TW201116504A

TW201116504A - Organic thin-film transistor

Info

Publication number: TW201116504A
Application number: TW099132207A
Authority: TW
Inventors: Hiroaki Nakamura; Naoki Kurihara; Hirofumi Kondo; Masatoshi Saito; Yuki Nakano
Original assignee: Idemitsu Kosan Co
Priority date: 2009-09-25
Filing date: 2010-09-23
Publication date: 2011-05-16
Also published as: JP2015109455A; WO2011036866A1; JPWO2011036866A1; JP5677306B2

Abstract

Provided is an organic thin-film transistor in which a substrate is provided with an organic semiconductor layer, an insulation layer, and three terminals, for a gate electrode, a source electrode, and a drain electrode, at least. Current between the source and the drain is controlled by applying a voltage to the gate electrode. The provided organic thin-film transistor has a charge-injection layer between the organic semiconductor layer and the source electrode, and another between the organic semiconductor layer and the drain electrode. Said charge-injection layers contain a compound represented by formula (1). (1) In the formula, Ar1 is a substituent represented by formula (2). Ar2 is either a C6-60 divalent aromatic hydrocarbon that may have a substituent or a C2-60 divalent aromatic heterocyclic group that may have a substituent. Ar3 is a substituent represented by formula (3), and n is an integer between 1 and 20. (2) (3)

Description

201116504 六、發明說明：【發明所屬之技術領域】本發明係關於一種有機薄膜電晶體。更詳細而言，係關於一種藉由使與源極電極及汲極電極接合之電荷注入層含有八有低接觸電阻之化合物，而可高速動作及低電壓驅動的有機薄膜電晶體。【先前技術】201116504 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an organic thin film transistor. More specifically, it relates to an organic thin film transistor which can be driven at a high speed and at a low voltage by a compound having eight low contact resistances in a charge injection layer bonded to a source electrode and a drain electrode. [Prior Art]

碍朕ϋ晶體（TFT .........廣文地用乍瑕顯示裝置等之顯示用之開關元件。具有代表性之TFT之剖面結構示於圖！。如圖i所示，TFT於基板上依序具有問極電極、絕緣體層、有機半導體層，並於有機半導體層上：具有隔開特定間隔而形成之源極電極及汲極電極。有機半導體層形成通道區域，藉由於閉極電極上施加之電慶而控制源極電極與汲極電極之間流通之電流’藉此進行開/ 關（ΟΝ/OFF)動作。先月』4 TFT係使用非晶％或多晶石夕而製作，但使用石夕 ::乍TFT時所使用之C一—i。… 學氣相沈積）裝置非赍田主 _ P貝，因而存在使用TFT之顯示裝置 1之大型化會伴隨製造成本大幅增加的問題點。又，由於 2二或多晶石夕之成膜製程係於非常高之溫度下進行’故而存在可用作基柘夕W Η 7敌脂基板等的問題料之種類有限，無法使用輕質之樹為解決上述問.顥，& 石夕的TFT。作^/出有使用有機物代替非晶石夕及多晶為以有機物形成TFT時所使用之成膜方法， 151050.doc 201116504 已知有真空蒸鍍法或塗布法等，藉由該等成膜方法，可抑制製造成本上升且實現元件之大型化，可將成膜時所需之製程溫度設為較低之溫度。故而，使用有機物之打丁具有選擇基板所使用之材料時限制較少的優點，其實用化=到期待。使用有機物之TFT有諸多報告，例如可列舉非專利文獻 1〜16等。作為TFT之有機化合物層巾所使用之有機物，p型材料中，可將共軛系聚合物或噻吩等之多聚體（專利文獻丨〜5 等）、金屬酞菁化合物（專利文獻6等）、稠五苯等縮合芳香族烴（專利文獻7及8等）等單獨使用或以與其他化合物之混合物之狀態而使用。又，η型材料中，例如於專利文獻9中揭示有以义卜举四甲酸二針（NTCDA)等，於專利文獻1〇中揭示有敦化欧菁。 «亥等有機TFT存在源極電極及汲極電極與有機半導體之接觸電阻較大，驅動電壓較高的問題。進而，若接觸電阻變付過大，則存在場效遷移率降低，〇n/〇ff比亦降低之缺點。通常於有機TFT中，場效遷移率係使用下述式（1)及（2)而 °十算出式（1)為於稱為線性區域的沒極電壓較小之區域成立之式，式（2)為於稱為飽和區域的沒極電壓較大之區域成立之式： 15I050.doc 201116504 [數1] (vG-vth)-lvD (1) (式中，ID:没極電流’ vD:及極電壓，Vg :閘極電壓， Vth:—臨界電壓，μ:場效遷移率’ c:每單位面積之絕緣膜電容，L:通道長度，w:通道寬度）。於有機半導體與源極電極及沒極電極之接合為歐姆接合 (ohmic contact)，不存在電荷注入能障之理想情況下，I 述式中之μ與物質固有之值接近。然而，㉟常有機半導體與金屬電極之間存在接觸電阻，故而於汲極電壓較小之區域，電流與電壓之關係與⑴式間產生偏差，㈣域之開關特性不佳。進而，於金屬/有機半導體界面電壓下降，相應地，有機半導體上所施加之有效電壓下降，故而計算出之式（1)及（2)之場效遷移率較小，存在應答速率或開關比下降’驅動電壓上升等問題。為解決該問題，通常係於源極電極及汲極電極與有機半導體之間***中間層（電荷注入層）。作為該中間層之材料，例如於專利文獻11中使用有機電致發光（EL， electroluminescence)元件之電洞注入材料（4,4，_雙[苯基（3_ 甲基苯基）胺基]聯苯）(TPD)及電子注入材料（2_(4_聯苯基）— 5-(4-第三丁基苯基）-1，3,4-呤二哇）(P]BD)。專利文獻12揭示有，源極電極及汲極電極分別含有載子轉送膜與載子傳導膜，且構成與有機半導體接觸之載子轉 151050.doc 201116504 送膜的金屬之功函數與有機半導體之游離電位接近。又，專利文獻13揭示有於源極電極及汲極電極與有機半導體膜之間***有含有無機物之電荷注入層的有機薄膜電晶體。另外，於專利文獻Μ中，在電極與有機半導體層之間設置有奈米叙f 〇於專利文獻15中形成含有銅酿菁等之中間層，於專利文獻16中形成聚偏二氣乙婦等之具有永電偶極矩之中間層。於專利文獻17令，使用六氮聯三伸苯系之材料形成中間層。 ;非專利文獻1 7巾’嘗試藉由以五氟苯硫電極進行處理’而提高電極與有機半導體之間的電荷注入效率。又，亦考慮將上述技術進行組合，於專利文獻㈣，於電極與有機半導體之間分別***含有具有電洞傳輸性之有機化合物與金屬氧化物之層、以及含有具有電子傳輸性之有機化合物與鹼金屬或鹼土金屬之層。然而，使用該等所揭示之材料雖可稍猶降低電壓，但立性能對於實用而言並不充分。 /、作為其他低電愿化技術，於非專利文獻㈣，將源極電極、有機半導體層及沒極電極縱向積層，將閘極電極*** 於源極電極與沒極電極之間。若採用縱型電晶體結構，則可使用與㈣EL元件相同之電荷傳輸材料（非專利文獻Η 係使用銅酞菁作為電荷傳輸材料），故而可減小與電極之接觸電阻，促進電荷注人，實現低電Μ化。然而’於上述縱型電晶體結構中，存在若改良自電極之電荷注入’則斷開電流（0FF eurrent)變大，從而〇n/〇ff比 151050.doc 201116504 下降的問題。又，於專利文獻19中，作 a , 另戍寻腰電晶體之有機半導體層中所使用之材料，搞千等 _ y、有兩末％為苯基，2個以上之二鍵與1個以上之二價芸、方香族經基或芳香族雜> 接μ 結於其間的化合物。^族雜％基父替鍵蚀田仏、 …、而並未揭不亦未暗示將該化合物使用於分別設置於有機半導體層與源極電極間以及上述有機半導體層與汲極電極間的電荷注入層中。此處，有機半導體層擔把負使電何自源極電極向汲極電極遷移之：能’㈣需要含有遷移率較大之材料。並且，於Insufficient crystals (TFTs ... are widely used for display devices such as display devices, etc. The cross-sectional structure of a representative TFT is shown in Fig. i. A substrate electrode, an insulator layer, and an organic semiconductor layer are sequentially disposed on the substrate, and the organic semiconductor layer has a source electrode and a drain electrode formed at a predetermined interval. The organic semiconductor layer forms a channel region by closing The electric current applied to the electrode is controlled to control the current flowing between the source electrode and the drain electrode, thereby performing an on/off operation (ΟΝ/OFF). The first month of the TFT system uses amorphous % or polycrystalline stone. It is produced, but the use of Shi Xi::C-i.. used in the TFT process.) The device is not the main _P, so the large size of the display device 1 using TFT is accompanied by a large manufacturing cost. Increased problem points. In addition, since the film formation process of 2nd or polycrystalline stone is carried out at a very high temperature, there are a limited number of problems that can be used as a base substrate, etc., and lightweight materials cannot be used. The tree solves the above question. 颢, & 石夕夕 TFT. A method of forming a film using an organic material instead of an amorphous stone and a polycrystal to form a TFT with an organic substance is known, and a vacuum deposition method, a coating method, or the like is known as a film forming method. According to the method, the manufacturing cost can be increased and the size of the element can be increased, and the process temperature required for film formation can be set to a lower temperature. Therefore, the use of the organic material has the advantage of being less restrictive when selecting the material used for the substrate, and its practical use = expectation. There are many reports on TFTs using organic materials, and examples thereof include Non-Patent Documents 1 to 16. In the p-type material, a polymer such as a conjugated polymer or thiophene (Patent Document No. 5 or the like) or a metal phthalocyanine compound (Patent Document 6, etc.) can be used as the organic material used for the organic compound layer of the TFT. Condensed aromatic hydrocarbons such as pentacene (Patent Documents 7 and 8, etc.) are used singly or in a mixture with other compounds. Further, among the n-type materials, for example, Patent Document 9 discloses that a tetracarboxylic acid two-needle (NTCDA) or the like is disclosed, and Patent Document 1 discloses a Dunhua phthalocyanine. «Hei and other organic TFTs have problems in that the source electrode and the drain electrode have a large contact resistance with an organic semiconductor and a high driving voltage. Further, if the contact resistance is excessively increased, there is a disadvantage that the field effect mobility is lowered and the 〇n/〇ff ratio is also lowered. Generally, in an organic TFT, the field effect mobility is expressed by the following formulas (1) and (2), and the equation (1) is a formula in which a region having a small electrode voltage is called a linear region, and 2) For the region with a large voltage with a small pole called a saturated region: 15I050.doc 201116504 [Number 1] (vG-vth)-lvD (1) (where: ID: no current) 'vD: And the pole voltage, Vg: gate voltage, Vth: - threshold voltage, μ: field effect mobility 'c: insulation film capacitance per unit area, L: channel length, w: channel width). The bonding between the organic semiconductor and the source electrode and the electrodeless electrode is an ohmic contact, and in the ideal case where there is no charge injection energy barrier, the μ in the I equation is close to the inherent value of the material. However, there is a contact resistance between the 35-normal organic semiconductor and the metal electrode. Therefore, in the region where the drain voltage is small, the relationship between the current and the voltage is deviated from the equation (1), and the switching characteristic of the (4) domain is poor. Further, the voltage at the interface of the metal/organic semiconductor is lowered, and accordingly, the effective voltage applied to the organic semiconductor is lowered, so that the field-effect mobility of the equations (1) and (2) is calculated to be small, and there is a response rate or a switching ratio. Drop 'driver voltage rise and other issues. To solve this problem, an intermediate layer (charge injection layer) is usually interposed between the source electrode and the drain electrode and the organic semiconductor. As a material of the intermediate layer, for example, a hole injection material of an organic electroluminescence (EL) element (4,4,_bis[phenyl(3-methylphenyl)amino group] is used in Patent Document 11 Benzene) (TPD) and electron injecting material (2_(4-diphenyl)-5-(4-t-butylphenyl)-1,3,4-anthracene) (P]BD). Patent Document 12 discloses that a source electrode and a drain electrode each include a carrier transfer film and a carrier conductive film, and constitute a carrier function in contact with an organic semiconductor. 151050.doc 201116504 A work function of a metal to be fed and an organic semiconductor The free potential is close. Further, Patent Document 13 discloses an organic thin film transistor in which a charge injection layer containing an inorganic substance is interposed between a source electrode and a drain electrode and an organic semiconductor film. Further, in the patent document, an intermediate layer containing copper phthalocyanine or the like is formed between the electrode and the organic semiconductor layer, and a polyethylene-containing phthalocyanine is formed in Patent Document 15. An intermediate layer having a permanent electric dipole moment. In Patent Document 17, an intermediate layer is formed using a material of a hexanitrotriazine system. Non-Patent Document 1 7' attempts to improve the charge injection efficiency between the electrode and the organic semiconductor by treating with a pentafluorobenzene sulfur electrode. Further, it is also considered to combine the above-mentioned techniques. In Patent Document (4), a layer containing an organic compound having a hole transporting property and a metal oxide, and an organic compound having electron transporting property are interposed between the electrode and the organic semiconductor, respectively. a layer of an alkali or alkaline earth metal. However, the use of such materials reveals a slight reduction in voltage, but the stand-up performance is not sufficient for practical use. / As another low-powering technology, in the non-patent literature (4), the source electrode, the organic semiconductor layer, and the electrodeless electrode are vertically stacked, and the gate electrode is inserted between the source electrode and the electrodeless electrode. If a vertical transistor structure is used, the same charge transport material as the (IV) EL element can be used (non-patent literature uses copper phthalocyanine as a charge transport material), so that the contact resistance with the electrode can be reduced, and charge injection can be promoted. Achieve low power. However, in the above-described vertical transistor structure, if the charge injection from the electrode is improved, the off current (0FF eurrent) becomes larger, so that the 〇n/〇ff ratio is lower than 151050.doc 201116504. Further, in Patent Document 19, a is used, and the material used in the organic semiconductor layer of the lumbar transistor is obtained, and the _ y, the two ends are phenyl, two or more of the two bonds and one The above-mentioned divalent quinone, aryl-fraternal or aromatic hetero-> The family heterogeneous base is used to replace the bond between the organic semiconductor layer and the source electrode and the charge between the organic semiconductor layer and the drain electrode, respectively. Inject into the layer. Here, the organic semiconductor layer is responsible for the transfer of electrons from the source electrode to the drain electrode: (4) It is required to contain a material having a large mobility. And, in

具有電何注入層之有；f熱镇胳 +曰I ，機潯膜電晶體中，對有機半導體遷移率以外之功能要求程度較 , 平低尤其疋如本發明之有機缚、電晶體般於電荷注入層t使用有機化合物之情形時，有機物彼此接觸，故而界面間電荷容易順暢地遷移。因此，遷移率以外之功能之重要性更低。处另一方面’電荷注入層要求具有自電極注入電荷之功能。電荷注入層之遷移率亦舌亜、杪手亦室要，但若考慮電荷注入層之膜厚適合的是0.3麵〜刚㈣，與較好的是5帅〜⑽二之通道長度相比極短，則其遷移率之重要性低於有機半導體層所要求之遷移率。例如’專利文獻"中之中間層材料所使用之TPD或削、以及專利文獻15中所使用之銅駄菁的遷移率並不高。電荷注入層要求具有降低與含有金屬等無機材料之電極之接觸電阻的功能。又’由於電荷之授受，於源極及汲極電極與電荷注入層之界面會反覆發生氧化還原。故而，要 I51050.doc 201116504 求電荷注入層用之材料具有對氧化還原之耐受性如此，作為有機半導體層用較為優異之材料地轉用作電荷注入層用之材料。 "、w左4易 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平8_228〇34號公報 [專利文獻2]曰本專利特開平8_228〇35號公報 [專利文獻3]日本專利特開平9_232589號公報 [專利文獻4]曰本專利特開平1〇_125924號公報 [專利文獻5]日本專利特開平j 〇_丨9〇〇〇丨號公報 [專利文獻6]曰本專利特開2000474277號公報 [專利文獻7]日本專利特開平5_55568號公報 [專利文獻8]曰本專利特開2〇〇號公報 [專利文獻9]曰本專利特開平】〇_〗3548丨號公報 [專利文獻1 〇]日本專利特開平n_25 1601號公報 [專利文獻11]曰本專利特開平10-125924號公報 [專利文獻12]曰本專利特開2〇〇4_55652號公報 [專利文獻13]日本專利特開2005-327797號公報 [專利文獻14]日本專利特開2004-356530號公報 [專利文獻15]日本專利特開2005_72495號公報 [專利文獻16]日本專利特開2005-109028號公報 [專利文獻17]日本專利特開2007-520075號公報 [專利文獻18]日本專利特開2006-324655號公報 [專利文獻19] WO 2008/044695號手冊 151050.doc 201116504 [非專利文獻] [非專利文獻 1]A. 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RES. & DEV.，第 45卷，1號，第 11 頁，2001年 [非專利文獻 16] A· R_ Murphy等人，Chemical Review，第107卷，第1066頁，2007年 [非專利文獻 17] Marcia M. Payne 等人 J. Am· Chem. S〇c. ’ 第 127卷，第 4986 頁，2005 年 [非專利文獻 18] K. Kudo等人 jpn. j. Appl. phyS.，第 38 卷’第256頁，1999年【發明内容】本發明係為解決上述課題而完成者，其目的在於提供一種應答速率（驅動速率）為高速，且開/關比較大，可以低電壓驅動的有機薄膜電晶體及利用其之有機薄膜發光電晶體。本發明者等人為達成上述目的而反覆進行積極研究，結果發現藉由在有機薄膜電晶體之電荷注入層中使用下述通式⑴所表示之化合物’可達成上述目的，從而完成本發其係於基板上至之三端子、以及亦即，本發明係提供一種薄膜電晶體，夕》又置有閘極電極、源極電極及汲極電極 J51050.doc 201116504 絕緣體層及有機丰遙 h 體層，藉由對閘極電極施加電壓而> 制源極-汲極間電流 l而控者，於上述有機半導體層與源極間设置有電荷注λ恩，汉極入層，且上述電荷注入層含有下述式表示之化合物：飞U)所 [化1] A«y _ Αγ》· Άγ3 (1) η AO係以下述式（3)表 [式⑴式中，Arj、以下述式（2)表示示： [化2]There are electrical injection layers; f thermal stencil + 曰I, in the enamel film, the functional requirements other than organic semiconductor mobility are relatively low, especially as in the organic binding and transistor of the present invention. When the charge injection layer t is an organic compound, the organic substances are in contact with each other, so that the inter-interface charge easily migrates smoothly. Therefore, features other than mobility are less important. On the other hand, the charge injection layer is required to have a function of injecting charges from the electrodes. The mobility of the charge injection layer is also required for the tongue and the hand. However, if the film thickness of the charge injection layer is considered to be 0.3 face to just (four), it is preferably compared with the length of the channel of 5 handsome ~ (10) two. Short, the mobility is less important than the mobility required for the organic semiconductor layer. For example, the TPD or the cut used in the intermediate layer material in the 'Patent Document" and the copper phthalocyanine used in Patent Document 15 are not high. The charge injection layer is required to have a function of lowering the contact resistance with an electrode containing an inorganic material such as a metal. Further, due to the transfer of charge, redox occurs repeatedly at the interface between the source and the drain electrode and the charge injection layer. Therefore, it is required that the material for the charge injection layer has resistance to redox, and it is used as a material for the charge injection layer as an organic semiconductor layer. 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 7] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 15] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin [Patent Document 17] Japanese Patent Laid-Open 2007-52007 [Patent Document 18] Japanese Patent Laid-Open Publication No. Hei. No. 2006-324655 [Patent Document 19] WO 2008/044695 No. 151050.doc 201116504 [Non-Patent Document 1] [Non-Patent Document 1] A. Assadi et al., Applied Physics Letter, Vol. 53, p. 195, 1988 [Non-Patent Document 2] G. Guillaud et al., Chemical Physics Letter, Vol., p. 503, 1990 [Non-Patent Document 3] X. Peng et al. Applied Physics Letter, Vol. 57, p. 2013, 1990 [Non-Patent Document 4] G. Horowitz et al., Synthetic Metals, vol. 41-43, p. 1127, 1991 [Non-Patent Document 5] S. Miyauchi Et al., Synthetic Metals, Vol. 41-43, 1991 [Non-Patent Document 6] F. Garnier et al., Science, Vol. 265, p. 1684, 1994 [Non-Patent Document 7] A. R. Brown et al. Human, Synthetic Metals, Vol. 68, p. 65, 1994 [Non-Patent Document 8] A. Dodabalapur et al., Science, Vol. 268, p. 270, 1995 [Non-Patent Document 9] T. Sumimoto et al. , Synthetic Metals, Vol. 86, p. 2259, 1997 [Non-Patent Document 1] K·Kudo et al. , Thin Solid Films, Vol. 331, p. 51, 1998 [Non-Patent Document 11] K. Kudo et al., Synthetic Metals, Vol. 102, p. 900, 1999 [Non-Patent Document 12] K. Kudo et al. Man, Synthetic Metals, pp. 15105.doc • 9· 201116504 111-112, 11th buy, 2000 [Non-Patent Document 13] W. Geens et al., Synthetic Metals, Vol. 122, p. 191, 2001 [ Non-Patent Document 14] Lay-Lay Chua et al., Nature, Vol. 434, March 10, 2005, p. 194 [Non-Patent Document 15] CD Dimitrakopoulos et al., IBM J. RES. & DEV., Vol. 45, No. 1, page 11, 2001 [Non-Patent Document 16] A·R_ Murphy et al., Chemical Review, Vol. 107, p. 1066, 2007 [Non-Patent Document 17] Marcia M. Payne et al. J. Am. Chem. S〇c. 'Vol. 127, p. 4986, 2005 [Non-Patent Document 18] K. Kudo et al. jpn. j. Appl. phyS., vol. 38, p. 256, 1999 [Invention] The present invention has been made to solve the above problems, and an object thereof is to provide a response rate (drive rate) to a high speed. And the on/off is relatively large, and the organic thin film transistor which can be driven by a low voltage and the organic thin film light-emitting electric crystal using the same can be used. The inventors of the present invention have conducted active research in order to achieve the above object, and have found that the above object can be attained by using the compound represented by the following formula (1) in the charge injection layer of the organic thin film transistor, thereby completing the present invention. The present invention provides a thin film transistor, and the gate electrode, the source electrode and the drain electrode J51050.doc 201116504 insulator layer and the organic Fengyao h body layer are provided on the substrate. By applying a voltage to the gate electrode and controlling the source-drain current l, a charge is applied between the organic semiconductor layer and the source, and a gate is implanted into the layer, and the charge injection layer is formed. A compound represented by the following formula: Fly U) [Chemical Formula 1] A «y _ Α γ" · Ά γ3 (1) η AO is expressed by the following formula (3) [in the formula (1), Arj, by the following formula (2 ) indicates: [Chemical 2]

