TW201304148A - Thin-film transistor and manufacturing method therefor - Google Patents
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/464—Lateral top-gate IGFETs comprising only a single gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Thin Film Transistor (AREA)
Abstract
Description
本發明係關於新穎的薄膜電晶體及其製造方法、以及具有如上所示之薄膜電晶體的電路。 The present invention relates to novel thin film transistors and methods of making the same, and to circuits having the thin film transistors shown above.
近年來，半導體膜被使用在以薄膜電晶體(TFT)為代表的半導體元件、太陽電池等各種用途。 In recent years, semiconductor films have been used in various applications such as semiconductor elements typified by thin film transistors (TFTs) and solar cells.
現在主要被使用的無機半導體膜，尤其使用矽作為半導體材料的無機半導體膜係在製造時使用化學氣相成長(CVD)或濺鍍等真空製程，因此製造成本高。此外，在無機半導體膜中，由製程溫度來看，不易形成在高分子薄膜等之上。此外，無機半導體膜係不易響應在未來被期待實用化之輕量且為可撓性的元件或RF-ID(Radio Frequency IDentification)等之低成本的要求。 Inorganic semiconductor films which are mainly used nowadays, in particular, inorganic semiconductor films using germanium as a semiconductor material are manufactured by a vacuum process such as chemical vapor deposition (CVD) or sputtering, and thus are expensive to manufacture. Further, in the inorganic semiconductor film, it is difficult to form on a polymer film or the like from the viewpoint of process temperature. Further, the inorganic semiconductor film is less likely to respond to low-cost requirements such as lightweight and flexible elements or RF-ID (Radio Frequency IDentification) which are expected to be put into practical use in the future.
為解決如上所述之課題，提出使用由有機半導體材料所製作的有機半導體膜。在有機半導體膜的製造中所使用的真空蒸鍍裝置或塗佈裝置，與在無機半導體膜的製造中所被使用的CVD裝置或濺鍍裝置相比較，較為廉價。此外，在有機半導體膜的製造中，由於製程溫度低，因此亦可將有機半導體膜，在高分子薄膜或紙等上形成半導體膜。 In order to solve the above problems, it is proposed to use an organic semiconductor film made of an organic semiconductor material. The vacuum vapor deposition apparatus or the coating apparatus used in the production of the organic semiconductor film is relatively inexpensive compared with the CVD apparatus or the sputtering apparatus used in the production of the inorganic semiconductor film. Further, in the production of the organic semiconductor film, since the process temperature is low, the organic semiconductor film can be formed into a semiconductor film on a polymer film or paper.
在此，以有機半導體膜的形成方法而言，已知有：將含有有機半導體材料的溶液塗佈在基材、印模(stamp) 等，接著將溶媒去除的溶液法(例如澆鑄法、旋塗法、接觸印刷法般的印刷法、浸漬法等)、及使有機半導體材料蒸鍍在基材的蒸鍍法。該等方法之中的溶液法，一般而言，已知關於製造成本、製造速度等為較佳，因此已被進行各種研究。但是，藉由溶液法來安定地獲得品質高的有機半導體膜，並不一定被充分達成。 Here, in the method of forming an organic semiconductor film, it is known to apply a solution containing an organic semiconductor material to a substrate, a stamp. Then, a solution method in which a solvent is removed (for example, a casting method, a spin coating method, a printing method such as a contact printing method, a dipping method, or the like), and a vapor deposition method in which an organic semiconductor material is vapor-deposited on a substrate. The solution method among these methods is generally known to be preferable in terms of production cost, production speed, and the like, and thus various studies have been conducted. However, it is not always sufficient to obtain a high-quality organic semiconductor film by a solution method.
有機半導體的電荷移動度已知強力取決於其結晶性、結晶形態，且已知單結晶的有機半導體中的電荷移動度係取決於其結晶方位。因此，為了以最大限度引出有機半導體的特性，使結晶性的有機半導體膜作面內配向，使移動度成為最大的分子軸朝有機半導體元件的通道長方向作配向的內容已被提出。 The degree of charge mobility of an organic semiconductor is known to be strongly dependent on its crystallinity, crystal morphology, and it is known that the degree of charge mobility in a single crystal organic semiconductor depends on its crystal orientation. Therefore, in order to maximize the characteristics of the organic semiconductor, the crystalline organic semiconductor film is aligned in the plane, and the molecular axis having the largest mobility is aligned toward the channel length direction of the organic semiconductor element.
關於此，在專利文獻1以及非專利文獻1及2中係提出將屬於經擦摩(磨擦)處理的聚合物層等的配向膜形成在基材上，在該配向膜上形成有機半導體膜，接著，使有機半導體膜升溫至液晶轉移溫度，藉由配向膜的作用，使有機半導體膜作配向，藉此形成面內具有單軸異向性的有機半導體膜。亦即，在該等文獻中係提出將有機半導體膜形成在用以使有機半導體材料以面方向作配向的配向膜上。 In the case of Patent Document 1 and Non-Patent Documents 1 and 2, an alignment film belonging to a rubbing (friction)-treated polymer layer or the like is formed on a substrate, and an organic semiconductor film is formed on the alignment film. Then, the organic semiconductor film is heated to the liquid crystal transition temperature, and the organic semiconductor film is aligned by the action of the alignment film, thereby forming an organic semiconductor film having uniaxial anisotropy in the plane. That is, in these documents, it is proposed to form an organic semiconductor film on an alignment film for aligning the organic semiconductor material in the plane direction.
