WO2013089323A1 - Nouveau polymère de dicétopyrrolopyrrole et élément électronique organique l'utilisant - Google Patents

Nouveau polymère de dicétopyrrolopyrrole et élément électronique organique l'utilisant Download PDF

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WO2013089323A1
WO2013089323A1 PCT/KR2012/002870 KR2012002870W WO2013089323A1 WO 2013089323 A1 WO2013089323 A1 WO 2013089323A1 KR 2012002870 W KR2012002870 W KR 2012002870W WO 2013089323 A1 WO2013089323 A1 WO 2013089323A1
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organic
polymer
bis
compound
thin film
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권순기
홍정아
김슬옹
김윤희
강일
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경상대학교산학협력단
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Definitions

  • the present invention relates to an organic-based conductor compound for organic electronic devices such as organic thin film transistors (OTFTs) and their uses. More specifically, the present invention relates to a dieketopi-electron donor compound in a derivative. It is a novel organic-based conductor compound with a high pi-electron layered chip, which is related to organic electronic devices using dieketopy loaf as a condenser and organic-based conductor layer. Background
  • organic thin film transistors are plastics such as display devices such as portable computers, organic EL devices, smart cards, electric tags, pagers, mobile phones, and memory devices such as cash machines and identification tags.
  • OFT organic thin film transistors
  • the organic thin film transistor using organic semiconductor has the advantages of simple manufacturing process and low cost production compared to the organic thin film transistor using amorphous silicon and polysilicon, and plastic substrates for the implementation of flexible display.
  • many studies have been conducted due to the advantages of over-compatibility, especially in the case of using polymer-free conductors, which can reduce the manufacturing cost compared to low molecular weight-based conductor compounds. Have.
  • Compounds include P3HT [poly (3-nucleothiophene)] and
  • F8T2 poly (9,9-dioctylfluorene-co-bithiophene)].
  • OTFT uniqueness feature is however a number of, which is an important evaluation "gacheok charge mobility and off ratio (on / off ratio) to turn, the most important evaluation standard is a charge transfer.
  • Charge transfer turning way type the thin film formed of a semiconductor material ( Structure and morphology), driving voltage and so on.
  • Figure 1 is a substrate / gate / insulating layer / electrode layer (source, drain) / oil-based conductor layer
  • An insulating layer is formed on top of the gate electrode, and an organic base layer and a source and a drain electrode are sequentially formed thereon.
  • the driving principle of the organic thin film transistor of the above structure is described as an example of a P-type semiconductor as follows: First, when a voltage is applied between the source and the drain, the current is proportional to the voltage under low voltage. When a positive voltage is applied to the gate here, the positive charges are driven by the electric field by the applied voltage, so that all of the positive charges are pushed up the top of the semiconductor layer.
  • the core material is organic semiconductors. It can be divided into n-type or P-type oil-based conductors according to electron or hole transfer. In general, when molecular-weighted organic semiconductors are used to form an oil-based conductor layer, low-molecular oil-based conductors are easy to purify The charge transfer characteristics are excellent because they can be almost eliminated.However, these organic semiconductors cannot be spin coated and printed, and the thin film must be manufactured by vacuum deposition, which makes the manufacturing process more complicated and expensive compared to polymer-based conductors. In the case of polymer free-based conductors, high-purity purification is difficult, but heat resistance is excellent and spinco And the printing is possible there is a beneficial advantage in the manufacturing process and cost, mass production.
  • Korean Patent Publication No. 2011-0091711 discloses a polymerizer in which an S-containing heteroaromatic ring is directly bonded to a diketopyrrolopyrrole group.
  • An object of the present invention is to alternately polymerize diketopyrrolop, one of the electron acceptor materials, and an electron donor material, which is an aromatic material in which a derivative and a vinylene bond are introduced, to have high air stability and coplanarity of the main chain.
  • an electron donor material which is an aromatic material in which a derivative and a vinylene bond are introduced.
  • Another object of the present invention is to provide a diketopyrrolopyrrole polymer, which is an organic semiconductor compound having high solubility and high molecular weight, which has viscosity and easy spin coating at room temperature, thereby allowing solution processing.
  • Another object of the present invention is to provide a polymer of diketopyrrolopy, an organic semiconductor compound having a high charge mobility, which is used in organic electronic devices.
  • Another object of the present invention is to provide a novel diketopyrrolopyrrole according to the present invention.
  • An organic thin film transistor comprising a polymer in an organic semiconductor layer is provided. Challenge solution
  • the present invention relates to an organic semiconductor compound for organic electronic devices such as an organic thin film transistor (OTFT) and its use. More specifically, the present invention is configured such that a compound containing a diketopyrrolopyrrole derivative as an electron acceptor compound and a vinylene group as an electron donor compound is alternately integrated.