石反數1〜30之烷基、碳數1〜30之_代烷基、碳數卜”之烷氧基、碳數1〜3 0之鹵代烧氡基、破數丨〜3〇之烧硫基碳數 1〜30之鹵代烷硫基、碳數丨〜川之烷基胺基、碳數2〜3〇之二烷基胺基（烷基可相互鍵結而形成含有氮原子之環結構）、碳數1〜30之烷基磺醯基、碳數丨〜儿之鹵代烷基績醯基、碳數6~60之芳香族烴基、碳數1〜6〇之芳香族雜環基、碳數 3〜30之烷基矽烷基、或氰基’該等各基可具有取代基；尺广尺5及R6~R1()中’鄰接者彼此可形成飽和或不飽和之環狀結構）； 151050.doc 201116504An alkyl group having an inverse number of 1 to 30, an alkyl group having a carbon number of 1 to 30, an alkoxy group having a carbon number, a halogenated fluorenyl group having a carbon number of 1 to 3, and a number of 丨~3〇 a halogenated alkylthio group having 1 to 30 carbon atoms, a alkylamino group having a carbon number of 川~chuan, and a dialkylamino group having 2 to 3 carbon atoms (the alkyl groups may be bonded to each other to form a ring containing a nitrogen atom) (Structure), an alkylsulfonyl group having 1 to 30 carbon atoms, a halogenated alkyl group having a carbon number of 丨~, an aromatic hydrocarbon group having 6 to 60 carbon atoms, an aromatic heterocyclic group having 1 to 6 carbon atoms, The alkylalkylene group having a carbon number of 3 to 30 or the cyano group may have a substituent; in the wide-footed 5 and R6 to R1 (), the adjacent members may form a saturated or unsaturated cyclic structure. ; 151050.doc 201116504

Ah為可具有取代基之碳數6〜6〇之二價芳香族烴基、可具有取代基之碳數2〜60之二價芳香族雜環基； η為1〜20之整數]。又，本發明係提供一種於有機薄膜電晶體中，利用源極-沒極間流通之電流而獲得發光，且藉由對閉極電極施、加電壓而控制發光的有機薄膜發光電晶體。本發明之有機薄膜電晶體之應答速率（驅動速率）高速化’且開/關比較大，驅動電壓亦較低，&而作為電晶體之性^高’且亦可用作可發光之有機薄膜發【實施方式】本發明之有機薄膜電晶體係於基板上至少設置有間極電和、源極電極及汲極電極 r 半# 才之一离子以及絕緣體層及有機雷法 9由對閘極電極施加電壓而控制源極-汲極間 -，於上述有機半導體層與源極·汲極間設置有電荷物且上述電荷注入層含有下述式⑴所表示之化合 [化3]Ah is a divalent aromatic hydrocarbon group having 6 to 6 carbon atoms which may have a substituent, and a divalent aromatic heterocyclic group having 2 to 60 carbon atoms which may have a substituent; η is an integer of 1 to 20]. Further, the present invention provides an organic thin film light-emitting transistor which obtains light emission by using a current flowing between a source and a gate in an organic thin film transistor, and controls light emission by applying a voltage to the closed electrode. The organic thin film transistor of the present invention has a high response rate (drive rate) and is relatively large on/off, and has a low driving voltage, and can be used as an organic light source. Film development [Embodiment] The organic thin film electro-crystal system of the present invention is provided with at least an interpolar charge, a source electrode and a drain electrode, and an insulator layer and an organic layer 9 A voltage is applied to the electrode to control the source-drain-to-drain, and a charge is provided between the organic semiconductor layer and the source and the drain, and the charge injection layer contains a compound represented by the following formula (1).

~~Ar3 (1) 示，Ar3係以T述於通式（1)φ，Λ〆、、 1 )ψ Ar丨係以下述通式（2)表通式（3)表示： [化4] J51050.doc 12 201116504~~Ar3 (1) shows that Ar3 is represented by T in the general formula (1) φ, Λ〆, 1) ψ Ar丨 is represented by the following general formula (2): (Chemical 4) J51050.doc 12 201116504

於通式（2)及（3)中，分別獨立為氫原子、鹵素原子、碳數1〜30之烷基、碳數卜30之鹵代烷基、碳數丨〜％之烧氧基、碳數1〜3 0之鹵代烷氧基、碳數^30之烷硫基、碳數1〜30之鹵代烷硫基、碳數uo之烷基胺基、碳數2〜3〇之二烷基胺基（烷基可相互鍵結而形成含有氮原子之環結構）、碳數1〜3 0之烷基磺醯基、碳數丨〜3 〇之鹵代烷基磺醯基、碳數6〜60之芳香族烴基、碳數丨〜⑼之芳香族雜環基、碳數3〜30之烷基矽烷基、或氰基，該等各基可具有取代基。In the general formulae (2) and (3), each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, a halogenated alkyl group having a carbon number of 30, an alkoxy group having a carbon number of 丨%, and a carbon number. a halogenated alkoxy group of 1 to 30, an alkylthio group having a carbon number of 30, a halogenated alkylthio group having 1 to 30 carbon atoms, an alkylamino group having a carbon number of uo, and a dialkylamino group having 2 to 3 carbon atoms ( The alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom, the alkylsulfonyl group having a carbon number of 1 to 30, the haloalkylsulfonyl group having a carbon number of 丨3 to 3, and the aromatic having a carbon number of 6 to 60. a hydrocarbon group, an aromatic heterocyclic group having a carbon number of (~(9), an alkylalkylene group having 3 to 30 carbon atoms, or a cyano group, and each of the groups may have a substituent.

Ri〜Rs及R6〜R1G中，鄰接者彼此可形成飽和或不飽和之環狀結構。以下，對上述所表示之各基之具體例進行說明。作為上述il素原子，可列舉：氟、氣、溴及碘原子。作為上述烷基，可列舉：甲基、乙基、丙基、異丙基、In Ri~Rs and R6~R1G, adjacent ones can form a saturated or unsaturated cyclic structure. Hereinafter, specific examples of the respective bases described above will be described. Examples of the il element atom include fluorine, gas, bromine and iodine atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

5二丁暴、正戍基、正己正癸基、正十一院基、正基、正庚基、正辛基、正正壬基、十一烧基、正十二烧基、正十四燒基等。作為上述鹵代烷基，例如可列舉：氣甲基、丨—氣乙基、 2-氯乙基、2-氣異丁基、 2,3-二氣-第三丁基、1 L2-—氣乙基、ι，3-二氯異丙基、 1，2,3-三氣丙基、溴曱基、丨_溴乙 1-溴乙 151050.doc ·】3· 201116504 基、2-溴乙基、2-溴異丁基、1，2-二溴乙基、1,3-二溴異丙基、2,3-二漠-第三丁基、1，2,3-三漠丙基、蛾甲基、1 -蛾乙基、2-蛾乙基、2-換異丁基、1,2-二埃乙基、1，3-二峨異丙基、2,3-二碘-第三丁基、1，2,3-三碘丙基 '氟甲基、^ 氟乙基、2-氟乙基、2-氟異丁基、1，2-二氟乙基、二氟曱基、三氟曱基、五氟乙基、全氟異丙基、全氟丁基、全氟環己基等。上述烷氧基係以-OX1表示之基，作為X1之例，可列舉與上述烧基所說明者相同之例，上述鹵代烧氧基係以_〇χ2所表示之基’作為X2之例’可列舉與上述鹵代烧基所說明者相同之例。上述烧硫基係以-SX1所表示之基，作為X!之例，可列舉與上述烧基所說明者相同之例，上述鹵代院硫基係以_SX2 所表示之基，作為X2之例，可列舉與上述鹵代烷基所說明者相同之例。上述烧基胺基係以-ΝΗΧ1所表示之基，二炫基胺基係以-NX X所表示之基，X1及X3分別可列舉與上述烷基所說明者相同之例。再者，二烷基胺基之烷基可相互鍵結而形成含有氮原子之環結構，作為環結構，例如可列舉：吡 0各、°比咯咬、派。定等。上述烷基磺醯基係以-SAX〗所表示之基，作為χι之例，可列舉與上述烧基所說明者相同之例，上述_代烧基確酿基係mo2x2所表示之基’作為χ2之例’ ▼列舉與上述齒代烷基所說明者相同之例。 151050.doc -14- 201116504 作為上述芳香族烴基，基、菲基、第基、該翻列舉··苯基、蔡基、葱决电基、稠四苯基、稠五苯基等。，作為上述芳香族雜環基，例如可列舉其弁苯基、苯并呋喃基、M、，一噻吩苯其… 南基*开售吩基、啥啉基、味唾基、_ 本开夫喃基、二苯并嗟吩基、苯并喧二唾基等。 - 作為上述燒基矽烷基 &…分別可列〜=:xxx所表示之基， ^上这烷基所說明者相同之例。作為上述飽和環狀結構，可列舉 π 環、環己烷環、Μ-)号烷環等。 < …被戊烷作為上述不飽和環狀結構，可列舉與說明者相同之例。不《敎坆基所於通式（1)中’ Αΐ"2為可呈有敢冲| ^ . a有取代基之碳數6〜60之二價若5二丁暴,正戍基,正己正癸基,正十一院基,正基,正庚基,正辛基,正正壬基,十一烧基,正十二烧基,正十四烧Base. Examples of the above halogenated alkyl group include a gas methyl group, a fluorene-oxyethyl group, a 2-chloroethyl group, a 2-isobutyl group, a 2,3-digas-tertiary butyl group, and a L2-air group B. Base, i,3-dichloroisopropyl, 1,2,3-trimethylpropyl, bromomethyl, oxime bromide 1-bromoethyl 151050.doc ·]3· 201116504 base, 2-bromoethyl , 2-bromoisobutyl, 1,2-dibromoethyl, 1,3-dibromoisopropyl, 2,3-di-di-tert-butyl, 1,2,3-tri-propyl, Moth methyl, 1-cyclomethyl, 2-moth ethyl, 2-isoisobutyl, 1,2-diethyl, 1,3-diisopropyl, 2,3-diiod- Tributyl, 1,2,3-triiodopropyl 'fluoromethyl, fluoroethyl, 2-fluoroethyl, 2-fluoroisobutyl, 1,2-difluoroethyl, difluorodecyl , trifluoromethyl, pentafluoroethyl, perfluoroisopropyl, perfluorobutyl, perfluorocyclohexyl and the like. The alkoxy group is a group represented by -OX1, and examples of X1 include the same examples as those described for the above-mentioned alkyl group, and the halogenated alkoxy group is an example of X2 represented by _〇χ2. 'The same examples as those described above for the halogenated alkyl group can be mentioned. The sulfur-burning group is a group represented by -SX1, and examples of X! include the same examples as those described for the above-mentioned alkyl group, and the halogenated group is a group represented by _SX2, and is represented by X2. Examples thereof are the same as those described for the above haloalkyl group. The above-mentioned alkyl group is a group represented by -?1, and the dihydrogenamine group is a group represented by -NX X, and examples of X1 and X3 are the same as those of the above-mentioned alkyl group. Further, the alkyl groups of the dialkylamino group may be bonded to each other to form a ring structure containing a nitrogen atom, and examples of the ring structure include pyridyl groups, a specific ratio of abbreviations, and a chirality. Order. The alkylsulfonyl group is a group represented by -SAX, and examples of the oxime may be the same as those described for the above-mentioned alkyl group, and the base represented by the above-mentioned base is mo2x2 Example of χ 2 ' ▼ The same examples as those described above for the aldentyl group. 151050.doc -14- 201116504 The above aromatic hydrocarbon group, a group, a phenanthryl group, a group, a phenyl group, a phenyl group, an onion group, a condensed tetraphenyl group, a condensed pentaphenyl group or the like. Examples of the aromatic heterocyclic group include a fluorenylphenyl group, a benzofuranyl group, an M, and a thiophene benzoquinone. The south base* is sold as a phenyl group, a porphyrin group, a succinyl group, and a bromo A thiol group, a dibenzopyenyl group, a benzofluorenyl group, and the like. - As the above-mentioned alkyl group, the base group represented by ~=:xxx, and the same example as the alkyl group described above. Examples of the saturated cyclic structure include a π ring, a cyclohexane ring, and an anthracene ring. < ... pentane The unsaturated unsaturated ring structure is the same as the above. If the 敎坆基 is in the general formula (1), Αΐ"2 is a daring | ^ . a carbon with a substituent of 6 to 60

香族烴基、可具有取代基 W 基。叫之一彳貝方香族雜環作為上述碳數6〜6Q之：價芳香族㈣，較㈣％ 6〜30之芳香族烴基，例如可 “疋反數犮-+細萘 '恩、菲、稠四 :、快或稠五苯等之二價殘基，較好的是苯、蔡、*、菲、稠四苯、筷、稠五苯之二價殘基。心作為上述碳數2〜60之二價芳香族雜環基，較好的是石户數 6〜6〇(較好的是碳數8〜6G)之縮合多環二夕％式方香族雜環基較好的是含有笨環或蔡環之好的是含有苯環之結構。例如可。更 .,, 匕各、吡啶、嘧啶、咪唑、噻唑、二噻吩并苯、苯切、苯并二。塞吩、二苯并售吩、笨并嘆吩并==并 I51050.doc 15 201116504 本并°夫°南或二与苯、苯并噻吩、價殘基。二苯并呋喃等之二價殘基，與吩、二笨并噻吩、苯并呋喃、較好的是二嘆吩并、—苯并咳·喃之二作為Ar2之取代基可列舉碳數1The aromatic hydrocarbon group may have a substituent W group. It is called a 彳Beixiangxiang heterocycle as the above carbon number 6~6Q: valence aromatic (four), more than (four)% 6~30 aromatic hydrocarbon group, for example, "疋犮犮 - + fine naphthalene" 恩, phenanthrene , thick four:, fast or thick pentacene and other divalent residues, preferably benzene, Cai, *, phenanthrene, thick tetraphenyl, chopsticks, divalent residues of pentacene. Heart as the above carbon number 2 a divalent aromatic heterocyclic group of -60, preferably a condensed polycyclic hexavalent aryl group of a heterocyclic ring of 6 to 6 Å (preferably a carbon number of 8 to 6 G). It is a structure containing a benzene ring or a ring of a ring containing a benzene ring. For example, 匕, pyridine, pyrimidine, imidazole, thiazole, dithienobenzene, benzene, benzophene, phenanthrene, Diphenyl is sold as phenophene, stupid and sighed == and I51050.doc 15 201116504 Benxi or South and di and benzene, benzothiophene, valence residue. Dibenzofuran and other divalent residues, and Phenol, diphenyl thiophene, benzofuran, preferably dip benzophene, benzoheptyl pentane as a substituent of Ar 2 may be exemplified as carbon number 1

、-I、π基所說明之基。 1〜30之烷基、或碳數可列舉上述R丨〜R1()所表於通式（1)中，11為1〜2〇之整數，η 複數，較好的是1〜5之整數。於上述通式（2)、（3)中， 2〇之整數，η可為1亦可為2以上之較好的是R,、R2、r4、r5、心、Rr I及R10全部為氫原子，心及以之至少一者為鹵素原子、碳數1 12之烧基、碳數卜8之鹵代烷基、碳數i 之鹵代烷氧基、或碳數2〜16之二烷基胺基（烷基可相互鍵結而形成含有氮原子之環結構），當心及Rs不為函素原子、烧基代烷基、自代烷氧基、或二烷基胺基時，為氮原子。又’ R;及Rs之至少一者為碳數卜^之直鏈狀烷基之情況亦較好。於本發明中’通式（1)所表示之化合物較好的是下述通式（4)所表示之化合物： [化5], -I, π base base. The alkyl group of 1 to 30 or the carbon number is exemplified by the above R丨~R1() in the formula (1), 11 is an integer of 1 to 2 Å, and η is plural, preferably an integer of 1 to 5. . In the above formulae (2) and (3), an integer of 2〇, η may be 1 or 2 or more, preferably R, R2, r4, r5, ruthenium, Rr I and R10 are all hydrogen. At least one of an atom, a heart and at least one of a halogen atom, a carbon number of 12, a halogenated alkyl group of carbon number 8, a halogenated alkoxy group of carbon number i, or a dialkylamino group of carbon number of 2 to 16 ( The alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom. When the ring and Rs are not a functional atom, an alkyl group, a self alkoxy group or a dialkylamine group, they are nitrogen atoms. Further, it is also preferable that at least one of R and Rs is a linear alkyl group having a carbon number. In the present invention, the compound represented by the formula (1) is preferably a compound represented by the following formula (4): [Chemical 5]