此外，在專利文獻2以及非專利文獻3~7中，將溶液狀態或熔融狀態的有機半導體材料，一面供予強力切斷，一面進行成膜，藉此形成具有單軸異向性的有機半導體層的內容已被提出。 Further, in Patent Document 2 and Non-Patent Documents 3 to 7, an organic semiconductor material in a solution state or a molten state is formed while being strongly cut, thereby forming an organic semiconductor having uniaxial anisotropy. The content of the layer has been proposed.
其中，在專利文獻3中提出在基材上形成使有機半導體材料相對基材以垂直方向作配向的配向膜，將有機半導體膜，以液晶相溫度由印模等脫模性基板轉印在該配向膜上，藉由配向膜的作用，使有機半導體膜相對基材以垂直方向作配向的內容。亦即，在該文獻中提出藉由使有機半導體材料相對基材以垂直方向作配向，使有機半導體膜的面內方向的移動度提升。 In Patent Document 3, it is proposed to form an alignment film on the substrate in which the organic semiconductor material is aligned in the vertical direction with respect to the substrate, and to transfer the organic semiconductor film to the release substrate such as a stamp at a liquid crystal phase temperature. On the alignment film, the organic semiconductor film is aligned in the vertical direction with respect to the substrate by the action of the alignment film. That is, in this document, it is proposed to increase the mobility of the organic semiconductor film in the in-plane direction by aligning the organic semiconductor material with respect to the substrate in the vertical direction.
[專利文獻1]日本特開2008-192773號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-192773
[專利文獻2]日本特開2004-356422號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-356422
[專利文獻3]日本特開2009-200479號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-200479
[非專利文獻1]H.Sirringhaus etc., Mobility enhancement in conjugated polymer field-effect transistor through chain alignment in a liquid-crystaline phase “Appl. Phys. Lett., VOL. 77, NO. 3, 17, 2000, 406-408 [Non-Patent Document 1] H. Sirringhaus etc., Mobility enhancement in conjugated polymer field-effect transistor through chain alignment in a liquid-crystaline phase "Appl. Phys. Lett., VOL. 77, NO. 3, 17, 2000, 406-408
[非專利文獻2]L.Kindera etc., “Structural ordering and enhanced charier mobility in organic polymer thin film transistors” Synthetic Metals, 146, 2004, 181-185 [Non-Patent Document 2] L. Kinderta etc., "Structural ordering and enhanced charier mobility in organic polymer thin film transistors" Synthetic Metals, 146, 2004, 181-185
[非專利文獻3]A. Hector etc., “High-performance organic thin-film transistors through solution-sheared deposition of small-molecule organic semiconductors” Adv. Matter., 20, 2008, 2588-2594 [Non-Patent Document 3] A. Hector etc., "High-performance organic thin-film transistors through solution-sheared Deposition of small-molecule organic semiconductors” Adv. Matter., 20, 2008, 2588-2594
[非專利文獻4]M.Karakawa etc., “High-performance poly(3-hexylthiophene) field-effect transistors fabricated by a slide-coating method” Applied Physics Express 1 (2008) 061802 [Non-Patent Document 4] M. Karakawa etc., "High-performance poly(3-hexylthiophene) field-effect transistors fabricated by a slide-coating method" Applied Physics Express 1 (2008) 061802
[非專利文獻5]S.Nagamatsu etc., “Backbone Arrangement in” Friction-Transferred “Regioregular Poly(3-alkylthiphene)s” Macromolecules, 36 (2003) 5252 [Non-Patent Document 5] S. Nagamatsu etc., "Backbone Arrangement in" Friction-Transferred "Regioregular Poly (3-alkylthiphene)s" Macromolecules, 36 (2003) 5252
[非專利文獻6]J.-F.Chang etc., “Enhanced Mobility of Poly(3-hexylthiophene) Transistors by Spin-Coating from High-Boiling-Point Solvents” Chem. Mater., 16 (2004) 4772 [Non-Patent Document 6] J.-F. Chang et., "Enhanced Mobility of Poly (3-hexylthiophene) Transistors by Spin-Coating from High-Boiling-Point Solvents" Chem. Mater., 16 (2004) 4772
[非專利文獻7]Y.Koshiba etc., “Fabrication of One-Dimensionally Oriented Fluoren-Thiophene Copolymer Thin Films and Anisotropic Transistor Characterization” Jpn. J. Appll. Phys., 49 (2010) 01AE13 [Non-Patent Document 7] Y. Koshiba etc., "Fabrication of One-Dimensionally Oriented Fluoren-Thiophene Copolymer Thin Films and Anisotropic Transistor Characterization" Jpn. J. Appll. Phys., 49 (2010) 01AE13
本發明之目的在提供新穎的薄膜電晶體及其製造方法、以及具有如上所示之薄膜電晶體的電路。 SUMMARY OF THE INVENTION An object of the present invention is to provide a novel thin film transistor and a method of manufacturing the same, and a circuit having the thin film transistor as shown above.
