TW488095B - Organic light emitting diode, transparent electrode substrate and manufacture method - Google Patents

Abstract

This invention provides a manufacture method of the transparent electrode substrate containing organic functional groups of indium-tin-oxide-silicon on the surface. An aqueous solution of a siloxane type compound with a specific concentration is prepared, which is used to immerse an indium-tin-oxide (ITO) transparent substrate with a surface containing hydroxyl group for a specific period of time to form the transparent electrode substrate containing organic functional groups of indium-tin-oxide-silicon on the surface. This invention also provides an organic light emitting diode of the transparent electrode substrate containing organic functional groups of indium-tin-oxide-silicon on the surface.

Description

Description of the invention (1) [Background of the invention] The invention g The invention relates to an organic light emitting diode which can accelerate the hole transfer and improve the quality of a hole. In particular, it refers to a kind of organic light emitting diode: the life of the body m pieces High-resolution substrate with high luminous efficacy and its manufacturing method; 4 ;: Department; ==: A kind of transparent electrode electrode plate and organic conjugated polymer II; the transparency of the organic material and its manufacturing method. A transparent electrode substrate with surface-bound tightness J1 Description of the know-how 1 990 Research group of the University of Cambridge, England, found poly-styrene

The polymer material of Cp〇1 [(p-—Phenylene Vlnylene; pv)] can be used as the material of the light-emitting layer of the bipolar monopolar body, which has caused a boom in the research of organic electroluminescent display technology worldwide. Due to the organic electroluminescence display technology, in addition to the thin and light, low power consumption and high resolution of modern LCD displays, its essence has superior wide viewing angle characteristics, high response speed and high brightness and darkness ^, and has a simple process. And the advantages of low cost. In addition, the excellent ultra-thin film-forming properties of polymers can be used to produce very thin and flexible light-emitting devices. I believe that the dream of rollable displays will be realized in the future. Polymer light-emitting diodes are based on a polymer whose light-emitting layer (light-emitting portion) is generally called PLED (polymer light emitting diode), and a conventional polymer light-emitting diode (organic light-emitting diode). The system mainly includes a substrate, a transparent electrode layer, a light-emitting portion, and a metal electrode layer. The transparent electrode layer, the light-emitting portion, and the metal electrode layer are sequentially formed on the substrate. Generally speaking, the transparent electrode layer is composed of an indium tin oxide (I τ 0) electrode.

Page 4 V. Invention description (2) --- It is composed of layers, ITO is a semi-transparent and high work function electric 4, hole-injection positive electrode material, which is an inorganic material, / 同 / The main main light-emitting part is mainly formed by an organic polymer. As mentioned above, ^ I of general inorganic compounds and organic compounds. =. Because = the joint surface # 7 between the I T0 electrode substrate and the organic conjugated polymer layer has a problem that it is not easy to dissolve each other, which easily causes the light-emitting characteristics to not be improved. How to develop new technologies to improve the joint surface is really important to solve the inorganic matter. The type of I T0 electrode substrate is next to the right. A Oobinhachi Kogata See the poles ... k You Biao's organic matter The problem of the interface of the factory yoke knife. Generally, a low-conducting Leigu eight conductive layer is used to reduce the ^ A car's low-voltage electric knife as electricity and luminous efficiency. Layer = this barrier, in order to improve the stability of the device ..., and 'this method still has the following disadvantages: high scores; t ^: machine-inorganic interface problem could not be solved, because the newly added interface bonding problem belongs to organic substances and inorganic When the type ITO substrates still exist, because there are two or two, the electrostatic suction bow formed on the I το electrode substrate by the spin coating method. I force: interface problems will cause the organic polymer to rotate only with the weak material. Ling H1 τ〇 on the electrode substrate, so that most of the high score ~ Fuyu cloth waste. [Summary of the Invention] The purpose of the present invention is to provide an organic interface junction door which can effectively solve organic and non-transparent substrates of the present invention and a method for manufacturing the same. The object is to provide a method for accelerating hole transfer and improvement.

