic vacuum for 5 hours. The fourth step of the second step is preferable because a positively charged surface can be obtained and then the surface is immersed in an alkaline aqueous solution or an acidic aqueous solution during self-assembly. Fourthly, the surface charge of such a device is independent of pH, so an alkaline or acidic solution can be used. In the alternative, the ITO surface is functionalized with thiol groups, and different steps are required to make such a surface independent of pH. In this alternative example, in the second step, the first layer of the coupling layer is shown as layer 6 again in the preparation of the layer-by-layer self-assembly. The substrate was heated again in a vacuum oven to 165-170 ° C in a dynamic vacuum for 2-3 hours, and the physically adsorbed water was removed before the surface was silylated. The substrate was then briefly cooled to 100 ° C in air again, and immersed in a 200 ml toluene bath containing 5-vol% 3-chloropropyltrimethoxysilane. The reaction bath was warmed to 95-97 ° C for 2 hours, carefully removing water vapor. The ITO surface thus obtained was functionalized with fluorenyl (-SH) and attached to the end of the short c3 alkyl chain. The silylated substrate was washed in this order at 2 x 100 ml and 1 x methanol and dried under a nitrogen spray. At this time, visual inspection of the specular reflection on the surface of Ting 〇 shows that the paper size is suitable for financial standards (CNS) Ai) specifications (2iQx297 public magic -17- --------- batch clothing ---- --ir ------ Itching. (Please back up the 16 -.- ¾ .. Note before filling out this page) A7 B7 V. Description of the invention (15) Optically clarify the surface of the uniform sentence, few scattered particles exist in the * with needle On the ITO membrane of the hole> Then replace the second step here. The thiol group is preferably oxidized to the pH-insensitive acidic acid group (-S03). In order to achieve this, the substrate is immersed in room temperature (2nd generation) at 200 Ml of water containing 10 ml of formic acid and 30 ml of hydrogen peroxide over 30 minutes. The oxidized substrate was in 2 × 100 ml of water, 1 × 100 ml of dilute sodium hydroxide (0.02 M) '2x100 ml of 0,45 μm Filter the water and then 1 × 100 ml of 0-45 μm filtered isopropanol (IPA) in this order, wash and blow dry under a nitrogen spray. Visual inspection at this time shows that the surface remains optically clear and uniform. Also in this alternative, change In the third step, the interface layer (the icon is shown as layer 8) is again constituted by layer-by-layer self-assembly interface layers. The assembly is performed at room temperature in a laminar flow box. The ITO base material after derivatization is performed. Each assembly cycle assembles a double layer, that is, a pair of sublayers that cooperate together. This alternative example includes the following steps: (i) Immersion in a polymer anion electrolyte bath (static) for 14 minutes; ( ii) Bath (mild agitation) in fresh water (Millipore) for 10 seconds: (iii) Submerged in polymer cation bath (static) for 14 minutes; (iv) bath in fresh water (Millipore) (mild) Stirring) lasts for 10 seconds. The assembled film is preferably not dried between successive steps. The solution is carried to the next step and cross-contamination is minimized through careful handling and cleaning. The interface layer of this alternative example is again an insulating polymer The polymer anion electrolyte bath once again contained 20 ml of water (Millipore), 21 mg of poly (styrene sulfonic acid, sodium salt) (Aldrieh, MW 70k), 30 mg of sodium gasification and hydrochloric acid. The paper is suitable for China. Standard (CMS) A4 specification (2) 0297 mm (read the precautions on the back of the first cabinet and then use the code VK). Order -18- 425346 Μ in the Ministry of Economic Affairs Central #-printed by the Bureau of Industry and Consumer Cooperatives Fifth, the description of the invention (16) Adjust the pH to about 3. The polymeric cation bath (in this example the interface layer is an insulating polymer) contains 20 ml of water (Millipore) '8 mg poly (allylamine hydrochloride) (Aldrich, MW 50-65k) , 30 mg of sodium chloride and hydrochloric acid aqueous solution to adjust the pH to about 3. After the self-assembly steps ⑴ to (iv), the double layer contains a sublayer of the structural formula of Figure 2 (a) and a layer of Figure 2 (b). Sublayer of the structural formula. In the fourth step, the MEH-PPV layer (shown as layer 10 in Figure 1) is spin-coated on the device. 90 nm poly (2-methoxy, 5- (2'-ethyl) -hexyl-p-phenylene vinylene) [MEH-PPV] by spin-coating 0.5% by weight of MEH-PP V at 2000 rpm The aerosol solution was deposited on the substrate-polymer assembly over 1 minute. In the fifth step, the device constructed so far is subjected to heat treatment. The semi-finished device is baked in a dynamic vacuum (P < 10-4 mbar) at 100t! Remove free water within hours. The substrate was then slowly cooled to 501 over a period of 2 hours and still under vacuum. The sixth step is the metal electrode deposition step, "without breaking the vacuum, a thickness of 200 nanometers of calcium layer at a base pressure of 6x10-6 mbar, and a thermal evaporation of the resist layer to obtain 4.4 at 1 \ ^ 1 ^-?? 7 Square millimeter device. The final 100 nm-thick aluminum layer was then evaporated to protect the calcium electrode. This completes the first example of the OLED of the present invention. As for the control, in order to implement the idea of the present invention here and compare the better performance characteristics with examples, MEH-PPV is also directly coated on RCA-cleaned 1-Ni. A device made of RCA-cleaned ITO is hereinafter referred to as a "knowledge device". According to the first example device with an insulating polymer interface layer, it was obtained on 7 paper scales applicable to China National Winter Standard (CNS) A4 (2 丨 0X297). ---------- t --- --- ίτ ------ ^ (Please read the notes on the back before filling out this page) -19- Printed by the Consumers' Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs ^ 4 2 5 3 4 6 λ? in V. Invention Explanation (17) The maximum efficiency of 0.92 cd / A, compared with the conventional device at 0.16 cd / A at 7 volts, indicating an improvement of 5.8. According to the first example of the device using an insulating polymer interface layer, the device has a current density of 170 mA / cm2, the comparison of the conventional device is 930 mA / cm2 'representing a reduction factor of 5. According to the first example, the device with an insulating polymer interface layer has the highest power efficiency of 0.45 lm / W at 6 volts compared with 7 volts at 7 volts. 0 · 79 lm / W, which indicates an increase factor of 5.8. According to the first example, the device with an insulating polymer interface layer has a maximum brightness of 2100 cd / m2 at 8 volts, compared to the conventional device of 1300 cd / m2 at 7 volts. Indicates an increase factor of 1.6. In order to illustrate the excellent performance of the OLED assembled by the present invention, reference is now made to Figures 3 '4 and 5. Figure 3 4 and FIG. 5 illustrate exemplary assembled device of the invention with respect to the conventional device of Comparative Experiment Results reached "3, 4 and

