TW392369B - Manufacturing method for high polymer light emitting diode capable of emitting nearly white light broadband spectrum - Google Patents

Abstract

The present invention discloses a high polymer light emitting diode capable of emitting nearly white light broadband spectrum, which comprises: a transparent electrode (anode), a metal electrode (cathode), an organic light emitting layer, and an additive electric hole transmitting layer and/or electron transmitting layer, wherein the organic light emitting layer comprises the adulterant composed of the copolymer of poly(phenylene vinylene), PPV, capable of emitting blue-green light and the derivative with PPV alkoxyl substitute capable of emitting red light that the emitted light color is almost the yellow-white light of sunlight with appropriate ratio between the two. The electric-excited spectrum is broad and covers the visible light range and will not be changed by increasing the voltage. Furthermore, by adding a layer of electric hole transmitting layer and a layer of electron transmitting layer, the initial voltage of device is reduced and the light emitting efficiency is increased. In addition, the present invention also discloses the preparation method for the high polymer light emitting diode which includes: melting said two kinds of light-emitting conjugate high polymer in organic solvent and mixing the blue-light-emitting high polymer with red-light-emitting high polymer in a weight ratio of 150:1~10:1 to become an uniform solution; then, spraying the solution on electrode substrate (as anode) and achieving an uniform film after dehydration; and dipping another electrode (as cathode) in a highly vacuum environment.

Description

Α7 Β7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention () The invention relates to a novel polymer light-emitting diode capable of emitting near-white light in a broad spectrum and a method for producing the same. More specifically, the present invention relates to a light-emitting diode including an organic light-emitting layer, which includes a blue-green light-containing polyparaphenylene vinyl (PPV) copolymer and a red-light-emitting PPV. Blends of alk 5oxy substituted derivatives, and methods of making the same. The study of organic light-emitting diodes was made by Tang et al. (Appl. Phys · Let ·, 51 (1987) 914) in 1987 by evaporation, and the structure was made of ITO / diamine / Alq3 / Mg: Ag. Among them, ITO is indium tin oxide (indium / tin oxide) 'Alq3 is tris (8-hydroxyquinoline) 10 aluminum], because the element has an external quantum efficiency of 1% and looo cd / m2 high brightness (10V), so research on organic light emitting diodes has begun to develop rapidly. In 1990, the research group of Cavendish Laboratory, University of Cambridge, UK used PPV as the light-emitting layer, ITO as the positive electrode, and Ca as the negative electrode to produce a light-emitting diode with a structure of ITO / PPV / Ca. The quantum efficiency was 0.05% (Nature , 15 347 (1990) 539; US Pat. 5,247,190 (1993); 5,425,125 (1995); 5,401,827 (1995)) ο So far, the most basic organic light-emitting diode element is a single-layer organic light-emitting layer, this layer It is placed between a transparent electrode (when the positive electrode) and a gold 20 metal electrode (when the negative electrode). In addition, in order to improve the luminous efficiency of an organic light emitting diode device, the device may include two organic layers. The first layer is a hole transfer layer and the second layer is an organic light emitting layer; or the first layer is an organic light emitting layer. The second layer is an electron transport layer. These two organic layers are placed on a transparent electric (please read the precautions on the back before filling this page)

-* This paper size applies to Chinese national standards (<:} ^) / '4 specifications (2 丨 〇 > < 297 public celebration) A7 B7 Printed by the Central Standard of the Ministry of Economic Affairs 扃 Shellfish Consumer Cooperatives ) Between the electrode (when positive) and a metal electrode (when negative). There are still devices with three organic layers. The arrangement order is a hole transport layer, an organic light-emitting layer, and an electron transport layer. This three-layer organic layer is placed on a transparent electrode (when the positive electrode) and a metal electrode (when the negative electrode). The light emission process of this element is that when a 5-light monopolar body is added with partial wear, under the action of the electric field, the holes and electrons start from the positive and negative electrodes, respectively, and pass through the respective energy barriers in the light-emitting layer phase. An exciton is formed, and then the exciton decays from the excitatory state back to the ground state and emits light. PPV polymers are widely used in the production of 10 light-emitting diodes because of their excellent fluorescence. However, because PPV is neither soluble nor hot-melt, a precursor solution is needed to coat the film, and then PPV is obtained after removing the reaction by heating and vacuuming. In order to simplify the process of the component, a long carbon chain is linked on the PPV side. Alkyl group or alkoxy group to improve its solubility (us Pat. 5,408,109 (1995)), making it soluble in common organic solvents, and also changing its energy gap. In addition, block copolymers can also be synthesized by copolymerization. This copolymer was first synthesized by Karasz (Macromolecules, 26 (1993) 1188, Macromolecules, 26 (1993) 6570) using the Wittig reaction to include rigid and soft links Co-polymer, in which the rigid and hard segment part is the para-phenylene vinylene bond segment, the luminous color can be changed by controlling its length, and the soft base part is an alkyl group, an ether group, and an ester Base, whose function is to improve its solubility and film-forming properties. At present, the light colors emitted by polymer light-emitting diodes include blue light, green light, and even infrared light. In addition to the light color determined by the choice of a single light-emitting substance, it can also be obtained by blending two or more polymers. get on. This kind of research -4- 20 This paper size applies to Chinese national standards (CNS > A4 size (210X297 cm)) (Please read the notes on the back before filling this page)