488095

Organic light-emitting diode with high light-emitting diode lifetime and light-emitting efficiency. -A feature of the present invention is to provide a transparent electrode substrate having an indium tin-oxygen-silicon functional group on its surface and a method for manufacturing the same. Indium tin body. Another feature of the present invention is to provide an organic light emitting diode / electrode including a transparent electrode substrate having a surface and an oxygen-silicon-organic functional group. [Detailed description of the preferred embodiment] The following is a detailed description based on the drawings. A preferred embodiment of the present invention. Electrode substrate and its manufacturing method · The present invention adopts chemical methods to improve the problem of inorganic type 丨 To electrode substrate / organic conjugated polymer interface, the principle is: 2 tin oxide surface on the ITO electrode substrate and the air After water molecules are in contact, they are liable to carry hydroxyl groups on the surface of their substrates, so they are mixed with silicon-containing alkoxy compounds such as ^ glycidylpropyldimethoxy 甲 silane [3 — glycid 〇xypr〇pyi (dwethoxy) methylsilane], N-phenylaminopropyltrimethoxysilane, or 3- (2-aminoethylamino) propyltrimethoxysilane and the like seem to be used at first, then ΙΤ0 The hydroxyl groups on the surface of the substrate easily interact with silicon-containing alkoxy groups, and the alkoxy groups leave, so that the oxygen of the hydroxyl groups is combined with silicon, and then the surface modification compound of the indium tin-oxygen-silicon bond is formed. This bond is a covalent bond, which is a strong bond. Therefore, it is possible to closely combine the beauty of the IT0 electrode, which is an inorganic type, with this stone-containing compound. In addition, the alkoxy-type soil compound containing this stone, The other end is a functional group that is soluble in organic matter, such as epoxy group, 1 group and alkyl group. 'If organic polymer is formed into a film by spin coating method 488095 V. Description of the invention (4) = No electrode substrate modified on the surface, because after modification, the end is… which is contained in organic functional type I, so It can be easily bonded to organic, ytterbium molecules. Therefore, silicon-containing alkoxy compounds are like the arm of a human's which contains Shi Xixuanoxy group, so it can be combined with inorganic type] 仞 electrode substrate And the other end contains organic-type functional groups, so it can be combined with a polymer-consumptive polymer. Through this cross-linking, the interface tightness between the inorganic ITO electrode substrate and the organic conjugated polymer interface can be increased, which can accelerate the electricity. Hole transfer improves device life and luminous efficacy. The following is a detailed description of the method for manufacturing a transparent electrode substrate according to the present invention by taking 3- (2-aminoethylamino) propyltrimethoxysilane as an example 'and referring to FIG. 1. In the examples, "Silicon-containing alkoxy compounds used in immersion substrates (I τ 0 electrode substrates) were first dissolved in water, for example, 3- (2-aminoethylamino) propyltrimethoxylithium. To form a concentration as 〇 · 〇1 ～ 1% (v / v) of aqueous solution containing cyanine-containing dazzling milk type compound. After that, an IT 0 electrode substrate with a nitrogen oxide surface and a silicon-containing alkoxy type dissolved in the aqueous solution The compound reacts. The entire reaction time is 5 minutes. At this time, as shown in FIG. 1, the lone electron on the oxygen oxygen atom of the hydroxyl group in the surface of the ITO electrode substrate having the hydroxyl group easily attacks the silicon-containing alkoxy type. The silicon atom of the compound is further removed; the methoxy group on the 5th atom leaves in the manner of methanol (CH3OH) to form dioxy_ Fossil and bad milk-based stone burned steel tin-oxygen ~ Shixi In addition, because the methanol produced in the anti-deer is easy to dissolve in the aqueous solution, and because of the low concentration of methanol, it is not easy to attack the silicon containing the alkoxy compound containing silicon and indium tin oxide Atoms, so the formed indium tin-oxygen ~ silicon bond can stably exist

Page 7 V. Description of Invention (5) Yes. Tin, oxygen-silicon bond ί: 1Γ f: 'The substrate containing the reaction (that is, indium has been formed, which is very beautiful. It becomes a transparent electro-chemical soil with indium tin-oxygen-silicon-organic functional groups. It is worth mentioning that in In this embodiment, this group means 疋 means 3- (2-aminoethylamino) propyl group. Urban direct agriculture_light-emitting triple compound ^ ^ = is specifically described for the organic light-emitting diode of the present invention. 板 11 The transparent display 14. The electrode layer 12, a light-emitting portion 13, and the metal electrode layer f 3 f plate 11 may be composed of a glass material or an organic plastic material. 泫 The transparent electrode layer 12 is formed on the substrate 12, The transparent electrode layer 12 is made by using the above-mentioned method for manufacturing a lunar electrode substrate of the present invention. The pole is provided with an indium tin-oxygen-silicon-organic functional group on its surface. The light-emitting portion 13 is formed on the transparent electrode layer 2 for excitation and light. In the present invention, the light-emitting portion 13 may be a polymer light-emitting layer, such as polyvinyl carbazole (poly (N_vinylcarbazole), ρνκ polymer organic light-emitting layer doped with organic dye, is a mixed polyvinyl carbazole, (poly (Nv inylcarbazole). ρνκ) and (2- (4-biphenylyl) -5- (4-tert-butylphenyl) l, 3,4-oxadiazole; PBD), and then doped with organic dyes (such as coumarin derivatives page 8 V. Description of the invention (6) Polymer organic light-emitting layer (coumarin 6; C6)). Lightning = electricity ST is formed on the light-emitting part 13 for connection with a negative electrical electrode. In the present invention, the The light-emitting part 13 can be composed of m, M, and two: "formed by alloy" or Mg / A1, _,