Figures 5 and 5 illustrate the efficiency, power efficiency, and brightness of the device, respectively. Various devices were manufactured as described in the first example, but the number of double layers deposited in the third step changed. • Devices containing 1, 2, 4, and 10 double layers or pairs of sublayers were performed by performing steps ⑴ to (iv) — 2nd, 4th, 4th and 10th assembly β Points 2 to 4 in the figure IP-ΐ 'ιρ_2, IP-4 and IP-10 indicate that the device assembled according to the first example contains 1, 2, 4, and 10 pairs Layer of results. The results verify that the best power efficiency can be obtained using the two insulated polymer double layers illustrated in Figures 2 (a) and (b). In the second example, the device was manufactured as in the first example above, but the polymeric anion bath in the third step contained 20 ml of water (Millipore) and 22 mg of poly (benzyl sulfonic acid, sodium salt) (A) drich 'MW 70k), 30 mg sodium gaseous solution and hydrochloric acid aqueous solution to adjust the pH to about 3; and polymerized cations with 20 ml of water (closed paper ruler Yuncai Guanjiazhuan (CNS) cell (21 () χ 297: ϋ · -20- --.-- ^ ----- ^ ------ iT ------ ^ (Please read the notes on the back before filling out this page) Employees' Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Yin poly 425346 Λ7 _______ »? V. Description of the invention (18) " " Libo), 0.76 g 3_0 weight .. Gasification of tetrahydrobiphene iron precursor to poly (phenylene-ethylene) The methanol solution '30 mg of sodium gaseous solution and hydrochloric acid aqueous solution was adjusted to a pH of about 3. After the self-assembly steps (i) to (iv), the double layer again had a sublayer of the structural formula shown in Figure 2 (c) and a layer of 2 ( d) The sublayer of the structural formula. It is found that the fifth heat treatment step can produce a short total length of the pPV_ precursor polymer to form a semi-conductive polymer. The device with a polymer interface layer has a maximum efficiency of 0.73 cd / A at 6.5 volts, indicating a comparison of the conventional device improvement factor 4.6. According to the second example, the device with a semiconductive polymer interface layer has a current density of 970 mA / cm2, this is similar to the conventional device. According to the second example, the device with a semi-conductive polymer interface layer has the highest power efficiency of 0.364 lm / W at 6 volts, which indicates an increase factor of 4 6 compared to the conventional device. According to the second The device with a semiconducting polymer interface layer has the highest brightness of 7900 cd / m2 at 7.5 volts, which means that the increase factor of the conventional device is 6 〇β In the second example, multiple devices were manufactured as described in the first example, but the The number of two-layer deposition in three steps changes "A device containing 丨, 2, 4, and 10 double-layers is formed again. The device efficiency, power efficiency, and maximum brightness value are shown in Figures 3, 4, and 5, respectively. Figures 3 to 5 The middle points SP-1, SP-2, SP-4, and SP-10 indicate the results of the 1, 2, 4, and 10 double-layer devices assembled according to the second specific example. The results verify the efficiency, power efficiency, and maximum brightness. Two double layers or two pairs of semiconductive layers in Figures 2 (c) and (d), respectively In the third example, the device was manufactured as described in the first example but the polymeric anion bath in the third step contained 20 ml of water (Millipore), 16 mg of sulfonated polyaniline, 30 mg of sodium gaseous and concentrated Adjust the pH to about 11 with nitrogen; and the size of the polymer cation bath containing this paper applies the Chinese national standard {CNS) A4 specification (210X297) _ 2] 7 ~ '---------- ref- ---- π ------ Brigade (Please read the notes on the back before filling out this page) Yin Ju 425346 Λ7 __Ιί7 V. Description of the invention (19) 20 ml of water (Millipore), 17 mg of hexa- (dimethrine) desert (Aldrich), 30 mg of sodium vaporization and concentrated ammonia to adjust the pH to about η. After deposition of the interface layer, the substrate was briefly immersed in a 0.2 M hydrochloric acid solution to protonate the interface layer to obtain a conductive form of polyaniline. This third example claims a structure in which the interface polymer layer is a conductive polymer, and the double layer contains a sublayer of the structural formula of Fig. 2 (e) and a sublayer of the structural formula of Fig. 2 (f) = > The third assembled device, which contains a conductive polymer interface layer, has the highest efficiency of 0.44 cd / A at 6.5 volts, which represents an improvement factor of 2.8 over the conventional device. The device containing the conductive polymer interface layer assembled according to the third example has a current density of 1430 mA / cm2, which indicates an increase factor of 1.5 over the conventional device. According to the third example, the device containing the conductive polymer interface layer has the maximum power efficiency. A value of 0.23 lm / W at 6 volts indicates a factor of 3.0 higher than that of the conventional device. The device with a conductive polymer interface layer according to the third example has a maximum brightness of 7300 cd / m2 at 7 volts, which indicates an increase factor of 5.6 over the conventional device. Various devices were manufactured as described in the first example, but the number of double layers deposited in the third step changed again. Re-use devices with 1, 2, 4, and 10 double or paired sub-layers. In Figures 3 to 5, points CP-1, CP-2, CP-4, and CP-10 indicate the results of a device assembled according to the third specific example containing 1, 2, 4, and 10 double layers, respectively. The results verify that the efficiency and power efficiency and the highest brightness are all less sensitive than the conventional device. The improved efficiency and power efficiency are relatively insensitive to the number of double layers with conductive layers in Figures 2 (e) and (f) in the range of 1 to 10, but the use of thin The interface layer has the best brightness because the current density of the thin interface layer increases when the driving voltage is specified. A method for classifying the properties of a polymer layer by its thickness will now be described. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 cm) -22- ---- r ----- 1 ------, 1T ------ line (read first read Note on the back, please fill in this page again) 425346 Λ7 R? Central Ministry of Economic Affairs • Standard M. Member X Consumer and Du printed 5. V. Invention Description (20 This example illustrates the manufacture of organic light-emitting diodes (OLED) Schematic illustration in Figure 6), containing 5BTF8 complex (also refer to Figure 7) as a light emitting material 50; a calcium-aluminum cathode 51 and an intermediate layer based on pedOT: PSS and PPV are located beside the ITO anode 53. The silane-based coupling layer 54 (see also Figure 8) is between PEDOT: PSS / PPV and ITO 53. The device is formed on a glass substrate 55, and light is emitted through the glass when a voltage is applied between the anode and the cathode during operation. It is indicated by arrow 56. The polyelectrolyte self-assembly method is used to stack the interface layer 52. This method is particularly noticeable as an ultra-thin, continuous and conformable polymer multilayer film (preferably on a properly treated substrate), The method involves sequential adsorption (deposition) of a type of polymerization with a sign of electrostatic charge Decomposition, and then adsorb another polyelectrolyte with another symbol of electrostatic charge. Repeat the steps to form a multilayer film. Each assembly cycle consists of alternately immersing the substrate in two polyelectrolyte solutions, which are deposited in solution to form a continuous pair. Sub-layers, with a thorough cleaning step between each step. Multi-layer film bi-layers are thus assembled in each assembly cycle. The following method provides a more enhanced effect than the previous reference report. First, this method can produce a -layer intermediate layer instead of all Emission layer; this can achieve independent control previously impossible. Secondly, this method is based on the intermediate layer composition / property classification in the growth direction. 'This classification can be specially processed to achieve significant improvements in LED performance. The base trimethylol residue is subjected to a surface stone compound reaction to prepare a properly treated IT0 surface. The polyelectrolyte is self-assembled in a laminar flow box without a secret piece. The city t ρ_ 搀 箱 bribe: pss (from the paper size Applicable to China National Ladder Standard (CNS) I .1 _ 1 Pack II Order i 1 I- 丨 Line (Please read the precautions on the back before filling this page) -23- 425346 Λ7 _________ Η 7 V. Description of the invention (21) ~ (Please read the notes on the back before filling this page) Bayer) as a polymeric anion. This material contains closely related paired PEDOT and PSS polymers, with negative charge continued. The ratio of the acid radical (at pss) to the positively-charged thiophene ring (at PEDOT) is about 3, so the polymer is negatively charged to the whole. For the self-assembled pair, poly (p-_dimethyldimethylbenzyl gasified tetrahydrofluorene) is used. (Phenol 锵 KPPV-THT). This polymer can remove tetra argon at elevated temperature and stop the thiophene and hydrochloric acid to obtain a co-p-phenylene vinylene (PPV) sequence, which is beneficial to support electrical delivery (here is Hole transport) and injection through the deposited layer in a single direction, but preventing electrons from leaking through the layer and / or one or two of its adjacent layers in the opposite direction. Then spin coating was used to deposit a 860 angstrom 5 BTF8 light-emitting polymer layer, and then thermal evaporation was performed to deposit a 2000 angstrom thick calcium cathode and a 1,000 angstrom aluminum top layer. Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative, several different types of devices are manufactured to illustrate the invention. Device The control device consisted of a PEDOT: PSS hole transport layer with a thickness of 320 angstroms, which was spin-coated directly onto the ITO substrate, with an emissive layer spin-coated on p £ DOT: PSS. Device II includes a PEDOT: PSS / PPV 6-layer film deposited on a silylated IT0 substrate by self-assembly of a polyelectrolyte. 5BTF8 was then deposited on the interlayer film by spin coating. The middle layer of PEDOT is approximately completely doped (that is, highly conductive). The device II includes a 6-layer film of PEDOT: PSS / PPV, but the degree of PEDOT doping decreases during assembly, so the final double-layer PedOT is largely un-doped (ie, poorly conductive). Device IV was stacked in the same way as Device III, but an extra layer of polyethylene sulfonate / PPV was assembled as the top layer of the PEDOT.PSS / PPV membrane. Device V is stacked in a similar manner to device Π but PEDOT is largely unmixed. The PEDOT impurity concentration of the assembly solution can be easily adjusted with the hydrazine control reaction. -24- This paper is scaled to the standard of China National Standard (CNS) A4 (210X297). Printed by the Central Standards Bureau of the Ministry of Economic Affairs and printed by Industrial Consumer Cooperative 425346 Λ7 Η7 V. Description of the invention (22) 'Hydrazine can reduce p-doped PEDOT and form nitrogen as a by-product "PEDOT with such a reduced degree of doping (or usually a gradual change) can be assembled into an intermediate layer. In order to prevent the charge and ions from being transported at the same time, the intermediate layer of the formazan will cause the degree of doping. In this medium, NH4 + ions are used instead of the more active H + ions to maintain a neutral charge. The manufacture of five exemplary devices (devices 1-V) will now be described. Details of the process of the device I-V (1) ITO surface derivation uses the following procedure to prepare an ITO surface with a completely defined pH-insensitive and redox-inactive fourth security functional group: ITO-coated glass substrate (10 ohm / Square, Balzer) First to the drawing, borrow the RCA formula (water: hydrogen peroxide: ammonia, 10: 2: 〇0.6, 50--60 ° C '30 minutes) and clean 'then vacuum (i65_17 (rc, ι50 minutes) for baking to remove the physically adsorbed water, and cooling in the glove bag under dry nitrogen. When placed in the glove bag, the substrate was treated in a silylation bath (95 ° C, 2 hours) to form _ CH2CH2CH2NH2 group attached Connected to the surface of ITO. Silaneization bath (20 ml) containing 5 vol% 3-aminopropyltrimethoxysilane (Aldri) in HPLC grade methylbenzyl (AldrichK was dried on 4 angstrom molecular sieve beforehand). Then the substrate was dried Grade toluene (1x50ml) 'HpLC grade methanol (2x50ml), HPLC grade isopropanol (2x50ml) was washed in this order. Visual inspection under oblique irradiation showed no sign of hard oxygen gel formation. Care may be formed. Then the substrate is in a dark place (25t, 3 Hours) in a methylation bath and the fourth-CH2CH2CH2NH2 becomes propyltrimethylammonium ion that is pH-insensitive and inactive in gasification reduction. F-based bath paper standard tf7 national national standard (CNS) grid ( 210 \ 297 Gongchu) " ~-" Pian Shui III HJ I n —I i—11 Yong (Please read the precautions on the back before filling out this page) -25- 42534 6 Workers of the Central Bureau of Standards, Ministry of Economic Affairs Printed by Consumer Cooperative Λ7 B? 5. Description of the Invention (23 ml) contains 5 vol% methyl iodide (Aldrich) and 0.5 vol% triethylamine as acid scavengers on HPLC and Ν, Ν-dimethyl 曱 醯Amine (Aldrich). The substrate was then washed with deionized water (3x50 mL), HPLC and isopropanol (1x50 mL) and dried in a drying cabinet at 50 ° C. Visual inspection at this stage showed that the derived ITO surface remained approximately clear. (2) Preparation of PEDOT: PSS assembly solution containing controlled PEDOT doping degree Four kinds of PEDOT..PSS solution with decreasing doping degree (P1 to P4) were prepared from commercially available materials (Bayer's test product A14071). 2.0 ml of completely doped PEDOT: PSS dark blue solution (1.6 w / v% total solids) was reacted with 55 w / v% hydrazine hydrate (Aldrich) with the following volume: 0.00 ml (without) preparation material P1, 20 ml of preparation material P2, 1.0 ml of preparation material P3, 8. 