I51050.doc • 16 · 201116504I51050.doc • 16 · 201116504

:通式⑷：，Rl〜Rl4分別表示與通式⑴中之、〜… 之基，可列舉相同之具體例，R丨〜R5、RPR R13〜u ’鄰接者彼此可形錢和或不料之環狀結構2，可列舉與上述相同之具體例。又，4 i〜20之整數，較好的是1〜5之整數。於上述通式（4)中，較好的是Rn〜Ri^別獨立為氮原子、齒素原子、碳數丨〜12之烷基、碳數丨〜8之齒代烷基、碳數1〜8之烧氧基、碳數1〜8之烧硫基、碳數2〜8之二烧基胺基(烷基可相互鍵結而形成含有氮原子之環結構）、碳數 1〜8之烷基磺醯基、或氰基。又，於通式（4)中，較好的是Ri、R2、Rs、R6、^及 R9〜R"全部為氫原子’ R3AR8之至少一者為_素原子、碳數1〜12之烷基、碳數i〜8之鹵代烷基、碳數卜8之_代烷氧基、或碳數2〜16之二烷基胺基（烷基可相互鍵結而形成含有氮原子之環結構），當1及Rs不為鹵素原子、烷基、鹵代烧基、_代烷氧基、或二烷基胺基之時，為氫原子。又，如上所述，I及Rs之至少一者為碳數卜12之直鏈狀烷基之情況亦較好。進而，於通式（4)中，較好的是Rl〜Rl4之任一者為氟原子、氰基、三氟甲基、或五氟乙基。於本發明中，通式（1 )所表示之化合物較好的是下述通式（5 )所表示之化合物： [化6] 151050.doc -17- 201116504 r9: General formula (4): R1 to Rl4 respectively represent a group of the formula (1), and the same specific examples, and R邻接~R5, RPR R13~u 'adjacent ones can be shaped and/or unexpected. The ring structure 2 can be exemplified by the same specific examples as described above. Further, an integer of 4 i to 20 is preferably an integer of 1 to 5. In the above formula (4), it is preferred that Rn to Ri are independently a nitrogen atom, a dentate atom, an alkyl group having a carbon number of 1212, a carboxyl group having a carbon number of 丨8, and a carbon number of 1. Alkoxy groups of ～8, a sulfur-burning group having a carbon number of 1 to 8, and a dialkylamino group having 2 to 8 carbon atoms (the alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom), and the carbon number is 1 to 8 Alkylsulfonyl, or cyano. Further, in the formula (4), it is preferred that Ri, R2, Rs, R6, and R9 to R" all are hydrogen atoms. At least one of R3AR8 is a _ element atom and an alkyl group having 1 to 12 carbon atoms. a halogenated alkyl group having a carbon number of i to 8, a cycloalkoxy group having a carbon number of 8 or a dialkylamino group having a carbon number of 2 to 16 (the alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom) When 1 and Rs are not a halogen atom, an alkyl group, a halogenated alkyl group, a _alkoxy group or a dialkylamino group, they are a hydrogen atom. Further, as described above, it is also preferable that at least one of I and Rs is a linear alkyl group of carbon number 12. Further, in the formula (4), it is preferred that any of R1 to Rl4 is a fluorine atom, a cyano group, a trifluoromethyl group or a pentafluoroethyl group. In the present invention, the compound represented by the formula (1) is preferably a compound represented by the following formula (5): [Chem. 6] 151050.doc -17- 201116504 r9

r8 r7 (5)R8 r7 (5)

Ri〜Rio與式（1)相同。 R1S〜R22分別獨立為氫原子、碳數卜％之烷基、碳數 1〜30之鹵代烷基、碳數^30之烷氧基、碳數卜”之鹵代烷氧基、碳數1〜30之烷硫基、碳數丨〜儿之齒代烷硫基、碳數 1〜30之烷基胺基、碳數2〜3〇之二烷基胺基（烷基可相互鍵結而形成含有氮原子之環結構）、碳數卜3〇之烷基磺醯基、碳數1〜30之_代烷基磺醯基、碳數6〜6〇之芳香族烴基、妷數1〜60之芳香族雜環基、碳數3〜3〇之烷基矽烷基、或氰基，該等各基可具有取代基’作為該等各基之具體例，可列舉與上述通式之尺广心❶相同之具體例。又，R丨〜K及Re〜Rlc中，鄰接者彼此可形成飽和之環狀結構，作為環狀結構之具體例，可列舉與上述相同之具體例0 於通式（5)中，較好的是Ri、r2、r4、R5、R6、心、R9、 R1〇及R〗5〜R22全部為氫原子，化及尺8之至少一者為函素原子、碳數1〜12之烷基（尤其是直鏈狀之烷基）、碳數丨〜8之鹵代烷基、碳數卜8之_代烷氧基、或碳數2〜16之二烷基胺基（炫基可相互鍵結而形成含有氮原子之環結構），當& 151050.doc 201116504 及h不為鹵素原子、烷基、鹵代烷基、鹵代烷氧基、或二烷基胺基時，為氫原子。進而’於通式（5)中，較好的是R广心之任一者為氟原子、氰基、二氟甲基、或五I乙基。以下，列舉本發明之有機薄膜電晶體的有機半導體層中所使用之通式⑴、⑷及(5)所表示之化合物的具體例：但並不限定於遠寺·Ri~Rio is the same as formula (1). R1S to R22 are each independently a hydrogen atom, an alkyl group having a carbon number of 5%, a halogenated alkyl group having a carbon number of 1 to 30, an alkoxy group having a carbon number of 30, a halogenated alkoxy group having a carbon number, and a carbon number of 1 to 30. An alkylthio group, a carbon number 丨~ child dentate alkylthio group, an alkylamino group having 1 to 30 carbon atoms, and a dialkylamino group having 2 to 3 carbon atoms (the alkyl groups may be bonded to each other to form a nitrogen-containing group) Atomic ring structure), alkyl sulfonyl group of carbon number, alkyl sulfonyl group of 1 to 30 carbon atoms, aromatic hydrocarbon group of carbon number 6 to 6 fluorene, aromatic group of 1 to 60 a heterocyclic group, an alkylalkylene group having a carbon number of 3 to 3 Å, or a cyano group, and each of the groups may have a substituent 'as a specific example of the respective groups, and examples thereof include the above-mentioned general formula In the case of R丨~K and Re~Rlc, the adjacent ones can form a saturated ring structure, and specific examples of the ring structure include the same specific examples as described above. In the above, Ri, r2, r4, R5, R6, R, R9, R1 and R are all hydrogen atoms, and at least one of the ring and the ring 8 is a carbon atom. ~12 alkyl (especially a linear alkyl group, a halogenated alkyl group having a carbon number of 丨8, a hydroxy group having a carbon number of 8 or a dialkylamino group having a carbon number of 2 to 16 (the thio group may be bonded to each other to form a contained a ring structure of a nitrogen atom), when & 151050.doc 201116504 and h are not a halogen atom, an alkyl group, a halogenated alkyl group, a halogenated alkoxy group, or a dialkylamino group, a hydrogen atom. Further, in the formula (5) In the above, it is preferred that any of the R-centers is a fluorine atom, a cyano group, a difluoromethyl group, or a penta-I ethyl group. Hereinafter, the organic semiconductor layer of the organic thin film transistor of the present invention is used. Specific examples of the compounds represented by the general formulae (1), (4) and (5): but not limited to the far temple

[化8][化8]

151050.doc -19. 201116504 (12) (13) (14) (15)151050.doc -19. 201116504 (12) (13) (14) (15)

(20> (21) (22) (23) [化 ll] f3c (24) cf3 (25)(20> (21) (22) (23) [Look] f3c (24) cf3 (25)

-s^Q*〇-^Q-s- (27) / (28) [化 12] -20- 151050.doc ?2- 201116504 -°2〇*〇*〇- (29) ^02O— (30) f5C-〇hQ—d> O-CF； (31) F3C-0 (32) [化 13] K>< 0^-0—oo (33) (34)-s^Q*〇-^Qs- (27) / (28) [12] -20- 151050.doc ?2- 201116504 -°2〇*〇*〇- (29) ^02O— (30) f5C -〇hQ-d>O-CF; (31) F3C-0 (32) [Chemical 13] K>< 0^-0-oo (33) (34)

OrOr

(26) -o(26) -o

(27) o- [化 14](27) o- [Chemistry 14]

-<y-<y

(40)(40)

〇-F (41)〇-F (41)

I51050.doc -21 - 201116504I51050.doc -21 - 201116504

[化 17][Chem. 17]

(57) (58) 151050.doc ·22· 201116504(57) (58) 151050.doc ·22· 201116504

[化 18][Chem. 18]

151050.doc -23- (67) 201116504151050.doc -23- (67) 201116504

151050.doc -24- 201116504151050.doc -24- 201116504

FF

151050.doc -25- 201116504 [化 24]151050.doc -25- 201116504 [Chem. 24]

(92) (93)(92) (93)

(96) <97) [化 25](96) <97) [Chem. 25]

[化 26] 151050.doc -26- 201116504 (106) ~JQr^Or^JOr^Or (107)[化26] 151050.doc -26- 201116504 (106) ~JQr^Or^JOr^Or (107)

{108) (109) cf3 (110){108) (109) cf3 (110)

F FF F

Qr^OQr^O

F [化 27] F (111) F F 時 ♦ (112) 〇 of <113) (114) (115) Of (116) -of (117) ♦ (”8) (119) of- (120) -o <^-Qr (121) [化 28] 〇-^〇)8&0 -Οι^ύ^-Ότ (122)/ (123) (125) •2Ί · (124) 151050.doc 201116504 (126) (127) [化 29] (128) 7 (129) (ISO/ (131) \ (132) n (133) [化 30] (134) 035) (136) (137) 〇f^〇Vr〇 (138) (139) (140)/17 (141)F [化27] F (111) FF ♦ (112) 〇of <113) (114) (115) Of (116) -of (117) ♦ ("8) (119) of- (120) - o <^-Qr (121) [化28] 〇-^〇)8&0 -Οι^ύ^-Ότ (122)/ (123) (125) •2Ί · (124) 151050.doc 201116504 (126 (127) [化29] (128) 7 (129) (ISO/ (131) \ (132) n (133) [化30] (134) 035) (136) (137) 〇f^〇Vr〇 (138) (139) (140)/17 (141)

O^Q)—O (142) 7 18 (143) o^oWo (144) 19 Ο45) (y^oj^o (146) 2〇 (147> [化 31] -28- 151050.doc 201116504O^Q)—O (142) 7 18 (143) o^oWo (144) 19 Ο45) (y^oj^o (146) 2〇 (147> [Chem. 31] -28- 151050.doc 201116504

[化 3 2][Chem. 3 2]

[化 33][化33]

(160)(160)

(162) f3ch^^C〇cV^G^cf3 (163) 151050.doc -29- 201116504(162) f3ch^^C〇cV^G^cf3 (163) 151050.doc -29- 201116504

(164) [化 34](164) [34]

[化 35][化35]

[化 36] I51050.doc -30- 201116504[化36] I51050.doc -30- 201116504

[化 37][化37]

[化 38] 151050.doc -31 - 201116504[化38] 151050.doc -31 - 201116504

[化 39][化39]

式（1)所表示之化合物較好的是游離電位為5.2 eV以上，更好的是5.3 eV以上。又，式（1)所表示之化合物之游離電位之上限例如為7.0 e V。於式（1)所表示之化合物之游離電位為5.2 e V以上之情形時，難以氧化故而大氣穩定性較高。 151050.doc -32- 201116504 上述游離電位例如可藉由光電子光行測定。或循裱伏安法進於如本發明之有機壤趙;φ B _ n專膜電晶體之電子純度較高之材料可獲得場效遷移率牛中糟，使用件。因此，較理想的是視 / t車又咼的器管柱層析法、再“：：對式⑴所表示之化合物利用曰〜在丹、，.〇日曰、瘵餾、昇華箄古生上的是反覆使用該等純化方法：：以純化。較好可提高純度。進而，視需要較種方法’藉此叉干乂狂心的疋反覆進行以上作為純化之最終步驟之昇華純化。較好的是使用： ^ 方法而使以 HPLC(high perf〇man 山〇細°g响，高效液相層析法询定的式⑴所表干2 合物之純度為90%以上的材料化之M m 的㈣’進而好的是❹95%以上The compound represented by the formula (1) preferably has a free potential of 5.2 eV or more, more preferably 5.3 eV or more. Further, the upper limit of the free potential of the compound represented by the formula (1) is, for example, 7.0 e V. When the free potential of the compound represented by the formula (1) is 5.2 e V or more, it is difficult to oxidize and the atmospheric stability is high. 151050.doc -32- 201116504 The above free potential can be determined, for example, by photoelectron light. Or the voltammetric method is applied to the organic soil Zhao as in the present invention; the material with higher electron purity of the φ B _ n film transistor can obtain the field effect mobility of the cattle, and the use piece. Therefore, it is desirable to use the column chromatography method of the image/t-car and the ":: to use the compound represented by the formula (1) to use 曰~ in Dan,, 〇曰, 瘵, 升, 升箄古古The purification method is used repeatedly: to purify. Preferably, the purity can be improved. Further, the sublimation purification as the final step of purification is carried out by the method of the present invention as needed. It is preferred to use: ^ method to obtain HPLC (high perf〇man 〇〇 , , , , , , , , 高效高效高效高效高效高效高效高效高效高效 HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC HPLC M (four)' and then better than ❹ 95%

之材料，尤其好的是俏用Q 疋使用"％以上之材料，藉此，有可能此夠提向有機薄膜電晶體之 ^ M 4gr , 遷移率或開/關比，降低驅動電壓，發揮出材料本來所具有之性能。以下’對本發明之有明。有機潯膑電晶體之元件構成進行說作為本發明之有機薄膜電晶體之元件構成，只要是於基板上至少設置有閘極電極、源極電極、沒極電極之三端子、以及絕緣體層及有機半導體層，於上述有機半導靜與源極-沒極間設置有電荷注入層，#由對閑極電極施加電壓而控制源極-汲極間電流的薄膜電晶體，則並無限制’可具有眾所周知之元件構成。該等之中，作為具有代表性之有機薄膜電晶體之元件構成，將元件a〜d示於圖 151050.doc •33· 201116504 5如此’根據電極之位置、層之積層順序等之不同而已知有幾種構成，本發明之有機薄膜電晶體具有場效電晶體（FET · Field Effect Transistor)結構。有機薄膜電晶體具有·有機半導體層（有機化合物層），以相互隔開特定間隔且對向之方式而形成的源極電極及汲極電極’以及自源極電極、汲極電極分別隔開特定距離而形成之閘極電極；並藉由對閘極電極施加電壓而控制源極_汲極電極間流通之電流。此處’源極電極與汲極電極之間隔係根據使用本發月之有機薄膜電晶體之用途而決定’通常為〇 1 mm，較好的是} μηι〜1〇〇 μιη，進而好的是5 〜。元件A〜D之中，以圖4之元件c為例更詳細地進行說明，元件C之有機薄膜電晶體4於基板1〇上依序具有閘極電極7〇及絕緣體層60，於絕緣體層60上形成有機半導體層5〇，於其上具有隔開特定間隔而形成之一對源極電極20與汲極電極30，進而，於源極電極2〇及汲極電極儿與有機半導體層之間***有電荷注入層4〇。有機半導體層5〇形成為通道區域，藉由於閘極電極70上施加之電壓而控制源極電極2〇及極電極3 〇之間流通之電流，藉此進行開/關動作。於本發明中，含有式（1)所表示之化合物之電荷注入層4〇係積層於源極電極20與有機半導體層50間以及汲極電極3〇與有機半導體層50間，藉此可減小源極電極2〇及汲極電極3〇與有機半導體層50之接觸電阻，降低驅動電壓。 (有機半導體層）作為本發明中所使用之有機半導體，並無特別限制。可 J5i050.doc -34- 201116504 使用通常所揭示之用於有機TFT中之有機半導體。以下揭示具體例。 (有機半導體層中所使用之材料）為獲侍車乂阿之场效遷移率’通常使用結晶性材料。具體而言，可例示如下之材料： ⑴萘、蒽、稠四苯、稍五苯、稠六苯、稍七苯等可具有取代基之并苯（acene)類，例如^雙（苯乙稀基）苯、14-雙 (2-甲基苯乙蝉基）苯、M•雙（3_甲基苯乙稀基卿腫）、 Μ·雙（4_甲基苯乙烯基）苯、聚苯乙炔等具有以C6H5-ch=ch-c6h5所表示之苯乙稀基結構之化合物以及該等化合物之低聚物或聚合物； (2)以下所示之含有噻吩環之化合物： ⑷ α-4Τ、α-5Τ、α-6Τ、η 7Τ 〇τ 7Τ α_8τ之衍生物等可具有取代基之噻吩低聚物； ⑻聚己基違吩、聚（9,9_二辛基g基·2,7_二基共♦塞吩）㈣y(9,9，-di〇ctymuorenyl_2,7_diyl_c〇bithi〇phene)^ 噻吩系高分子； ⑷二苯并。塞吩衍生物、α，α，•雙（二吩并[3,2_b:2.，3,_d] 噻吩）、」噻吩并噻吩-噻吩之共低聚物、并五噻吩 (pentathienoacene)等之縮合低聚噻吩尤其是具有噻吩并苯骨架或二嘆吩并苯骨架之化合物、笨并d塞吩并苯并嘆吩衍生物； ⑺又’砸吩低聚物’無金屬酞菁、銅醜菁、錯酜菁、氧鈦酿菁’料琳，、笨并α卜琳等。卜嘛類，四硫富瓦稀 151050.doc -35- 201116504 (TTF，tetrathiafulvalene)及其衍生物，紅螢締及其衍生物等； (4)四氰對醌二曱烷（TCNQ)、11，11，12，12-四氰基茶_26_ 醌二甲烷（TCNNQ)等之醌低聚物，C60、C70、pCBM^6 6]_ phenyl-C61-butyric acid methyl ester)等富勒埽類，N 苯基- 3,4,9，10-花四缓酸二醯亞胺、n，N’ -二辛基_349 10 茈四羧酸二醯亞胺（C8-PTCDI)、NTCDA、1，4,5,8-蔡四缓酸二醯亞胺（NTCDI)等四羧酸類等。再者’有機半導體層中所使用之材料較好的是與後述之電荷注入層中所使用之材料為不同材料。 (基板）本發明之有機薄膜電晶體中之基板係擔負支持有機薄用電晶體之結構之功能者，作為其材料，除玻璃以外亦可〇The material is especially good. Q 疋 uses more than %% of the material. Therefore, it is possible to raise the M 4gr, mobility or on/off ratio of the organic thin film transistor, and lower the driving voltage. Out of the material's inherent performance. The following is a description of the present invention. The element configuration of the organic germanium transistor is described as an element structure of the organic thin film transistor of the present invention, as long as at least three terminals of a gate electrode, a source electrode, and a electrodeless electrode are provided on the substrate, and an insulator layer and an organic layer are provided. In the semiconductor layer, a charge injection layer is disposed between the organic semiconductor conduction and the source-no-pole, and a thin film transistor that controls a source-drain current by applying a voltage to the idle electrode is not limited. It has a well-known component composition. Among these, as a typical organic thin film transistor, the elements a to d are shown in Fig. 151050.doc • 33· 201116504 5 such that 'the position of the electrode, the order of the layers, and the like are known. There are several configurations, and the organic thin film transistor of the present invention has a field effect transistor (FET) structure. The organic thin film transistor has an organic semiconductor layer (organic compound layer), and the source electrode and the drain electrode ', which are formed at a predetermined interval and opposed to each other, and the source electrode and the drain electrode are separated from each other. The gate electrode is formed by the distance; and the current flowing between the source and the drain electrodes is controlled by applying a voltage to the gate electrode. Here, the interval between the source electrode and the drain electrode is determined according to the use of the organic thin film transistor of the present month, which is usually 〇1 mm, preferably μηι~1〇〇μιη, and further preferably 5 ~. Among the elements A to D, the element c of FIG. 4 is described in more detail as an example. The organic thin film transistor 4 of the element C has a gate electrode 7 and an insulator layer 60 sequentially on the substrate 1 in the insulator layer. An organic semiconductor layer 5 is formed on the 60, and a pair of the source electrode 20 and the drain electrode 30 are formed with a certain interval therebetween, and further, the source electrode 2 and the drain electrode and the organic semiconductor layer are formed. A charge injection layer 4 is interposed therebetween. The organic semiconductor layer 5 is formed as a channel region, and the current flowing between the source electrode 2A and the electrode 3b is controlled by the voltage applied to the gate electrode 70, thereby performing an on/off operation. In the present invention, the charge injection layer 4 containing the compound represented by the formula (1) is laminated between the source electrode 20 and the organic semiconductor layer 50 and between the drain electrode 3 and the organic semiconductor layer 50, whereby The contact resistance between the small source electrode 2 and the drain electrode 3A and the organic semiconductor layer 50 lowers the driving voltage. (Organic Semiconductor Layer) The organic semiconductor used in the present invention is not particularly limited. J5i050.doc -34- 201116504 The organic semiconductors commonly used in organic TFTs are used. Specific examples are disclosed below. (Materials used in the organic semiconductor layer) In order to obtain the field-effect mobility of the car, the crystalline material is usually used. Specifically, the following materials can be exemplified: (1) an acene which may have a substituent such as naphthalene, anthracene, fused tetraphenyl, pentacene, hexabenzene, or slightly heptabenzene, for example, bis (styrene) Benzene, 14-bis(2-methylphenylethyl)benzene, M•bis(3-methylphenylethyl), bismuth(4-methylstyryl)benzene, poly a phenylacetylene or the like having a styrene structure represented by C6H5-ch=ch-c6h5 and an oligomer or a polymer of the same; (2) a compound containing a thiophene ring shown below: (4) α- a thiophene oligomer which may have a substituent such as a derivative of 4Τ, α-5Τ, α-6Τ, η 7Τ 〇τ 7Τ α_8τ; (8) a polyhexyl group, a poly(9,9-dioctylg group·2, 7_diyl ♦ phenophene) (iv) y (9,9,-di〇ctymuorenyl_2,7_diyl_c〇bithi〇phene)^ thiophene-based polymer; (4) dibenzo. a co-oligomer, a pentathienoacene, etc. The condensed oligothiophene is especially a compound having a thienobenzene skeleton or a two-sex phenacene skeleton, a stupid d-dephenobenzophenone derivative; (7) a 'porphin oligomer> a metal-free phthalocyanine, copper ugly Jing, wrong phthalocyanine, oxytitanium phthalocyanine 'material Lin, stupid and alpha berlin and so on. Bu, thiophene 151050.doc -35- 201116504 (TTF, tetrathiafulvalene) and its derivatives, red fluorescein and its derivatives; (4) tetracyanoquinone dioxane (TCNQ), 11 , 11,12,12-tetracyano tea _26_ 醌甲烷 methane (TCNNQ) and other oligomers, C60, C70, pCBM^6 6]_ phenyl-C61-butyric acid methyl ester) and other fullerene , N phenyl - 3,4,9,10-flower four-acid diimide imine, n,N'-dioctyl_349 10 phthalic acid diimine (C8-PTCDI), NTCDA, 1 , 4, 5, 8 - tetracarboxylic acid such as tetracycline (NTCDI). Further, the material used in the organic semiconductor layer is preferably a material different from the material used in the charge injection layer to be described later. (Substrate) The substrate in the organic thin film transistor of the present invention is responsible for supporting the structure of the organic thin transistor, and as a material thereof, it can be used in addition to glass.