本案發明人等發現藉由構成有機半導體材料的芳香環所形成的面為相對基板呈大致垂直豎立的構形(conformation)，而且可以特定的方法來成膜有機半導體材料在有機半導體膜的面內作配向的有機半導體膜，而思及下列薄膜電晶體及其製造方法、以及電路。 The inventors of the present invention have found that the surface formed by the aromatic ring constituting the organic semiconductor material is a substantially vertical alignment with respect to the substrate, and the organic semiconductor material can be formed in the plane of the organic semiconductor film by a specific method. As an organic semiconductor film to be aligned, the following thin film transistors and their manufacturing methods, and circuits are considered.
〈1〉一種薄膜電晶體，其係具有源極電極、汲極電極、閘極電極、閘極絕緣膜、及有機半導體膜，藉由閘極絕緣膜，使源極電極及汲極電極與閘極電極呈絕緣，而且藉由被施加至閘極電極的電壓，由源極電極往汲極電極通過半導體膜所流通的電流受到控制，該薄膜電晶體之特徵為：上述有機半導體膜由具有芳香環的有機半導體材料所構成，藉由構成上述有機半導體材料的芳香環所形成的面為相對基板呈大致垂直豎立的構形，而且上述有機半導體材料的移動度成為最大的分子軸，在有機半導體膜的面內，朝源極電極與汲極電極之間的電場方向作配向。 <1> A thin film transistor having a source electrode, a drain electrode, a gate electrode, a gate insulating film, and an organic semiconductor film, and a gate electrode and a gate electrode and a gate electrode are provided by a gate insulating film The electrode is insulated, and the current flowing from the source electrode to the drain electrode through the semiconductor film is controlled by a voltage applied to the gate electrode, wherein the thin film transistor is characterized in that the organic semiconductor film has a fragrance a ring-shaped organic semiconductor material, wherein a surface formed by the aromatic ring constituting the organic semiconductor material has a substantially vertical configuration with respect to the substrate, and the mobility of the organic semiconductor material becomes the largest molecular axis in the organic semiconductor In the plane of the film, the direction of the electric field between the source electrode and the drain electrode is aligned.
〈2〉如上述(1)之薄膜電晶體，其中，上述有機半導體材料的主鏈的分子軸方向在有機半導體膜的面內，源極電極與汲極電極之間的電場方向的±60°以內。 [2] The thin film transistor according to the above (1), wherein a molecular axis direction of a main chain of the organic semiconductor material is in a plane of the organic semiconductor film, and a direction of an electric field between the source electrode and the drain electrode is ±60°. Within.
〈3〉如上述(1)或(2)之薄膜電晶體，其中，不與使上述有機半導體材料朝面方向作配向的配向膜相接。 <3> The thin film transistor according to the above (1) or (2), which is not in contact with an alignment film that causes the organic semiconductor material to face in a plane direction.
〈4〉如上述(1)至(3)中任一者之薄膜電晶體， 其中，在面內呈直交的2方向的電荷移動度的比{(電荷移動度為最大的方向的電荷移動度)/(與其呈直交的方向的電荷移動度)}的值大於1.5。 <4> The thin film transistor according to any one of (1) to (3) above, Among them, the ratio of the charge mobility in the two directions orthogonal to the inside of the plane {the (the degree of charge mobility in the direction in which the charge mobility is the largest) / (the degree of charge mobility in the direction orthogonal thereto) is greater than 1.5.
〈5〉如上述(1)至(4)中任一者之薄膜電晶體，其中，上述有機半導體膜係藉由接觸印刷法而得。 The thin film transistor according to any one of the above (1) to (4) wherein the organic semiconductor film is obtained by a contact printing method.
〈6〉如上述(1)至(5)中任一者之薄膜電晶體，其中，上述有機半導體材料為可成為液晶狀態的有機半導體材料。 The thin film transistor according to any one of the above (1) to (5) wherein the organic semiconductor material is an organic semiconductor material which can be in a liquid crystal state.
〈7〉如上述(1)至(6)中任一者之薄膜電晶體，其中，上述電荷移動度的比的值為5以上。 The thin film transistor according to any one of the above (1), wherein the ratio of the charge mobility is 5 or more.
〈8〉如上述(1)至(7)中任一者之薄膜電晶體，其中，上述有機半導體膜的電荷移動度成為最大的方向的電荷移動度為0.01cm2/(V‧s)以上。 The thin film transistor of any one of the above-mentioned (1) to (7), wherein the charge mobility of the organic semiconductor film in the direction in which the charge mobility is the largest is 0.01 cm 2 /(V‧s) or more .
〈9〉如上述(1)至(8)中任一者之薄膜電晶體，其中，上述有機半導體膜與對水的接觸角為50度以上的基板或膜相接。 The thin film transistor according to any one of the above (1), wherein the organic semiconductor film is in contact with a substrate or a film having a contact angle with water of 50 degrees or more.
〈10〉一種電路，其係具有100個以上之薄膜電晶體的電路，其特徵為：上述薄膜電晶體之中的至少80%為上述(1)至(9)中任一者之薄膜電晶體。 <10> A circuit comprising 100 or more thin film transistors, characterized in that at least 80% of the thin film transistors are thin film transistors of any one of (1) to (9) above. .
