TW201020275A - Hole-transport material for polymer light-emitting diode and fabrication thereof - Google Patents

Abstract

The present invention discloses a hole-transport material for polymer light-emitting diode, wherein the hole-transport material comprising a hyperbranched triarylamine polymer, and the hyperbranched triarylamine polymer is derivated from a triarylamine monomer with at least a tosylate group. In addition, the max brightness of the polymer light-emitting diode is over 20000cd/m<SP>2</SP>.

Description

201020275 VI. Description of the Invention: [Technical Field] The present invention relates to a material for a hole conducting layer, and more particularly to a material for a hole conducting layer comprising a hyperbranched triarylamine polymer. [Prior Art] The principle of organic electroluminescence can be explained simply as follows: under the applied voltage, the holes and electrons are injected from the anode and the cathode respectively. Under the action of the electric field, the electrons and the holes move toward each other when the two are in the organic light. When the material meets and combines to excite photons, then when it is returned to the lower energy ground state by the higher energy excited state, energy is released, and the energy can be released in the form of light or heat. Since the efficiency of the organic electroluminescent device depends mainly on whether the electrons and holes can effectively emit light in the luminescent layer. When the electrons or holes are close to the poles, they are quenched by the metal. Most organic If the material is not transporting electrons or holes, it will cause the photons to be close to the two poles, which will reduce the efficiency. There are two ways to improve them: one is to directly modify the structure of the organic material itself, and to add it to both electron and hole conduction. Characteristic functional groups. The second method is to use a multi-layer structure to help the electrons and holes to be injected into the organic layer in a balanced manner. In the multilayer structure design, a hole conduction layer (HTL) and a hole injecting layer (HIL) are added between the emission layer (EML) and the ITO anode; In one aspect, an electron transport layer (201020275 ETL) and an electron injecting layer (EIL) are added between the light emitting layer and the metal cathode cathode. The purpose of this multi-layered sister structure is to balance the injection and conduction of electrons into the electron tunnel, and to increase the efficiency of the combination of electrons and holes in the light-emitting layer to achieve maximum luminous intensity and quantum efficiency. ). Among them, the electron conducting layer and the hole conducting layer are used to adjust the moving speed of electrons and holes, so that the rates of the two are similar. There are several important points in designing and synthesizing the above-mentioned electronic or hole-conducting materials: h must have high resistance and _ recording. 2. It is necessary to reduce the energy barrier of the hole transport layer/anode or the electron conduction layer/cathode interface. It has been reported that the longer the energy barrier is, the longer the use time of the organic light-emitting element. 3 can naturally form a good film type. Because in the thin film layer of organic electron or electron transport material, after a long time _ (four), there will be aging phenomenon in the junction (four), and this phenomenon is the main cause of the darkening of the component after power-on. With this in mind, it is still necessary to study new electronic or hole-conducting materials to develop new materials with high heat resistance and (4) qualitative, low interface energy barriers and low initial voltage to increase organic light-emitting components © The service life and improved luminous brightness and luminous efficiency. SUMMARY OF THE INVENTION In order to meet the requirements of the industry, the present invention provides a hole conducting layer material in view of the above background. A hole conducting layer material, the above-mentioned hole amine amine polymer (hyperbranched is characterized in that a conductive layer material comprises a high branched metal 4 201020275 triarylamine polymer) to form the above-mentioned hyperbranched triarylamine polymer The singular is derived from a triarylamine monomer comprising at least one tosylate group, wherein the triarylamine monomer comprising at least one tosylate group hydrolyzes to form a Methylbenzenesulfonic acid and an electrophilic triarylamine monomer, and the electrophilic triarylamine monomer will produce a self-condensation reaction of Friedel-Crafts type, thereby forming the above-mentioned hyperbranched triarylamine polymer . Another feature of the present invention is to provide an organic light-emitting diode, wherein the organic light-emitting diode system utilizes cyclic voltammetry to electrically polymerize the above-mentioned hyperbranched triarylamine polymer and form a hole-conducting layer of an organic light-emitting diode. The brightness of the above organic light-emitting diode can be up to 20,000 cd/m 2 or more. According to the features described above, the present invention discloses a hole conducting layer material which can be applied to an organic light emitting diode.实施 [Embodiment] The direction of the invention discussed herein is a hole conducting layer material. In order to thoroughly understand the present invention, a detailed description will be provided. The implementation of this issue is not limited to the specific details familiar to those skilled in the art. Other components or steps that are gone in the past are not described in the details to avoid unnecessary inventions. The present invention will be described in detail in addition to the scales of the present invention, and the present invention can be used in the following embodiments, and the scope of the present invention is limited to the following patent scope: 5 201020275. A first embodiment of the present invention discloses a hole conducting layer material for use in polymer light-emitting diodes, the hole conducting layer material comprising a hyperbranched triarylamine (hyperbranched triarylamine) The single system forming the above-mentioned hyperbranched triarylamine polymer is derived from a triarylamine monomer comprising at least one tosylate group. Wherein some of the above-mentioned triarylamine monomers comprising at least a tosylate group are hydrolyzed to form a methylbenzenesulfonic acid and an electrophilic triarylamine monomer, and the above is electrophilic The triarylamine monomer forms a self-condensation reaction of the Friedel-Crafts type to form the above-mentioned hyperbranched triarylamine polymer. The general formula of the above triarylamine monomer containing at least a tosylate group is as follows:

Where 'A is CH2 and x is 2 to 8. The general formula of the above electrophilic triarylamine monomer is as follows:

6 201020275 In a preferred embodiment of the present embodiment, one of the above-described hyperbranched triarylamine polymers is as follows:

A second embodiment of the present invention discloses a method for forming a material of a hole conducting layer, wherein the forming method comprises: providing a triarylamine monomer comprising at least one tosylate group, the above comprising at least The triarylamine monomer of the tosylate group is hydrolyzed to form a methylbenzenesulfonic acid and an electrophilic triarylamine monomer, and the above electrophilic triarylamine monomer The above-mentioned highly branched triarylamine polymer is formed by a self-condensation reaction of Friedel-Crafts type, whereby the above-mentioned hole conducting layer material is completed. The general formula of the above triarylamine monomer containing at least one benzenesulfonate group is as follows: 7 201020275

Wherein A is CH2 and x is 2 to 8.

The general formula of the above electrophilic triarylamine monomer is as follows:

In a preferred embodiment of the present embodiment, one of the above-mentioned hyperbranched triarylamine polymers is as follows:

Wherein m is from 3 to 9 and η is from 3 to 9. 201020275 A third embodiment of the present invention discloses an organic light-emitting diode (p〇lyma Light-Emitting Diode), comprising: an anode, a hole-transporting layer on the anode, and a hole-transporting layer An emitting layer on the conductive layer of the hole and a cathode on the light emitting layer.

Wherein the above-mentioned hole conducting layer comprises a hyperbranched triarylamine polymer, and the single system forming the above-mentioned hyperbranched triarylamine compound is derived from a group comprising at least a tosylate group (tosylate) Group) triarylamine monomer. Wherein some of the above-mentioned triarylamine monomers comprising at least one tosylate group are hydrolyzed to form a methylbenzenesulfonic acid and an electrophilic triarylamine monomer, and the above is electrophilic. The triarylamine monomer forms a self-condensation reaction of the Friedel-Crafts type to form the above-mentioned hyperbranched triarylamine polymer. Further, the thickness of the hole conducting layer is less than or equal to 10 nm, and the brightness of the above organic light emitting diode is 20,000 cd/m2 or more. The general formula of the above triarylamine monomer containing at least a tosylate group is as

9 201020275 where A is CH2 and x is 2 to 8. The general formula of the above electrophilic triarylamine monomer is as follows:

In a preferred embodiment of the present embodiment, one of the above-mentioned hyperbranched triarylamine polymers

The general style is as follows:

Wherein m is from 3 to 9 and η is from 3 to 9. A fourth embodiment of the present invention discloses a method for forming an organic light-emitting diode (Polymer Light-Emitting Diode). The method for forming the method includes: firstly, providing an anode, electropolymerization - highly branched triarylamine 201020275 a polymer (hyperbranched triarylamine polymer) to form a hole-transporting layer on the anode, and secondly, a light-emitting layer on the hole-transporting layer, and finally a cathode On the above luminescent layer. Wherein the above-mentioned hyperbranched triarylamine polymer is derived from a triarylamine monomer comprising at least one tosylate group of the tosylate group, wherein the above-mentioned three aromatic groups containing at least one tosylate group (tosylate group) Hydrolysis of amine mono φ to form a methylbenzenesulfonic acid and an electrophilic triarylamine monomer, and the above electrophilic triarylamine monomer is self-condensed by Friedel-Crafts type to form the above-mentioned hyperbranched triaryl Amine polymer. Further, the thickness of the above-mentioned hole conducting layer is less than or equal to 10 nm, and the brightness of the above organic light emitting diode is 20,000 cd/m2 or more. The general formula of the above triarylamine monomer containing at least a tosylate group is as follows:

Wherein A is CH2 and X is 2 to 8. The general formula of the above electrophilic triarylamine monomer is as follows: 201020275

In a preferred embodiment of the present embodiment, one of the above-mentioned hyperbranched triarylamine polymers is as follows:

Wherein m is from 3 to 9 and η is from 3 to 9. Example 1 Preparation of a highly branched triarylamine polymer (ΡΜΤΡΑ) The following precursors were pre-configured: 4-(N,N, Diphenylamino) benzyl alcohol Anhydrous DMF (40 mL) was placed in a round bottom using an aldehyde grouping reaction of an aromatic ring. In a flask, the flask was placed in an ice bath environment, and POCl3 (25.4 g, 150 mmol) 12 201020275 was added dropwise to the flask and stirred. After reacting for 30 minutes, TPA (36.8 g, 150 mmol) was slowly added to the flask. Next, the above mixture was heated for 2 hours (90 ° C) 'then' to add crushed ice to the beaker to cool the temperature, followed by dropwise addition of a saturated NaOAc solution to neutralize the pH of the above mixture to pH 6-8, which • Secondary extraction with di-methane, placing the extract in a container, washing the extract with water, removing the remaining water with MgS〇4 and concentrating, thereby obtaining a yellow solid 4-(N,N' Diphenylamino Benzyldehyde, yield 66%, 4 NMR (400 MHz, CDC13) (5 9.78 (s, 1H), 7.65 (d, J = 8.8 Hz, 2H), ❹ 7.32 (m, 4H), 7.14-7.16 (m , 6H), 7.00 (d, J = 8.8 Hz, 2H); 13C NMR (100 MHz, CDC13) δ 190.13, 153.11, 145.92, 131.13, 129.56, 128.91, 126.19, 124.95, 119.18; MALDI-TOF-MS:m /z 273.1151 (M+), wherein 4-(N,N' Diphenylamino) benzyl alcohol was extracted by column chromatography to extract 4-(N,N' Diphenylamino) benzyl alcohol (22.1 mg » 80.9 mmol) Dissolved in ethanol (280 mL) and added NaBH4 (1.68 g, © 44.3 mmol) dropwise, wherein the above NaBH4 was dissolved in aqueous NaOH (0.1 M, 15 mL), and then reacted at room temperature for 4 hours. The product is extracted with di-methane, and the extract is placed in a container, and the extract is washed with water, and the remaining water is removed by MgS04 and concentrated. The unpurified product is recrystallized, thereby obtaining one. 4-(N,N' Diphenylamino) benzyl alcohol, yield 99%, NMR (400 MHz, CDC13) δ 7.20-7.25 (m, 6H), 7.04-7.07 (m, 13 201020275 6H), 6.97 -7.10 (m, 2H), 4.17 (d, J = 5.2 Hz, 2H), 1.77 (t, 5.2 Hz, 1H); 13C NMR (100 MHz, CDC13) δ 147.14, 146.87, 134.48, 128.80, 127.85, 123.80 , 123.61, 122.40, 65.10; MALDI-TOF-MS: m/z 275.1303(M+) » First, mix NaH (0.41g ' 16.9mg) with DMF (10mL) in a double flask, and secondly, 4-( N,N' Diphenylamino) benzyl alcohol (4.2 g, 16.9 mmol) was dissolved in DMF (10 mL) and added to the above-mentioned double-necked flask, followed by stirring for a while and then adding butyl succinyl sulfonate (1,4-butane). Ditosylate, ll.Og, 27.6 mmol) and reacted at room temperature for 2 days, followed by the addition of methanol to terminate the reaction, wherein methanol and part of DMF were removed by rotary evaporator, leaving the residue Washed with water and purified methane gas using two extraction. At last,

Obtained as a pale yellow liquid product (1), yield 45%, 1H NMR (400 MHZ, CDCl3): 5 7.76 ((i, J) 8.4

Hz, 2H), 7.30 (d, J ) 8.4 Hz, 2H), 7.19-7.21 (m, 4H), 7 13 (dn 8.4 Hz, 2H), 6.97-7.06 (m, 8H), 4.36 (s, 2H ), 4.03 (t, 6 Hz 2H) 3.42 (t,6 Hz, 2H), 2.41 (s, 3H), 1.73-1.76 (m, 2H), 1.6〇-i.6'5(m' 2H), Among them, the product (1) was purified by column chromatography. Further, the above product (1) was allowed to stand overnight to obtain a highly branched triarylamine polymer (PMTPA), wherein the above product (1) was partially hydrolyzed to form a methylbenzenesulfonate.