用金屬氧化物或氮化物等無機化合物、塑膠膜（pE (polyethylene terephthalate，聚對苯二甲酸乙二酯）、叩 (P〇lyethersulfone，聚醚砜）、pc(p〇iycarb〇nate，聚碳西酯））、金屬基板或者該等之複合體或積層體等。又，於秦由基板以外之構成要素可充分支持薄膜電晶體之結構之# 形時，亦可不使用基板。又’作為基板之材料，多使用石」 (si)晶圓。於此情形時，可將Si本身用作如圖6所示之間相電極兼基板12。又，亦可料之表面氧化，形成⑽而$ 用作絕緣體層62。於此情形時，如圖㈣示，有時亦^ 板兼閉極電極U基板12上形成㈣之金屬層，作為導麟連接用電極。 I5J050.doc • 36 - 201116504Inorganic compounds such as metal oxides or nitrides, plastic films (pE (polyethylene terephthalate), bismuth (P〇lyethersulfone), pc (p〇iycarb〇nate, polycarbon) A oxime)), a metal substrate or a composite or laminate thereof. Further, in the case where the constituent elements other than the substrate can sufficiently support the structure of the thin film transistor, the substrate may not be used. Further, as a material of the substrate, a stone (si) wafer is often used. In this case, Si itself can be used as the phase electrode and substrate 12 as shown in Fig. 6. Further, the surface of the material may be oxidized to form (10) and used as the insulator layer 62. In this case, as shown in Fig. 4, a metal layer of (4) is formed on the plate and the closed electrode U substrate 12 as an electrode for guiding the connection. I5J050.doc • 36 - 201116504

V电徑J 作為本《明之有機薄膜電晶體中之閘極及汲極電極的材料，σI3 極、源極電極〜要疋導電性材料則並I特別"，可使用鉑、金、.銀、鋅 …、特另J限制’ 跟螺、鉻'銅、鐵、錫銦、鈀、碲、銖'銥'鋁銻、鉛'鈕、 «了、錯、海、缚化銦錫(ΙΤΟ)、摻氟氧化鋅、鋅、减錫、氧銀毁及碳聚、鐘、鈹、鈉H '墨、玻璃石墨、饵、π # 甲鈣、钪、鈦、錳、 '°豕、，"* '鈉-卸合金、鎂/鋼混合物、録/銀.θ入物鋁混合物、鎂/銦、$人榀b 、/銀此合物、鎂/ 鎊/銦混合物、鋁/氧化鋁混合等，該等可藉由资轳尜十古鐘/銘昆合物错由顧法或真空蒸鑛法而成膜。於本發明之有機薄膜電晶體中作極，亦可利用#用4人 ’、。電極、汲極電 …用使用包含上述導電性材 (paste)、油墨、分耑该势饮及科刀政液專流動性電極材料而形A i 作為溶劑或分散介抖而I成者。又， |貝苟仰制對有機半導的是含有60質量。/〇以上 π貝傷，較好上义水、較好的是9〇質量的溶劑或分散介質。作為含有金 7 可使用眾所周知之導電性“子之为散物’例如 Λ〇, , ^水㈣’通常較好的是含有粒押為 0.5 nm〜50 nm、！ ηηι〜1Λ π 孤仏 A ^ ^ Μ ηηι之金屬微粒子之分散物。為该金屬微粒子之材枓作卞之材科’例如可使用鉻、銅 '鐵、錫、録n ^ 鎳、叙“7 釔㉙、銦、鈀、碲、銖、銥、、’’了、錯、紹、鶴、辞等。較好的是使用主要包含金屬微粒子分散^ j材料之分散穩定劑，將該等分今物估意有機溶劑之分散介質中形成刀放物’使用該分散物電極。作為此種金屬微粒子之 I51050.doc •37- 201116504 分散物之製造方法，可列舉：氣相蒸發法、濺鍍法、金屬氣相合成法等物理生成法，膠體法、共沈澱法等於液相中還原金屬離子而生成金屬微粒子的化學生成法，.較好的是藉由曰本專利特開平11-76800號公報、日本專利特開平u_ 80647號公報、曰本專利特開平u_319538號公報、曰本專利特開2000-239853號公報等中所示之膠體法，日本專利特開2001_254185號公報、日本專利特開2〇〇1_53〇28號公報、曰本專利特開2〇〇1_35255號公報、曰本專利特開？㈧^ U4157號公報、日本專利特開2〇〇〇_123634號公報等中所揭不之氣相蒸發法而製造的金屬微粒子之分散物。 ^使用該等金屬微粒子分散物成形上述電極，將溶劑乾燥後，視需要於loot〜30(rc，較好的是15〇。(：〜2〇〇1之範圍内根據形狀進行加熱，藉此使金屬微粒子熱融著，形成具有目標形狀之電極圖案。 ^而，作為間極電極、源極電極及沒極電極之材料，使 ,藉由‘雜等而導電率提尚之眾所周知之導電性聚合物亦較好。例如’亦可較好地使用：聚苯胺、聚t各、聚嗟、聚（二氧乙基㈣）(PEDGT)與聚苯乙料酸之錯合物上述例中’形成源極電極及汲極電極之材料亦以與何注入材料之接觸面的電阻較小者為佳。此時之電阻如 7述即製作電流控制料時與場效遷㈣對應，為獲得j :遷移率，電阻必須儘可能小。形成接觸電阻存在各彳原因。例如有電極與有機化合物之附著力、附著面積，1 151050.doc •38· 201116504 =有機化合物之界面上的相互仙（界面上之極化何遷移、鏡像效應等)等原因。其中，重要的是電極材料之功函數與電荷注人層之能階的大小關係。若將電極材料之功函數(w)設為a’將電荷注入層之游離電位(Ip)設為b，㉟電荷注入層之電子系見和力(Af)設為c，則較好的是滿足以下之關係式。此處，a、b及C均為以真空能階作為基準之正值。於P型有機薄膜電晶體之情形時，較好的是5 eV(式（1)) ’進而好的是b-a<l _0 eV。若電極材料與電荷注入層之關係可維持上述關係，則可獲得高性能之器件，尤其好的是選擇功函數儘可能大之電極材料，較好的是功函數為4_0 eV以上，進而好的是功函數為4.2 eV以上。關於金屬之功函數之值，只要自例如化學便覽基礎篇 11-493頁（修訂第3版日本化學會編丸善股份有限公司發行1983年）中所揭示的具有4.0 eV或其以上之功函數之有效金屬之上述列示中挑選即可。高功函數金屬主要有V-circuit J is used as the material of the gate and the drain electrode in the organic thin film transistor of the present invention. The σI3 electrode and the source electrode are required to be conductive materials, and I can use platinum, gold, and silver. , zinc ..., special J limit 'snail, chrome 'copper, iron, tin indium, palladium, bismuth, 铢 '铱' aluminum bismuth, lead 'button, «ha, wrong, sea, bound indium tin (ΙΤΟ) , fluorine-doped zinc oxide, zinc, tin-reduced, oxy-silver-destroyed and carbonized, bell, bismuth, sodium H 'ink, glass graphite, bait, π #甲钙, 钪, titanium, manganese, '°豕,," * 'Sodium-unloaded alloy, magnesium/steel mixture, recorded/silver.θ inclusion aluminum mixture, magnesium/indium, $榀b, /silver, magnesium/pound/indium mixture, aluminum/alumina mixed, etc. These can be formed by Gufa or vacuum distillation method by the ten-year clock/Ming Kun compound. In the organic thin film transistor of the present invention, it is also possible to use #4'. The electrode and the electrode are formed by using the above-mentioned conductive material, ink, bifurcated potential drink, and Kokusai government liquid flow electrode material to form A i as a solvent or dispersion. Also, the shellfish is made of 60 masses for organic semiconducting. / 〇 above π shell injury, preferably upper water, preferably 9 〇 mass of solvent or dispersion medium. As the gold-containing 7 can be used, it is known that the conductivity "child is a bulk matter" such as yttrium, ^ water (four)' is generally preferred to contain a granule of 0.5 nm to 50 nm, ηηι~1Λ π 仏仏 A ^ ^ 分散 ηηι The dispersion of metal particles. For the material of the metal particles, for example, chromium, copper 'iron, tin, n ^ nickel, “ "7 钇 29, indium, palladium, rhodium, ruthenium can be used. , 铱, , '', wrong, Shao, crane, resignation, etc. It is preferred to use a dispersion stabilizer mainly comprising a metal fine particle dispersion material, and to form a knife-distributing material in the dispersion medium of the organic solvent. I51050.doc • 37- 201116504 As such a method of producing a dispersion, a physical production method such as a vapor phase evaporation method, a sputtering method, or a metal vapor phase synthesis method may be mentioned, and the colloid method and the coprecipitation method are equal to the liquid phase. A chemical method for producing a metal fine particle by reducing a metal ion, and a method of producing a metal fine particle by a method of the present invention is preferably disclosed in Japanese Laid-Open Patent Publication No. H11-76800, Japanese Patent Application Laid-Open No. Hei. The colloidal method shown in Japanese Laid-Open Patent Publication No. 2000-239853, and the like, Japanese Patent Laid-Open Publication No. 2001-254185, Japanese Patent Laid-Open Publication No. Hei. No. Hei.曰This patent is open? (A) A dispersion of metal fine particles produced by the vapor phase evaporation method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. The electrode is formed by using the metal fine particle dispersion, and after drying the solvent, it is heated according to the shape in the range of loot to 30 (rc, preferably 15 Å. The metal microparticles are thermally fused to form an electrode pattern having a target shape. ^, as a material of the interpole electrode, the source electrode, and the electrodeless electrode, the well-known conductive polymer is improved by the conductivity of the impurity. It is also preferred. For example, it can also be preferably used: polyaniline, polyt, polyfluorene, poly(dioxyethyl (tetra)) (PEDGT) and polystyrene acid complexes. The material of the source electrode and the drain electrode is preferably smaller than the contact surface of the implant material. The resistance at this time corresponds to the field effect (4) when the current control material is prepared as described in the seventh paragraph, in order to obtain j: Mobility, resistance must be as small as possible. There are various reasons for the formation of contact resistance. For example, the adhesion of electrodes to organic compounds, adhesion area, 1 151050.doc •38· 201116504 = mutual immortality at the interface of organic compounds (interface Polarization, migration, mirror For example, such as effect, etc.), the important thing is the relationship between the work function of the electrode material and the energy level of the charge injection layer. If the work function (w) of the electrode material is set to a', the charge potential is injected into the free potential of the layer. (Ip) is set to b, 35. The electron-trapping force (Af) of the charge injection layer is c, and it is preferable to satisfy the following relationship. Here, a, b, and C are all based on the vacuum level. The positive value of the reference. In the case of a P-type organic thin film transistor, it is preferably 5 eV (formula (1))' and further preferably b-a < l _0 eV. If the electrode material is related to the charge injection layer If the above relationship can be maintained, a high-performance device can be obtained, and it is particularly preferable to select an electrode material having a work function as large as possible, preferably a work function of 4_0 eV or more, and preferably a work function of 4.2 eV or more. The value of the work function of the metal is valid as long as it has a work function of 4.0 eV or more as disclosed in the page 11-493 of the Basics of Chemicals (Revised 3rd edition of the Chemical Society of Japan, Maruzen Co., Ltd., 1983). The above list of metals can be selected. The high work function metals are mainly

Ag(4.26、4.52、4.64、4.74 eV)、Α1(4·06、4.24、4.41 eV)、Au(5.1、5·37、5.47 eV)、Be(4.98 eV)、Bi(4.34 eV)、Cd(4_08 eV)、Co(5.〇 eV)、Cu(4.65 eV)、Fe(4.5、 4.67 ' 4,81 eV)、Ga(4.3 eV)、Hg(4.4 eV)、Ir(5.42、5.76 eV)、Mn(4.1 eV)、Mo(4.53、4.55、4.95 eV)、Nb(4.02、 4.36、4.87 eV)、Ni(5.04、5.22、5.35 eV)、Os(5.93 eV)、 Pb(4.25 eV)、Pt(5.64 eV)、Pd(5.55 eV)、Re(4.72 eV)、 Ru(4.71 eV)、Sb(4.55、4.7 eV)、Sn(4.42 eV)、Ta(4.0、 151050.doc • 39· 201116504 4.15 4.8 eV) ' Ti(4.33 eV) ' V(4.3 eV)、W(4.47、4.63、中’較好的是貴金屬（Ag、 Fe、Ga、lr、Μη、Mo、 5.25 eV)、Zr(4.05 eV)。該等之 Au、Cu、Pt)、Ni、Co、〇s、Ag (4.26, 4.52, 4.64, 4.74 eV), Α1 (4·06, 4.24, 4.41 eV), Au (5.1, 5.37, 5.47 eV), Be (4.98 eV), Bi (4.34 eV), Cd ( 4_08 eV), Co(5.〇eV), Cu (4.65 eV), Fe (4.5, 4.67 '4,81 eV), Ga (4.3 eV), Hg (4.4 eV), Ir (5.42, 5.76 eV), Mn (4.1 eV), Mo (4.53, 4.55, 4.95 eV), Nb (4.02, 4.36, 4.87 eV), Ni (5.04, 5.22, 5.35 eV), Os (5.93 eV), Pb (4.25 eV), Pt ( 5.64 eV), Pd (5.55 eV), Re (4.72 eV), Ru (4.71 eV), Sb (4.55, 4.7 eV), Sn (4.42 eV), Ta (4.0, 151050.doc • 39· 201116504 4.15 4.8 eV ) 'Ti(4.33 eV) ' V (4.3 eV), W (4.47, 4.63, medium 'preferred are noble metals (Ag, Fe, Ga, lr, Μη, Mo, 5.25 eV), Zr (4.05 eV). Such Au, Cu, Pt), Ni, Co, 〇s,

Pd Re、Ru、V、W。金屬之外’較好的是IT〇、聚苯胺 icPEDOT： PSS(p〇ly(ethylenedi〇xythiophene) : poly(styrene sulfonic acid)，聚（二氧乙基噻吩）_聚（苯乙烯磺酸））等導電性聚合物及碳。作為電極材料，只要功函數滿足上述式 (I)，則可含有一種或複數種該等高功函數之物質，並無特別限制。於η型有機溥膜電晶體之情形時，較好的是a c<i 5 eV(式（II)) ’進而好的是a_c<1.〇 eV。若電極材料與電荷注入層之關係可維持上述關係，則可獲得高性能之器件，尤其好的是選擇功函數儘可能小之電極材料，較好的是功函數為4.3 eV以下，進而好的是功函數為3.7 eV以下。作為低功函數金屬之具體例，只要自例如化學便覽基礎篇11-493頁（修訂第3版曰本化學會編丸善股份有限公司發行1983年）中所揭示的具有4.3 eV或其以下之功函數之有效金屬之上述列示中挑選即可，可列舉：Ag(4.26 eV)、Pd Re, Ru, V, W. Outside the metal, 'IT较好, polyaniline icPEDOT: PSS(p〇ly(ethylenedi〇xythiophene): poly(styrene sulfonic acid), poly(dioxyethylthiophene)-poly(styrenesulfonic acid)) Isometric polymer and carbon. As the electrode material, as long as the work function satisfies the above formula (I), one or a plurality of such high work functions may be contained, and there is no particular limitation. In the case of an n-type organic germanium film transistor, it is preferred that a c < i 5 eV (formula (II))' is further preferably a_c < 1. 〇 eV. If the relationship between the electrode material and the charge injection layer can maintain the above relationship, a high-performance device can be obtained, and it is particularly preferable to select an electrode material having a work function as small as possible, preferably a work function of 4.3 eV or less, and thus good. The work function is 3.7 eV or less. As a specific example of the low work function metal, it is possible to have a work of 4.3 eV or less as disclosed in, for example, page 11-493 of the Basics of Chemicals (Revised 3rd Edition, Sakamoto Chemical Society, Maruzen Co., Ltd., 1983). The selection of the above-mentioned effective metals of the function can be selected, for example, Ag (4.26 eV),

