WO2013089444A2 - Nouveau polymère de dicétopyrrolopyrrole et élément électronique organique utilisant celui-ci - Google Patents

Nouveau polymère de dicétopyrrolopyrrole et élément électronique organique utilisant celui-ci Download PDF

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WO2013089444A2
WO2013089444A2 PCT/KR2012/010816 KR2012010816W WO2013089444A2 WO 2013089444 A2 WO2013089444 A2 WO 2013089444A2 KR 2012010816 W KR2012010816 W KR 2012010816W WO 2013089444 A2 WO2013089444 A2 WO 2013089444A2
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organic semiconductor
polymer
sevse
diketopyrrolopyrrole polymer
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권순기
김윤희
강일
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경상대학교산학협력단
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Definitions

  • the present invention relates to an organic semiconductor compound for organic electronic device such as an organic thin film transistor (OTFT) and its use. More specifically, the present invention relates to a diketopyrrolopyrrole polymer and an organic electronic device using the same as an organic semiconductor layer as a novel organic semiconductor compound having a high pi electron stack by introducing an electron donor compound into a diketopyrrolopyrrole derivative. will be.
  • OFT organic thin film transistor
  • OFTs organic thin film transistors
  • the organic thin film transistor using the organic semiconductor has the advantages of simpler manufacturing process and lower cost production compared to the organic thin film transistor using amorphous silicon and polysilicon, and is compatible with the plastic substrates for implementing the flexible display. Due to this superior advantage, many researches are being made recently.
  • the use of a polymer organic semiconductor has the advantage that the manufacturing cost can be reduced compared to the low molecular organic semiconductor compound because of the advantage that the thin film can be easily formed by the solution process.
  • Representative semiconductor compounds for polymer-based organic thin film transistors developed to date include P3HT [poly (3-hexylthiophene)] and F8T2 [poly (9,9-dioctylfluorene-co-bithiophene)].
  • P3HT poly (3-hexylthiophene)
  • F8T2 poly (9,9-dioctylfluorene-co-bithiophene
  • FIG. 1 is a cross-sectional view illustrating a structure of a general organic thin film transistor including a substrate, a gate, an insulating layer, an electrode layer (source, drain), and an organic conductive layer, and a gate electrode is formed on the substrate.
  • An insulating layer is formed on the gate electrode, and an organic semiconductor layer, and a source and a drain electrode are sequentially formed on the gate electrode.
  • the driving principle of the organic thin film transistor having the above structure will be described below with an example of a p-type semiconductor. First, when a current is applied by applying a voltage between the source and the drain, a current proportional to the voltage flows under a low voltage.
  • the organic thin film transistors which are constructed on the principle described above, include electrodes (source and drain), substrates and gate electrodes requiring high thermal stability, insulators having high dielectric properties and dielectric constants, and semiconductors that transfer charges well.
  • the core material is organic semiconductor.
  • Organic semiconductors can be classified into low molecular organic semiconductors and high molecular organic semiconductors according to molecular weight, and are classified into n-type organic semiconductors or p-type organic semiconductors according to whether electrons or holes are transferred. In general, when a low molecular weight organic semiconductor is used in forming an organic semiconductor layer, the low molecular weight organic semiconductor is easy to purify and almost removes impurities, so the charge transfer characteristics are excellent.
  • Korean Patent Publication No. 2011-0091711 and Korean Patent Publication No. 2009-0024832 disclose polymers in which an S-containing heteroaromatic ring is directly bonded to a diketopyrrolopyrrole group.
  • the materials that have emerged so far do not exhibit sufficient expansion of pi electrons, so it is necessary to develop a polymer semiconductor material exhibiting sufficient pi electron overlap.