Ca / Al net metal layer. = Said 'Because the organic light emitting diode system of the present invention includes a surface', the transparent electrode layer 12 having indium tin-oxygen-silicon-organic functional group, because: the organic light emitting diode system of the present invention can be easily The organic-type functional group of the transparent electrode layer 12 is connected to the organic common polymer of the light-emitting portion 13 above. In addition, because one end of the transparent electrode layer 12 of the organic light-emitting diode of the present invention contains a silaneoxy group 'It can be combined with the 170 substrate of the inorganic type. Through this cross-linking, the tightness of the interface between the inorganic substrate and the organic conjugated polymer interface can be increased, which can accelerate the hole's transmission and increase the life of the device. And luminous efficacy. In the following, three different implementations and a conventional comparative example will be given to illustrate the efficacy of the organic light-emitting diode of Ben Sheming. In addition, in each embodiment, the light-emitting part mainly uses polyvinyl carbazole ( PVK) polymer organic light-emitting layer doped with organic dye. ', ^ (Example 1) (represented by si 1 ane-1) First, configure solution 1: Add 100 mg of PVK and 40 mg of PBD to 6. 5 In mL of chloroform, sonicate for another 20 minutes. Then, configure solution 2 • Add 6 mg of C6 to 20 ml of chloroform, and also sonicate with ultrasonic for 10 minutes until the particles are completely dissolved. Then, 1 ml of solution 2 was added to solution i

488095 V. Description of the invention (7) A solution containing P V K: P B D: C6 = 0 0: 40: 6 in chloroform with a final ratio of 7.5 m L was prepared. Finally, the solution 3 was obtained by filtering with f i 1 ter of 0.45 // L. Then, silicon-containing alkoxy compounds (such as τ-glycidoxypropyl

Diglyoxysilane (3-glycidoxypropyl (dimethoxy) methylsilane]; represented by silane-1) 0.1359g was dissolved in 250mL of deionized water, and the cleaned I TO electrode substrate was put into this solution for 5 minutes, and then , Place the substrate in an oven at 120 ° C for 30 minutes. Then, the solution 3 was taken out 3 0 0 // L and dropped on the modified I TO electrode substrate (ie, the transparent electrode substrate of the present invention) and spin-coated 3 at a rotation speed of 3 0 0 0 r · p · m · In 0 seconds, the main light-emitting layer is formed on the IT0 electrode substrate, and then the Ca / Al upper electrode is evaporated, so that the modified LED element can be obtained. (Example 2) (Indicated by s i 1 a n e-2) First, configure solution 1: 100 mg of PVK and 40 mg of PBD were added to 6.5 mL of chloroform, and then ultrasonically oscillated for 20 minutes. Next, configure solution 2: add 6 mg of Ce to 20 mL of chloroform, and also oscillate ultrasonically for 10 minutes until the particles are completely dissolved. Subsequently, 1 ml of the solution 2 was added to the solution 1 to prepare a solution containing PVK: PBD: C6 = 1 0 0: 4 0: 6 in 7.5 mL of chloroform. Finally, the solution 3 was obtained by filtering through f i 11 e r of 0 · 4 5 // L. Then, a silicon-containing alkoxy compound (such as N-phenylaminopropyltrimethoxy silane [N-phenylamino propyl trimethoxy silane]; represented by silane-2) 〇.1468g was dissolved in 2 5 OmL Remove the water, place the cleaned I TO electrode substrate in this solution for 5 minutes, and then place the substrate in a 120 ° C oven for 30 minutes. Then, take out solution 3 3 0 0 // L drop on the modified I TO electrode substrate (ie, the present invention