0 ml of preparation material P4; each was placed in a sealed amber shot vial together with a sufficient amount of distilled water to adjust the total reaction volume to 100 ml, and the reaction mixture was warmed to 7 0 ° c for 3 hours, during which PEDOT was removed. The solution was then left overnight. Did not see Shen kill. Measurement of the UV absorption spectrum of the resulting solution (shown in Figure 9) indicates successful selective doping. The IM solution spectrum is characteristic of fully doped pEDOT (about 30% doped), while the characteristics of the P4 solution are not doped with pEDOT (ie, about 0% doped). The spectra of P2 and P3 are somewhere in between, since the corrected intensity of the 620 nm π-π * transition is estimated to be approximately 25% and 200 /, respectively. . Four linear probes are arranged on a micron-thick film cast on a glass substrate to measure the DC paper size of this paper is applicable to China National Standards (CNS) Λ4 specifications (210x297), -26- 1 n. I i It II i I:-1 n ice (please read the precautions on the back before filling in this page) Λ7 425346 R? V. Description of the invention (24) The conductivity is also in accordance with the decreasing degree of impurity: P1 is 1.0 S / cm, P2 is 0.01 S / cm, P3 is 0.008 S / cm and P4 is 0.004 S / cm. In order to prepare the PEDOT: PSS assembly solution, each 9.5 ml of PI to P4 solution was mixed with 10 ml of 50 mM sodium hydroxide aqueous solution to fix the final ionic strength at 25 mM. The pH was adjusted to 11 by adding 50 microliters of 35 w / v% ammonia solution. . This gives about 0.15 w / v% total polymer solids in the assembly solution. The vaporized sodium solution is prepared with deionized water. The ionic strength of the solution is 25 mM, which removes the effects of free impurities from commercial polyelectrolytes and provides a self-assembled constant ionic background. (3) Preparation of PPV-THT assembly solution For preparation? ?乂 -Butyl ^ assembly solution, 2.05 g of poly (p-xylyltetrahydrophenanthrene hydrochloride) in methanol solution (1.1 w / v% total solids, prepared according to standard reference procedures, for example, reference RA Wessling, "Polymerization of Dixylyl Dialkyl Sulfonate 5", Polymer Science Journal, Polymer Symposium 72, 55-66, 1985) Mix 18 ml of 25 mM sodium gas solution and add 50 μl by borrowing Adjust the pH to 11 with a 35 w / v% ammonia solution. Therefore, the PPV-THT content of the assembly solution is about 0.1 w / v%. (4) Self-assembly of polyelectrolyte In order to form an interlayer film, self-assembly of polyelectrolyte is performed in a laminar flow box at room temperature (22 ° C) within 2 hours after the preparation of the polyelectrolyte solution. (a) In order to assemble the two-layer intermediate layer of device 115, the ITO substrate after derivatization was immersed in P1 solution for 10 minutes, and vigorously washed in 2x30 ml of fresh deionized water for 1 minute; then immersed in PPV-THT solution for 10 minutes. , And finally washed in 2x30 ml of fresh deionized water for 1 minute. This cycle is repeated 5 times. This paper size is applicable to the Chinese National Standard (CNS) Α · 4 specification (2ίΟΧ297 公 尨) ----------- ¢ ------ 'Order ----- -. ^ (Please read the notes on the back and fill in this page first) Printed by the Central Bureau of Accreditation of the Ministry of Economic Affairs, Bei-Gong Consumer Cooperative, 42534 6 Λ7 B7 V. Description of the invention (25) And the assembly is completely mixed with PEDOT: PSS / PPV 6-double-layer film on ΠΌ anode "(b) Before device III, the three double-layer intermediate layers are manufactured in accordance with the above-mentioned device II. Then the PEDOT: PSS assembly solution was changed to P2 for the next assembly cycle, then to P3 and finally to P4. The ideal composition of the polymer multilayer film thus obtained is 3 bilayer 30% doped (completely doped) PEDOT, followed by 1 bilayer 25% doped PEDOT, then 1 bilayer 20% doped PEDOT, and finally 1 bilayer undoped PEDOT . (c) Six double-layer interlayer films before Device IV were made as described above for Device III. Subsequent additional assembly cycles of the polymeric anionic solution in poly (styrene sulfonate, sodium salt) followed by the polymeric cationic solution of PPV-THT are used to assemble the top layer of PSS / PPV on the PEDOT: PSS / PPV membrane. Poly (styrene sulfonate) solution was prepared by adding 24 mg of poly (styrene sulfonate, sodium salt) (molecular weight = 70,000; obtained from Aldrich) to 20 ml of a 25 mM sodium vaporized solution. Manufactured by adjusting the pH to 11 with 35 w / v% ammonia solution. When the assembly process is completed, the substrate is transferred to a vacuum heating device, placed inside the glove box and baked at 70 ° C in a dynamic vacuum (pressure less than 10-6 mbar) for 2 hours and expelled by a self-assembled polyelectrolyte membrane Loosely bound water molecules and convert the PPV-THT moiety into a short conjugated segment of the oligo-p-phenylene vinylene sequence. It was found that higher baking temperatures can produce significantly unproductive leakage currents during low-voltage operation of the device. All subsequent steps are performed in the glove box. (5) Emission polymer and metal cathode deposition A 860 angstrom 5BTF8 film was spin-coated at 1400 rpm from a 1.5 w / v% p-xylene solution on top of a self-assembled polymer film. 2000 Angstrom calcium layer at 20 Angstroms per second at a base pressure of 1 (T6 mbar thermal evaporation by shallow anti-corrosion layer on the basic paper size of each device applies Chinese National Standard (CNS) A4 specification (210 × 297 cm)) --'- -------- ^ ------ 1Τ ------ ^ (Please read the notes on the back before filling out this page) Member of the Central Standards Bureau of the Ministry of Economic Affairs-" Printed by Consumer Cooperatives-28 -425346 A7 —-------________ ιυ Description of the invention (π) 8 M square millimeter (namely) light-emitting diodes are defined on the material. Then a thin aluminum protective layer with a thickness of 1000 Angstroms is evaporated on calcium (6) Control device The double-layer control device I was prepared by preparing an ITO-cleaned ITO substrate and spin-coating a 320 angstrom pEDOT: PSS film on a substrate at a rate of 1850 rpm from an 0.8 w / v% aqueous solution. Then, Bake at 70 ° C as indicated in part (4), and then deposit a 860 angstrom 5BTF8 film as described in part (5), and then deposit a 2000 angstrom calcium layer and a 1,000 angstrom aluminum protective layer. All the five devices are manufactured in the same batch due to the change in the scattering. Figures 10-14 show the typical performance of device IV. The above figure shows the device brightness and the passing device. Current density plotted against the applied voltage with respect to