A7 5 _____ B7 ____- 'printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention () Earliest by Yoshino (Jpn. J. Appl. Phys., 32 (1993) L921) using poly (di · octyloxy Phenylethylene] [Poly (di-octyloxyphenylenevinylene)] (PdOPV) is blended with Alq3 to make a component. The component's light color gradually changes from orange (the color of PdOPV) to yellow as the applied voltage increases. Green 5 (light color of Alq3); Heeger (J. Electronic Materials, 20 (1991) 945) also converted poly (2-cholestanoxy-5-thexyldimethylsiltyl-l, 4-phenylene vinylene) (CS-PPV) and 2- ( 4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-Zadi C 2- (4-biphenylyl) -5- (4-tert-butylpnehyI) -1,3 , 4-oxadiazole)] (PBD) was blended to make components, and it was found that the PBD content had no effect on the shape of the electrical excitation (EL) 10 spectrum; and Karasz (J. Appl. Phys., 76 (1994) 2419) Poly (9-vinyl β-block) [p0ly (9-vinylcarbazole)] (PVK) and PPV copolymer [conjugated non-conjugated multiblock copolymer (CNMBC) 〔In different proportions A new radiation peak appeared on the EL 15 spectrum when the PVK content was 3% (the EL spectrum is different from the original two kinds of polymers) when the PVK content was 3%. This is because PVK and CNMBC have Interactions are caused by laser complexes.

Inganas (Nature; 372 (1994) 444) uses polypyrimidine derivative blends with different side chain substituents as the light-emitting layer. When a voltage is applied, it first emits the light color of a low-energy 20-gap polymer. As the voltage increases, the high-energy The light color of the gap polymer also begins to show that 'getting a component that controls the light color by a change in voltage. This result is different from the original purpose of making a white light component. This is why the blend still has significant phase separation, so that The reason why white light cannot be obtained; therefore, the research group (Appl. Phys. Lett "68 (1996) 147) applied the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) in three different paper sizes in 1996- -------- / Equipment-V -...-, (Please read the notes on the back before filling out this page) I *-£ < £ Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention () Carcinphene derivatives. Poly (3-methyl-4-octylthiophene) [p〇iy (3-methyl-4-octylthiophene)] (PMOT), poly (3- ring Hexylpyrophene) [poly (3-cyclohexylthiophene)] (PCHT), and poly [3- (4-octylphenyl) 2,2'-di0 thiophene (P〇ly [3- (4-octylphenyl) 2,2, -bithiophene]) (PTOPT)) was blended with 5 polymethyl methacrylate (PMMA), and PMMA was used as a binder, and PMOT was used as a weight ratio. When: PCHT: PTOPT: PMMA is 10: 4: 1: 1, the best conditions for white light emission are obtained. When the operating voltage is 20v, the EL light wavelengths λοιβχ are 465 nm and 620 nm. Between the initial voltage (tum-on voltage) and 20V, its light color still changes with the voltage. In addition, the addition of PMMA to 10 reduces the light-emitting part of the element, which reduces its luminous efficiency. Polar body, so far, its electrical excitation spectrum has been extended from ultraviolet light to infrared light. The emission spectrum of the light-emitting diode is not only affected by the conjugate structure of the main chain, but also with different functional substituents. The energy gap can be controlled to obtain different light color outputs. In addition, it can also be blended with several polymers with different energy gaps to control the application of different voltages to obtain different light color outputs, and even obtain white light diodes. However, white light emitting diodes in the literature are red at low voltages. White light can only be emitted at 20V. As a result of research by the present inventors, a new nearly white light-emitting polymer light-emitting diode with a wide frequency range of 20 can be obtained at various voltages. In summary, this The invention relates to a novel polymer light-emitting diode capable of emitting near-white light in a broad frequency spectrum, which is characterized in that it includes a blend of two polymers as a light-emitting layer, which can emit near ____________ at different voltages. 6 -_ ___ This paper conforms to the national standard of China (Cn " T) Μ specifications ΰΐ〇 × 297mm > — ^ '' (Read the notes on the back ^^^ before filling in this page). τ '7 7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ________ B7 V. Description of the invention () White broadband light color. In another part, the present invention proposes a novel polymer light emitting diode capable of emitting near-white light in a broad frequency spectrum, which is characterized in that it includes a layer containing a blend of two polymers as a light emitting layer Hole transfer 5 layer and / or electron transfer layer. In another part, the present invention relates to a novel method for producing a polymer light emitting diode capable of emitting near-white light in a broad frequency spectrum, which comprises a polyparaphenylene vinyl (PPV) copolymer which can emit blue-green light. A red light-emitting PPV compound substituted derivative was prepared at an appropriate weight ratio, and 10 was applied on an electrode substrate (when the positive electrode), and another electrode (when the negative electrode) was plated under high vacuum. Schematic description The present invention will be described in more detail later with reference to the embodiments and drawings, in the drawings: 15 Figure 1 shows the element ITO / PPVCOC10: C100-CNPPV (200: 1) / A1 under different applied voltages Electrical excitation spectrum "The second one is the electrical excitation spectrum of the element ITO / PPVCOC10: C10O-CNPPV (150: l) / Al at different applied voltages. Figure 3 shows the electrical excitation spectrum of the component ito / ppvcocio: cioo-cnppv (ioo: i) / ai at different applied voltages. Figure 4 shows the components ITO / PPVCOC10: PdOPV (14: l) / Ca / Ag in different paper sizes. The Chinese National Standard (CNS) A4 specification (210X297 mm) is applicable. (Please read the notes on the back before filling this page)