Page 10 488095 V. Description of the invention (8) Transparent electrode substrate) Spin-coated at a rotation speed of 3 0 0 r · p · m · for 30 seconds to form a main light-emitting layer on the I T0 electrode substrate. After the upper electrode of Ca / Al is vapor-deposited, the modified LED element can be obtained. (Example 3) (Expressed as APTMS) First, configure solution 1: 100 mg of PVK and 40 mg of PBD were added to 6.5 mL of chloroform, and then ultrasonically oscillated for 20 minutes. Next, configure solution 2: add 6mgiC6 to 20mL of chloroform, and also oscillate with ultrasound for 10 minutes until the particles are completely dissolved. Subsequently, 1 mL of solution 2 was added to solution 1 to prepare a solution containing PVK: PBD: C6 = 1 0 0: 40 ·· 6 in 7.5 mL of chloroform. Finally, the filtered solution was filtered through f i 1 ter of 0.45 // L to obtain dissolved spring solution 3. Then, 0.1279 g of a silicon-containing alkoxy compound (such as 3- (2-aminoethylamino) propyltrimethoxysilane) (referred to as APTMS) was dissolved in 2 5 0 mL of deionized water, put the clean IT0 electrode substrate into this solution for 5 minutes, and then take out solution 3 3 0 0 // L drop on the modified I TO electrode substrate (ie, the transparent of the present invention (Electrode substrate) was spin-coated for 30 seconds at a rotation speed of 3 0 0 0 r. Ρ · m., So that the main light-emitting layer was formed on the I TO electrode substrate, and then the upper electrode of Ca / Al was evaporated to obtain a modification. The next LED element. (Comparative example) (conventional PLEDs production method; expressed as PVK + PBD + C6) First, configure solution 1: 100 mg of PVK and 40 mg of ® (2- (4-biphenylyl) -5- (4-tert-butylphenyl) l, 3,4-oxadiazole; PBD) was added to 6.5 mL of chloroform, and then sonicated for 20 minutes. Next, configure solution 2: 6mgiC6 was added to 20 mL of chloroform, and the same was also oscillated with ultrasound for 10 minutes until the particles were completely dissolved. Then, will

488095 福 5. Description of the invention (9) lmL of solution 2 was added to the solution 丄 to prepare a final ratio of 7.5mL in chloroform

Solution containing PVK: PBD: c6 = 100: 40: 6. Finally, the solution 3 was obtained by filtering through 0.45 // L of f 1 1 ter. Then, the solution 3 was taken out 3〇〇 # [Drop onto the β〆 好 IT 0 electrode substrate spin-coated for 30 seconds at a speed of 3000r · p · m · 'to make the main light-emitting layer into IT. On the electrode substrate, the Ca / A1 upper electrode is evaporated to obtain the LED element. As shown in FIG. 3, as shown in FIG. 3, the ITO electrode substrate (APTMS, silane-1 and silane-2) modified by the method of the above embodiment and the ITO electrode substrate (pVK + PBD + C6) which has not been modified by the present invention. ), Using a spin-coating method to form a main light-emitting layer on top of it and measuring its photo-excitation light spectrum "(Photoluminescence) and normalize the intensity, it can be seen that no displacement has occurred in the main band, indicating that the emitted The fluorescent color has not changed. As shown in FIG. 4, the I τ〇 electrode substrate (APTMS, silane-1, and silane-2) modified by the method of the above embodiment and the ιτο electrode substrate (PVK + PBD + C6) not modified by the present invention, The spin-coating method was used to form the main light-emitting layer on top of it and the photoluminescence spectrum was measured. It can be found that the signal of the PL of the LED element modified by the oxygen-containing compound containing Shixi was significantly enhanced. The effect of the invention can be seen. 1 Also shown in FIG. 5, the I το electrode substrate (silane-1; silane-2; APTMS) modified by the method of the above embodiment and the 1.0 electrode substrate that has not been modified by the present invention are prepared by a spin coating method. The main light-emitting layer was formed on it, and the Ca / Al electrodes were respectively plated, and then the relationship between the brightness and the voltage was measured.

Page 12 488095 V. Description of the invention (ίο) It is obvious that at the same voltage, the LED elements modified with silicon-containing alkoxy compounds have significantly higher luminous brightness than the modified ones. In addition, the specific embodiments provided in the detailed description of the preferred embodiments are only for easy explanation of the technical content of the present invention, and are not intended to limit the present invention to the embodiment in a narrow sense. The scope of patent application can be implemented in various ways.