I. The lower graph of each figure shows the power efficiency and the quantum efficiency of the device as a function of applied voltage. The following table summarizes the driving voltage and power efficiency of each device at the selected brightness. The data are obtained by averaging 3-4 devices of various types. ----------- Install ------, 玎 ------ ^ (Please read the notes on the back before filling out this page) Employees' Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Printed drive power efficiency to 10 to 10 to 100 to 100 to 1000 P to 1000 cd / m2 cd / m2 cd / m2 cd / m2 cd / m2 cd / m2 cd / m2 drive power efficiency drive voltage power efficiency drive voltage efficiency voltage (V) (lm / W) (V) Rate (lm / W) (V) (lm / W) Device 1 3.5 Device Ϊ 3.3 Device III 3.1 Device IV 3.1 Device V 3.4 0.6 5.1 23 4.0 20 3.8 17 3.8 21 4.5 2 2 12 11 lx 1 7- * sc5 * ri5-r ^ 6 00 0 5 The result indicates that the middle layer of PEDOT: PSS / PPV is compared separately. -29- This paper size applies Chinese National Standard (CNS) A4 specifications ( 2〗 × 297 Male f > 425346 A7 H7 V. Description of the invention (27) The power efficiency of the control device stacked with PEDOT: PSS is significantly improved. From the above table, it can be seen that the low driving voltage of about 3-4 V and about 1 〇Cd / m2 brightness, intermediate layer II to V can achieve 30 to 40 times improvement in power efficiency. At lower voltages, the efficiency of the device is higher. Just after the device is turned on, it is easy to reach 20-30 lm / Power efficiency of W (Refer to Figure 15 for the power efficiency versus brightness of the device.) The power efficiency decreases with the increase of the driving voltage and brightness. However, even at 1000cd / m2, the high brightness can still achieve an improvement over the control device 2 To 3 times. One way to move the high Im / W value to high brightness is to increase the thickness of the 5BTF8 layer. The special thickness can be increased to about 1,000, 12,000, 1500, or even about 2000 Angstroms. PEDOT: PSS The / PPV intermediate layer structure is believed to provide hole transport but electronic blocking function, which helps to recombine the charge and assist in limiting the excitation emission layer. The semi-conductive pPV layer in the layered PEDOT: PSS / PPV assembly is particularly terminated The layer believes that it plays an important role in this aspect. The semi-conversion PPV is expected to have a LUMO degree of electron transport that is tens of electron volts higher than that of PEDOT, F8BT and F8 (refer to Figure 16a). .The electron of Dongdong is better than the device to redistribute the electric field to improve the balance of the electrons and holes injected into the device. The ppV layer can also help to isolate the subsequent excitations that do not directly contact the ITO anode. Non-radiation loss. In its aspect, PEDOT provides hole transport function to the middle layer, assisting with the emission layer to shoot holes through the middle layer β net effect for electron-hole balance plus electron-hole complement improvement and radiation recombination department Serving high. It is believed that this can lead to an improvement in the power efficiency observed in the middle layer device. As a result, the driving voltage of the transport layer required for the selected light output is applied to the national standard (CNS > A4 specification (21〇x297; ^ ~ y ------ --.----) for this Bλ degree). --- Private clothing ------ ΐτ ------ ^ (Please read the notes on the back before filling in this page) Employees of the Central Standards Bureau of the Ministry of Economic Affairs printed by the cooperative 42534 6 Central Standards Bureau of the Ministry of Economic Affairs Printed by Shelley Consumer Cooperative Λ7 ____ ιυ __ 丨 _ 1 ··-·· -—— ·· ».«,-,,----J_________ ♦ One_One_Five 'Invention Description (28) — The t-layer device is significantly reduced. This is highly desirable because it can reduce the electrical stress during the device's operation, which usually results in an extended operating life. The decrease in drive voltage is most pronounced for graded middle-layer devices III and IV. For example, The voltage required for the 1000 cd / m2 voltage drop was reduced from 7.1 volts in the control device I to 6.3 volts in the middle layer device, and to 5 5 volts for the graded intermediate layer devices 111 and 1 ¥. With electronic graded intermediate layer The improvement of the device has greatly facilitated the easy injection of current, together with a small increase in power efficiency, which has reduced the proportion of the impact. It is clearly verified in Figure 7 that it is a pass The plot of current density versus applied voltage across different devices '' and Figure 18 are plots of drive voltage versus brightness for various devices. It is therefore clear that the classification of electronic properties can be established in the middle layer, and this classification can be improved OLED performance. It is believed that the conductivity or HOMO concentration classification of the hole transport can produce the situation schematically shown in Figure i6b. The intermediate layer is manufactured in which the hole- or electron transport-like ill is closely matched with the energy of her neighboring layer during the close match (and (Or graded nature), which can reduce the mismatch of thermodynamic energy of charge transport between adjacent layers of RTT. The thermodynamic barrier of the injection interface is compared with the conventional double-layer device (such as the use of a completely doped PEDOT layer, which generates a PEDOT layer and emission). The electronic steep interface between polymers) can reduce and reduce the steepness. It also prevents the electric field from appearing at the interface by allowing the gradual change of the intermediate layer itself. This can reduce the accumulation of charge on the interface, which often leads to increased device degradation. This kind of spatial classification of the electronic properties of the intermediate layer can allow the OLED to reach a lower driving voltage. Into a more balanced electron-hole injection. As mentioned above, at least one polymer layer has electronic and / or optical properties and its thickness changes across the layer. Some aspects of this aspect of the invention are better (but this paper is also suitable for China) National Standard (CNS) A4 specification (210X297 male-slave) • —II »I · n I _ >„ -¾ clothing-(Please read the precautions on the back before filling this page) I. ^. -31- Economy Central Prototype Bureau of the Ministry of Industry and Engineering Cooperative Printing Co., Ltd. 425346 A7