〈11〉一種薄膜電晶體之製造方法，其係如上述(1)至(9)中任一者之薄膜電晶體之製造方法，其藉由包含以下步驟的方法來製造上述有機半導體膜：提供有機半導體材料呈溶解及/或分散的有機半導體溶液的步驟； 將上述有機半導體溶液適用在印模上，使其乾燥而在上述印模上獲得有機半導體膜的步驟；及將上述有機半導體層以上述有機半導體材料呈液晶化的溫度進行轉印的步驟。 (11) A method of producing a thin film transistor, which is the method for producing a thin film transistor according to any one of the above (1) to (9), wherein the organic semiconductor film is produced by a method comprising the steps of: providing The organic semiconductor material is in the form of a dissolved and/or dispersed organic semiconductor solution; The organic semiconductor solution is applied to a stamp and dried to obtain an organic semiconductor film on the stamp; and a step of transferring the organic semiconductor layer at a temperature at which the organic semiconductor material is liquidified.
〈12〉如上述(11)之方法，其中，使用在印刷面具有上述印模的滾輪來進行上述轉印的步驟。 <12> The method according to the above (11), wherein the step of performing the transfer is performed using a roller having the above-described stamp on the printing surface.
〈13〉一種薄膜電晶體之製造方法，其係如上述(1)至(9)中任一者之薄膜電晶體之製造方法，其係藉由包含以下步驟的方法來製造上述有機半導體膜：在基板或膜上提供由具有芳香環的有機半導體材料所構成的有機半導體膜的步驟；及以上述有機半導體材料呈液晶化的溫度，對上述有機半導體層由外部施加應力，使上述有機半導體材料在上述有機半導體膜的面內作配向的步驟。 <13> A method of producing a thin film transistor, which is the method for producing a thin film transistor according to any one of the above (1) to (9), wherein the organic semiconductor film is produced by a method comprising the following steps: a step of providing an organic semiconductor film composed of an organic semiconductor material having an aromatic ring on a substrate or a film; and applying a stress to the organic semiconductor layer from the outside at a temperature at which the organic semiconductor material is liquidified to cause the organic semiconductor material The step of aligning in the plane of the above organic semiconductor film.
〈14〉如上述(11)至(13)中任一者之方法，其中，上述有機半導體膜與對水的接觸角為50度以上的基板或膜相接。 The method of any one of the above-mentioned (11) to (13), wherein the organic semiconductor film is in contact with a substrate or a film having a contact angle with water of 50 degrees or more.
本發明之薄膜電晶體係可以較為高速來發揮功能。此外，藉由生成有機半導體膜之本發明之方法，可生成在本發明之薄膜電晶體中所被使用的有機半導體膜。 The thin film electro-crystalline system of the present invention can function at a relatively high speed. Further, an organic semiconductor film used in the thin film transistor of the present invention can be produced by the method of the present invention for producing an organic semiconductor film.
本發明之薄膜電晶體係具有源極電極、汲極電極、閘極電極、閘極絕緣膜、及有機半導體膜，藉由閘極絕緣膜，使源極電極及汲極電極與閘極電極呈絕緣，而且藉由被施加至閘極電極的電壓，由源極電極往汲極電極通過有機半導體膜所流通的電流受到控制。 The thin film electro-crystal system of the present invention has a source electrode, a drain electrode, a gate electrode, a gate insulating film, and an organic semiconductor film, and the gate electrode and the gate electrode are formed by the gate insulating film Insulation, and the current flowing from the source electrode to the drain electrode through the organic semiconductor film is controlled by the voltage applied to the gate electrode.
在本發明之薄膜電晶體中，有機半導體膜係由具有芳香環的有機半導體材料所構成。在此，在該有機半導體膜中，藉由構成有機半導體材料的芳香環所形成的面為相對基板呈大致垂直豎立的構形。 In the thin film transistor of the present invention, the organic semiconductor film is composed of an organic semiconductor material having an aromatic ring. Here, in the organic semiconductor film, the surface formed by the aromatic ring constituting the organic semiconductor material has a configuration that is substantially perpendicular to the substrate.
此外，在該有機半導體膜中，有機半導體材料的移動度成為最大的分子軸係在有機半導體膜的面內，以有機半導體元件的通道長方向，亦即源極電極與汲極電極之間的電場方向作配向。具體而言，例如在該有機半導體膜中，有機半導體材料的主鏈的分子軸方向係在有機半導體膜的面內，源極電極與汲極電極之間的電場方向的±60°以內、±45°以內、±30°以內、±20°以內、或±10°以內。 Further, in the organic semiconductor film, the molecular axis of the organic semiconductor material has the largest molecular axis in the plane of the organic semiconductor film, and is in the channel length direction of the organic semiconductor element, that is, between the source electrode and the drain electrode. The direction of the electric field is aligned. Specifically, for example, in the organic semiconductor film, the molecular axis direction of the main chain of the organic semiconductor material is in the plane of the organic semiconductor film, and within ±60° of the electric field direction between the source electrode and the drain electrode, Within 45°, within ±30°, within ±20°, or within ±10°.
該有機半導體膜係可不與使有機半導體材料朝面方向作配向的配向膜相接，亦可例如在正下方未具有如上所示之配向膜。 The organic semiconductor film may not be in contact with an alignment film that aligns the organic semiconductor material in the surface direction, and may have, for example, an alignment film as described above directly below.
在本發明之薄膜電晶體中所使用的有機半導體膜中，如第1圖所示，為取得藉由構成有機半導體材料(1)的 芳香環所形成的面(2)相對基板(10)呈大致垂直豎立的構形的狀態，而且有機半導體材料(1)在有機半導體膜的面內作配向。 In the organic semiconductor film used in the thin film transistor of the present invention, as shown in Fig. 1, in order to obtain the organic semiconductor material (1) The surface (2) formed by the aromatic ring is in a substantially vertical configuration with respect to the substrate (10), and the organic semiconductor material (1) is aligned in the plane of the organic semiconductor film.