  • An object of the present invention is to alternately polymerize a diketopyrrolopyrrole derivative, one of the electron acceptor materials, and an electron donor material, an aromatic material in which a vinylene bond is introduced, to have high air stability and to increase coplanarity of the main chain. It is to provide a diketopyrrolopyrrole polymer containing a double bond that can exhibit a sufficient pi electron expansion by having an expanded conjugated structure.
  • 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 and viscosity to facilitate spin coating at room temperature to enable solution processing.
  • Another object of the present invention is to provide a diketopyrrolopyrrole polymer, which is an organic semiconductor compound having a high charge mobility applied to an organic electronic device.
  • Another object of the present invention is to provide an organic thin film transistor including the novel diketopyrrolopyrrole polymer according to the present invention in an organic semiconductor layer.
  • the present invention relates to an organic semiconductor compound for organic electronic device such as an organic thin film transistor (OTFT) and its use. More specifically, the present invention relates to a p-type polymer organic semiconductor compound used as an active layer material of an organic thin film transistor configured to alternately polymerize a diketopyrrolopyrrole derivative as an electron acceptor compound and a compound containing a vinylene group as an electron donor compound. Dyketopyrrolopyrrole polymer and an organic electronic device using the same.
  • the organic semiconductor compound of the present invention is a diketopyrrolopyrrole polymer represented by the following formula (1), by introducing a vinylene group (V) increases the coplanarity of the main chain (electron density) by having an expanded conjugated structure Improves intermolecular interactions and high mobility.
  • R 1 and R 2 are each independently (C 1 -C 50) alkyl or (C 6 -C 50) aryl;
  • L 1 and L 2 are each independently selected from the following structures
  • V is ego
  • X 1 to X 3 are each independently Se, O, NH, or NR ′;
  • a 1 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 hydrogen, hydroxy group, amino, (C1-C50) alkyl, (C6-C50) aryl, (C1-C50) alkoxy, mono or di (C1-C50) alkylamino, (C1- C50) alkoxycarbonyl or (C1-C50) alkylcarbonyloxy;
  • n is an integer of 1 or 2, and when m is 2, each of V and L 2 may be the same or different from each other;
  • n is an integer from 1 to 1,000.
  • Is selected from the following structures.
  • R 1 and R 2 are each independently (C1-C50) alkyl, more preferably (C24-C50) alkyl, most preferably (C28-C50) alkyl.
  • Alkyl includes straight or branched chain alkyl.
  • the diketopyrrolopyrrole polymer of the present invention may be specifically selected from the following compounds, but is not limited thereto.
  • n is an integer of 1 to 1,000.
  • the diketopyrrolopyrrole polymer of the present invention is selected from the following compounds.
  • n is an integer of 1 to 1,000.
  • the diketopyrrolopyrrole polymer of the present invention is selected from the following compounds.
  • the charge mobility rapidly increases, for example, to have a very remarkable effect of more than twice the charge mobility compared to the carbon number 24. It is good.
  • n is an integer of 1 to 1,000.
  • the final compound may be prepared through an alkylation reaction, a Grignard coupling reaction, a Suzuki coupling reaction, a Stiletto 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 a conventional organic chemical reaction in addition to the above production method.
  • the diketopyrrolopyrrole polymer according to the present invention can be used as a material for forming an organic semiconductor layer of an organic electronic device, specific examples of the manufacturing method of the organic thin film transistor to which it is applied are as follows.
  • n-type silicon used in a conventional organic thin film transistor.
  • This substrate contains the function of the gate electrode.
  • a glass substrate or a transparent plastic substrate having excellent surface smoothness, ease of handling, and waterproofness may be used as the substrate.
  • a gate electrode must be added on the substrate.
  • Substances that can be employed as the substrate include glass, polyethylenenaphthalate (PEN), polyethylene terephthalate (PET), polycarbonate (PC), polyvinyl alcohol (PVP), polyacrylate (Polyacrylate). , Polyimide, polynorbornene and polyethersulfone (PES).
  • an insulator having a high dielectric constant which is commonly used, may be used.