Al(4.06、4.28 eV)、Ba(2_52 eV)、Ca(2.9 eV)、Ce(2.9 eV)、Cs(1.95 eV)、Er(2.97 eV)、Eu(2_5 eV)、Gd(3.i eV)、Hf(3.9 eV)、In(4.09 eV)、K(2.28)、La(3.5 eV)、 Li(2.93 eV)、Mg(3.66 eV)、Na(2.36 eV)、Nd(3.2 eV)、 Rb(4.25 eV)、Sc(3.5 eV)、Sm(2_7 eV)、Ta(4.0、4.15 eV)、Y(3.1 eV)、Yb(2.6 eV)、Zn(3.63 eV)等。該等之 15I050.doc •40- 201116504 中，較好的是Ba、Ca、Cs、 L、Mg、Na、Nd、Rb、γ、^ Hf K、La、 % 3 i- +· -ψ n。作為電極材料，只晋刀山數滿足上述式(ίΙ)，則可含有功函數之物質，* &好 5'稷數種s亥等低双疋物並無特別限制。缺觸大氣中 ’、、、，低功函數金屬若接孔中之水分或氧則容易劣化，故而較理想的是視需要以Ag及Au#在空氣中穩定之的疋視需要之膜厚為！0 nm以上，膜厚越严目,丁破覆。被覆所必需之影響，但實際使用時Si越可保護其不受氧或水一下。時為“生產性等理由，較理想的是作為上述電極之形成方法供、盛放 L ] 了精由瘵鍍、電子束基鍍濺鍍、大氣壓電榮法、離 …、，士接 a ^ ▲ 收化学乳相沈積、電沈積、非電解鍍覆、旋塗、印 v n 彳乂策墨寺手段而形成。又，作為視需要所進行之圖宰幕所周知之光微影法或剝離=法，有如下方法:使用性薄胺# # 以上述方法形成之導電之全屬-… 精由熱轉印、噴墨等於链或銅等之金“上形成抗#劑進行#刻的方法。又性聚合物之溶液或分散液、 % 3 ’ I屬你支粒子之合斯游笪古接藉由噴墨法而圖案化，還， ±泠稭田政〜法或雷射剝離法等由塗敷膜形成圖案。另外号 ^ j使用.將含有導電性聚合物或金屬微粒子之導電性油墨 μ, t u 導電性漿料等藉由凸版、凹版、平版、網版印刷等印刷法而圖案化的方法。二ΓΓ成之電極之膜厚，只要有電流導通則並無特 =二是，進而好的是4 — 祀右為此較好之範圍内，則由於膜厚較薄而不會 151050.doc 201116504 使電阻提高電Μ下降。又’由於膜厚並不過厚，故而形成膜無需化費時間，於積層保護層或有機半導體層等其他層之情形時，可不產生階差而平滑地形成積層膜。又，於本貫施形態之有機薄膜電晶體中，例如為進而提间電荷/主入效率，可於電荷注入層與源極電極及汲極電極之間設置緩衝層。對於0型有機薄膜電晶體而言，緩衝層 . 較理想的是有機EL之陰極中所使用之Li]p、Li2〇、CsF、Al (4.06, 4.28 eV), Ba (2_52 eV), Ca (2.9 eV), Ce (2.9 eV), Cs (1.95 eV), Er (2.97 eV), Eu (2_5 eV), Gd (3.i eV) ), Hf (3.9 eV), In (4.09 eV), K (2.28), La (3.5 eV), Li (2.93 eV), Mg (3.66 eV), Na (2.36 eV), Nd (3.2 eV), Rb (4.25 eV), Sc (3.5 eV), Sm (2_7 eV), Ta (4.0, 4.15 eV), Y (3.1 eV), Yb (2.6 eV), Zn (3.63 eV), and the like. Among these, 15I050.doc • 40-201116504, preferred are Ba, Ca, Cs, L, Mg, Na, Nd, Rb, γ, Hf K, La, % 3 i- +· -ψ n. As the electrode material, only the number of the Jindaoshan meets the above formula (ίΙ), and it can contain a substance of a work function, and there are no particular restrictions on the number of 疋海. In the absence of the atmosphere, the low-work function metal is easily degraded if it is in the water or oxygen in the hole. Therefore, it is desirable to use Ag and Au# to stabilize the air in the air as needed. ! Above 0 nm, the film thickness is more stringent, and the crack is broken. The effect of the coating is necessary, but the more Si is used, the more it protects it from oxygen or water. At the time of "productiveness and the like, it is preferable to supply and hold L as the above-mentioned electrode forming method.] Fine plating by ruthenium plating, electron beam-based plating, atmospheric piezoelectric glory, separation, and a ^ ▲ It is formed by chemical emulsion deposition, electrodeposition, electroless plating, spin coating, and printing of vn 墨墨墨寺. Also, as the image is carried out as needed, the light lithography or peeling is well known. The method has the following methods: use thin amine # # The whole conductive type formed by the above method - ... The method of "forming the anti-# agent on the gold by thermal transfer, ink jet equal to chain or copper". A solution or dispersion of a further polymer, % 3 'I belongs to the particle of your branch, and is patterned by an inkjet method, and also, by the method of the inkjet method or the laser stripping method. The coating film forms a pattern. Further, a method of patterning a conductive ink μ, t u conductive paste containing a conductive polymer or metal fine particles by a printing method such as relief printing, gravure, lithography or screen printing is used. The thickness of the electrode of the second electrode is as long as there is current conduction, then there is no special = two, and it is better that 4 - 祀 right is in the better range, because the film thickness is thin, it will not be 151050.doc 201116504 Increase the resistance and reduce the power. Further, since the film thickness is not too thick, it takes no time to form the film, and in the case of laminating a protective layer or another layer such as an organic semiconductor layer, the laminated film can be smoothly formed without causing a step. Further, in the organic thin film transistor of the present embodiment, for example, a buffer layer may be provided between the charge injection layer and the source electrode and the drain electrode in order to further increase the charge/main charge efficiency. For the 0-type organic thin film transistor, the buffer layer is preferably Li]p, Li2〇, CsF used in the cathode of the organic EL.

NaC〇3、KC1、MgF2、CaC〇3等具有鹼金屬、鹼土金屬離子鍵之化合物。又，亦可***Alq等有機中用作電子注入層、電子傳輸層之化合物。對於p型有機薄膜電晶體而言，較理想的是FeC13， TCNQ、F4-TCNQ、HAT 等氰基化合物，CFx 或 Ge〇2、 si〇2、m〇〇3、v2〇5、v〇2、v2〇3、Mn〇、Mn3〇4、Zr〇2 W03、Ti02、In2〇3、Zn0、Ni〇、Hf〇2、Ta2〇5、Re〇3、A compound having an alkali metal or an alkaline earth metal ion bond such as NaC〇3, KC1, MgF2, or CaC〇3. Further, a compound which is used as an electron injecting layer or an electron transporting layer in an organic material such as Alq may be inserted. For p-type organic thin film transistors, preferred are cyano compounds such as FeC13, TCNQ, F4-TCNQ, HAT, CFx or Ge〇2, si〇2, m〇〇3, v2〇5, v〇2. , v2〇3, Mn〇, Mn3〇4, Zr〇2 W03, Ti02, In2〇3, Zn0, Ni〇, Hf〇2, Ta2〇5, Re〇3,

Pb〇2等鹼金屬、鹼土金屬以外之金屬氧化物，Zns、ZnSe 等無機化合物。該等氧化物於大多情形時會引起氧空位，該氧空位適合於注入電洞。進而亦可為TpD或NpD等胺系化合物或CuPc等有機EL元件中用作電洞注入層、電洞傳輸層之化合物。又，較理想的是包含兩種以上之上述化合物者。 (絕緣體層） ^ 作為本發明之有機薄膜電晶體中之絕緣體層之材料，只要是具有電性絕緣性且可形成為薄膜之材料則並無特別限制，可使用金屬氧化物（包含矽之氧化物）、金屬氮化物（包 151050.doc -42- 201116504 含矽之氮化物）、高分子、有機低分子等室溫下之電阻率為10 QCm以上之材料，尤其好的是比介電係數較高之無機氧化物皮膜。作為無機氧化物，可列舉：氧化矽、氧化鋁、氧化钽、氧化鈦、氧化錫、氧化釩、鈦酸鋇锶、鍅鈦酸鋇、锆鈦酸鉛、鈦酸鉛鑭、鈦酸锶、鈦酸鋇、氟化鋇鎂 '鑭氧化物、齓氧化物、鎂氧化物、鉍氧化物、鈦酸鉍、鈮氧化物、鈦酸锶鉍、鈕酸锶鉍、五氧化组、钽鈮酸鉍、三氧化釔及組合該等所成之化合物’較好的是氧化矽、氧化鋁、氧化鈕、氧化鈦。又，亦可較好地使用氮化矽（Si#4、SixNy(x、y>0))、氮化鋁等無機氮化物。進而，絕緣體層亦可由含有金屬醇鹽之前驅物質形成，將該前驅物質之溶液例如被覆於基板上，對其進行包含熱處理之化學溶液處理，藉此形成絕緣體層。作為上述金屬醇鹽中之金屬，例如可自過渡金屬、鑭系元素或主族元素中選擇，具體而言可列舉：鋇（Ba)、锶 (SO、鈦（Ti)、叙（Bi)、紐（Ta)、錯（Zr)、鐵（Fe)、鎳⑼）、錳（Μη)、鉛（Pb)、鑭（La)、鋰（Li)、鈉（Na)、鉀 $卜铷 (Rb)、絶（CS) ' 鲂（Fr)、鈹（Be)、鎂（Mg)、約（Ca)、銳 (Nb)釔（T1)、汞（Hg)、銅（Cu)、鈷（c〇)、铑（处）、銃（^) 及釔（Y)等。又，作為上述金屬醇鹽中之醇鹽，例如可列舉自下述化合物衍生之醇鹽：包含甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇等之醇類，包含甲氧基乙醇、乙氧基 15I050.doc -43· 201116504 乙醇、丙氧基乙醇、丁氧基乙醇、戊氧基乙醇、庚氧基乙醇、甲氧基丙醇、乙氧基丙醇、丙氧基丙醇、丁氧基丙醇、戊氧基丙醇、庚氧基丙醇之烷氧基醇類。於本發明中，若絕緣體層包含上述材料，則容易於絕緣體層中發生極化，可減低電晶體動作之臨界電壓。又，於上述材料中’尤其是亦可使用Si3N4、SixNy、SiONx(：x、 y>〇)等氮化矽形成絕緣體層。作為使用有機化合物之絕緣體層’亦可使用聚醯亞胺、聚醯胺、聚酯、聚丙烯酸酯、光自由基聚合系或光陽離子聚合系之光硬化性樹脂、含有丙烯腈成分之共聚物、聚乙稀醇、酚醛清漆樹脂及氰乙基聚三葡萄糖等。除此以外，亦可使用蠟、聚乙烯、聚氯平、聚對苯二甲酸乙二酯、聚曱醛、聚氯乙烯、聚偏二氟乙烯、聚砜、聚醯亞胺氰乙基聚三葡萄糖、聚（乙烯基苯g分）（PVP)、聚（曱基丙烯酸曱酯）（pmma)、聚碳酸酯（PC)、聚苯乙烯（PS)、聚稀煙、聚丙浠醯胺、聚（丙烯酸）、盼越清漆樹脂、可溶紛酸樹脂、聚醯亞胺、聚二曱苯、環氧樹脂，此外亦可使用聚三葡萄糖等具有高介電係數之高分子材料。作為絕緣體層中所使用之有機化合物材料、高分子材料’尤其好的是具有斥水性之有機化合物，藉由具有斥水性，可抑制絕緣體層與有機半導體層之相互作用，利用有機半導體本來具有之凝集性而提高有機半導體層之結晶性，從而提高器件性能。作為如此之有機化合物之例，可列舉 Yasuda 等人於 Jpn. J. Appl. Phys. Vol. 42 (2003) pp. 151050.doc -44- 201116504 6614-6618中揭示之聚對二甲苯衍生物或ja_化…等人於 Chem. Mater.，Vol • W (2004) ρρ. 4543-4555 中所揭示者。又，於使用圖2及圖5所示之頂閘極結構時，若使用此種有機化合物作為絕緣體層之材料，則可減小對有機半導體層造成之損傷而成膜，故而係有效之方法。上述絕緣體層可為使用有複數種如上述之無機或有機化合物材料的混合層，亦可為該等之積層結構體。於此情形時，亦可視需要混合或積層介電係數較高之材料與具有斥水性之材料，藉此控制器件之性能。作L盖^述絕緣體層可為陽極氧化膜或含有該陽極氧化膜作為構成。陽極氧化獏較好的是進行封孔處理。陽極氧化㈣错由眾所周知之方法對可陽極氧化之金屬進行陽極氧㈣成。作為可進行陽極氧化處理之金屬，可列舉銘或 =極ί化處理之方法並無特別限制，可使用眾所周知 /糟由進订陽極氧化處理可形成氧化被膜。極氧化處理中所伸用夕Φ^ “ 所使用之電解液，只要是可形成多孔質氧化皮膜之電解液則可使用任意者，草酸、鉻酸1酸、胺基㈣、苯：以卜，佳入本石頁酸寻或將該等之兩種進仃-、且合之混合酸或該等之鹽。陽根據所使用之電解1之；之處理條件 —〜有各種變化，無法-概而疋較為適合的是：電解液之濃度為卜解液之溫度為5〜70L電流密度為〇5 電 H00伏特，電解時 ’電塵為刀鐘之範圍。較好之陽極 I5I050.doc -45- 201116504 氧化處理係使用硫酸、磷酸或硼酸之水溶液作為電解液以直流電流進行處理之方法，但亦可使用交流電流。該等駿之濃度較好的是5〜45質量％，較好的是於電解液之溫度 20〜5〇C、電流密度0.5〜20 A/cm2下進行20〜250秒之電解處理。作為絕緣體層之厚度，若層之厚度較薄，則對有機半導體施加之有效電壓變大，故而可減低器件自身之驅動電麼、臨界電壓，但相反源極-閘極間之漏電流變大，故而必須選擇適當之膜厚，通常為1 nm〜5 μηι，較好的是5 nm〜2 μηι，進而好的是1〇〇 nm~l μιη。又’可於上述絕緣體層與有機半導體層之間實施任意之配向處理。作為其較好之例，有於絕緣體層表面實施斥水化處理等，減低絕緣體層與有機半導體層之相互作用從而提高有機半導體層之結晶性的方法，具體而言可列舉如下方法：使矽烷偶合劑，例如十八烷基三氯矽烷、三氣甲矽氮烷或烷磷酸、烷磺酸、烷羧酸等自組裝配向膜材料j 液相或氣相狀態下與絕緣膜表面接觸而形成自組裝膜，；後實施適度之乾燥處理。又亦可使 J J使用如液晶配向所使j 的於絕緣膜表面設置含有聚醯亞胺等之膜，然後對其表1 進行摩擦處理之方法。 ' ^ 作為上述絕緣體層之形成方法，可列舉：真空蒸铲法分子束蟲晶法、離子團束法 '低能離子束法、:離二法、㈣法、滅經法，日本專利特開平⑽彻號公報曰本專利特開平U-133205號公報、曰本專利特開· 15I050.doc -46« 201116504 ^1804號公報、日本專利特開綱(M47209號公報、日本、$ 2GG(M85362號公報中所揭示之大氣|電聚法等二::裎;或噴塗法、旋塗法、刮塗法、浸塗法、澆鑄 4 2塗法、棒塗法、模塗法等藉由塗布之方法，印刷或噴墨等藉由圖案化之方、、共一、之方法專濕式製程’可根據材料而使用 "方法。濕式製程可使用：視需要使用界面活性劑等分 =將無機氧化物之微粒子分散於任意之有機溶劑或水如^布所得液體並乾燥的方法；或塗布氧化物前驅物例 °〜體之溶液並乾燥’即所謂的溶膠凝膝法。特：I之有：薄膜電晶體，之有機半導體層之膜厚並無、、制，通常為〇.5 〜1 ，較好& θ 9 ㈣权好的是2nm〜250 nm。 =，有機半導體層之形成方法並無特職制，可適用眾斤周知之方法，例如可藉由分子束蒸鍍法（MBE(_iecuiar —epuaxy)法）、真空蒸錢法、化學氣相沈積法將材料 ΓΓ溶劑中所得之溶液的浸塗法、旋塗法、洗鑄法、棒 =:Γ法等印刷'塗布法及烘烤、電聚合、自溶液之層之材料而形成。之方去，由如上所述之有機半導體二高有機半導體層之結晶性則場效遷移率提高，故而於使用軋相成膜（蒸鍍、濺鍍等）中之基板溫度保持為高溫。理想的是成膜八，皿度較好的是50〜25〇t：，進而^是7〇〜15〇t。又’無論採用何種成膜方法，若於成 =吏：施退火則可獲得高性能器件，故度較好的是心_，進而好的是7〇〜細。c，時間較好的 15I050.doc .47· 201116504 是10分鐘〜12小時，進而好的是1〜ι〇小時。於本發明中，電荷注入層中可使用自通式（1)、（4)或（5) 中選擇之一種材料，亦可組合複數種或使用稠五苯或噻吩低聚物等眾所周知之半導體而形成含有複數種材料之混合 ·/專膜，或者亦彳將由該等材料單獨形成之層或混合膜積層而形成電荷注人層。又’亦可分別對源極電極、没極電極設置不同之電荷注人層。電荷注人層之膜厚較好的是〇1 nm〜1 μπι，進而好的是〇.3 nm〜1〇〇 nm，成膜法可使用與有機半導體層相同之成膜法。又，電荷注入層亦可如圖7之42所示，形成為於有機^ 導體層52與源極_汲極電極之間，亦設置於未設置源極^ 極電極之部分的態樣。於此情形時，可不使用金屬罩而言] 置電荷注入層，故而於生產性方面而言有利。作為本發明之有機薄膜電晶體之形成方法，並無特则制’可使用眾所周知之方法’但若於完全不接觸大氣之況下根據所期望之元件構成而進行基板投入、問極電極开成、絕緣體層形成、有機半導體層形成、電荷注入層开成、源極電極形成、沒極電極形成為止之一系列的元：製作步驟’則可防止由於與大氣接觸而導致大氣中之水分或氧等對元件性能造成傷害，故而較好。於不可避免地必需時接觸時：較好的是有機半導體層成膜之後的步占王不接觸大氣之步驟’且於即將進行有機半導體居成膜之前，對積層有機半導體層之面(例如於元件β之情开: 時’絕緣層之一部分積層有源極電極、沒極電極之表面乂 i5i050.doc -48· 201116504 藉由紫外線照射、紫外線/臭氧 ^ . t 扣乳包聚、氬電漿等進仃>月潔化、活性化，然後積層有機半導體層。進而’例如考慮到大氣中所含之氧、水等對有機半導體層之影響’可於有機薄膜電晶體元件之外周面之 — I分形成阻氣層。作為形成阻氣層之材料，可使用此領常用者，例如可列舉：聚婦 " ^ ^ 1乙烯％、乙烯-乙烯醇共聚物、乳乙婦、聚偏二氯乙烯、聚氯三氟乙婦等。另外，亦可使用上述絕緣體層中所例示之具有絕緣性之無機物。又’本發明提供—種於上述有機薄膜電晶體中，利用源極-汲極間流通之電流而獲得發、楮田對閘極電極施加電壓而控制發光的有機薄膜發光電晶體。本”之有機㈣電晶體亦可制自源極、_電極注何而用作發光元件。，可將有機薄膜電晶體用作兼八發光元件（有機EL)之功能之有機薄膜發光電晶體。1 可稭由利用閘極電極控制源極-汲極電極間流通之電流而控制發光強度。由於可將用w〃技，將用以控制發光之電晶體與發光元件“-體，故而可提高顯示器之開口率或因製作製程簡易化而可減少成本，於實用上非常有利。於用電晶體時，上述詳細說明中所述之内容已充分，但為使本發明之有機薄膜電晶體作為有機發光電晶體而動作，必須㈣極、汲極之一者注入電洞，自另-者注入電子，為提南發光性能，較好的是滿足以下條件。 (源極、汲極）本發明之有機薄膜發φ带寻腰發先電晶體中，為提高電洞之注入 151050.doc -49- 201116504 性’較好的是源極所明電洞注入電極質的電極。及極之至少一者為電洞注入性電極。係含有上述功函數為4 2 eV以上之物又’為提高電子之注入性，一者為電子注入性電極。所謂述功函數為4.3 ev以下之物質者為電洞注入性，且另一者為膜發光電晶體。較好的是源極、汲極之至少電子注入性電極，係含有上的電極。進而好的是具備一電子注入性之電極的有機薄進而好的是於其中-電極下具備電洞注入層，且於另電極下具備電子注人層的有機薄膜發光電晶體。 [實施例] 其次，使用實施例更詳細地說明本發明。合成例1 (化合物（1)之合成）根據以下合成路徑合成上述化合物（丨）： [化 40]An alkali metal such as Pb〇2 or a metal oxide other than an alkaline earth metal, or an inorganic compound such as Zns or ZnSe. These oxides cause oxygen vacancies in most cases, which are suitable for injection into holes. Further, it may be used as an amine-based compound such as TpD or NpD or an organic EL device such as CuPc as a compound for a hole injection layer or a hole transport layer. Further, it is preferred to include two or more of the above compounds. (Insulator layer) ^ The material of the insulator layer in the organic thin film transistor of the present invention is not particularly limited as long as it is electrically insulating and can be formed into a film, and a metal oxide (including oxidation of ruthenium) can be used. Materials, metal nitrides (including 151,050.doc -42-201116504 containing niobium nitride), polymers, organic low molecular weight, etc., at room temperature, the resistivity is 10 QCm or more, especially the specific dielectric constant Higher inorganic oxide film. Examples of the inorganic oxide include cerium oxide, aluminum oxide, cerium oxide, titanium oxide, tin oxide, vanadium oxide, barium titanate, barium strontium titanate, lead zirconate titanate, lead titanate strontium, barium titanate, Barium titanate, strontium magnesium fluoride 镧 oxide, cerium oxide, magnesium oxide, cerium oxide, barium titanate, cerium oxide, barium titanate, barium strontium, pentoxide, citric acid Antimony, antimony trioxide and a combination of these compounds are preferably cerium oxide, aluminum oxide, oxidic knob, or titanium oxide. Further, an inorganic nitride such as tantalum nitride (Si#4, SixNy (x, y > 0)) or aluminum nitride can be preferably used. Further, the insulator layer may be formed of a precursor material containing a metal alkoxide, and the solution of the precursor material may be coated on a substrate, for example, and subjected to a chemical solution treatment including heat treatment to form an insulator layer. The metal in the metal alkoxide may be selected, for example, from a transition metal, a lanthanoid element, or a main group element, and specifically, barium (Ba), cerium (SO, titanium (Ti), or (Bi), New (Ta), wrong (Zr), iron (Fe), nickel (9), manganese (Μη), lead (Pb), lanthanum (La), lithium (Li), sodium (Na), potassium 铷 (Rb) ), absolutely (CS) '鲂 (Fr), 铍 (Be), magnesium (Mg), about (Ca), sharp (Nb) 钇 (T1), mercury (Hg), copper (Cu), cobalt (c〇 ), 铑 (处), 铳 (^), and 钇 (Y). Further, examples of the alkoxide in the metal alkoxide include alkoxides derived from the following compounds: alcohols including methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and the like, including methoxyl. Ethanol, ethoxyl 15I050.doc -43· 201116504 Ethanol, propoxyethanol, butoxyethanol, pentyloxyethanol, heptoxyethanol, methoxypropanol, ethoxypropanol, propoxy Alkoxy alcohols of propanol, butoxypropanol, pentyloxypropanol and heptoxypropanol. In the present invention, if the insulator layer contains the above material, polarization is likely to occur in the insulator layer, and the threshold voltage of the transistor operation can be reduced. Further, in the above materials, in particular, an insulator layer may be formed using tantalum nitride such as Si3N4, SixNy, or SiONx (: x, y > 〇). As the insulator layer using an organic compound, a polyimide, a polyamide, a polyester, a polyacrylate, a photoradical polymerization or a photocationic polymerization photocurable resin, or a copolymer containing an acrylonitrile component may be used. , polyethylene glycol, novolak resin and cyanoethyl polytriglucose. In addition, wax, polyethylene, polychloroprene, polyethylene terephthalate, polyfurfural, polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyethylenimine cyanoethyl poly Triglucose, poly(vinylbenzene g) (PVP), poly(decyl methacrylate) (pmma), polycarbonate (PC), polystyrene (PS), polydue, polyacrylamide, A poly(acrylic acid), a clarified varnish resin, a soluble acid resin, a polyimide, a polybenzazole, an epoxy resin, or a polymer material having a high dielectric constant such as polytriglucose. An organic compound material or a polymer material used in the insulator layer is particularly preferably an organic compound having water repellency, and by having water repellency, interaction between the insulator layer and the organic semiconductor layer can be suppressed, and the organic semiconductor is originally used. Aggregation improves the crystallinity of the organic semiconductor layer, thereby improving device performance. As an example of such an organic compound, a parylene derivative disclosed in Yasuda et al., Jpn. J. Appl. Phys. Vol. 42 (2003) pp. 151050. doc-44-201116504 6614-6618 or Ja_化... et al., in Chem. Mater., Vol. W (2004) ρρ. 4543-4555. Further, when the top gate structure shown in FIGS. 2 and 5 is used, if such an organic compound is used as the material of the insulator layer, the damage to the organic semiconductor layer can be reduced to form a film, so that it is effective. . The above insulator layer may be a mixed layer using a plurality of inorganic or organic compound materials as described above, or may be a laminated structure of the above. In this case, it is also possible to mix or laminate a material having a high dielectric constant and a material having water repellency, thereby controlling the performance of the device. The L-covering insulator layer may be an anodized film or a anodic oxide film. The anodized ruthenium is preferably subjected to a plugging treatment. Anodizing (4) The anode can be anodically oxidized by a well-known method. As the metal which can be anodized, there is no particular limitation on the method of treating the electrode or the electrode, and the oxide film can be formed by a known anodizing treatment. In the extreme oxidation treatment, the electrolyte used may be any one as long as it is an electrolyte capable of forming a porous oxide film. Oxalic acid, chromic acid, amino acid (IV), benzene:佳入本石页酸寻 or these two kinds of 仃-, and the mixed acid or the salt of the same. Yang according to the use of electrolysis 1; the processing conditions - ~ have various changes, can not - The 疋 is more suitable: the concentration of the electrolyte is the temperature of the solution is 5~70L, the current density is 〇5, the electricity is H00 volt, and the electrolysis is the range of the knife clock. The better anode I5I050.doc -45 - 201116504 Oxidation treatment is a method in which an aqueous solution of sulfuric acid, phosphoric acid or boric acid is used as an electrolytic solution to treat with a direct current, but an alternating current can also be used. The concentration of these is preferably 5 to 45 mass%, preferably Electrolytic treatment is carried out for 20 to 250 seconds at a temperature of the electrolyte of 20 to 5 Torr C and a current density of 0.5 to 20 A/cm 2 . As the thickness of the insulator layer, if the thickness of the layer is thin, the effective voltage applied to the organic semiconductor Become bigger, thus reducing the device itself Driving power, threshold voltage, but the leakage current between the source and the gate becomes larger, so it is necessary to select an appropriate film thickness, usually 1 nm to 5 μηι, preferably 5 nm to 2 μηι, and thus good It is 1 〇〇 nm~l μιη. Further, any alignment treatment can be performed between the insulator layer and the organic semiconductor layer. As a preferred example, the surface of the insulator layer is subjected to water repellency treatment to reduce the insulator layer. The method of increasing the crystallinity of the organic semiconductor layer by interaction with the organic semiconductor layer, specifically, a method of argon coupling agent such as octadecyltrichloromethane, trimethylazepine or alkanephosphoric acid, The alkanesulfonic acid, the alkanecarboxylic acid, and the like are assembled into a film material to contact the surface of the insulating film to form a self-assembled film, and then subjected to a moderate drying process. A film containing polyimide or the like is provided on the surface of the insulating film, and then the surface of the insulating film is subjected to a rubbing treatment. ' ^ As a method for forming the insulating layer, a vacuum distilling method molecule may be mentioned. Insect crystal method, ion cluster method, low energy ion beam method, two-way method, (four) method, and annihilation method, Japanese Patent Special Kaiping (10), the syllabus, the patent, the special patent, U-133205, and the special patent · 15I050.doc -46« 201116504 ^1804, Japanese Patent Laid-Open (M47209, Japan, $2GG (M85362), the atmosphere|electropolymerization method, etc. 2::裎; or spraying method, By spin coating method, knife coating method, dip coating method, casting 4 2 coating method, bar coating method, die coating method, etc., by coating method, printing, inkjet or the like by patterning, a total of one, the method The special wet process 'can be used according to the material' method. Wet process can be used: if necessary, use surfactant aliquot = method of dispersing fine particles of inorganic oxide in any organic solvent or water, such as liquid, and drying; or coating oxide precursors Solution and drying 'the so-called sol-gel method. Special: I have: thin film transistor, the thickness of the organic semiconductor layer is not, and is usually 〇.5 〜1, preferably & θ 9 (4) is preferably 2nm~250 nm. =, the formation method of the organic semiconductor layer has no special system, and can be applied to a well-known method, for example, by molecular beam evaporation (MBE (_iecuiar - epuaxy) method), vacuum evaporation method, chemical vapor deposition method The solution obtained by immersing the material in a solvent is formed by a dip coating method, a spin coating method, a washing method, a bar method, a bar method, a coating method, baking, electropolymerization, and a material from a layer of a solution. Further, since the crystallinity of the organic semiconductor two-high organic semiconductor layer as described above increases the field-effect mobility, the substrate temperature in the roll-forming film formation (evaporation, sputtering, etc.) is maintained at a high temperature. It is desirable to form a film of eight, and the dish size is preferably 50 to 25 〇t:, and then ^ is 7 〇 to 15 〇t. Further, no matter what kind of film formation method is used, if the film is formed by annealing, the high-performance device can be obtained, and the degree is preferably _, and further preferably 7 〇 to fine. c, the time is better 15I050.doc .47· 201116504 is 10 minutes ~ 12 hours, and then good is 1 ~ ι 〇 hours. In the present invention, one selected from the general formula (1), (4) or (5) may be used in the charge injection layer, or a plurality of well-known semiconductors such as fused pentene or thiophene oligomer may be used. Instead, a mixed/multi-layer film containing a plurality of materials is formed, or a layer formed of these materials alone or a mixed film layer is laminated to form a charge injection layer. Further, different charge injection layers may be provided for the source electrode and the electrodeless electrode, respectively. The film thickness of the charge injection layer is preferably nm1 nm to 1 μm, and further preferably 〇.3 nm to 1 〇〇 nm, and the film formation method can use the same film formation method as the organic semiconductor layer. Further, as shown in Fig. 7 and 42, the charge injection layer may be formed between the organic conductor layer 52 and the source-drain electrode, and also in the portion where the source electrode is not provided. In this case, the charge injection layer can be disposed without using a metal cover, which is advantageous in terms of productivity. As a method of forming the organic thin film transistor of the present invention, there is no special method 'a well-known method can be used', but the substrate is input and the electrode is opened according to the desired element structure without completely contacting the atmosphere. One of a series of elements: the formation of an insulator layer, the formation of an organic semiconductor layer, the formation of a charge injection layer, the formation of a source electrode, and the formation of a electrodeless electrode: the production step can prevent moisture or oxygen in the atmosphere due to contact with the atmosphere. It is better to cause damage to component performance. When it is inevitable to contact when necessary: it is preferred that the step of the organic semiconductor layer after the film formation is not in contact with the atmosphere' and the surface of the organic semiconductor layer is laminated immediately before the organic semiconductor is formed into a film (for example, When the element β is opened: When one part of the insulating layer is laminated, the surface of the source electrode and the electrode of the electrode is 乂i5i050.doc -48· 201116504 by ultraviolet irradiation, ultraviolet/ozone ^ t buckle milk encapsulation, argon plasma In the meantime, it is cleaned and activated, and then an organic semiconductor layer is laminated. Further, for example, the influence of oxygen, water, or the like contained in the atmosphere on the organic semiconductor layer can be applied to the periphery of the organic thin film transistor. — I form a gas barrier layer. As a material for forming a gas barrier layer, a commonly used one can be used, for example, a woman's " ^ ^ 1 ethylene%, ethylene-vinyl alcohol copolymer, milk tea, and polypyramid Dichloroethylene, polychlorotrifluoroethylene, etc. In addition, an insulating inorganic substance exemplified in the above insulator layer may be used. Further, the present invention provides a seed source in the above organic thin film transistor, using a source An organic thin film light-emitting transistor that controls the light emission by applying a voltage to the gate electrode by the current flowing between the pole and the drain. The organic (four) transistor of the present invention can also be used from the source and the electrode. As a light-emitting element, an organic thin film transistor can be used as an organic thin film light-emitting transistor which functions as an eight-light-emitting element (organic EL). 1 The straw can be used to control the current flowing between the source-drain electrodes. Controlling the luminous intensity. Since the transistor and the light-emitting element for controlling the light emission can be used, the aperture ratio of the display can be increased or the manufacturing process can be simplified, and the cost can be reduced, which is very advantageous in practical use. When the transistor is used, the contents described in the above detailed description are sufficient. However, in order to operate the organic thin film transistor of the present invention as an organic light-emitting transistor, one of the (four) poles and the drain must be injected into the hole. In addition, the electrons are injected, and for the illuminating performance of the smear, it is preferable to satisfy the following conditions: (source, bungee) The organic film of the present invention is made in the φ band-finished first crystal, in order to improve the hole injection. 151050.doc -49- 201116504 The 'good' is the electrode of the source hole injected into the electrode. At least one of the poles is a hole injecting electrode. The system has the above work function of 4 2 eV or more. In order to improve the injectability of electrons, one is an electron injecting electrode. The material having a working function of 4.3 ev or less is a hole injecting property, and the other is a film emitting transistor. At least the electron injecting electrode of the pole and the bungee is an electrode containing the upper electrode. Further preferably, the organic thin electrode having an electron injecting electrode is preferably a hole injecting layer under the electrode and the other electrode An organic thin film light-emitting transistor having an electron-injecting layer is provided. [Examples] Next, the present invention will be described in more detail by way of examples. Synthesis Example 1 (Synthesis of Compound (1)) The above compound (丨) was synthesized according to the following synthetic route: [Chem. 40]