在此，該面(2)為相對基板(10)呈大致垂直豎立的構形，而且呈單軸配向係可在例如in-plane的X線繞射(XRD)解析中，藉由僅觀察因該面的間隔而起的峰值來作確認。 Here, the face (2) is a configuration that is substantially perpendicular to the opposite substrate (10), and the uniaxial alignment system can be observed in X-ray diffraction (XRD), for example, in-plane, by observing only The peak from the interval of the faces is confirmed.
相對於此，如專利文獻2以及非專利文獻3~5所示，已知將溶液狀態或熔融狀態的有機半導體材料，一面供予強力切斷一面進行成膜時，未使用配向膜，即可達成有機半導體材料的配向，但是如第2圖所示，藉由構成有機半導體材料的芳香環(1)所形成的面(2’)為相對基板(10)呈大致平行層積的構形來作配向(非專利文獻5)。 On the other hand, as disclosed in Patent Document 2 and Non-Patent Documents 3 to 5, it is known that when an organic semiconductor material in a solution state or a molten state is formed while being strongly cut, the alignment film is not used. The alignment of the organic semiconductor material is achieved, but as shown in Fig. 2, the surface (2') formed by the aromatic ring (1) constituting the organic semiconductor material is configured to be substantially parallel to the substrate (10). Orientation (Non-Patent Document 5).
如上所示，該面(2’)為相對基板(10)呈大致平行層積的構形係可藉由例如在out-of-plane的X線繞射(XRD)解析中，確認該面(2‘)的繞射峰值、及在in-plane的X線繞射(XRD)解析中，觀察因沿著烷基側鏈(C12H25)的結晶化方向而起的複數片晶(lamella)峰值來作確認。 As described above, the configuration in which the face (2') is substantially parallel to the opposite substrate (10) can be confirmed by, for example, X-ray diffraction (XRD) analysis of out-of-plane. 2') diffraction peak, and in the in-plane X-ray diffraction (XRD) analysis, observe a plurality of lamella (lamella) due to the crystallization direction along the alkyl side chain (C 12 H 25 ) The peak value is used for confirmation.
關於此，關於具有芳香環的有機半導體的構形與半導體特性的關係，係廣被研究。具體而言，藉由構成有機半導體材料(1)的芳香環所形成的面(2)具有相對基板(10)呈大致垂直豎立的構形(Edge-On構形(第1圖)) 時，相較於藉由構成有機半導體材料的芳香環(1)所形成的面(2’)為相對基板(10)呈大致平行層積的構形(Face-On構形(第2圖))，以電荷移動度為首的半導體特性較為優異已為一般所知(專利文獻3、非專利文獻1、6等)。 In this regard, the relationship between the configuration of an organic semiconductor having an aromatic ring and semiconductor characteristics has been widely studied. Specifically, the face (2) formed by the aromatic ring constituting the organic semiconductor material (1) has a configuration that is substantially perpendicular to the substrate (10) (Edge-On configuration (Fig. 1)) When the surface (2') formed by the aromatic ring (1) constituting the organic semiconductor material is a substantially parallel laminated structure with respect to the substrate (10) (Face-On configuration (Fig. 2) In addition, it is generally known that semiconductor characteristics including charge mobility are excellent (Patent Document 3, Non-Patent Documents 1, 6, etc.).
在本發明之薄膜電晶體中所使用的有機半導體膜中，有機半導體材料的主鏈的分子軸方向，在有機半導體膜的面內，以源極電極與汲極電極之間的電場方向呈單軸配向，藉此可在該電場方向中達成較大的電荷移動度。其中，在未配向的有機半導體膜中，有機半導體材料的配向方向的不均較大，藉此會有容易發生使用如上所示之有機半導體膜的薄膜電晶體的特性不均的問題。相對於此，本發明中所使用的有機半導體膜係呈單軸配向，因此如上所示之特性不均會變小。 In the organic semiconductor film used in the thin film transistor of the present invention, the molecular axis direction of the main chain of the organic semiconductor material is in the plane of the organic semiconductor film, and the direction of the electric field between the source electrode and the drain electrode is single. The axes are aligned so that a large degree of charge mobility can be achieved in the direction of the electric field. Among them, in the unaligned organic semiconductor film, the unevenness of the alignment direction of the organic semiconductor material is large, whereby the problem of the characteristic unevenness of the thin film transistor using the organic semiconductor film as described above is likely to occur. On the other hand, since the organic semiconductor film used in the present invention is uniaxially aligned, the unevenness in characteristics as described above is small.
因此，如本發明之薄膜電晶體般，藉由構成有機半導體材料的芳香環所形成的面為相對基板呈大致垂直豎立的構形，而且有機半導體材料的主鏈的分子軸方向在有機半導體膜的面內，朝源極電極與汲極電極之間的電場方向作配向時，可獲得以較為高速發揮功能的薄膜電晶體。 Therefore, as in the thin film transistor of the present invention, the surface formed by the aromatic ring constituting the organic semiconductor material has a substantially vertical standing configuration with respect to the substrate, and the molecular axis direction of the main chain of the organic semiconductor material is in the organic semiconductor film. In the in-plane, when the direction of the electric field between the source electrode and the drain electrode is aligned, a thin film transistor that functions at a relatively high speed can be obtained.