---- --- --__ IM V. Description of the invention (29) ^-Necessary) The general properties will be described later. Preferably, when the polymer layer includes a series of two layers, each layer is composed of two components, one of which is preferably a semiconductor (for example, pPV) and the other is preferably conductive (for example, PEDOT-PSS). The semiconductor (if present) preferably provides the energy level between the conductive material (if present) of the device and the emitting material. Preferably, the sublayer adjacent (or closest) to the emissive material is a semiconductor sublayer. There may be another layer (such as a conductive layer) between the last sublayer and the emissive material. The composition of the continuous double layer need not be the same, for example, different conductive materials can be used in each layer. One or more of the two layers may be substituted with more than two sublayers. Each sublayer is suitably made of a polymer material, preferably having a polymer chain depth (the exact thickness is determined by the configuration of the chain). In some preferred embodiments, the conductive energy level of the conductive material is changed between continuous double layers, and it is better to increase or decrease the HOMO or LUMO level between the continuous double layers toward the emitting material. Especially if the properties of the conductive material are changed in this way, another layer can be deleted and in fact the double layer can be replaced by a single layer. The process can be applied to devices other than light-emitting devices, especially for devices where charge injection is to be improved. It is believed that PSS can be doped with PPV to some extent. If PPV is converted by baking due to high temperature such as higher than 1 oo ° C, the degree of doping will increase. It should be noted that the middle layer device shows a clear (diode, etc.) conduction characteristic, similar to the conventional double-layer device, but opposite to the single-layer 5BTF8 device. Importantly, the present invention allows for precise control of electronic properties (e.g., doping of degradation) and grading effects. This method provides a layer-by-layer exploration technique to deposit an intermediate layer with a controlled change in one or more electronic and / or optical parameters. The paper size of this parameter applies to Chinese national standards (CNS > A4 specifications (210X297 mm)- 32- ------- ^ ------ ΪΤ ------ ^ (Please read the notes on the back and fill in the page first) Staff of the Central Standards Bureau of the Ministry of Economy 425346 Λ7 —---- 一 _______ 5. Description of the invention (30) For example, energy level or energy level distribution (especially responsible for charge carrier transport), effective work function 'electron affinity, dissociation energy and / or cross the middle layer Band gap of thickness. By matching one or more of these parameters with one or more material characteristics of the intermediate layer adjacent to the finished product of the device, excellent control over the height and width of the barrier (such as an energy barrier) can be achieved. Then additional control parameters can be provided while The best performance of light-emitting devices (especially organic light-emitting devices) can be obtained in terms of brightness, efficiency, lifetime, driving voltage, and / or color. This method also explores composition classification as a parameter matching that allows molecular interaction. Means of materials on both sides of the interlayer, so the predetermined adhesion between the two materials in contact with the intermediate layer can be maintained. The device performance can be further optimized. This method of grading the thickness of the PEDOT-PSS layer can be applied to other materials for special polymerization (Including oligomers). This method can be used to provide one or more of the following property changes through layer thickness: composition, doping concentration, electron affinity, dissociation potential, work function, band gap and molecular interactions to control charge injection and And / or adhesion. Preferably this change is provided by a PEDOT-PSS layer containing multiple sublayers with different compositions. Other materials can be used in devices that embody the foregoing principles. For example, itemization or other appropriately derived polyaniline 'poly Thiophenes' poly (vinylcarbazoles), poly (vinylnaphthalenes), and materials based on these or other materials.

In light emitting devices, the grading layer is suitable to be adjacent to the luminescent material, and may be located at the interface between the anode or contact anode layer (such as PEDOT) and the luminescent material; and / or at the cathode or the interface between the cathode layer and the luminescent polymer; and / or Interface between layers of luminescent material. The thickness of the classification layer is suitable for the range of 5 to 1000 Angstroms or more and preferably 5 to 200 Angstroms or more. D This paper size is applicable to the Chinese National Standard (CNS) Λ4 grid (210X297 cm), • Gutter ( Please read the notes on the back before filling out this page) -33- Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 425346 Λ7 ----— H? V. Description of the invention (31) * ~ ^ _ The classification layer is suitable for The polymer is preferably a polymer intermediate layer. Hierarchical layers are suitable for depositing a series of sublayers with different properties (such as different compositions) or for depositing a layer (or a series of sublayers) but using some or all of the steps or only the last deposition step followed by-modifying at least the last deposited layer / Sublayer properties are formed. Each layer or sublayer can be in the form of a film &amp; graded layer finished product is suitable for compositional changes in thickness direction. This results in a change in the electronic or molecular properties across its thickness. The spatial variation of the composition may be diffusive or steep, and may extend through all or part of the thickness of the layer. For example, changes can come from two or more complete discrete chemical entities (such as PEDOT and PPV, such as device I) set to change in a sequential manner 'or continuous changes in the degree of doping or dedoping of interlayer materials (such as device II-IV PEDOT has different degrees of charge on the main chain. When the layer is first manufactured, there may be a composition change, or it may be induced by physical and / or chemical treatment after manufacturing, such as exposure to electromagnetic radiation (such as ultraviolet radiation), Or high-energy particles such as those contained in plasma, or chemical reactions limited by one or more of diffusion, stereochemistry, time, reactivity, and concentration. In order to verify the advantages of the present invention, an ultra-thin polymer based on the present invention The general principle of the intermediate layer and the stepwise conveying intermediate layer, using the self-assembled changing materials to construct a large 16 mm square device. All the following devices contain spin-deposited 800 angstrom 5BTF8 as the emission layer and 1000 angstrom calcium overlaid with protective 5000 The anode contact of Isilin. A total of 24 pixels are manufactured for each type. Device X: ITO / ammonium propyl silane silyl coupling layer / (PEDOT: PSS / PPV-THTMPSS / PPV-THTVSBTFS / Ca / Ag. This paper size is applicable to China National Standard (CMS) A4 specification (210X297). -34- ----- L ----- Packing ----- -Order ------ Travel & <Please read the precautions on the back before filling out this page) Standards-Associate staff-Printed by Consumer Cooperative 425346 Λ7 ______ Η 7 V. Description of the invention (32) This device has super Thin (less than 100 angstroms) charge injection intermediate layer at the ITO anode interface, which is made of uniformly conductive polymer in an intermediate layer completely doped with PEDOT: PSS and covered with an ultra-thin (10 angstrom) half provided by PPV-THT Conductive layer. Device Y: ITO / ammonium propyl silane silyl coupling layer / (PEDOT: PSS / PPV-THTVfPSS / PPV-THTVSBTFS / Ca / Ag. This device has an