• V. Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Yinfan A7 B7 V. Description of the invention () Electrical excitation spectrum under applied voltage. Figure 5 shows the current density-electric field strength characteristics of ITO / PPVCOC10: PdOPV (14: l) / Ca / Ag; the illustration shows 1TO / SPAN: PVA (1: 1) / PPVCOC10: P (lOFV (14: iyCa) / Ag element current density-electric field intensity characteristic 5. As mentioned above, in a part of the present invention is related to a novel polymer light emitting diode capable of emitting near-white light broadband spectrum including a transparent electrode ( (For the positive electrode), a metal electrode (for the negative electrode), an organic light-emitting layer, an added hole-transporting layer and / or an electron-transporting layer. 10 The transparent electrode used in the novel polymer light-emitting diode of the present invention is familiar to the It is formed by evaporating indium / tin oxide (ITO) on an organic plastic substrate or glass, or is formed by coating a conductive polymer on an organic plastic substrate and glass, Used as a positive electrode. The negative electrode metal used in the novel polymer light emitting diode of the present invention may be 15 In, Al, A1: Li alloy, Mg / Ag, Mg: Ag alloy, Ca / Ag or Ca / Al, etc. The purpose is to obtain a white-emitting luminescent diode, because the white light spectrum covers In the visible light range, the present invention uses a PPV copolymer that emits blue-green light (the short wavelength portion of the visible light spectrum), and a PPV alkoxy-substituted derivative (long-wavelength portion of the visible light spectrum) that emits 20 red light Parts) ^ Because the luminous efficiency of PPV copolymerized europium is small, and the luminous efficiency of pvv-oxyl substituted derivatives is large, the doped paper used in the production of the light-emitting layer is in accordance with the national standard (CNS) A4 specification (CNS). 210X297mm -------- install II (please read the precautions on the back before filling this page),? Τ V. Description of the invention (A7 B7

When combined, the ratio of the PPV copolymer to the PPV alkoxy-substituted derivative is higher in the former, so that a broad-spectrum spectrum of nearly white light can be obtained. In the present invention, two kinds of polymer materials with similar chemical structures are selected, including a blue-green PPV copolymer (Structure I) and a red-light PPV alkoxy-substituted derivative (Structure II) »Structure I

Structure II

(Please read the notes on the back before filling in this page)% The Consumer Cooperation of the Central Government Bureau of the Ministry of Economic Affairs prints A3, A4 is Η,-(CH2) nCH3, -〇- (CH2) nCH3,-(CH2) n-〇- (CH2) nCH3,-(CH2-CH2-〇) nCH3 (n: 1 to 22). A5 is Η, -CN. A6 is -0 (CH2) no-, -OCH2-CH2- (〇CH2-CH2) no-, -oCO (CH2) noCo- (n = 1-12). 15 Bi, B2, B3, and B4 are -OCnH2n + 1 (n = 6 to 22), -0 (CH2-CH2-〇) nCH3 (n = 1 to 10), and B5 is H, -CN. 10 -9- + Paper Size Common Chinese National Standard (CNS) A4 Specification (21 OX 297 mm) Order t 'Α7