Page 13 488095

Brief description of the drawings [Simplified description of the drawings] FIG. 1 is a schematic diagram of forming a transparent electrode substrate having an indium tin-oxygen-silicon-organic organic substrate based on a preferred embodiment of the present invention. Figure 2 is a schematic diagram showing the structure of an organic light emitting diode according to a preferred embodiment of the present invention. Figure 3 is the modified version; [T〇 electrode substrate (ApTMS, siUne — 丨, and silane-2) and unmodified IT 0 electrode substrate (pVK + pBD + C6), using the “疋 transfer coating method” The main light-emitting layer is formed thereon, and its photoluminescence spectrum is measured, and the intensity spectrum is normalized. < Figure 4 is the modified IT0 electrode substrate (ApTMS, sUane — 丨 and silane-2) and the unmodified IT0 substrate (pVK + pBD + C6). The main light-emitting layer was formed by spin coating. A photoluminescence spectrum was measured thereon. Figure 5 shows the modified ITO electrode substrate (silane_1; sUane_2; APTMS) and the unmodified IT0 electrode substrate. The main light-emitting layer was formed on the substrate by spin coating, and Ca / A1 electrodes were plated on it. Relationship with voltage. '〃

Claims (1)

488095 VI. Application Patent Scope ------ 1 · An organic light-emitting diode, comprising: a substrate; a transparent electrode layer formed on the substrate for fish-pole connection, and the surface of which has indium Tin-oxygen-silicon-organic outside. Electron; s This base is bonded to a light-emitting part, which is formed on the transparent electrode layer, and light; and a double-excitation, light-emitting metal electrode layer is formed on the light-emitting part, which is connected by a r transparent electrode layer. The opposite electrode is connected. u and Yihe, where the where the 2 · The organic light emitting diode substrate described in item 1 of the scope of patent application is composed of a glass material. _ 3 · The organic light-emitting diode substrate described in item 1 of the scope of patent application is composed of organic plastic materials. — 4 · The organic light-emitting diode light-emitting part described in item 1 of the scope of the patent application includes a high-molecular organic light-emitting layer, and the molecule " ^^, > —Oxygen—Break ~ There are trips ^, and the matt layer ^ s energy groups are combined. 5. Organic polar as described in item 4 of the scope of patent application-70-polar body, wherein the high molecular organic light emitting layer is a poly (N-vinylcarbazole) 'PVK' doped organic dye Minute Page 15 — 488095 Organic light emitting layer. 6. A transparent electrode plate comprising: a substrate; and a surface having indium and a transparent electrode layer formed on the substrate with tin-oxygen-silicon-organic functional groups. 7. The organic light-emitting diode according to item 6 of the scope of patent application, wherein the substrate is made of a glass material. X 8 · The organic light emitting diode according to item 6 of the declared patent scope, wherein the substrate is made of an organic plastic material. ^ 9. Species ^ A method for manufacturing a bright electrode substrate, comprising the following steps: dissolving a silicon-containing alkoxy-type compound in water to form a certain aqueous solution of alkane-type 2 compound; and indium tin oxide having a hydroxyl group on the surface A transparent substrate (I το electrode substrate) was soaked in the silicon-containing alkoxy compound aqueous solution, and after a certain period of time, a transparent electrode having an indium tin-oxy-silicon-organic functional group on the surface was opened. The method for manufacturing a transparent electrode substrate as described in the item 9 of the scope, the steps of the method for manufacturing a transparent electrode substrate further include: baking the immersed transparent electrode substrate at a temperature and time of 疋. Page 16 488095 VI. Scope of patent application Baking. 1 1 · The method for manufacturing a transparent electrode substrate as described in item 9 of the scope of the patent application, wherein the concentration (V / V) of the silicon-containing alkoxy compound aqueous solution is 0 · (Π ~ 1%. 1 2 · such as The method for manufacturing a transparent electrode substrate according to item 9 of the scope of patent application, wherein the immersion time of the indium tin oxide transparent substrate (I T0 electrode substrate) is about 5 minutes. I 1 3. As described in item 9 of the scope of patent application A method for manufacturing a transparent electrode substrate, wherein the silicon-containing alkoxy compound is 3- (2-aminoethylamino) propyltrimethoxysilane. 1 4. The transparent electrode according to item 9 of the scope of patent application A method for manufacturing a substrate, wherein the silicon-containing alkoxy compound is T-glycidyl propyl dimethoxysilane. 1 5. The method for manufacturing a transparent electrode substrate according to item 9 of the scope of patent application, wherein, The silicon-containing alkoxy-type compound is N-phenylaminopropyltrimethoxy4 silane. 1 6. The method for manufacturing a transparent electrode substrate according to item 10 of the scope of patent application, wherein the transparent electrode substrate is baked. Roasting temperature is 80 ~ 160 ° C, baking Page 17 488095 Page 18