此外，本發明中所使用的有機半導體膜未與使有機半導體材料朝面方向作配向的配向膜相接時，可避免如上所示之配向膜會對有機半導體膜所造成之較不理想的影響， 例如在配向膜發生缺陷時及/或配向膜劣化時伴隨此的有機半導體膜的特性降低。而且另外，在使有機半導體材料以面方向作配向的配向膜主要被使用的聚醯亞胺由於表面能量較高，因此具有與其相接的有機半導體膜在電氣特性上較不利、容易取得有機半導體的芳香環對基板呈平行的構形的缺點，但是在如上所示之未與配向膜相接的本發明之有機半導體膜中，可避免如上所示之問題。 Further, when the organic semiconductor film used in the present invention is not in contact with the alignment film which aligns the organic semiconductor material in the surface direction, the adverse effect of the alignment film as described above on the organic semiconductor film can be avoided. , For example, when the alignment film is defective and/or the alignment film is deteriorated, the characteristics of the organic semiconductor film accompanying it are lowered. In addition, since the polyimide film which is mainly used for the alignment film in which the organic semiconductor material is aligned in the plane direction has a high surface energy, the organic semiconductor film which is in contact therewith is disadvantageous in electrical characteristics, and it is easy to obtain an organic semiconductor. The aromatic ring has a drawback that the substrate has a parallel configuration, but in the organic semiconductor film of the present invention which is not connected to the alignment film as described above, the problem as described above can be avoided.
其中，本發明之薄膜電晶體中所使用的有機半導體膜係可藉由製造有機半導體膜的本發明之方法來製造。 Among them, the organic semiconductor film used in the thin film transistor of the present invention can be produced by the method of the present invention for producing an organic semiconductor film.
在本發明中所使用的有機半導體膜中，在面內呈直交的2方向的電荷移動度的比{(電荷移動度為最大的方向的電荷移動度)/(與其呈直交的方向的電荷移動度)}的值、或面內的任意2方向的電荷移動度的比的最大值{(電荷移動度為最大的方向的電荷移動度)/(電荷移動度為最小的方向的電荷移動度)}亦可大於1.5。亦即，例如第3圖所示，在被配置在基板(10)上的本發明之有機半導體膜(20)中，電荷移動度為最大的方向(箭號22)的電荷移動度亦可大於電荷移動度為最小的方向(箭號24)的電荷移動度的1.5倍。 In the organic semiconductor film used in the present invention, the ratio of the charge mobility in two directions orthogonal to each other in the plane {(the degree of charge mobility in the direction in which the charge mobility is the largest) / (the charge movement in the direction orthogonal thereto) The value of the degree, or the maximum value of the ratio of the charge mobility in any two directions in the plane {(the degree of charge mobility in the direction in which the charge mobility is the largest) / (the degree of charge mobility in the direction in which the charge mobility is the smallest) } can also be greater than 1.5. That is, as shown in FIG. 3, in the organic semiconductor film (20) of the present invention disposed on the substrate (10), the charge mobility of the direction in which the charge mobility is maximum (arrow 22) may be larger than The charge mobility is 1.5 times the charge mobility of the direction (arrow 24).
在此，該電荷移動度的比的值或最大值亦可為例如2以上、10以上、20以上，50以下、30以下、20以下、或15以下。 Here, the value or the maximum value of the ratio of the charge mobility may be, for example, 2 or more, 10 or more, 20 or more, 50 or less, 30 or less, 20 or less, or 15 or less.
在本發明中所使用的有機半導體膜中，移動度成為最大的方向的電荷移動度亦可為例如0.01cm2/(V‧s)以上、0.05cm2/(V‧s)以上、或0.10cm2/(V‧s)以上。在此，關於本發明，電荷移動度{cm2/(V‧s)}係有機半導體膜的表面中的電荷移動度，表示電洞或電子亦即電荷的移動容易度。 In the organic semiconductor film used in the present invention, the degree of charge mobility in the direction in which the degree of mobility is the largest may be, for example, 0.01 cm 2 /(V‧s) or more, 0.05 cm 2 /(V‧s) or more, or 0.10. Cm 2 / (V‧s) or more. Here, in the present invention, the charge mobility {cm 2 /(V‧s)} is the degree of charge mobility in the surface of the organic semiconductor film, and indicates the ease of movement of a hole or an electron, that is, a charge.
本發明中所使用的有機半導體膜係可具有任意厚度，例如可具有1nm~1μm、或10nm~500nm的厚度。 The organic semiconductor film used in the present invention may have any thickness, and may have a thickness of, for example, 1 nm to 1 μm or 10 nm to 500 nm.
構成本發明中所使用的有機半導體膜的有機半導體材料係具有芳香環之任意有機半導體，尤其可成為液晶狀態的有機半導體材料。以如上所示之有機半導體材料而言，係可列舉例如稠五苯系、噻吩系、苝系、富勒烯系材料般的低分子系有機半導體分子、如聚烷基噻吩、聚苯撐乙烯、聚茀-噻吩共聚物等般的高分子系有機半導體分子。 The organic semiconductor material constituting the organic semiconductor film used in the present invention is any organic semiconductor having an aromatic ring, and particularly can be an organic semiconductor material in a liquid crystal state. Examples of the organic semiconductor material as described above include low molecular organic semiconductor molecules such as polypentene-based, thiophene-based, fluorene-based, and fullerene-based materials, such as polyalkylthiophene and polyphenylenevinylene. A polymer-based organic semiconductor molecule such as a polyfluorene-thiophene copolymer.