15 Preferably, the PPV is Al in the structure ⑴, the a2 group is _〇cH3; A3 ′ A4, the A5 group is Η; the A6 group is _〇 (CH2) n〇_, and 4 5 ′ 8,10 of the Integer. And also the better one, the pPV is the structural formula , A2 group is _0CH3; a3, A "H; & is _cn; A6 is one of (0) (CH2) n0-'and wherein η is an integer of 5, 8, 10. In addition, the better, The PPV alkoxy derivative is in structure (11), and Bι, B2, B3, and B4 are all -OCnH2n + 1, where n = 6, 8, 10; the B5 group is Η; and it is also preferred. The PPV pitoxy derivative is in structure (VII), where the B2 ′ B3 and B4 groups are both -OCnH2n + i, where n = 6, 8, 10; and the B5 group is -CN. In the present invention For the polymer synthesis used, see References. Macromolecules, 26 (1993) 1 188 > US Pat. 5,514,878 (1996), Synth. Met "29 (1989) E129» Blue-green light used in the examples of the present invention The PPV copolymer is called pppCOCIO for short; and there are two types of PPV alkoxy substituted derivatives that can emit red light: one is C10O-CNPPV and the other is PdOPV (the structure is as follows). CH3 ° v OCH3. Please read the note above

I Pack 4 ^-Order

Printed by PPVCOCIO, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

CHCH < y CHCH

C10O-CNPPV

-10 This paper size applies to China's national standard (CNS M4 specification (2 丨 0 × 297 mm)

I 11 V. Description of Invention (

PdOPV

〇C * HI7 CH: CH-H, tC | 0 A7 B7 Yin Fanjing, an employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, found that the blue-emitting polymer PPV is substituted for the red-emitting polymer such as pvvoxy When the weight ratio is within the range, a light emitting diode that can emit yellow and white light and has a wavelength in the range of 400 to 650 nm can be obtained. The novel polymer light-emitting diode of the present invention further includes an added hole-transporting layer and / or an electron-transporting layer. Generally speaking, for single-layer components, it has poor stability, low luminous efficiency, and high starting voltage. In order to improve the performance of the device, it is necessary to introduce a hole transfer layer and an electron transfer layer to improve the initial voltage, operating voltage, luminous efficiency and stability of the device. Heeger et al. (Nature, 357 (1992) 477) produced a component with a structure of ρΕΤ / ΡΑη- CSA / MEH-PPV / Ca 'in 1992 and coated it with polyethylene terephthalate Polyaniline 15 (Polyaniline, PAn) doped with camphor sulphonic acid (CSA) on the (PET) sheet was used as a positive electrode instead of ITO to obtain a flexible light-emitting diode. Heeger research group (J.Appl. Phys., 77 (1995) 694) produced the element structure in 1995 as iTO / PAn-CSA-PES / MEH-PPV / Li: Al (alloy), with PAn as the mesh electrode Diode to enhance the hole emission. In 1996 (J. Appl. Phys., 79 (1996) 934), they used soluble poly (2-decyloxy para-benzene) [卩 〇1 丫 (2-〇016〇3 ^ 1〇 \ 3 ^ -1,4-phene), DO-PPP] to produce a double-layer structural element ITO / PVK / 10 20 -11 with hole transfer layer PVK. This paper size is applicable to China National Standard (CNS) A4 (210X297) Li) (Please read the notes on the back before filling in this page)