  • Ba 0.33 Sr 0.66 TiO 3 (BST), Al 2 O 3 , Ta 2 O 5 , and La 2 Ferroelectric insulators selected from the group consisting of O 5 , Y 2 O 3 and TiO 2 , PdZr 0.33 Ti 0.66 O 3 (PZT), Bi 4 Ti 3 O 12 , BaMgF 4 , SrBi 2 (TaNb) 2 O 9 , Ba (ZrTi ) O 3 (BZT), BaTiO 3 , SrTiO 3 , Bi 4 Ti 3 O 12 , SiO 2 , SiN x and AlON, an inorganic insulator selected from the group consisting of polyimide, benzocyclobutene (BCB), parylene ( Organic leading bodies such as parylene, polyacrylate, polyvinylalcohol, and polyvinylphenol
  • the organic thin film transistor of the present invention is composed of the substrate 11, the gate electrode 16, the insulating layer 12, the organic base layer 13, the source 14, and the drain electrode 15. As shown in FIG. It includes both top-contact as well as bottom-contact types of substrate / gate electrode / insulation layer / source and drain electrode / derivative layer.
  • HMDS 1,1,1,3,3,3-hexamethyldisilazane
  • OTS octadecyltrichlorosilane
  • OTDS octadecyltrichlorosilane
  • the organic semiconductor layer employing the diketopyrrolopyrrole polymer according to the present invention may be formed into a thin film through vacuum deposition, screen printing, printing, spin casting, spin coating, dipping or ink spraying, 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 about 500 kPa.
  • the gate electrode 16 and the source and drain electrodes 14 and 15 may be conductive materials, but gold (Au), silver (Ag), aluminum (Al), nickel (Ni), chromium (Cr), and indium tin may be used. It is preferably formed of a material selected from the group consisting of oxides (ITOs).
  • FIG. 1-A cross-sectional view showing the structure of a general organic thin film transistor made of a substrate / gate / insulating layer (source, drain) / semiconductor layer.
  • TGA 11-Thermogravimetric Analysis
  • TGA 12-Thermogravimetric Analysis
  • TGA 13-Thermogravimetric Analysis
  • Triphenylphosphine 60.56 g, 0.2308 mol was dissolved in methylene chloride (MC) in a 500 mL three-neck round bottom flask, and the temperature was lowered to 0 ° C. and bromine (35.67 g, 0.2231 mol) was dropped ( dropping) and stir for 10 minutes. Then, 2-dodecylhexadecane-1-ol (33.0 g, 0.0803 mol) dissolved in methylene chloride (MC) was dropped and stirred for 16 hours. Extracted with methylene chloride (MC), the organic layer was washed with water, dried over MgSO 4 and the solvent was removed using a rotary evaporator.
  • MC methylene chloride
  • the polymer may be polymerized through a Stille coupling reaction.
  • the polymer may be polymerized through a Stille coupling reaction.
  • 3,6-bis3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-dodecylhexadecyl) -2,5-dihydro-pyrrolo [3,4 -c] pyrrole-1,4 (2H, 5H) -dione (Preparation Example 3, 0.30 g, 0.92 mmol) and (E) -1,2-bis (5- (trimethylstannyl) selenophen-2- Il) ethene (Preparation Example 1, 0.16 g, 0.92 mmol) is dissolved in chlorobenzene (4.5 mL) and subjected to nitrogen substitution.
  • the polymer may be polymerized through a Stille coupling reaction.
  • the OTFT device was fabricated in a top-contact manner, using 100 nm n-doped silicon as a gate and SiO 2 as an insulator. Surface treatment was performed by using a piranha cleaning solution (H 2 SO 4 : 2H 2 O 2 ) to wash the surface, Alfa's ODTS (octadecyltrichlorosilane) surface was used after SAM (Self Assemble Monolayer) treatment. The organic semiconductor layer was coated with 0.2 wt% chloroform solution using a spin-coater for 1 minute at 2000 rpm.
  • a piranha cleaning solution H 2 SO 4 : 2H 2 O 2
  • Alfa's ODTS octadecyltrichlorosilane
  • SAM Self Assemble Monolayer
  • organic semiconductor material As the organic semiconductor material, PDPPDTSE, P28DPP-SeVSe, or P32DPP-SeVSe synthesized in Examples 1 to 3, respectively, was used.
  • the thickness of the organic semiconductor layer was confirmed as 50 nm using a surface profiler (Alpha Step 500, Tencor). Gold used as the source and drain was deposited to a thickness of 100 nm at 1 A / s. The channel is 100 ⁇ m long and 1000 ⁇ m wide.
  • Keithley 4800 was used to measure the properties of the OTFT.
  • the charge mobility of the organic electronic device fabricated in Example 4 was obtained from the slope of the graph with (I SD ) 1/2 and V G as variables from the following saturation region current equation.
  • I SD is the source-drain current
  • ⁇ or ⁇ FET is the charge mobility
  • C 0 is the oxide capacitance
  • W is the channel width
  • L is the channel length