And the above-mentioned triarylamine monomer having an electrophilic property with an electrophilic triarylamine monomer generates a self-condensation reaction of Friedel-Crafts type, thereby producing a highly branched triarylamine polymer (PMTPA). ), the chemical reaction is as follows.

Friedel-Crafts Type polymerization

PMTPA

Wherein m is from 3 to 9 and n is from 3 to 9. 15 201020275 Further, the above PMTPA was measured by gel permeation chromatography: Mw = 10 200; Mn = 3400; DPI = 3.01. Elemental analysis: C丨9Hi5N, estimated value: C, 88.68; , 5_88; N, 5.44. Actual value: C, 85·39; Η, 5.85; N, 5.16. The molecular weight and thermal stability of the above PMTPA are shown in Table 1 below, wherein Mw: molecular weight, PDI: polymerization distribution index, Tg: and glass transition temperature Td: cracking temperature. Μ P Tg(° Td(° 102 3. 158 516 Example 2 Preparation of Organic Light-Emitting Diode Pre-configured Solution: Dissolving PVK (100 mg), PBD (30 mg) and Ir(ppy) 3 (40 mg) in three gas Brothel (8 mL), allowed to stand for several hours to complete dissolution, wherein undissolved particles and dust were removed by microfiltration technique. PMTPA was electropolymerized by cyclic voltammetry on an indium tin oxide-glass electrode, and The surface is rinsed with a gas mask to form a hole conducting layer on the electrode. Next, the pre-form solution is spin coated (3 rpm, 9 sec) onto the hole conducting layer and dried under vacuum. (7〇. (:, 1 minute), thereby forming a light-acting layer on the hole conducting layer, and secondly, depositing an opposite electrode (Mg/A1) on the above-mentioned light-acting layer 16 201020275 (deposition system: 5xlO_6Torr According to this, an organic light-emitting diode is completed. The deposition rate of the opposite electrode is: Mg: lA/s, A1: 4 A/s. In addition, the scanning electron microscope of the above-mentioned hole conducting layer is as shown in the first figure. The performance relationship diagram of the above organic light-emitting diodes is shown in Table 2 below: Table 2 CV eydc numbens H1L film thkkness (rmf i 3 10 IS 20 30 40 0&quot; Qc 0C Qc 43 9.4 13.6 249 lum-oit vdtag^ (V) ai cd/gi2 max bii^itiiess (od^m2) max efficieRcy (cd/A) Ν · Seto 123 ±0M ί\Μ±ϋ.ω 1 heavy '5 soil MS ϋ.5±0,20 il.2±a〇5 ΆΊ ±0.20 I3jS ±0.i0

NAfc 16670 at 21 V MI0st22 V 21230 lit 20 V mm ϋ 2〇v mmumy S9^)at 2i V 2757 ai 21 V NA* 8.9 8.9 10.4 10.1 9Λ 6泠46 where CV cycle numbers : Cyclic voltammetry cycles, HTL Film thickness : thickness of the hole conduction layer, turn_〇voltage: on voltage, max brightness. maximum brightness and max efficiency: maximum efficiency, and na indicates that the data is not up to the available value. Obviously, many modifications and differences may be made to the invention in light of the above description. It is therefore to be understood that within the scope of the appended claims, the invention may be The above are only the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any equivalent changes or modifications made without departing from the spirit of the present invention should be included in the following. Apply for a patent. 17 201020275 [Simple description of the diagram] The first picture is a scanning electron microscope image of the hole conduction layer in the second example.

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Claims (1)