1T 12 A7 B7 V. Explanation of the invention () Central Government Bureau of the Ministry of Economic Affairs, M.-Γ-. Consumer cooperatives, India and India DO-PPP / Ca, the element quantum efficiency can reach 1% to 3%, if more PAn layer is added , Then the initial voltage of ITO / PAn / PVK / DO-PPP / Ca can be reduced by 30%. The aforementioned PAn-CSA can be used as a hole transfer layer and a hole injection layer. In 1994 (Synth. Met., 5 67 (1994) 181), Mullen et al. Used PPV as the hole transfer layer to make a double-layered ITO / PPV / L-PPP / Ca diode, which can emit yellow light. The quantum efficiency is 0.6%, and the brightness can reach 1000cd / m2. The Cambridge Research Group (Appl. Phys. Lett., 61 (1992) 2793) added a layer of 2- (4-biphenyl) -5- (4 -Third butylbenzene 10-yl) -1,3,4-^: »^ [2- (4-biphenylyl) -5- (4-tert-butylpnehyl) -l, 3,4-oxadiazole)] (PBD ) The polymer layer dispersed in PMMA serves as an electron transport layer to enhance the conduction of electrons and restrict holes from passing through the polymer layer too quickly. In addition, holes accumulated at the PPV / PBD-PMMA interface will induce the transfer of electrons and make them quantum Efficiency oil increased by 0.05% to 0.8%. For the hole transfer layer, PPV, PVK and polyaniline (PAN) derivatives are generally used. The polyaniline (PAN) derivative used in the present invention is a sulfonic acid ring-substituted polyaniline (SPAN) (J. Am. Chem. Soc., 112 (1990) 20 2800; US Pat 5,159,031; Macromolecules * 29 (1996) 3950) (poly (aniline-co-N-propane sulfonic acid aniline) »PAPSAH) (J. Am. Chem. Soc., 1 16 (1994) 7939; J. Am. Chem Soc., 17 (1995) 10055; US Pat. 5,641,859), the element's initial electric field can be reduced by 1/3 (see fact-12- -------- / s ·-(please first Read the notes on the back and fill in this page) <-* Thread · This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) Printed A7 B7 by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Explanation () Example 5) or using poly (3,3,4-thiophene), in which the alkyl group is CnH2n + i, n = 2,4,6. In another part, in order to obtain the above-mentioned novel novel invention, A polymer light-emitting diode that emits near-white light in a broad frequency spectrum is a method for preparing the novel 5-light-emitting diode, which includes the above-mentioned structure (1), which can emit blue-green light. The copolymer of the para-phenylethylene light-emitting group and the soft group is dissolved in a suitable organic solvent with a pv alkoxy-substituted derivative having a side chain substitution of structure (II) and orange-red light, and an appropriate ratio is taken. The PPV copolymer and the PPV derivative solution are blended with each other to form a uniform sentence 10 solution. The blend solution is coated on the electrode substrate (positive electrode), and a uniform film is obtained after drying, and, Plating another electrode (negative electrode) under high vacuum. The PPV copolymer and PPV alkoxyr derivative suitable for use in the method of the present invention are those previously described. A method suitable for preparing a novel polymer light-emitting diode in the present invention In 15, the organic solvents used to dissolve the PPV copolymer and the PPV alkoxy derivative include aeroform, toluene, tetrahydrofuran, etc. The electrodes used in the method of the present invention are the foregoing, in which the metal of the metal electrode (negative electrode) It can be plated by thermal sublimation or sputtering. In an embodiment of the present invention, a step of adding a hole transfer layer between the positive electrode and the organic light-emitting layer 20 is further included. As described in SPAN, or PAPSAH aqueous solution is coated and dried. In another embodiment of the present invention, a step of adding an electron transfer layer between the organic light emitting layer and the negative electrode is further included. In yet another embodiment of the present invention, it also includes that both the positive electrode and the paper size are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (谙 Read the precautions on the back before filling this page)

1T A7 Μ B7 V. Description of the invention () A step of adding a hole transfer layer between the organic light emitting layer and an electron transfer layer between the organic light emitting layer and the negative electrode. The white light element produced by the method of the present invention is different from Kido