  • V G is the gate voltage
  • V is T is the threshold voltage.
  • the cutoff leakage current I off is a current flowing in the off state, and is determined as the minimum current in the off state in the current ratio.
  • the light absorption regions of the organic semiconductor compounds (PDPPDTSE, P28DPP-SeVSe, P32DPP-SeVSe) synthesized in Examples 1 to 3 were measured in a solution state (solution: CHCl 3 ) and a film state, and the results are shown in FIGS. 2 to 4. Shown.
  • Table 1 below describes the optical and electrochemical properties of the organic semiconductor compounds synthesized in Examples 1 to 3 (PDPPDTSE, P28DPP-SeVSe, P32DPP-SeVSe).
  • the HOMO value is a value calculated using the result value measured in FIGS. 5 to 7.
  • the band gap was obtained from the UV absorption wavelength in the film state. As shown in Table 1 below, even though the carbon number of the alkyl group is increased, the oxidation level is hardly different, and thus the HOMO level is similar.
  • 11 to 13 illustrate results obtained by measuring the decomposition temperature of the organic semiconductor compounds (PDPPDTSE, P28DPP-SeVSe, P32DPP-SeVSe) synthesized in Examples 1 to 3 using TGA.
  • the temperature at which 5% decomposition of PDPPDTSE occurred was measured at 435 ° C
  • P28DPP-SeVSe and P32DPP-SeVSe are both excellent in thermal stability.
  • FIG. 14 to 19 illustrate transfer curves of devices fabricated in Example 14 using the organic semiconductor compounds synthesized in Examples 1 to 3 (PDPPDTSE, P28DPP-SeVSe, and P32DPP-SeVSe).
  • PDPPDTSE organic semiconductor compounds synthesized in Examples 1 to 3
  • P28DPP-SeVSe organic semiconductor compounds synthesized in Examples 1 to 3
  • P32DPP-SeVSe the organic semiconductor compound synthesized in the present invention can be seen that the charge mobility is increased when the (annealing) at a high temperature of 200 °C or more.
  • the material has excellent thermal stability that can withstand high temperatures of 200 ° C or higher.
  • Table 2 below describes the characteristics of the device fabricated in Example 10 using the organic semiconductor compound (PDPPDTSE, P28DPP-SeVSe, P32DPP-SeVSe) synthesized in Examples 1 to 3.
  • the annealing temperature is 200 ° C.
  • the charge mobility and the annealing ratio increase as the carbon number of the alkyl group substituted in the organic semiconductor compound increases.
  • the alkyl group has 28 carbon atoms and 32 carbon atoms. It can be seen that it has a remarkable effect having a charge mobility of more than twice that much better than the 24 cases, and also has a significant synergistic effect in the point-to-point ratio.
  • a diketopyrrolopyrrole polymer having the following structure was used (J. Am. Chem. Soc. 2011, 133, 10364-10367).
  • the diketopyrrolopyrrole polymer of the present invention a vinylene group is necessarily introduced between selenophene and selenophene, while the comparative compound P (DPP-alt-DTBSe) has a structure in which selenophene and selenophene are connected in a single bond. It is different from the vinylene group of this invention. Therefore, the diketopyrrolopyrrole polymer of the present invention can form a longer conjugated structure due to the vinylene group, thereby making the interaction between molecules relatively larger, thereby making the polymer more rich in electron density. It can be seen.
  • the organic semiconductor compound according to the present invention that is, a diketopyrrolopyrrole polymer configured to alternately polymerize a compound containing a diketopyrrolopyrrole derivative as an electron acceptor compound and a vinylene group as an electron donor compound is mainly introduced by the introduction of a vinylene group.
  • a diketopyrrolopyrrole polymer configured to alternately polymerize a compound containing a diketopyrrolopyrrole derivative as an electron acceptor compound and a vinylene group as an electron donor compound is mainly introduced by the introduction of a vinylene group.
  • the organic thin film transistor employing these devices improves the charge mobility and the flashing ratio, and when the organic thin film transistor is used, it is possible to make an electronic device having excellent efficiency and performance.
  • the organic thin film transistor can also be manufactured by a solution process such as vacuum deposition, spin coating, or printing, thereby reducing the manufacturing cost of an electronic device using the organic thin film transistor.