  • OFT organic thin film transistor
  • the present invention relates to a diketopyrrolopyrrole polymer, which is a p-type polymer organic semiconductor compound used as an active layer material of an organic thin film transistor, and an organic electronic device using the same.
  • the electron density is improved, thereby increasing the intermolecular interaction and high mobility.
  • R 2 are each independently (C1-C50) alkyl or (C6-C50) aryl;
  • [21] and L 2 are each independently selected from the following structures
  • X, to X 3 are each independently S, Se, 0, NH, or NR ';
  • A, and A 2 are each independently hydrogen, cyano or -COOR ";
  • R 'and R are each independently (C1-C50) alkyl or (C6-C50) aryl;
  • R 3 to R 8 are each independently a hydrogen, hydroxy group, amino, (C1-C50) alkyl, (C6-C 5 0) aryl, (C1-C50) alkoxy, mono- or di (C1-C50 ) Alkylamino, (C1-C50) alkoxycarbonyl or (C1-C50) alkylcarbonyloxy;
  • m is an integer of 1 or 2, and when m is 2, each of V and L 2 may be the same as or different from each other;
  • n is an integer of 1 to 1,000.
  • __ Ll- (v ⁇ L 2) m — is selected from the following structures.
  • L ⁇ vL ⁇ m is selected from the following structures.
  • R and R 2 are preferably (C1-C50) alkyl, and the alkyl includes linear or branched alkyl.
  • the diketopyrrolopyrrole polymer of the present invention is specifically selected from the following compounds.
  • n is an integer of 1 to 1,000
  • the final compound may be prepared through alkylation reaction, Grignard coupling reaction, Suzuki coupling reaction, steel coupling reaction and the like.
  • the organic semiconductor compound according to the present invention is not limited to the above production method, and may be prepared by conventional organic chemical reactions in addition to the above production method.
  • the die ketopyrrolopy polymer according to the present invention may be used as a material for forming an organic semiconductor layer of an organic electronic device, and specific examples of the method of manufacturing the organic thin film transistor to which the polymer is applied are as follows.
  • the substrate 11 it is preferable to use n-type silicon used for a conventional organic thin film transistor.
  • This substrate contains the function of the gate electrode.
  • glass substrates or transparent plastic substrates that have excellent surface smoothness, ease of handling, and water resistance may be used.
  • a gate electrode must be added on the substrate.
  • Substances that can be employed as the substrate include glass, polyethyienenaphthalate (PEN),
  • PET Polyethylene terephthalate
  • PC Polycarbonate
  • PVP Polyvinylalcohol
  • Polyacrylate Polyimide
  • an insulator having a large dielectric constant which is commonly used, may be used. Specifically, Bao. 33 Sr 0 . 66 Ti0 3 (BST), A1 2 0 3 ,
  • PdZr o.3 3 Ti 0 .660 3 selected from the group consisting of Ti0 2 (PZT), Bi 4 Ti 3 0 12, BaMgF 4, SrBi 2 (TaNb) 2 0 9 , Ba (ZrTi) 0 3 (BZT), BaTi0 3 ,
  • Insulators selected from the group consisting of SrTi0 3 , Bi 4 Ti 3 0 12 , Si0 2 , SiN x and AION, or polyimide, BCB (benzocyclobutene), parylene, polyacrylate , Polyvinylalcohol and
  • Organic starch bodies such as polyvinylphenol can be used.
  • the structure of the organic thin film transistor of the present invention is as shown in FIG.
  • the substrate / gate electrode as well as the top-contact of the substrate 11 / gate electrode 16 / insulation layer 12 / organic semiconductor layer 13 / source 14 and drain electrode 15 / Insulating layer / source, drain electrode / includes the form of the bottom-contact (bottom-contact) of the organic conductor layer, and also the surface between the source (14) and drain electrode (15) and the organic semiconductor layer (13) HMDS (l, U, 3,3,3-hexamethyldisilazane),
  • OTS octadecyltrichlorosilane
  • OTDS octadecyltrichlorosilane
  • An organic semiconductor layer employing the die ketopyrrolopyrrole copolymer according to the present invention may be formed into a thin film by vacuum deposition, screen printing, printing, spin casting, spin coating, dipping, or ink spraying. And, at this time, the deposition of the organic semiconductor layer may be formed using a high temperature solution at 40 ° C or more, the thickness is preferably around 500 persons.
  • the gate electrode 16 and the source and drain electrodes 14 and 15 are conductive materials
  • ITO insultin oxide
  • Dyketopyrrolopyi containing a derivative and a vinylene group which is an electron donor compound.
  • the diketopyrrolopy polymer which is composed of alternating polymerization of polymers, increases the coplanarity of the main chain with the introduction of vinylene groups and has an expanded conjugated structure to enhance electron density, thereby enhancing intermolecular interactions. Excellent thermal stability.