Lett., 64 (1994) 815; 267 (1995) 1332) any 5 white light element prepared by blending small molecular dyes of different light colors in PVK; it is also different from Inganas blended with a variety of polythiophene Derived by adding PMMA as a binder, a component that shows white light only at a certain voltage. The color of light emitted by a general blend element will change with the voltage. 10 According to the research process of the present invention, it is known that the low energy gap polymer of such a device is easily damaged when the voltage is increased, so it is not practical. A good admixture element should emit all colors at the beginning, that is, a broad-band spectrum, and its spectrum will remain unchanged with increasing voltage. The white light diodes produced by the present invention can be applied to various display devices and background light sources of displays such as electronic watches, liquid crystal displays, and toys. Examples Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) The present invention will be further clarified by the following illustrative but not restrictive examples. 20 Example 1. Prepare aerosol solutions of PPVCOC10 and C10O-CNPPV (both at a concentration of 10 mg / ml), and take the ratio of solution pvccocio: cnppv to 200: 1 to obtain a blend solution. The solution was applied to the cleaned ITO glass by spin coating at a speed of 1000 rpm. -14- This paper size applies to Chinese national standards (CNS > A4 specifications (ΉΟ × 297mm) 15 A7 15 A7 Ministry of Economy The Consumer Standards Cooperative Work of the Central Bureau of Standards, Du Yinzhuang, 'Invention shows that its film thickness is 800 gas. Under a vacuum of 1 × 10-6 to rr, the metal can be illuminated. Its luminous area is 0.8 square centimeters #. This component Yellow and white light can be seen at 15V under applied voltage. The EL spectrum covers a wavelength range from 400 nm to 650 nm. When the voltage is increased, the rainbow spectrum curve is increased by 50%, showing that its light color does not change with voltage. Change (as shown in Figure 1). Example Two: Prepare chloroform solutions of PPVCOC10 and C10O-CNPPV (their / agricity are both 10 mg / ml), and take the solution PPVCOC10: CNPPV at a ratio of 150: 1. In this way, a blend solution was obtained. The solution was applied to the cleaned ITO glass by spin coating, the rotation speed was 1000 rpm, and the film thickness was 800 A. The evaporation was performed under the condition of a vacuum of ixi0-6 torr. Aluminum metal with a light emitting area of 0.8 square Cm. Yellow and white light can be seen at 15V under an applied voltage of this element. The wavelength range 15 covered by this el spectrum ranges from 415 11111 to 650 nm. When the voltage is increased, its EL spectrum curve increases in proportion, showing its The light color does not change with the voltage (as shown in Figure 2). Example Three: Prepare aerosol solutions of PPVCOC10 and C10O-CNPPV (both concentrations are 10 mg / ml). Take the 20 ratio of solution PPVCOC10: CNPPV to ι. 〇〇: ι, so as to obtain a blend solution. This solution was spin-coated on the cleaned ITO glass at a speed of 1000 rpm, and its film thickness was 800A. The vacuum was 1xl0_6 torr. Under the conditions of steaming 18 metals, its luminous area is 0.8 square centimeters. Add this component to -15- This paper size applies to China National Transfer (CNS) A4 «^ (21GX297 mm) (Please read the note on the back first (Fill in this page again) -1%

A7 16 B7 V. Description of the invention () The voltage, yellow and white light can be seen at 15V, and the wavelength range covered by this EL spectrum is from 415 nm to 650 nm. When the voltage is increased, the EL spectrum curve increases proportionally, showing that its light color does not change with the voltage (as shown in Figure 3). Examples 4 and 5 Prepare aerosol solutions of PPVCOC10 and PdOPV (both concentrations are 10 mg) / Ml), taking PPVCOC10: PdOPV ratio of 14: 1 and blending to obtain its blend solution. This solution was spin-coated on the cleaned ITO glass at a rotation speed of 1,000 rpm and a film thickness of 1200 A. Under vacuum condition of lxl0_6 ton *, 10-layer metal with low work function, calcium, and then silver plating as a protective layer are deposited, and its luminous area is 0.8 square centimeters. By applying an external voltage to this device, yellow and white light can be seen at 32V, and the EL spectrum covers a wavelength range from 450 nm to 650 nm. When the voltage is increased, the EL spectrum curve increases proportionally, showing that its light color does not change with the voltage (as shown in Figure 4, the starting electric field of 15 of this element is about 21 X 107 V / m as shown in Figure 5). Example 5. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs --------- ^ — \ '(Please read the precautions on the back before filling this page) Polyaniline substituted with acid groups on the ring ( A mixed aqueous solution of sulfonic acid ring-substituted polyaniline (SPAN) and poly (vinyl alcohol) (PVA) (proportion is 20 1/1, concentration is 35.5 mg / ml). Coated on the cleaned ITO glass (this layer is used as an electric hole transfer layer), and dried at 80 ° C under vacuum for 2 hours, and then the mixture PPVCOC10: PdOPV 14: 1 chloroform solution (concentration 10 mg / ml) by spin-coating method -16- This paper size applies to China National Standards (CNS) A4 (210X297 mm) Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Printing Cooperatives A7 17, B7 V. Description of the invention () Coated on the hole transfer layer that has been previously formed into a film, with a vacuum of lxl _ 6 torr first vaporize a layer of metal with a low work function, 弼, and then bond a layer of silver as a protective layer. Its luminous area is 0.8 square centimeters. The initial electric field of this element is about 14X107 as shown in Figure 6. V / m, this element is compared with the element of Example 5 and shows that the addition of SPAN and PVA admixture can reduce the initial electric field by about 1/3. In addition, polyaniline substituted with sulfonic acid group on nitrogen (poly (aniline- co-N-propane sulfonic acid aniline) »PAPASH) instead of SPAN, you can get similar results. (Please read the notes on the back before filling in the dream, -17- This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm>

Claims (1)