其中，為供參考，關於有機半導體材料可成為液晶狀態的溫度，例示如下：
其中，表1中的記號的涵義如下所述：PQT：聚〔雙(3-十二烷基-2-噻吩基)-2,2‘-二噻吩-5,5’-二基〕 Here, the meaning of the symbols in Table 1 is as follows: PQT: poly[bis(3-dodecyl-2-thienyl)-2,2'-dithiophene-5,5'-diyl]
F8T2：聚〔(9,9-二辛基茀基-2,7-二基)-co-聯噻吩〕 F8T2: poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene]
F8BT：聚〔(9,9-二辛基茀基-2,7-二基)-alt-苯并〔2,1,3〕噻二唑-4,8-二基〕 F8BT: poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-benzo[2,1,3]thiadiazole-4,8-diyl]
pBTTT(C10)：聚(2,5-雙(3-癸基噻吩-2-基)噻吩并〔3,2,b〕噻吩) pBTTT(C10): poly(2,5-bis(3-mercaptothiophen-2-yl)thieno[3,2,b]thiophene)
pBTTT(C12)：聚(2,5-雙(3-十二烷基噻吩-2-基)噻吩并〔3,2,b〕噻吩) pBTTT(C12): poly(2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2,b]thiophene)
pBTTT(C14)：聚(2,5-雙(3-十四烷基噻吩-2-基)噻吩并〔3,2,b〕噻吩) pBTTT(C14): poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2,b]thiophene)
在此，相轉移溫度係可如下而得。亦即，使用示差掃描熱量計，以依據JIS K7121-1987「塑膠的轉移溫度測定方法(Testing Methods for Transition Temperature of Plastics)」的示差掃描熱分析(DSC)，在比預測的轉移 溫度更低約50℃的溫度中，保持至裝置安定為止之後，以加熱速度10℃/分鐘，加熱至比所預測的轉移結束時為高約30℃的溫度，而得示差掃描熱分析曲線。之後，關於所得的示差掃描熱分析曲線，將液晶化及熔融的峰值頂點分別特定為液晶相轉移溫度及融解溫度。以示差掃描熱量計而言，係例如可使用TA Instruments(股)製的商品名：DSC Q10。 Here, the phase transition temperature can be obtained as follows. That is, using a differential scanning calorimeter to perform differential scanning in accordance with the differential scanning thermal analysis (DSC) according to JIS K7121-1987 "Testing Methods for Transition Temperature of Plastics" After the temperature was lower at about 50 ° C, the temperature was maintained at a heating rate of 10 ° C / min, and the temperature was increased to about 30 ° C higher than the predicted end of the transfer, and a differential scanning calorimetry curve was obtained. Thereafter, regarding the obtained differential scanning calorimetry curve, the peak apexes of liquid crystallinization and melting were specified as the liquid crystal phase transition temperature and the melting temperature, respectively. For the differential scanning calorimeter, for example, a trade name of DS Instruments Q10 manufactured by TA Instruments can be used.
本發明中所使用的有機半導體膜係可以任意方法來製造。該有機半導體膜係有以溶液法，亦即例如澆鑄法、旋塗法、接觸印刷法般的印刷法、浸漬法等進行製造，關於生產性等而言為較佳的情形。若本發明之有機半導體膜為藉由溶液法所得的膜時，係可藉由殘留在有機半導體膜中的微量溶媒的存在、膜的形狀及物性等，與藉由其他方法所製作者來作區別。本發明之有機半導體膜係可藉由例如製造有機半導體膜之本發明之方法來製造。 The organic semiconductor film used in the present invention can be produced by any method. The organic semiconductor film is produced by a solution method, that is, a printing method such as a casting method, a spin coating method, a contact printing method, or a dipping method, and is preferable in terms of productivity and the like. When the organic semiconductor film of the present invention is a film obtained by a solution method, it can be produced by other methods by the presence of a trace amount of a solvent remaining in the organic semiconductor film, the shape and physical properties of the film, and the like. the difference. The organic semiconductor film of the present invention can be produced by, for example, the method of the present invention for producing an organic semiconductor film.
其中，本發明之薄膜電晶體的有機半導體膜以外的層，例如電極層、介電質層等其他層係可以無機材料製作，亦可以有機材料製作。 Among the layers other than the organic semiconductor film of the thin film transistor of the present invention, for example, an electrode layer or a dielectric layer may be made of an inorganic material or an organic material.