N^kCul'N^kCul'

於300毫升之三口燒瓶中添加7 5〇 g(31 7 ，肛二溴苯、1_83 g(1.59 mmol)之四（三苯基膦）鈀、〇 6〇4 g(3 17 mmol)之碘化鋼（I) ’進行氬氣置換。於其中添加15〇毫升之三乙胺、10.5毫升（95.4 mmol)之乙炔苯，於氬氣環境下加熱回流9小時。於反應液中添加1〇〇毫升之水、1〇〇毫升之二氯曱烧，分離有機層’以無水硫酸鎂加以乾燥。以蒸發 151050.doc -50- 201116504 器進行減壓濃縮後，將所得固體以矽膠管柱層析法（溶出浴劑.一氣甲烧/己院=1/1〇)進行純化，獲得2.55 g(9 16 mmol，產率29%)之化合物（1)。係藉由〗H-NMR(90 MHz)及 FD-MS(field desorption mass spectrometry，場解吸質譜分析）測定而確定所得化合物為化合物（1)。 FD-MS之測定結果如以下所示。 FD-MS，理論值C48H3GS2=278，實測值，m/z=278 (M+， 100) 又，將化合物（1)以220°C進行昇華純化，結果藉由昇華純化而獲得之化合物（1)之純度為99 5〇/〇。上述FD-MS(場解吸質譜分析）測定中所使用之裝置及測定條件如以下所示。 <FD-MS 測定 > 裝置：HX 11〇(曰本電子公司製造）條件：加速電壓8 kV 掃描範圍m/z=50〜1 500 實施例1 (有機薄膜電晶體之製造）對Si基板（兼用作P型之比電阻丨ncm之閘極電極）藉由熱氧化法將表面氧化，於基板上製作3〇〇 nm2熱氧化膜作為絕緣體層。進而，藉由乾式蝕刻將於基板之一方形成之 Si〇2膜元王除去後，藉由賤鍍法以打爪之膜厚使鉻成膜，然後於其上藉由濺鍍以1〇〇 nm使金（Au)成膜而用作取出電極。 151050.doc 51 201116504 將該基板於中性洗滌劑、純水、丙酮及乙醇中各進行30 分釭之超音波清洗，進而進行臭氧清洗。其-人，將上述基板設置於真空蒸鍍裝置（ULVAc公司製 1¾ EX 4〇〇)中，於絕緣體層上以〇〇5 nm/s之蒸鍍速率使 1,4-雙（4-曱基苯乙稀基）苯（4MSB)成膜形成膜厚5〇⑽之有機半導體層。繼而’通過金屬I，使合成你"中製備之化5物（1)以〇.〇5 nm/s之蒸鍍速率成膜為膜厚2〇之電荷注入層。進而使金以50 nm之膜厚成膜，藉此以間隔（通道長度L)成為75 μιη之方式形成互不接觸之電荷注入層以及源極電極及;及極電極。此時係以源極電極與汲極電極之寬度（通道寬度W)成為5 mm之方式成膜，藉此製作有機薄膜電晶體（參照圖6)。對所得有機薄膜電晶體之閘極電極施加〇〜1〇〇 V之閘極電壓，於源極-汲極間施加電壓使電流流通。所得有機薄膜電aa體中，電子於有機半導體層之通道區域（源極·没極間）文到感應，該有機薄膜電晶體作為p型電晶體而進行動作。其結果，電流飽和區域之源極-汲極電極間之電流的開/關比為1X106。以式（2)計算出的有機薄膜電晶體之電洞之場效遷移率μ 及臨界電壓VT之結果為45 = 0.15 cm2/Vs，ντ=·20 V。又，自式（I)，計算出線性區域之場效遷移率九，結果為^ = 0· 1 5 cm2/Vs。將所彳于有機薄膜電晶體之功率曲線示於圖8 ^自圖8可判明，於汲極電壓為〇 V附近之區域（圓所包圍之部分），功率 151050.doc •52· 201116504 曲線為直線’接觸電阻減低。實施例2 除使用化合物（42)代替化合物〇)形成電荷注入層以外，以與實施例1相同之方式製造有機薄膜電晶體並進行評價。結果示於表1。實施例3 除使用化合物（1 62)代替化外，以與實施例1相同之方式評價。結果示於表1。實施例4 合物（1)形成電荷注入層以製造有機薄膜電晶體並進行荷注入層以外，電晶體並進行言平除使用化合物（9)代替化合物（丨）形成電以與實施例1相同之方式製造有機薄膜價。結果示於表1。實施例5 荷注入層以外電晶體並進；j亍評評除使用化合物（4 3)代替化合物（i)形成電以與實施例1相同之方式製造有機薄膜價。結果示於表1。實施例6 除使用化合物（60)代替化合物（1)形成電荷注入層以外以與實施例1相同之方式製造有機薄犋電晶體並進一價。結果示於表1。 τ 實施例7 除使用化合物（70)代替化合物（1)形成電以與實施例1相同之方式製造有機薄賤荷注入層以外電晶體並進; 評 151050.doc •53· 201116504 價。結果示於表】β 實施例8 何注入層以晶體並進；f亍除使用化合物⑽)代替化合物⑴形成電外，以與實施例丨相同之方式評價。結果示於表卜實施例9 除使用化合物（】7〗、#娃A 认、M (7l)代替化合物⑴形成電荷注入層ΰ 外’以與貫施例丨相同之主 4 次I知·有機薄膜電晶體並進个評價。結果示於表I。實施例1 0 用，N —辛基-3,4,9,1〇-花二曱醜亞胺（pTCDI_C8)代替I4又（4·甲基苯乙稀基）笨形成有機半導體層，使用化合物（65)代替化合物（1)形成口初ιυ巾成電何庄入層，代替Au將以以〇·05 之蒸鍍速率真空蒸鍍2〇 nm，其後將Ag以〇.〇f 之篆鍍速率4 It 5G nm而被覆Ca，形成源極電極及沒極電極，除此之外以與實施例j相同之方式製造有機薄膜電晶體。對所得有機薄膜電晶體之閘極電極施加〇〜+1〇〇 v之間極電壓使之進行n型驅動，除此之外以與實施例i相同之方式進行評價。結果示於表1。實施例11 將Mo〇3以0.05 nm/s之蒸鍍速率真空蒸鍍1〇 nm，***於含有Au之源極電極及汲極電極與含有化合物（6〇)之電荷注入層之間作為緩衝層，除此之外以與實施例6相同之方式 151050.doc 54· 201116504 製造有機薄膜電晶體並進行評價。結果示於表卜實施例12 除使用化合物（163)代替仆人札^ 人善化合物（65)形成電荷注入層以外，以與實施例10相同之方彳制.皮万式衣k有機薄膜電晶體並進行評價。結果示於表1。實施例1 3 代替蒸鍍化合物（1)，鋅由骑仆人^ 稭由將化合物（174)以〇 5質量％溶解於甲苯并使用該溶液藉由热法、土 j_、u 由方疋塗法成膜，然後於氮氣環境下於8 0 C下進行乾燥而形成雷斗风^•何/主入層，除此以外，以與實施例1相同之方式製造有曰 ” 3機/寻膜电晶體並進行評價。結果示於表1。實施例14 於實施例!之有機薄膜電晶體製造步驟中，在使用有化合物〇)形成電荷注入層日夺，不通過.金屬罩而將化合物⑴ 以〇·〇5 nm/s之蒸鍍速率形成為膜厚⑺〇〇1之電荷注入層，製造如圖7所示之電晶體。該元件之評價結果示於表i。曰比較例1 除不形成電荷注入層以外，以與實施例丨相同之方式製造有機薄膜電晶體並進行評價。結果示於表j。又，所得有機薄膜電晶體之功率曲線示於圖9。自圖9可知，於汲極電壓為0 v附近之區域（圓所包圍之部分），功率曲線彎折而偏離直線，接觸電阻較大，脫離式（1)之特性。比較例2 除不形成電荷注入層以外，以與實施例1〇相同之方式製 151050.doc •55· 201116504 造有機薄膜電晶體，進行評價。結果示於表1。 [表1] 電荷注入層材料有機半導體層材料(載子之種類）飽和區域特性(式(2)) 線性區域特性(式⑴）場效遷移率 ps[cm2/Vs] 臨界電壓 [V] 開關比 [-] 場效遷移率 pL[cm2/Vs] 功率曲線於汲極電壓0 V 附近之彎折實施例1 (1) 4MSB (P) 0.15 -10 Ι.ΙχΙΟ6 0.15 無實施例2 (42) 4MSB (P) 0.14 -9 1.8χ106 0.13 無實施例3 (162) 4MSB (P) 0.13 -12 1.5x10s 0.12 無實施例4 (9) 4MSB (P) 0.1 -11 0.92x106 0.1 無實施例5 (43) 4MSB (P) 0.2 -8 2.2χ106 0.22 無實施例6 (6〇) 4MSB (P) 0.1 -9 5.2χ106 0.12 無實施例7 (70) 4MSB (P) 0.13 -10 4.〇χ106 0.11 無實施例8 (110) 4MSB (P) 0.12 -10 1.9x106 0.12 無實施例9 (171) 4MSB (P) 0.13 -12 3.〇χ106 0.14 無實施例10 (65) PTCDI-C8 ⑹ 0.055 -7 2.3x10s 0.051 無實施例11 (60) 4MSB (P) 0.13 -8 1.9x106 0.12 無實施例12 (162) PTCDI-C8 (η) 0.06 -8 1.2χ105 0.55 無實施例13 (174) 4MSB (Ρ) 0.13 -7 1.8χ106 0.12 無實施例14 (1) 4MSB (Ρ) 0.13 -13 1.0x106 0.12 無比較例1 - 4MSB (Ρ) 0.09 -18 5.4x10s 0.052 有比較例2 - PTCDI-C8 (η) 0.021 -15 3.1χ104 0.021 有實施例15(有機薄膜發光電晶體之製造）對Si基板（兼用作P型之比電阻為1 Qcm之閘極電極）藉由 -56- 151050.doc 201116504 * ' 、、將表面氧化，於基板上製作300 nm之熱氧化膜作為絕緣體層。進而’藉由乾式㈣將於基板之—方形成之7 〇g (31 7 , anal dibromobenzene, 1_83 g (1.59 mmol) of tetrakis(triphenylphosphine)palladium, 〇6〇4 g (3 17 mmol) of iodide were added to a 300 ml three-necked flask. The steel (I) was replaced with argon. 15 ml of triethylamine and 10.5 ml (95.4 mmol) of acetylenebenzene were added thereto, and the mixture was heated under reflux for 9 hours under an argon atmosphere. Water, 1 ml of dichlorohydrazine, and the organic layer was separated and dried over anhydrous magnesium sulfate. After concentration under reduced pressure by evaporation 151050.doc -50-201116504, the obtained solid was obtained by gel column chromatography. Purification was carried out to obtain 2.55 g (9 16 mmol, yield 29%) of compound (1) by H-NMR (90 MHz). The compound obtained by the FD-MS (field desorption mass spectrometry) was determined to be the compound (1). The results of the FD-MS measurement are shown below. FD-MS, theoretical value C48H3GS2 = 278, measured value, m/z=278 (M+, 100) Further, the compound (1) was purified by sublimation at 220 ° C, and the compound obtained by sublimation purification (1) The purity is 99 5 〇 / 〇. The apparatus and measurement conditions used in the above FD-MS (field desorption mass spectrometry) measurement are as follows. <FD-MS measurement> Apparatus: HX 11〇 (Sakamoto Electronics Co., Ltd. Manufacturing condition: Acceleration voltage 8 kV Scanning range m/z = 50 to 1 500 Example 1 (Manufacturing of organic thin film transistor) The Si substrate (which is also used as a P-type specific resistance 丨ncm gate electrode) by heat The oxidation method oxidizes the surface, and a 3 〇〇 nm 2 thermal oxide film is formed on the substrate as an insulator layer. Further, after the Si 〇 2 film element formed by one side of the substrate is removed by dry etching, the ruthenium plating method is used. The thickness of the film of the claw forms a film of chromium, and then the gold (Au) is formed into a film by sputtering at 1 〇〇 nm to be used as a take-out electrode. 151050.doc 51 201116504 The substrate is in a neutral detergent, pure Ultrasonic cleaning was performed for 30 minutes in each of water, acetone, and ethanol, and ozone cleaning was performed. The substrate was placed in a vacuum vapor deposition apparatus (13⁄4 EX 4〇〇 manufactured by ULVAc Co., Ltd.) on the insulator layer. 1,4-bis(4-mercaptostyrene) at an evaporation rate of 〇〇5 nm/s Benzene (4MSB) is formed into a film to form an organic semiconductor layer having a film thickness of 5 Å (10), and then 'through the metal I, the compound 5 (1) prepared in the synthesis is prepared at a vapor deposition rate of 〇.〇5 nm/s. The film was a charge injection layer having a film thickness of 2 Å. Further, gold is formed into a film having a film thickness of 50 nm, whereby the charge injection layer and the source electrode and the electrode electrode which are not in contact with each other are formed at intervals (channel length L) of 75 μm. In this case, an organic thin film transistor was formed by forming a film having a width (channel width W) of the source electrode and the drain electrode of 5 mm (see Fig. 6). A gate voltage of 〇1 to 1 〇〇V was applied to the gate electrode of the obtained organic thin film transistor, and a voltage was applied between the source and the drain to allow current to flow. In the obtained organic thin film electric aa body, electrons are induced in the channel region (source/no-pole) of the organic semiconductor layer, and the organic thin film transistor operates as a p-type transistor. As a result, the on/off ratio of the current between the source-drain electrodes of the current saturation region is 1X106. The field effect mobility μ and the threshold voltage VT of the hole of the organic thin film transistor calculated by the formula (2) are 45 = 0.15 cm 2 /Vs, ντ = · 20 V. Further, from the equation (I), the field-effect mobility of the linear region is calculated to be IX, and the result is ^ = 0·15 cm2/Vs. The power curve of the organic thin film transistor is shown in Fig. 8 ^ It can be seen from Fig. 8 that in the region where the drain voltage is near 〇V (the portion surrounded by the circle), the power is 151050.doc •52· 201116504 Straight line 'contact resistance is reduced. (Example 2) An organic thin film transistor was produced and evaluated in the same manner as in Example 1 except that the compound (42) was used instead of the compound 〇) to form a charge injection layer. The results are shown in Table 1. Example 3 Evaluation was carried out in the same manner as in Example 1 except that the compound (1 62) was used instead. The results are shown in Table 1. Example 4 Compound (1) was formed into a charge injection layer to fabricate an organic thin film transistor and subjected to a charge injection layer, and the transistor was subjected to flattening except that the compound (9) was used instead of the compound (丨) to form electricity in the same manner as in Example 1. The way to make organic film prices. The results are shown in Table 1. Example 5 In addition to the injection layer, the transistor was adjoined; j. Evaluation The organic film was produced in the same manner as in Example 1 except that the compound (43) was used instead of the compound (i). The results are shown in Table 1. Example 6 An organic thin tantalum transistor was produced in the same manner as in Example 1 except that the compound (60) was used instead of the compound (1) to form a charge injection layer. The results are shown in Table 1. τ Example 7 In place of the use of the compound (70) in place of the compound (1), electricity was formed in the same manner as in Example 1 except that the organic thin charge injection layer was formed in the same manner as in Example 1; 151050.doc •53·201116504. The results are shown in Table 7. β Example 8 How the injection layer was crystallized; f亍 was evaluated in the same manner as in Example 亍 except that the compound (10) was used instead of the compound (1). The results are shown in Table 9. In addition to the use of the compound (7), #娃A, M (7l) instead of the compound (1) to form a charge injection layer ', the same as the main example 4 times I know · organic The film transistor was further evaluated. The results are shown in Table 1. Example 1 0, N-octyl-3,4,9,1〇-flower quinone imine (pTCDI_C8) was used instead of I4 (4·methyl) The styrene group is stupid to form an organic semiconductor layer, and the compound (65) is used instead of the compound (1) to form a layer of 口 υ 成成成成 , , , , , , , , , , , , , , , , , 代替代替代替代替代替代替代替代替代替代替代替代替The organic thin film transistor was produced in the same manner as in Example j except that Ag was coated with Ca at a ruthenium plating rate of 4 Å to 5 G nm to form a source electrode and a electrodeless electrode. Evaluation was carried out in the same manner as in Example i except that an electrode voltage of 〇 +1 〇〇〇〇 was applied to the gate electrode of the obtained organic thin film transistor to perform n-type driving. The results are shown in Table 1. Example 11 Mo〇3 was vacuum-deposited at a deposition rate of 0.05 nm/s at a thickness of 1 〇 nm, and was inserted into a source electrode and a drain electrode containing Au. An organic thin film transistor was produced and evaluated in the same manner as in Example 6 except that the charge injection layer of the compound (6 Å) was used as a buffer layer. The results are shown in the examples. 12 The skin film of the organic film was evaluated and evaluated in the same manner as in Example 10 except that the compound (163) was used instead of the servant (manufacturing compound) to form a charge injection layer. Table 1. Example 1 3 In place of the vapor-deposited compound (1), zinc was dissolved in toluene by a servant's straw from the compound (174) at a mass ratio of 5% by mass and using the solution by thermal method, soil j_, u The film was formed by a ruthenium coating method, and then dried under a nitrogen atmosphere at 80 ° C to form a shovel wind, which/main layer, and a 曰"3 machine was produced in the same manner as in Example 1. The film was evaluated and evaluated. The results are shown in Table 1. Example 14 In the organic thin film transistor manufacturing step of the embodiment, the charge injection layer was formed using the compound ruthenium, and the metal cover was not passed. Compound (1) at a vapor deposition rate of nm·〇5 nm/s A charge injection layer having a film thickness of (7) 〇〇1 was formed, and a transistor as shown in Fig. 7 was produced. The evaluation results of the device are shown in Table i. 曰 Comparative Example 1 Except that the charge injection layer was not formed, The organic thin film transistor was fabricated and evaluated in the same manner. The results are shown in Table J. Further, the power curve of the obtained organic thin film transistor is shown in Fig. 9. As is apparent from Fig. 9, the region near the gate voltage of 0 v (circle) In the enclosed portion, the power curve is bent and deviated from the straight line, and the contact resistance is large, and the characteristics of the formula (1) are deviated. Comparative Example 2 In the same manner as in Example 1 except that the charge injection layer was not formed, 151050 was fabricated. Doc •55· 201116504 Organic thin film transistor was fabricated and evaluated. The results are shown in Table 1. [Table 1] Charge injection layer material Organic semiconductor layer material (type of carrier) Saturated region characteristic (Equation (2)) Linear region characteristic (Equation (1)) Field effect mobility ps [cm2/Vs] Threshold voltage [V] Switch Ratio [-] Field-effect mobility pL[cm2/Vs] Power curve at a threshold of 0 V near the drain voltage Example 1 (1) 4MSB (P) 0.15 -10 Ι.ΙχΙΟ6 0.15 No example 2 (42) 4MSB (P) 0.14 -9 1.8χ106 0.13 No Example 3 (162) 4MSB (P) 0.13 -12 1.5x10s 0.12 No Example 4 (9) 4MSB (P) 0.1 -11 0.92x106 0.1 No Example 5 (43 4MSB (P) 0.2 -8 2.2χ106 0.22 No Example 6 (6〇) 4MSB (P) 0.1 -9 5.2χ106 0.12 No Example 7 (70) 4MSB (P) 0.13 -10 4.〇χ106 0.11 No implementation Example 8 (110) 4MSB (P) 0.12 -10 1.9x106 0.12 No Example 9 (171) 4MSB (P) 0.13 -12 3.〇χ106 0.14 No Example 10 (65) PTCDI-C8 (6) 0.055 -7 2.3x10s 0.051 None Example 11 (60) 4MSB (P) 0.13 -8 1.9x106 0.12 No Example 12 (162) PTCDI-C8 (η) 0.06 -8 1.2χ105 0.55 No Example 13 (174) 4MSB (Ρ) 0.13 - 7 1.8χ106 0.12 None Example 14 (1) 4MSB (Ρ) 0.13 -13 1.0x106 0.12 No Comparative Example 1 - 4MSB (Ρ) 0.09 -18 5.4x10s 0.052 Comparative Example 2 - PTCDI-C8 (η) 0.021 -15 3.1χ104 0.021 Example 15 (Manufacture of Organic Thin Film Light-Emitting Transistor) The Si substrate (which is also used as a P-type gate electrode with a specific resistance of 1 Qcm) is oxidized by a surface to form a 300 nm thermal oxide film as an insulator layer on the substrate by -56-151050.doc 201116504 * ' . Further, by dry (four), it will be formed on the substrate.

Si〇2膜完全除去後’藉由濺鍍法以20 nm之膜厚使鉻成膜」後於其上藉由錢鑛以1〇〇⑽使金（Au)成膜而用作取出電極。將該基板於中性洗務劑、純水、丙酮及乙醇中各進行30 分鐘之超音波清洗。其次’設置於真空蒸鑛裝置（ULVAC公司製造，Εχ-9〇〇) 中’於絕緣體層（Si〇2)上以〇〇5 nm/s之蒸錢速率將4_成膜，形成膜厚1GG nm之有機半導體發光層。繼而，設置通道長度75 μιη、通道寬度5 _之金屬罩使化合物。8〇)以蒸鑛速率G.G5 nm/s成膜為1G nm之電荷注人層。其次，於基板相對於蒸發源呈4 5度傾斜之狀態下通過金屬罩使金以 5〇 η"之膜厚成臈。其：欠，於使基板朝相反方向呈45度傾斜之狀態下以100 nm蒸鍵Mg，藉此製作具備互不接觸的實質為電洞注人性電極（Au)與電子傳輸性電極陶之源極電極及汲極電極的有機薄膜發光電晶體。於所製ie之有機薄膜發光電晶體之源極-汲極電極間施加-100 V’對閘極電極施加_1〇〇 v時獲得之藍色發光。 & 實施例1 6(頂部接觸型有機薄膜電晶體之製造）以如下所述之方式剪且古岡β _ ,, 、Ik具有圖4所不之結構之頂部接觸型有機薄膜電晶體。使用遮蔽罩，藉由_於玻璃基板上製作_⑽之⑽ 151050.doc •57· 201116504 膜作為閘極電極。進而於其上藉由熱化學氣相沈積以500 ⑽之厚度使聚（氣對二甲苯）(Parylene c)成膜，作為閉極絕緣層。其次，將上述基板設置於真空蒸鍍裝置（ULVAc公司製造，EX-400)中，於室溫下，於絕緣體層上以〇〇5 nm/si 蒸鍍速率將2,7-二苯基[1]苯并噻吩并[3,3_bHl]_|并噻吩 (DPh-BTBT)成膜，形成膜厚4〇 nmi有機半導體層。繼而，通過金屬罩使化合物（60)(2,6_雙（2_苯基乙炔基）蒽； DPEA)以0.05 nm/s之蒸鍍速率成膜為l〇 nm膜厚之電荷注入層。進而使金以50 nm之臈厚成膜，藉此以間隔（通道長度L)成為50 μπι之方式形成互不接觸之電荷注入層以及源極電極及没極電極。此時係以源極電極與没極電極之寬度 (通道寬度W)成為1 mm之方式成膜，藉此製作有機薄膜電晶體（參照圖4)。對所得頂部接觸型有機薄膜電晶體之閘極電極施加〇〜 25 V之閘極電壓，於源極_汲極間施加v之電壓使電流流通，除此以外以與實施例丨相同之方式，根據關於飽和區域特性之式（2)計算出電洞之場效遷移率…及臨界電壓 V t。結果示於表2。比較例3及4 將電荷庄入層分別替代為示於表2之化合物，除此以外以與貝施例16相同之方式製作有機薄膜電晶體，求得場效遷移率μ5及臨界電壓V"結果示於表2。 151050.doc -58- 201116504 [表2] 有機半導體層材料 (載子之種類） DPh-BTBT(p) —*— 電何注入層材料 —---, Ί' . ；;—""".· ' ί.-·'—~rr-r—ι d鉋和區域#性丫2Π , 场效遷移率 fcm2/Vsl 臨界電壓 rvi __160)_| 0.3 —__L T J -8.3 稠五笨 ---- 0.03 -13.9 ΜοΟι 0.08 -13.6 實施例16 比較例3 比較例4 之實施例1 6之元件較之接田法卞平又义ί木用稠五本（比較例3)或M〇〇3(比較例4)之το件’顯不更優異之場效遷移率與臨界電壓。尤宜於將用作通常之有機半導體之稠五笨用於電荷注入層之情形時，無法獲得良好之i μμ 之#效遷移率與臨界電壓，因此可知對構成有機半導體層之M面曰之材枓要求之特性與對構成電荷注入材層之材料要求之特性並不相同。 [產業上之可利用性] 藉^使用特定結構之化合物作為電荷注入層’本發明之有機4膜％晶體之應答速率（驅動速率）高速化，開/關比較大’驅動電壓變低’料電晶體之性能較高，1亦可用作可發光之有機薄膜發光電晶體。之· 月之有機溥膜電晶體可用於：用於薄膜顯示器之電子器件等顯示用電子機器、塑膠KXintegrated circuit， :體電路)卡或資訊標籤等可穿戴電子機器、生物感測器寻醫療機器或測定裝置。述中對本發明之幾個實施形態及/或實施例進行了詳細的說明，紫Iπ — β 可谷易地於實質上不偏離本發明之新穎之及效果之範圍内’對該等例示之實施形態及/或實施 15l050.doc •59· 201116504 例進行多種變更範圍内。因此，該等多種變更係包含於本發明之 ”玄^書所記載之文獻之内容被全部引用至本文中。【圖式簡單說明】 ^係表示薄膜電晶體之具有代表性之結構之剖面圖。圖0 2係表示本發明之有機薄膜電晶體之-實施形態之圖圖3係表示本發明之有冑薄膜電晶體之其他實施形態之圖圖4係表示本發明之有機薄膜電晶體之其他實施形態之圖5係表示本發明之有機薄膜電晶體之其他實施形態之圖。圖6係表示實施例1之有機薄膜電晶體之構成之圖。圖7係表示實施例14之有機薄膜電晶體之構成之圖。圖8係表示實施例1之有機薄膜電晶體之功率曲線之圖。圖9係表示比較例1之有機薄膜電晶體之功率曲線之圖。【主要元件符號說明】 1 薄膜電晶體 2、3、4、5 有機薄膜電晶體 10 基板 12 Si基板 2〇、22 源極電極、32 汲極電極 151050.doc • 60 · 201116504 40、42 電荷注入層 50、52 有機半導體層 60 ' 62 絕緣體層 70 閘極電極 151050.doc -61 -After the Si〇2 film was completely removed, the chromium was formed into a film by a sputtering method at a film thickness of 20 nm, and then gold (Au) was formed into a film by using a gold ore at 1 Torr (10) to be used as a take-out electrode. The substrate was subjected to ultrasonic cleaning for 30 minutes in a neutral detergent, pure water, acetone, and ethanol. Secondly, it was set in a vacuum distillation unit (manufactured by ULVAC, Εχ-9〇〇) to form a film thickness on the insulator layer (Si〇2) at a steaming rate of 〇〇5 nm/s to form a film thickness. Organic semiconductor light-emitting layer of 1 GG nm. Then, a metal cover with a channel length of 75 μηη and a channel width of 5 _ is used to make the compound. 8〇) A film of 1G nm charge is deposited at a steaming rate of G.G5 nm/s. Next, the thickness of the gold is 5〇 η" by the metal cover in a state where the substrate is inclined at 45 degrees with respect to the evaporation source. It is: under the condition that the substrate is tilted at an angle of 45 degrees in the opposite direction, and the Mg is vapor-deposited at 100 nm, thereby producing a source of a hole-injecting electrode (Au) and an electron-transporting electrode which are not in contact with each other. An organic thin film light-emitting transistor of a pole electrode and a drain electrode. The blue luminescence obtained when -100 V' was applied to the gate electrode by applying -100 V' between the source-drain electrodes of the organic thin film light-emitting transistor produced by the method. & Example 1 6 (Production of top contact type organic thin film transistor) A top contact type organic thin film transistor having a structure of the same as that of Fig. 4 was cut in the manner described below. Using a mask, a film of _(10)(10) 151050.doc •57·201116504 was fabricated as a gate electrode on a glass substrate. Further, poly(p-xylene) (Parylene c) was formed into a film by thermal chemical vapor deposition at a thickness of 500 (10) to serve as a closed-electrode insulating layer. Next, the above substrate was placed in a vacuum vapor deposition apparatus (manufactured by ULVAc Co., Ltd., EX-400), and 2,7-diphenyl was deposited on the insulator layer at a deposition rate of nm5 nm/si at room temperature [ 1] Benzothieno[3,3_bHl]_| thiophene (DPh-BTBT) was formed into a film to form a film thickness of 4 〇 nmi organic semiconductor layer. Then, the compound (60) (2,6-bis(2-phenylethynyl)anthracene; DPEA) was formed into a charge injection layer of a film thickness of 10 nm by an evaporation rate of 0.05 nm/s through a metal cover. Further, gold is formed into a film having a thickness of 50 nm, whereby a charge injection layer, a source electrode, and a electrodeless electrode which are not in contact with each other are formed at intervals (channel length L) of 50 μm. In this case, an organic thin film transistor (see Fig. 4) was formed by forming a film having a width (channel width W) of the source electrode and the electrodeless electrode of 1 mm. A gate voltage of 〇 25 25 V was applied to the gate electrode of the obtained top contact type organic thin film transistor, and a voltage of v was applied between the source and the drain to circulate a current, and otherwise, in the same manner as in Example ,, The field effect mobility of the hole... and the threshold voltage Vt are calculated according to the formula (2) regarding the characteristics of the saturated region. The results are shown in Table 2. Comparative Examples 3 and 4 An organic thin film transistor was produced in the same manner as in the Shell Example 16 except that the charge-incorporating layer was replaced with the compound shown in Table 2, and the field-effect mobility μ5 and the threshold voltage V" were obtained. The results are shown in Table 2. 151050.doc -58- 201116504 [Table 2] Organic semiconductor layer material (type of carrier) DPh-BTBT(p) —*—Electrical injection layer material—--, Ί' . ;;-""".· ' ί.-·'—~rr-r—ι d planing and area #性丫2Π , field effect mobility fcm2/Vsl threshold voltage rvi __160)_| 0.3 —__L TJ -8.3 thick five stupid - --- 0.03 -13.9 ΜοΟι 0.08 -13.6 Example 16 Comparative Example 3 Comparative Example 4 Example 1 The components of 6 are compared with the method of the field method, and the five pieces of the thick wood (Comparative Example 3) or M〇〇 3 (Comparative Example 4) το件' shows no better field effect mobility and threshold voltage. When it is preferable to use it as a general-purpose organic semiconductor for a charge injection layer, a good i μμ mobility and a threshold voltage cannot be obtained, and thus it is known that the M surface constituting the organic semiconductor layer is The characteristics required for the material are not the same as those required for the material constituting the charge injection layer. [Industrial Applicability] By using a compound having a specific structure as a charge injection layer, the response rate (drive rate) of the organic 4 film% crystal of the present invention is increased, and the on/off is relatively large, and the drive voltage is low. The performance of the transistor is high, and 1 can also be used as a light-emitting organic thin film light-emitting transistor. · Month's organic enamel film can be used for: electronic devices for display devices such as electronic devices for thin-film displays, plastic KXintegrated circuits, body-optic circuits, wearable electronic devices such as cards or information tags, and biosensors for medical devices. Or measuring device. In the above, several embodiments and/or embodiments of the present invention have been described in detail, and the purple Iπ-β can be easily implemented without departing from the novel and effectful aspects of the present invention. Form and / or implementation of 15l050.doc • 59 · 201116504 examples are subject to a variety of changes. Therefore, the various changes are included in the contents of the documents described in the "Hyoko" of the present invention. All of them are incorporated herein by reference. [Simple Description of the Drawings] ^ is a sectional view showing a representative structure of a thin film transistor. Fig. 0 is a view showing an organic thin film transistor of the present invention. Fig. 3 is a view showing another embodiment of the organic thin film transistor of the present invention. Fig. 4 is a view showing the other of the organic thin film transistor of the present invention. Fig. 5 is a view showing another embodiment of the organic thin film transistor of the present invention. Fig. 6 is a view showing the constitution of the organic thin film transistor of the first embodiment. Fig. 7 is a view showing the organic thin film transistor of the embodiment 14. Fig. 8 is a view showing a power curve of the organic thin film transistor of Example 1. Fig. 9 is a view showing a power curve of the organic thin film transistor of Comparative Example 1. [Explanation of main component symbols] 1 Thin film electric Crystal 2, 3, 4, 5 Organic thin film transistor 10 Substrate 12 Si substrate 2 〇, 22 Source electrode, 32 电极 electrode 151050.doc • 60 · 201116504 40, 42 Charge injection layer 50, 52 Organic semiconductor layer 60 ' 62 Insulator layer 70 Gate electrode 151050.doc -61 -