ultra-thin charge injection intermediate layer with graded transport The profile is manufactured by sequentially removing the hybrid of PEDOT: PSS during the growth period and finally covering it with an ultra-thin semi-conductive layer provided by PPV-THT. Device Z: ITO / PEDOT: PSS / 5BTF8 / Ca / Ag. This is a comparison device. The performance of devices X and Y is compared with this device. A 500 Å thick PEDOT: PSS layer was deposited by spin coating. Figures 19-21 show the typical performance of devices X to Z. The data clearly show that the control device can be obtained by manufacturing the device X with PEDOT: PSS / PPV ultra-thin porous transport layer (less than 100 angstroms) deposited by alternating polyelectrolyte adsorption. For similar performance, the control device is manufactured by the conventional spin-coating method with a much thicker PEDOT: PSS hole delivery layer. The highest brightness efficiency of device X is 5 lm / W, which appears at a driving voltage of 4.0 volts and a light output of 20 cd / m2, which is very similar to the control device z. Obtains rather slow conduction characteristics. The driving voltage required for 1000 cd / m2 is similar to the two cases (5.0 volts), at which time a driving current density of about 10 mA / cm2 passes through the device. At higher voltages, ‘ultra-thin Å’ PSS / PPV cover layers increase the resistance of the device and thus limit the drive current. This paper scale is applicable to China's standard of housekeeping (CNS) AUiL grid (210X297 male waste) -35- --.-------- seed clothing ------ ΐτ ------ ^ ( Please read the precautions on the back before filling this page) 425346 ^ Λ7 __H 7 V. Description of the invention (33) &quot; 'Comparison device X, device Y display brightness efficiency, which significantly improves the selected voltage through the device's drive current . Comparing the other two devices in this way can significantly increase their light output. The maximum brightness efficiency is about 13 lm / w at 30 volts. The clear continuity of device performance appears at 2_1 volts. The light output of 100 cd / m2 was achieved at 45 volts, and a current density of 10 mA / cm2 was obtained. Results verification can explore the significant changes inherent in the design principles of the present invention. The performance of LEDs can be improved through proper selection of materials and proper manufacture of ultra-thin charge-injection intermediate layers, and control and classification of transport properties in the thickness direction of this layer. ----- ~ Installation—— (Please read the precautions on the back before filling this page) Order ------ Wei M Ministry of Economic Standards 扃 Printed by Employee Consumer Cooperatives -36- This paper size applies to China Standard (CNS 丨 A4 specification (210X297)) 425346 Λ7 m V. Description of the invention (34 Component number comparison 2. Glass substrate 4. Indium tin oxide layer 6. Coupling layer 8 .... .. Interface layer 10... Emitting MEH-PPV layer 5 0 ... Emitting material 51 ... Calcium-aluminum cathode

52..PEDOT: PSS / PPV intermediate layer 53..1.O anode 54..silyl coupling layer 55..glass substrate 56..arrow (please read the precautions on the back before filling in this Page) * -ρ Γ Printed by the Central Bureau of Standards, Ministry of Economic Affairs, χ · Consumer Cooperative, -37- This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X297mmt)

Claims (1)

425346 Αδ Β8 C8 m 89. 8.24 Amendment VI. Application for Patent Scope No. 8711S410 Patent Application Amendment for Patent Scope Amendment Date: August 89 (Please read the notes on the back before filling this page) 1 · One A method for manufacturing an organic light-emitting device, the method includes the following steps: forming a first electrode of a device on a substrate; forming at least one polymer layer on the first electrode through self-assembly; and forming at least one organic light-emitting material without self-assembly Layer on the at least one polymer layer, and form a second electrode of the device on the at least one organic light emitting material layer; or form at least one organic light emitting material on the first electrode by self-assembly, and form at least one by self-assembly A polymer layer is on at least one organic light emitting material layer; and a second electrode of a device is formed on the at least one polymer layer. 2 * The method according to item 1 of the patent application scope, which further comprises removing physically adsorbed water from the surface of the substrate before forming at least one polymer layer. Line 3 · If the method in the scope of the patent application is applied for item 2, it will cause the physically adsorbed water to be removed by heating and printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The method further comprises forming a coupling layer before forming at least one polymer layer. 5_ According to the method of the patent application No. 4, the coupling layer is formed by a siliconized substrate. 6. The method of claim 1, 2 or 3, which further comprises preparing the surface of the substrate such that the surface charge of the substrate is independent of pH. 7- The method of applying for the scope of patents I, 2 or 3, wherein when the substrate contains ^ paper size, the Chinese National Standard (CNS) A4 specification X 297 is issued. 38 Printed by the Employees ’Cooperatives of the Ministry of Economics and Smart Finance I Bureau 425346 I ____ DS 6. When applying for a patented amine group 'The method further includes a quaternized amine group to form a positively charged quaternized species on the surface. 8. The method of claim 1, 2, or 3, wherein when the substrate contains a sulfo group, the method further includes a step of oxidizing a sulfonium group to form a negatively charged species on the surface. 9. If the method of applying for a patent scope item 1, 2 or 3 'wherein the substrate comprises a glass or plastic substrate "10. If the method of applying for a scope of patent application item 9 wherein the plastic material comprises a polyester' polyphosphatic acid ' Ester or poly (_amidamine)-or more. 11. The method of claim 1, 2, or 3, wherein the at least one self-assembled polymer layer includes one or more pairs of sub-layers that cooperate together. 12. The method of claim 11 in which the one or more pairs of common sublayers interact with each other through attraction, and the sublayers are different from each other. 13. The method of claim 12 which applies a negative charge to one of the sublayers in a pair and a positive charge to the other sublayer in the pair. 14. If the method of patent application park is called the method, in which the sub-layer of one or more pairs of cooperation is interacted by the giver / receiver interaction. The donor / recipient interaction is provided by hydrogen bonding. 16. If you apply for the method of phase money, the sub-layers of the paired sub-layers are 0.3-2 nm thick. 17. If you apply for the method of item 1, 2, or 3 in the scope of patent application, wherein the paper size of this at least one layer is applicable to China IA Standard (CNS) A4 specification (0—297 mm) ------- ----- β -------- Order --------- line &lt; Please read the notes on the back before filling in this page) -39- A8B8C8D8 425346 0.3-20 nm thick. For example, the method of claim 1, 2 or 3, -.u wherein the organic material comprises a conjugated polymer and / or a low molecular weight compound. 