  • the HOMO value decreases, that is, the electron density increases in the repeating unit, thereby having excellent charge mobility and oxidation stability, and thus may be used as an organic semiconductor layer of an organic thin film transistor. Therefore, the organic thin film transistor employing these devices improves the charge mobility and the flashing ratio. When the organic thin film transistor is used, it is possible to make an electronic device having excellent efficiency and performance.
  • Such organic thin film transistors can also be manufactured by a solution process such as vacuum deposition, spin coating or printing.
  • the manufacturing cost of the electronic device using the organic thin film transistor can be reduced.
  • FIG. 1 is a cross-sectional view showing the structure of a general organic thin film transistor fabricated from a substrate / gate / insulation layer (source, drain) / semiconductor charge.
  • Figure 6 - a view predict the HOMO and LUMO of the structure of Example 1 through a computer simulation (DFT) '
  • Annealed film state c) drawing showing annealed film state at 250 o C)
  • PDPPDBTE organic semiconductor compound
  • Fulasquel was added (E) -l, 2-bis (4-bromophenyl) tene (3 g, 8.7 mmol).
  • Tetrahydrofuran (THF) 250 mL
  • titanium (IV) chloride 6.5 mL
  • Tetrahydrofuran (THF) 250 mL
  • titanium (IV) chloride 6.5 mL
  • Example 1 Synthesis of PDPPDBTE
  • the polymer may be polymerized through a Stille coupling reaction.
  • the filtered solid is purified in the order of methanol, nucleic acid, toluene and chloroform via soxlet.
  • the down liquid was again precipitated in methanol, filtered through a filter, and dried to give PDPPDBTE, the title compound as a dark green solid (90% yield).
  • Mn 34000, polydispersity 1.78, ⁇ NMR (300 MHz, CDCl 3 ) [ppm]: ⁇ 8.93 (broad, 4H), 6.99-6.83 (broad, 6H), 3.88 (broad, 4H), 2.11 (m 2H ), 1.31-1.25 (m, 76H), 1.04-0.88 (m, 12H).
  • the polymer may be polymerized through a Stille coupling reaction.
  • the polymer may be polymerized through a Stille coupling reaction.
  • the polymer may be polymerized through a Stille coupling reaction.
  • the polymer may be polymerized through Suzuki coupling. In the flask
  • PDPPDBTA was obtained (yield: 90%).
  • Mn 20,000, polydispersity 1.68, ⁇ NMR (300 MHz, CDCl 3 ) [ppm]: ⁇ 8.93 (broad, 4H), 6.99-6.83 (broad, 5H), 3.88 (broad, 4H), 2.11 (m 2H ), 1.31-1.25 (m, 76H), 1.04-0.88 (m, 12H).
  • the polymer may be polymerized through Suzuki coupling. In the flask
  • the polymer may be polymerized through a Stille coupling reaction.
  • the OTFT device was fabricated in a top-contact manner, and 300 nm n-doped silicon was used.
  • Si0 2 was used as an insulator.
  • For surface treatment wash the surface using piranha cleaning solution (H 2 S0 4 : 2H 2 0 2 ), and then use SAM (Self Assemble) for the surface using Adrich's OTS (octadecyltrichlorosilane).
  • the organic semiconductor layer was coated with 0.7 wt% chloroform solution at a speed of 2000 rpm using a spin-coater for 1 minute.
  • As the organic semiconductor material PDPPDBTE synthesized in Example 1 was used.
  • the thickness of the organic semiconductor layer was 45 nm using a surface profiler (Alpha Step 500, Tencor). Gold used as the source and drain was deposited to a thickness of 50 nm at 1 A / s.
  • the length of the channel is 1000 ⁇ and the width is 2000 ⁇ .
  • the measurement of the characteristics of the OTFT uses Keithley 2400 and 236 source / measure units.
  • the charge mobility was obtained from the saturation region with a graph of (I SD ) ′′ 2 and V G as variables from the saturation region current equation.
  • I SD is the source-drain current
  • ⁇ or ⁇ ⁇ is the charge transfer
  • C 0 is the oxide film capacitive
  • W is the channel width
  • L is the channel length
  • V G is the gate voltage
  • V T is the threshold voltage.
  • the cutoff leakage current (10 ⁇ is the current flowing in the off state, and is obtained from the current ratio as the minimum current in the off state.
  • the light absorption region of the synthetic polymer compound (PDPPDBTE) synthesized in Example 1 was measured in a solution state and a film state, and the results are shown in FIG. 2.
  • the electrical synthesis of the synthetic polymer compound (PDPPDBTE) synthesized in Example 1 was performed. In order to analyze the chemical properties, cycles were carried out at 50 mV / s under a solvent of Bu 4 NClO 4 (0.1 molar concentration).