201020275 VII. Patent application scope: 1. A hole conducting layer material, the hole conducting layer material containing a high branching Sanfang The single system of polymer is derived from a triarylamine monomer comprising at least one tosylate group. 2. The hole conducting layer material according to claim 1, wherein a portion of the triarylamine monomer having at least one tosylate group is hydrolyzed to form a methylbenzenesulfonate. The acid is combined with an electrophilic triarylamine monomer, and the electrophilic triarylamine monomer is subjected to a self-condensation reaction of Friedel-Crafts type to form the still branched triarylamine polymer. 3. The material of the hole conducting layer according to claim 1, wherein the general formula of the triarylamine monoterpene containing the Q-toluenesulfonate group is as follows: Wherein A is CH2 and X is 2 to 8. 201020275 4. The hole conducting layer material according to claim 2, wherein the general formula of the electrophilic triarylamine monomer is as follows: ❹ 5. The material of the hole conducting layer according to claim 1, wherein the general formula of the highly branched triarylamine polymer is as follows: Wherein, m is 3 to 9, and η is 3 to 9 6. The hole conducting layer material according to claim 1, wherein the hole conducting layer material is applied to an organic light emitting diode (polymer light) -emitting diodes) ° 20 201020275 7. A method for forming a hole conducting layer material, wherein the hole conducting layer material comprises a hyperbranched triarylamine polymer, the method comprising: providing an inclusion a triarylamine monomer of at least one tosylate group, wherein the triarylamine monomer comprising at least one tosylate group is hydrolyzed to form a methylbenzenesulfonic acid and a An electrophilic triarylamine monomer, and the electrophilic triarylamine monomer is formed by a self-condensation reaction of Friedel-Crafts type to form the highly branched triarylamine polymer, thereby completing the hole conducting layer material. 8. The hole conducting layer material according to claim 7, wherein the general formula of the triarylamine monomer containing at least one tosylate group is as follows: °v° Ok where A is CH2 and x is 2 to 8. 9. The hole conducting layer material according to claim 7, wherein the general formula of the electrophilic triarylamine monomer is as follows: 21 201020275 10. The hole conducting layer material according to claim 7, wherein the general formula of the highly branched triarylamine polymer is as follows: 6 wherein m is 3 to 9 and η is 3 to 9. 11. The hole conducting layer material according to claim 7, wherein the hole conducting layer material is applied to a polymer light-emitting diodes. 12. an organic light emitting diode (Polymer Light-Emitting Diode), the organic light-emitting diode comprises: 22 201020275 an anode; a hole-transporting layer on the anode, the hole conducting layer comprising a high-branched Sanfang a macrobranched triarylamine polymer, the single system forming the hyperbranched triarylamine polymer is derived from a triarylamine monomer comprising at least one tosylate group; a luminescent layer The luminescent layer is on the hole conducting layer; and a cathode is located on the luminescent layer. 13. The hole conducting layer material according to claim 12, wherein a portion of the triarylamine monomer comprising at least one tosylate group is hydrolyzed to form a methyl sulfonate. The hyperbranched triarylamine polymer is formed by a self-condensation reaction with an electrophilic triarylamine monomer and the electrophilic diarylamine monomer in a Friedel-Crafts type. 14. The hole conducting layer material of claim 13, wherein the general formula of the triarylamine monomer comprising at least one tosylate group is as follows: 23 201020275 Wherein A is CH2 and χ is 2 to 8. 15. The hole conducting layer material according to claim 13, wherein the general formula of the electrophilic triarylamine monomer is as follows: 16. The hole conducting layer material of claim 12, wherein the general formula of the highly branched triarylamine polymerization is as follows: 24 201020275 where m is 3 to 9 and η is 3 to 9. 17. The organic light-emitting diode according to claim 12, wherein the thickness of the hole conducting layer is less than or equal to 10 nm. The organic light-emitting diode according to claim 12, wherein the brightness of the organic light-emitting diode is 20,000 cd/m 2 or more. 0 19. An organic light-emitting diode (Polymer Light- Emitting Diode), the forming method comprising: providing an anode; electropolymerization - a hyperbranched triarylamine polymer to form a hole-transporting layer at the anode Above, wherein the hyperbranched triarylamine polymer is derived from a triarylamine monomer comprising at least a tosylate group, wherein the triarylamine single system is self-condensed (self -condensation) forming the hyperbranched triarylamine polymer; forming a light-emitting layer on the hole-transPrating layer; forming a cathode on the light-emitting layer. 20. The hole conducting layer material of claim 19, wherein a portion of the triarylamine monomer comprising at least one tosylate group hydrolyzes 25 201020275 to form a methyl benzene sulfonate The acid is combined with an electrophilic triarylamine monomer, and the electrophilic triarylamine monomer is self-condensed by a Friedel-Crafts type to form the hyperbranched triarylamine polymer. The invention comprises the material of the hole conducting layer material according to claim 19, wherein the general formula of the at least one tosylate group trapped triarylamine monomer is as follows: Wherein A is CH2 and X is 2 to 8. 22. The material for a hole conducting layer according to claim 20, wherein the general formula of the electrophilic triarylamine monomer is as follows: 23. The hole conducting layer material of claim 19, wherein the general formula of the highly branched triarylamine polymerization is as follows: 26 201020275 The organic light-emitting diode according to claim 19, wherein the thickness of the hole conducting layer is less than or equal to 10 nm. The organic light-emitting diode according to claim 19, wherein the organic light-emitting diode has a luminance of 20,000 cd/m2 or more. 27