Apply for a patent Fanyuan Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative printing 1. A novel light-emitting diode capable of emitting near-white broadband spectrum 'includes: a transparent electrode (positive electrode)-metal electrode (negative electrode) 5-organic light emitting Layer; and a hole-transporting layer and / or an electron-transporting layer; wherein the organic light-emitting layer includes a pPV copolymer (blue containing a para-phenylethylene light-emitting group and a soft group in a main chain represented by the following formula (I)) (blue Green light series polymer) 'and a type of 10PPV derivative (red light series polymer) substituted with the following side formula (Π) of the blend' Structure I Structure II where: A1, A2 are fluorene, -OCH3; A3 and A4 are Η,-(CH2) nCH3, -〇- (CH2) nCH3 '-(CH2) n-〇_ (CH2) nCH3,-(CH2-CH2-〇) nCH3 (η = 1 ~ 22); 15 A5 is H, -CN; 8 6 is -〇 (CH2) n〇_, _〇CH2-CH2- (〇CH2- CH2) n〇-, _________- _-18- ---- Λ -------, tT ------ ψ 1. (Please read the note on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 specifications ( 210X297 mm) 19 19 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A8 B8 C8 D8 VI. Patent application scope -OCO (CH2) n〇CO- (n = 1 ~ 12); Βι, Β2, Β3, Β4 are -OCnH2n + 1 (n = 6 to 22), -0 (CH2-CH2-o) nCH3 (n = Bu 10); and B5 is Η, -CN. 5 2. The light-emitting diode according to item 1 of the scope of patent application, wherein a hole-transporting layer is added between the positive electrode and the organic light-emitting layer. 3. For example, the light-emitting diode of the scope of the patent application, wherein an electron-transporting layer is added between the organic light-emitting layer and the negative electrode. 4. For example, the first diode in the scope of patent application, wherein a hole transfer layer is added between the 10 positive electrode and the organic light emitting layer, and a layer of electrons is added between the organic light emitting layer and the negative electrode. Delivery layer. 5. For example, the light-emitting diode of item 1 of the scope of the patent application, wherein the electrode substrate used is composed of indium tin oxide deposited on an organic plastic substrate or glass or a conductive polymer is coated on an organic material. 15 made of plastic substrate and glass. 6. For the light-emitting diode of item 1 of the patent application scope, the negative electrode used may be In, Al, Al: Li alloy, Mg / Ag, Mg: Ag alloy, Ca / Ag or Ca / Al. 7. For example, the light-emitting diode of item 1 of the scope of patent application, in which the 20 PPV copolymer used is Aι in formula (I), the A2 group is -OCH3; the A3, A4, and A5 groups are fluorene; the A6 group is -0 ( CH2) n0-, and 11 is an integer of 5, 8, 10. -19-This paper uses China National Standard (CNS) A4 (210X297mm) V.i ', ^-(Please read the precautions on the back before filling this page), π Patent scope 8. For example, the light-emitting diode in the scope of the patent application, the PPV copolymer used is Ai in formula ，, the A2 group is -GCH3; the eight-four group is Η ', the a5 group is _CN, and the A6 group is-. (CH2) n0-, and wherein n is an integer of 5, 8, 10. 5 9 · If the light-emitting diode of item 1 of the scope of patent application, the PPV street organism used is Bl, B2, B3, B4 in formula (Π) are all _ 〇CnH2n + i 'where η = 6,8, 10; and "the radical is a person who has a base. 1 10. If the light-emitting diode of item 1 of the patent application park, the PPV derivative used is B-1, B2, B3, and B4 in formula (11) are -10 〇CnH2n + 1 ', where n = 6, 8, 10; and β5 group is _CH. 11. If the light-emitting diode of the first scope of the patent application, the blue light-emitting polymer of the formula (I) used The blending weight ratio of the red light-emitting polymer of formula (11) is 15: 0: 1 to 10/1. | 12. If the light-emitting diode 15 body of the first or the sixth item of the patent application scope, The negative electrode metals used therein are plated by thermal sublimation method and sputtering method. 13. For example, the light-emitting diodes of the scope of patent application No. 1, 2, 4, or 5, wherein the conductive polymer is a ring Sulfonyl-substituted polyaniline (SPAN) on nitrogen 'Sulfonyl-substituted polyaniline (pApSAH), or 20 poly (3-hexylsulfonyl pyrimidine), where alkyl is CnH2n + i, n = 2, 4, 6 〇14_ A kind of emission nearly white Production of light-emitting diodes with a wide frequency spectrum-20 This paper New Zealand is applicable @ 国 @ 准 （CNS） 八 4 听 · (210X297 mm) 21 A8 B8 C8 D8 The method of applying for a patent scope is a formula (I) The PPV copolymer (blue-green light series polymer) containing a para-phenylethylene light-emitting group and a soft group in the main chain shown, and a PPV derivative (red light series polymer) substituted