19. The method according to item 18 of the scope of patent application, a semi-conductive co-consumptive polymer. The organic material in the method includes the method according to item 19 of the patent application, and the organic material includes PPV or a derivative thereof. 21 'The method according to item i, 2 or 3 of the scope of patent application', wherein the at least one layer of organic light-emitting material is 30-1000 nm thick ^ 22. A method for manufacturing an organic light-emitting device, the method includes the following steps to form a device The first electrode is on the substrate; the physically adsorbed water is removed from the surface of the first electrode to form a layer coupling layer, and at least one polymer layer is formed on the first electrode by self-assembly; and at least one organic light emitting material layer is formed on the at least one layer. -A polymer layer; or forming at least one organic light emitting material layer on the first electrode, removing physical adsorbed water from the at least one organic light emitting material layer, forming a coupling layer, and forming at least one polymer layer by self-assembly The at least one organic light emitting material layer; and forming a second electrode of the device on the at least one organic light emitting material layer. 23. The method of claim 1, 2, 3, or 22, wherein the at least one polymer layer has electronic and / or optical properties that change across the thickness of the layer. The paper's wattage is subject to the Chinese National Standard (CNS) A4 specification. (210 X 297 mm)-I ----- 3 ^ ·· — —! — Order --I --- IJ ί Please read the notes on the back before filling out this page) Employees ’Consumption of Intellectual Property, Ministry of Economic Affairs Printed by the cooperative -40- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 425346 ns C8 ----™ ________ VI. The scope of patent application. 24. The method of claim 23, wherein the method additionally includes the step of processing at least one polymer layer to form a spatial change in electronic and / or optical properties. 25. The method of claim 24, wherein the at least one polymer layer comprises a conjugated material; and the step of forming a spatial change in electronic and / or optical properties includes reducing the conjugated degree of the conjugated material. 26_ The method of claim 24, wherein the step of treating at least one I layer includes exposing the polymer layer to a reactant to promote a chemical reaction in the transport layer. 27. The method as claimed in item% of the patent application, wherein the reaction is an oxidation or reduction reaction. 28. The method of claim 26, wherein the reactant is an oxidizing agent. 29. The method according to item 26 of the patent application, wherein the reactant is oxygen. 30. The method according to item 26 of the patent application, wherein the reactant is a plasma. 31. The method of claim 23, wherein the step of forming at least one polymer layer includes forming the polymer layer with electronic and / or optical properties across a state where its thickness changes. 32. The method of claim 31, wherein the polymer layer is deposited into a series of sublayers. 33. The method according to item 31 of the scope of patent application, wherein the polymer layer is a novelty of the paper size (CNSM4 specification (210 · 297 mm) ------------ ^- ------ Order -------- line &lt; Please read the notes on the back before filling this page) -41- 4 2 5 3 4 6 A8 R8 C8 D8 Consumption by Employees of Intellectual Property Bureau, Ministry of Economic Affairs Cooperative printed 6. The scope of the patent application is accumulated-a series of double-layer forms, each of which contains two layers of different materials. 34. The method of claim 31, wherein the polymer layer is deposited and comprises a series of material sub-layers whose electronic and / or optical properties are different from each other. 35. The method of claim 34, wherein the properties of the material sublayer are graded across the thickness of the polymer layer. 36. The method of claim 34, wherein the material comprises poly (styrene sulfonic acid). 37. The method of claim 34, wherein the sublayer is doped to achieve differences in electronic and / or optical properties. 38. The method of claim 36 in the scope of patent application, wherein in at least several of: Yatang Zhong poly (benzyl sulfonic acid) is doped with poly (ethylene ethoxyphene). 39. The method according to item 23 of the patent application, wherein the property is energy level or energy level distribution. 40. The method according to item 39, wherein the property is dissociation potential. 41. The method of claim 23 in the patent scope 'where the dissociation potential of the polymer layer in the direction from the-electrode to the light emitting layer deviates from the conductivity of the electrode to be changed "42_ The method of patent scope 23 The dissociation potential of the polymer polymer in the direction from the _th electrode to the light-emitting layer changes toward the HOMO degree of the light-emitting layer. 43. The method according to item 23 of the scope of patent application, wherein the light-emitting paper size of the light-emitting layer is in accordance with China National Standard (CNS) A4 (210 X 297 mm) ---------- II Agricultural ------ I— Order ----------- Line (Please read the precautions on the back before filling this page) -42- A8B8C8S 425346 6. The scope of patent application is based on the first electrode The direction to the second electrode changes. 44 · —A kind of manufacturing is carried before self-assembly? 11 Method of Correlating Surface Charge with Surface 'This method includes a step of treating the surface so that the surface charge becomes independent of pH. 45. A method of preparing an amine-containing surface before self-assembly, the method comprising the step of quaternizing the amine group. 46. A method for manufacturing a surface containing a base before self-assembly, the method comprising the step of oxidizing the base. 47. An organic light emitting device, which is obtained according to a method as defined in item 1, 2, or 3 of the scope of patent application. 48. An organic light-emitting device comprising: at least one organic light-emitting material layer interposed between a first electrode and a second electrode; at least one organic light-emitting material is not formed by self-assembly; and at least one polymer layer The at least one polymer layer is formed between one of the first and second electrodes and at least one organic light-emitting material by self-assembly. 49. The organic light-emitting device according to item 48 of the patent application park, wherein the at least one polymer layer has electronic and / or optical properties that vary across the thickness of the layer. (Please read the precautions on the back before filling out this page) Clothing -------- Order --- I ----. Consumption cooperation between employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed This paper applies Chinese national standards (CNS) A4 size (210 X 297 males) -43-