Claims

201116504 七、申請專利範圍： 1· 一種有機薄膜電晶體，其係於基板上至少設置有閑極電極、，源極電極及汲極電極之三端子、以及絕緣體層及有機半導體層，藉由對閘極電極施加電壓而控制源極_没極間電流者；於上述有機半導體層與源極電極間、以及上述有機半導體層與没極電極間分別具有電荷注入層，上述電荷注入層含有下述式（1)所表示之化合物： [化 41] \ /η (式中’人^為下述式（2)所表示之取代基； ΑΓ2為可具有取代基之碳數6〜60之二價芳香族烴基、或可具有取代基之碳數2〜6〇之二價芳香族雜環基； Ar3為下述式（3)所表示之取代基： [化 42]201116504 VII. Patent application scope: 1. An organic thin film transistor, which is provided with at least a spare electrode, a source electrode and a three-terminal electrode of a drain electrode, and an insulator layer and an organic semiconductor layer on the substrate, by means of a gate a voltage is applied to the electrode to control the source-to-no-pole current; a charge injection layer is provided between the organic semiconductor layer and the source electrode, and between the organic semiconductor layer and the electrodeless electrode, and the charge injection layer includes the following formula (1) The compound represented by the formula: [Chemical Formula 41] \ /η (wherein, human ^ is a substituent represented by the following formula (2); ΑΓ 2 is a divalent aromatic having 6 to 60 carbon atoms which may have a substituent a hydrocarbon group or a divalent aromatic heterocyclic group having 2 to 6 carbon atoms which may have a substituent; Ar3 is a substituent represented by the following formula (3):

(式中’ R丨〜R10分別為氫原子、鹵素原子、碳數1〜％之烷基、奴數1〜30之鹵代烷基、碳數1〜30之烷氧基、碳數 1〜30之鹵代烧氧基、碳數丨〜3〇之院硫基、碳數1〜之鹵代烷硫基、碳數1〜30之烷基胺基、碳數2〜3〇之二烷基胺 151050.doc 201116504 基（兩個烷基可相互鍵結而形成含有氮原子之環結構）、碳數1〜30之烷基磺醯基、碳數1〜30之鹵代烷基續醯基、碳數6〜60之芳香族烴基、碳數1〜6〇之芳香族雜環基、碳數3〜30之烷基矽烷基、或氰基，該等基可進而具有取代基； Ri〜RS及Re〜R10中，鄰接之兩個基可相互鍵結而形成飽和或不飽和之環狀結構）； η為1〜20之整數）。 2·如請求们之有機薄膜電晶體’其中上述式⑴之_為可具有取代基之碳數6〜60之二價芳香族烴基。 3· ^求項1之有機薄膜電晶體’其中上述式（1)之Ar2為可 /、有取代基之苯、萘、蒽、菲、稠四苯、筷、或稠五苯所對應之二價殘基。且月求項1之有機薄膜電晶體，其中上述式（1)之Ar2為可 2有取代基之碳數6〜6 G之二價縮合多環式芳香族雜環基。 :求項4之有機薄膜電晶體’其中上述式(1)之Ar2為可 :二取：基之°比咯、吡啶、嘧啶、咪唑、噻唑、二噻吩并本、笨并嗔- 一唑、°圭啉、苯并噻吩、二苯并噻吩、苯〇、或二笨并呋喃所對應之二價殘基。 6. 如請求項〗之古仏* 、汉丞機薄膜電晶體，其中上述式為i。 7. 如請求項〗少士两i _ 有機薄膜電晶體，其中上述式（1)之η為2以上〈登數。 8. 如清求項1之機薄膜電晶體，其中上述式（2)及（3)中， 151050.doc 201116504 R2 R4 ' r5 ' R6 ' R7 > r9^R]〇^^ ^ ^ ( R3及Rs之至y纟為鹵素原子、碳數卜12之烷基、碳數1〜8之鹵代烷基、碳數1〜8之鹵代烷氧基、碳數炫基胺基、或碳數2〜16之二縣絲（兩_基可相互鍵結而形成含有氮原子之環結構），不為該等基之^8為氫原子。 9·如請求項1之有機薄膜電晶體，其中上述式⑴所表示之化合物為下述式（4)所表示之化合物： [化 43](wherein R 丨 R R10 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to % carbon atoms, a halogenated alkyl group having a number of 1 to 30, an alkoxy group having 1 to 30 carbon atoms, and a carbon number of 1 to 30; a halogenated alkoxy group, a carbon number of 丨~3〇, a thiol group having a carbon number of 1 to a halogenated alkylthio group, an alkylamino group having a carbon number of 1 to 30, and a dialkylamine having a carbon number of 2 to 3, 151,050. Doc 201116504 (two alkyl groups can be bonded to each other to form a ring structure containing a nitrogen atom), an alkylsulfonyl group having a carbon number of 1 to 30, a halogenated alkyl group having a carbon number of 1 to 30, a carbon number of 6~ An aromatic hydrocarbon group of 60, an aromatic heterocyclic group having 1 to 6 carbon atoms, an alkylalkyl group having 3 to 30 carbon atoms, or a cyano group, which may further have a substituent; Ri~RS and Re~R10 The adjacent two groups may be bonded to each other to form a saturated or unsaturated cyclic structure; η is an integer of 1 to 20). 2. The organic thin film transistor of the present invention, wherein _ of the above formula (1) is a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent. 3. The organic thin film transistor of claim 1 wherein Ar2 of the above formula (1) is a benzene, a naphthalene, an anthracene, a phenanthrene, a condensed tetraphenyl, a chopstick, or a thick pentacene having a substituent. Valence residue. Further, in the organic thin film transistor of the above item 1, wherein Ar2 of the above formula (1) is a divalent condensed polycyclic aromatic heterocyclic group having 6 to 6 G carbon atoms which may have a substituent. : The organic thin film transistor of claim 4, wherein Ar2 of the above formula (1) is: two: base ratio, pyridine, pyrimidine, imidazole, thiazole, dithiophene, stupid and oxazole, a divalent residue corresponding to guanoline, benzothiophene, dibenzothiophene, benzoquinone, or dibenzofuran. 6. In the case of the claim item, the 仏*, 丞机 machine film transistor, wherein the above formula is i. 7. If the claim item is a small one, two i _ organic thin film transistors, wherein η of the above formula (1) is 2 or more. 8. For the thin film transistor of claim 1, wherein in the above formulas (2) and (3), 151050.doc 201116504 R2 R4 ' r5 ' R6 ' R7 > r9^R] 〇 ^ ^ ^ ^ ( R3 And Rs to y 纟 is a halogen atom, a carbon number 12 alkyl group, a carbon number of 1 to 8 haloalkyl group, a carbon number of 1 to 8 haloalkoxy group, a carbon number amine group, or a carbon number of 2 to 16 The second filament (the two bases may be bonded to each other to form a ring structure containing a nitrogen atom), and the other is not a hydrogen atom. The organic thin film transistor of claim 1, wherein the above formula (1) The compound represented by the following formula (4): [Chem. 43]

Ri 1〜Ru分別為氫原子、鹵素原子、碳數丨〜3〇之院基、碳數1〜30之幽代烷基、碳數卜儿之烷氧基、碳數卜儿之鹵代烷氧基、碳數卜扣之烷硫基、碳數卜儿之_代烷硫基坡數1〜30之烧基胺基、碳數2〜30之二烧基胺基（兩個烧基可相互鍵結而形成含有氮原子之環結構）、碳數丨〜3 〇之烧基項醯基、碳數卜川之鹵代烷基磺醯基、碳數6〜6〇之芳香族烴基、碳數丨〜60之芳香族雜環基、碳數3〜30之烷基矽烷基、或氰基，該等基可進而具有取代基； Rl1與R]2以及R13與Rl4可分別相互鍵結而形成飽和或不飽和之環狀結構）。 151050.doc 201116504 ι〇·如請求項9之有機薄膜電晶體，其中上述式（4)iRn〜Rl4 分別為氫原子、鹵素原子、碳數1〜12之烷基、碳數1〜8 之鹵代烷基、碳數1〜8之烷氧基 '碳數1〜8之烷硫基、碳數1〜8之烷基胺基、碳數2〜8之二烷基胺基（兩個烷基可相互鍵結而形成含有氮原子之環結構）、碳數1〜8之烷基磺醯基、或氰基。 11.如請求項9之有機薄膜電晶體，其中上述式（4)中，、 R2 ' R4、r5、R6、心及^〜R】4全部為氫原子，汉3及汉8之至少一者為鹵素原子、碳數1〜12之烷基、碳數1〜8之鹵代烷基、碳數1〜8之鹵代烷氧基、碳數卜8之烷基胺基、或碳數2〜16之二烷基胺基（兩個烷基可相互鍵結而形成含有氮^ @ & μ、 '、子之裱結構）’不為該等之R3或R8為氫原子。 A如請求項9之有機薄膜電晶體’其中上述式⑷之Rl〜Rl4 之：：者為氟原子、氰基、三氟甲基、或五氟乙基。 13_如5月求項1〇之有媸ρ '寻骐電晶體，其中上述式（4)之R丨〜R14 14·如1主求塌f氟原子、氰基、三氟甲基、或五氟乙基。 1 5.如請求項9之有機】5二之有機薄膜電晶體，其中上述式⑷之n為1。溥膜電晶體，其中上述式（4)之11為2以上之整數。 16.如請求項1之有 - 化合物為下述2膜電晶體’其中上述式⑴所表示之 [化44]式(5)所表示之化合物： 151050.doc (5) 201116504 r9Ri 1 to Ru are each a hydrogen atom, a halogen atom, a carbon number of 〇~3〇, a decyl group having a carbon number of 1 to 30, an alkoxy group of a carbon number, and a halogenated alkoxy group of a carbon number. , an alkylthio group of a carbon number, an alkyl group of a carbon number of 1 to 30, and a dialkylamino group having a carbon number of 2 to 30 (two groups may be mutually bonded) a ring structure containing a nitrogen atom, a ruthenium group having a carbon number of 丨3 to 3, a halogenated alkylsulfonyl group of a carbon number, an aromatic hydrocarbon group having a carbon number of 6 to 6 Å, and a carbon number 丨~ An aromatic heterocyclic group of 60, an alkylalkylene group having 3 to 30 carbon atoms, or a cyano group, which may further have a substituent; R11 and R]2 and R13 and Rl4 may be bonded to each other to form a saturated or Unsaturated ring structure). The organic thin film transistor of claim 9, wherein the above formula (4) iRn to Rl4 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkyl halide having 1 to 8 carbon atoms, respectively. Alkoxy group having a carbon number of 1 to 8, an alkylthio group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms (two alkyl groups may be used. Bonded to each other to form a ring structure containing a nitrogen atom, an alkylsulfonyl group having 1 to 8 carbon atoms, or a cyano group. 11. The organic thin film transistor according to claim 9, wherein in the above formula (4), R2 'R4, r5, R6, and the cores are all hydrogen atoms, at least one of Han 3 and Han 8 And it is a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated alkoxy group having 1 to 8 carbon atoms, an alkylamino group having a carbon number of 8, or a carbon number of 2 to 16 The alkylamino group (the two alkyl groups may be bonded to each other to form a structure containing nitrogen ^ @ & μ, ', and a sub-structure) is not such that R3 or R8 is a hydrogen atom. A. The organic thin film transistor of claim 9, wherein R1 to R14 of the above formula (4) are: a fluorine atom, a cyano group, a trifluoromethyl group, or a pentafluoroethyl group. 13_For example, in May, there is a 媸ρ 'seeking transistor, in which R 丨 R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R Pentafluoroethyl. 1 5. The organic thin film transistor according to claim 9, wherein n of the above formula (4) is 1. A ruthenium film transistor in which 11 of the above formula (4) is an integer of 2 or more. 16. The present invention as claimed in claim 1 - the compound is a film of the following two films, wherein the compound represented by the above formula (1) is represented by the formula (5): 151050.doc (5) 201116504 r9

r8 r7 (式中’ Ri〜R丨0與上述式（i)相同； Ris〜R22分別為氫原子、碳數卜川之烷基、碳數U0之鹵代烷基、碳數1〜30之烷氧基、碳數uo之鹵代烷氧基、碳數1〜30之烷硫基、碳數卜川之鹵代烷硫基、碳數 1〜30之烷基胺基、碳數2〜3〇之二烷基胺基（兩個烷基可相互鍵結而形成含有氮原子之環結構）、碳數卜％之院基石黃醯基、碳數1〜30之_代燒基確醯基、碳數6〜6〇之芳香族烴基、碳數卜60之料族雜環基、碳數3〜3g之縣石夕院基、或氰基，該等基可進而具有取代基卜 1 7.如請求項1至1 6中任一頂夕古秘# 項之有機薄膜電晶體，其中上述電街注入層與上述半導體層係由不同材料構成。 18.如請求項丨至16中任一項、十、、s & ,機溥膜電晶體，其中於上述源極電極與電荷注入層之間、 _ 、上荷、、主入s 及上述汲極電極與電何，主入層之間分別具有緩衝層。、也 19·如請求項1至16中任-項之有機薄膜電晶m 源極-汲極間流通之電流而獲得 —立”糸利用施加電壓而控制發光。 …且藉由對閘極電極 2〇·如請求項1至16中任一項之式（1)所表- 入專膜電晶體’其中、+. k )所表不之化合物之游離電 f上述电位為5.2 eV以上。 151050.docR8 r7 (wherein Ri~R丨0 is the same as the above formula (i); Ris~R22 are each a hydrogen atom, an alkyl group of a carbon number, a halogenated alkyl group having a carbon number of U0, and an alkoxy group having a carbon number of 1 to 30. a halogenated alkoxy group having a carbon number of uo, an alkylthio group having a carbon number of from 1 to 30, a halogenated alkylthio group of a carbon number, an alkylamine group having a carbon number of from 1 to 30, and a dialkyl group having a carbon number of from 2 to 3 Amino group (two alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom), a carbon number of the compound of the basestone, a ruthenium group, a carbon number of 1 to 30, a carbon number of 6 to 6 〇 The aromatic hydrocarbon group, the carbon number of the group of 60, the heterocyclic group of the carbon number, the carbon number of 3 to 3 g of the county, or the cyano group, and the group may further have a substituent 1 1. As claimed in claims 1 to 1. An organic thin film transistor according to any one of the preceding claims, wherein the electrical street injection layer and the semiconductor layer are composed of different materials. 18. As claimed in any one of the following items, ten, s & The 溥 film transistor, wherein between the source electrode and the charge injection layer, _, the upper load, the main input s, and the above-mentioned drain electrode and electricity, respectively, the main entry layer has a slow The layer is obtained by the current flowing between the source and the drain of the organic thin film electrocrystal m of any one of claims 1 to 16, and the light is controlled by applying a voltage. Gate electrode 2 〇 · As shown in the formula (1) of any one of claims 1 to 16, the free electric charge of the compound represented by the specific film transistor 'where, +. k ) is 5.2 eV. Above. 151050.doc