  • the measurement results using cyclic voltammetry are shown in FIG. 3, and voltage was applied through coating using a carbon electrode during the measurement.
  • thermal stability of the oil-based conductor compound (PDPPDBTE) synthesized in Example 1 was measured.
  • the glass transition temperature was measured at 260 ° C.
  • the melting temperature was measured at 277 ° C.
  • crystallization was performed.
  • the temperature value is measured at 26 C, indicating that it has a quality characteristic.
  • Figure 5 shows the synthesis of the organic base compound (PDPPDBTE) synthesized in Example 1
  • Decomposition temperature is measured using TGA. 5% of PDPPDBTE . The temperature at which decomposition occurs was measured at 421 0 C, indicating that PDPPDBTE has excellent thermal stability.
  • FIG. 6 the distribution state of electrons according to the energy level of a molecule is illustrated through DFT calculation.
  • HOMO energy level of the organic semiconductor compound (PDPPDBTE) synthesized in Example 1 it can be seen that electrons are spread throughout the molecular structure.
  • LUMO energy level the electrons of the electron donor move toward the electron acceptor, and these results show that the charge separation of energy is performed well.
  • Example 7 shows AFM images (a: room temperature, b: 200 ° C) of the device fabricated in Example 8 using the organic semiconductor compound (PDPPDBTE) synthesized in Example 1.
  • PDPPDBTE organic semiconductor compound
  • the organic semiconductor compound synthesized in the present invention is excellent in thermal stability and can be seen that the charge mobility when the annealing (annealing) can be seen that the material is excellent.
  • Table 2 below describes the characteristics of the device fabricated in Example 8 using the organic semiconductor compound (PDPPDBTE) synthesized in Example 1. As the annealing temperature increases, the charge mobility increases, the threshold voltage increases, and the flashing ratio decreases.
  • Diketopyrrolopyrrole polymers which are configured to alternately polymerize diketopyrrolopie derivatives and a compound containing an electron donor compound vinylene group, increase and expand coplanarity of the main chain with the introduction of vinylene groups.
  • the electron density is improved, thereby increasing the intermolecular interaction and showing excellent thermal stability.
  • the HOMO value is lowered, that is, As the electron density increases in the repeating unit, it has excellent charge mobility and oxidation stability, and can be used as an organic-based conductor layer of organic thin film transistors. Therefore, organic thin film transistors employing these organic films have improved charge mobility and flashing ratio. When using transistors, it is possible to make electronic devices with excellent efficiency and performance.
  • These organic thin film transistors can also be manufactured by solution processes such as vacuum deposition, spin coating or printing.
  • the manufacturing cost of electronic devices using organic thin film transistors can be reduced.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

La présente invention concerne un composé semi-conducteur organique pour un élément électronique organique tel qu'un transistor organique à film mince (OTFT) et une utilisation de ce composé. De façon plus spécifique, la présente invention concerne : un polymère de dicétopyrrolopyrrole constituant un nouveau composé semi-conducteur organique ayant un chevauchement d'électrons pi élevé par introduction d'un composé donneur d'électrons dans un dérivé dicétopyrrolopyrrole ; et un élément électronique organique dans lequel une mobilité de charge et un rapport marche/arrêt sont améliorés par l'utilisation du dérivé dicétopyrrolopyrrole comme couche semi-conductrice organique.
PCT/KR2012/002870 2011-12-15 2012-04-16 Nouveau polymère de dicétopyrrolopyrrole et élément électronique organique l'utilisant WO2013089323A1 (fr)

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CN105837799A (zh) * 2016-04-19 2016-08-10 中国科学院化学研究所 一类二羰基桥连吡咯并吡咯二酮聚合物及其制备方法与应用
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KR101630173B1 (ko) * 2014-01-17 2016-06-24 경상대학교산학협력단 비대칭 헤테로고리-비닐렌-헤테로고리계 다이케토피롤로피롤 중합체, 이를 채용하고 있는 유기 전자 소자 및 이를 제조하기 위한 단량체
WO2015108360A1 (fr) * 2014-01-17 2015-07-23 경상대학교산학협력단 Polymère de dicétopyrrolopyrrole asymétrique contenant un hétérocycle-vinylène-hétérocyclique, dispositif électronique organique l'utilisant, et monomère pour le préparer
KR101600031B1 (ko) * 2014-03-24 2016-03-07 경상대학교산학협력단 비대칭 다이케토피롤로피롤 중합체 및 이를 함유하는 유기 전자 소자
KR102143429B1 (ko) * 2014-03-25 2020-08-11 경상대학교산학협력단 다이케토피롤로피롤 중합체 및 이를 채용하고 있는 유기 전자 소자
CN109897168A (zh) * 2019-02-26 2019-06-18 中国科学院化学研究所 一类基于二噻吩丙烯腈的不等规聚合物及其制备方法与应用

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