with a side chain represented by the following formula (II) ), Structure I Structure II A3 'A4 group is Η,-(CH2) nCH3, · 0-((: Η2) η (: Η3,-(CH2) n-0- (CH2) nCH3,-(CH2-CH2-0) nCH3 (η = 1 ~ 22); A5 is based on Η, -CN;, 10 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 15 — — —— — — — II Yuan | II-Order (please read the note on the back first) ^^ Please fill in this page again) The A6 group is -0 (CH2) n〇_, -〇CH2_CH2- (OCH2-CH2) n〇-, -〇CO (CH2) nOCO- (n = 1 ~ 12); Bi , B2, B3, and B4 groups are -0CnH2n + 1 (n = 6 ~ 22), -0 (CH2-CH2-0) nCH3 (n = 1 ~ 10); B5 group is H, -CN; will contain The PPV copolymer of the structure I and the PPV derivative of the structure II are respectively dissolved in an organic solvent, and an appropriate proportion of the copolymer and the PPV derivative are taken. 21-For private paper, use China National Standard (CNS) A4 specification (210X297 (Mm) D8 々, after patent application, the organisms are blended with each other to obtain a uniform solution. The blend solution is coated on the electrode substrate (as the positive electrode), and a uniform film is obtained after drying. Plating another electrode (as the negative electrode) under vacuum. 15. The manufacturing method described in item 14 of the scope of patent application, Medium 5 further includes the step of adding a hole-transporting layer between the positive electrode and the organic light-emitting layer. 16. The manufacturing method as described in item 14 of the scope of patent application, which further includes the step of adding the organic light-emitting layer and the negative electrode. Step of adding an electron transfer layer in between. 10 17. The manufacturing method according to item 14 of the scope of patent application, further comprising adding a hole transfer layer between the positive electrode and the organic light emitting layer. The step of adding an electron-transporting layer between the organic light-emitting layer and the negative electrode. 18. The production method as described in item 14 of the scope of patent application, wherein the solvent used is aerosol, toluene, tetrahydro "furan Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 19. The manufacturing method described in item 14 of the scope of patent application, where the electrode substrate used is indium tin oxide Formed by vapor deposition on organic plastic substrate or glass; or formed by coating conductive polymer on organic plastic substrate and glass. 20 2 0. As described in item 14 of the scope of patent application As the method of operation, the anode metal used is In, Al, Al: Li alloy, Mg / Ag, Mg: Ag alloy, Ca / Ag, or Ca / Al. -22-This paper size applies to Chinese national standards (CNS > Α4 Specifications (210 × 297 mm) 6. Application scope of patent 21 * The production method described in item 14 of the scope of patent application, where the PPV copolymer used is Ai in formula (I), and the A2 group is -OCH3; A3 'A4 'A5 group is Η; A6 group is -0 (CH2) n0-, and n is an integer of 5'8,10. 5 22. The production method according to item 14 of the scope of the patent application, wherein the PPV copolymer used is Ai in formula (I), the A2 group is · OCH3; A3 'A4 group is Η;' A5 group is- CN; A6 group is · 〇 (CH2) nO-, and ^〗, an integer of 8, 10. 23. The production method according to item 14 of the scope of the patent application, wherein the PPV derivative used in 10 is Bι, B2, B3, and B4 in formula (II) is -0CnH2n + 1, where η = 6 , 8,10; and the B5 group is the person who is the one. 24_ The production method according to item 14 of the scope of patent application, wherein the PPV derivative used is Bι, B2, B3, and 84 in the formula (π) are -OCnH2n + i, where 'η = 6,8 , 10; and the B5 group is -CN. 15 25. The manufacturing method according to item 14 of the scope of patent application, wherein the blending weight ratio of the blue light emitting polymer of formula (I) to the red light emitting polymer of formula (11) is 5 〇: 1 ~ 1 〇 / j. 26. The manufacturing method according to item 1 or 7 of the scope of the patent application, wherein the negative electrode metals used are bonded by thermal sublimation and sputtering. 20 11 · The manufacturing method according to item 1, 2, 3 or 6 of the scope of the patent application, wherein the conductive polymer is a sulfonic acid group-substituted polyaniline (SPAN) on a ring, and a sulfonic acid group-substituted polyamine on a nitrogen. Aniline (PAPSAH), or 24 24 Poly (3-alkylsulfonic acid pyrimidine) with patent application scope A8 B8 C8 D8, Pak Pak Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, in which the alkyl group is CnH2n + l, n = 2 4, 6 〇 (Please read the notes on the back before filling in this page), binding · -24- This paper size applies to China National Standard (CNS) A4 specification (210X297 cm)