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Abstract

La présente invention concerne un composé semi-conducteur organique pour un élément électronique organique tel qu'un transistor à couches minces organique (OTFT) et son utilisation. La présente invention concerne plus particulièrement un polymère de dicétopyrrolopyrrole en tant que nouveau composé semi-conducteur organique à chevauchement d'électrons pi élevé par introduction d'un composé donneur d'électrons dans un dérivé de dicétopyrrolopyrrole, et concerne également un élément électronique organique dont la mobilité de la charge et le rapport on/off sont améliorés au moyen du polymère de dicétopyrrolopyrrole sous forme d'une couche de semi-conducteur organique.
PCT/KR2012/010816 2011-12-15 2012-12-13 Nouveau polymère de dicétopyrrolopyrrole et élément électronique organique utilisant celui-ci WO2013089444A2 (fr)

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KR101547843B1 (ko) * 2013-11-11 2015-08-27 경상대학교산학협력단 신규한 알킬 할라이드 화합물 및 이의 제조방법
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
CN104774319B (zh) * 2015-04-08 2017-02-01 中国科学院化学研究所 一种二(苯并噻吩)乙烯聚合物及其制备方法与应用
CN105837799B (zh) * 2016-04-19 2018-04-03 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
JP6725098B2 (ja) * 2016-06-08 2020-07-15 エルジー・ケム・リミテッド 有機トランジスタおよびガスセンサ
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050067381A (ko) * 2002-07-10 2005-07-01 클라리안트 게엠베하 신규한 다이케토피롤로피롤 안료
KR20080093125A (ko) * 2006-02-18 2008-10-20 클라리언트 인터내셔널 리미티드 증가된 견뢰성을 갖는 다이케토피롤로피롤 안료 및 이의 제조 방법
KR20090122207A (ko) * 2007-02-19 2009-11-26 클라리언트 파이넌스 (비브이아이)리미티드 높은 투명도를 갖는 다이케토피롤로피롤 공결정
KR20100014913A (ko) * 2007-03-07 2010-02-11 클라리언트 파이넌스 (비브이아이)리미티드 다이케토피롤로피롤을 기재로 한 안료 제제

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI290164B (en) * 1999-08-26 2007-11-21 Ciba Sc Holding Ag DPP-containing conjugated polymers and electroluminescent devices
CN100572419C (zh) * 2003-10-28 2009-12-23 西巴特殊化学品控股有限公司 新颖的二酮基吡咯并吡咯聚合物
KR100890145B1 (ko) * 2006-06-15 2009-03-20 주식회사 엘지화학 티아졸로티아졸 유도체 및 이를 이용한 유기 전자 소자
KR101235353B1 (ko) * 2011-01-21 2013-02-20 광주과학기술원 싸이에닐렌비닐렌 단위를 포함하는 공중합체 및 이를 이용한 유기 전자소자

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050067381A (ko) * 2002-07-10 2005-07-01 클라리안트 게엠베하 신규한 다이케토피롤로피롤 안료
KR20080093125A (ko) * 2006-02-18 2008-10-20 클라리언트 인터내셔널 리미티드 증가된 견뢰성을 갖는 다이케토피롤로피롤 안료 및 이의 제조 방법
KR20090122207A (ko) * 2007-02-19 2009-11-26 클라리언트 파이넌스 (비브이아이)리미티드 높은 투명도를 갖는 다이케토피롤로피롤 공결정
KR20100014913A (ko) * 2007-03-07 2010-02-11 클라리언트 파이넌스 (비브이아이)리미티드 다이케토피롤로피롤을 기재로 한 안료 제제

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