例如第4圖所示，本發明之薄膜電晶體亦可為(a)底部閘極/頂部接觸型(BGTC型)、(b)底部閘極/底部接觸型(BGBC型)、(c)頂部閘極/頂部接觸型(TGTC型)、及(d)頂部閘極/底部接觸型(TGRC型) 之任一者。在該等本發明之薄膜電晶體130、140、150及160中，具有源極電極134、144、154、164、汲極電極135、145、155、165、閘極電極131、141、151、161、閘極絕緣膜132、142、152、162、及半導體膜133、143、153、163，藉由閘極絕緣膜，使源極電極及汲極電極與閘極電極呈絕緣，而且藉由被施加至閘極電極的電壓，由源極電極往汲極電極通過半導體膜所流通的電流會受到控制。 For example, as shown in FIG. 4, the thin film transistor of the present invention may also be (a) bottom gate/top contact type (BGTC type), (b) bottom gate/bottom contact type (BGBC type), (c) top Gate/top contact type (TGTC type), and (d) top gate/bottom contact type (TGRC type) Either. In the thin film transistors 130, 140, 150 and 160 of the present invention, there are source electrodes 134, 144, 154, 164, drain electrodes 135, 145, 155, 165, gate electrodes 131, 141, 151, 161, the gate insulating film 132, 142, 152, 162, and the semiconductor film 133, 143, 153, 163, the gate electrode and the drain electrode are insulated from the gate electrode by the gate insulating film, and by The voltage applied to the gate electrode is controlled by the current flowing from the source electrode to the drain electrode through the semiconductor film.
本發明之電路係具有薄膜電晶體100個以上、1,000個以上、10,000個以上、或100,000個以上，而且該等薄膜電晶體之中的至少80%、至少90%、至少95%為本發明之薄膜電晶體。 The circuit of the present invention has 100 or more thin film transistors, 1,000 or more, 10,000 or more, or 100,000 or more, and at least 80%, at least 90%, and at least 95% of the thin film transistors are the present invention. Thin film transistor.
藉由如上所示之本發明之電路，可有益地利用在高速發揮作用的本發明之薄膜電晶體的特性。 By the circuit of the present invention as shown above, the characteristics of the thin film transistor of the present invention which functions at a high speed can be advantageously utilized.
製造有機半導體膜之第1本發明之方法係包含：提供有機半導體材料呈溶解及/或分散的有機半導體溶液的步驟；將有機半導體溶液適用在印模上，使其乾燥，而在印模上獲得有機半導體膜的步驟；及將有機半導體層，以有機半導體材料呈液晶化的溫度進行轉印的步驟。 The first method of the present invention for producing an organic semiconductor film comprises the steps of: providing an organic semiconductor material in an organic semiconductor solution which is dissolved and/or dispersed; applying an organic semiconductor solution to a stamp to dry it, and on the stamp a step of obtaining an organic semiconductor film; and a step of transferring the organic semiconductor layer at a temperature at which the organic semiconductor material is liquidified.
藉由製造有機半導體膜之本發明之方法，可製造在本 發明之薄膜電晶體中所使用的有機半導體膜。 The method of the present invention for producing an organic semiconductor film can be manufactured in the present An organic semiconductor film used in the inventive thin film transistor.
具體而言，藉由製造有機半導體膜之本發明之方法，將有機半導體層，以有機半導體材料呈液晶化的溫度進行轉印，藉此可一面進行藉由印模所為之轉印，一面在印模與基材之間，對液晶狀態的有機半導體膜施加應力，藉此可使藉由構成有機半導體材料的芳香環所形成的面，以相對基板呈大致垂直豎立的構形作配向。 Specifically, by the method of the present invention for producing an organic semiconductor film, the organic semiconductor layer is transferred at a temperature at which the organic semiconductor material is liquidified, whereby the transfer can be performed by the stamp while Between the stamp and the substrate, stress is applied to the organic semiconductor film in a liquid crystal state, whereby the surface formed by the aromatic ring constituting the organic semiconductor material can be aligned in a substantially vertical configuration with respect to the substrate.
雖並非為依理論來作限定者，但是之所以可藉由本發明之方法，使該面以相對基板呈大致垂直豎立的構形作配向，被認為是基於以下所示之理由。 Although it is not limited by theory, the reason why the surface is aligned in a substantially vertical configuration with respect to the substrate by the method of the present invention is considered to be based on the following reasons.
1.當使用溶液法而在印模上製造有機半導體膜時，在空氣側界面，有機半導體材料的芳香環以相對印模呈大致垂直豎立的構形自我組織化。此係由於空氣在理論上具超疏水性，因此對有機半導體造成的影響少，藉此至少在有機半導體膜的空氣側，取得有機半導體材料本身最為安定的構形之故。 1. When an organic semiconductor film is formed on a stamp using a solution method, at the air side interface, the aromatic ring of the organic semiconductor material self-organizes in a substantially vertical standing configuration with respect to the stamp. Since the air is theoretically superhydrophobic, the effect on the organic semiconductor is small, and at least on the air side of the organic semiconductor film, the most stable configuration of the organic semiconductor material itself is obtained.
2.如第6圖(a)所示，若將所配向的液晶狀態的有機半導體膜(210)，使用例如滾筒(230)而由印模(220)轉印至基材(250)等時，在印模(220)與基材(250)之間，對有機半導體膜(210)施加應力，尤其施加切斷應力。藉此，被認為有機半導體膜(210)的有機半導體材料的芳香環一面維持對印模預先呈大致垂直豎立的構形，一面如第6圖(b)所示，對特定的方向，例如箭號(231)所示滾筒的旋轉方向(261)、或其垂直方向( 262)作配向。此時，藉由將轉印溫度形成為有機半導體膜的液晶相溫度範圍，有機半導體膜成為液晶相，對於些微的切斷應力，亦可輕易進行分子配向。 2. As shown in Fig. 6(a), when the organic semiconductor film (210) in the liquid crystal state to be aligned is transferred from the stamp (220) to the substrate (250) or the like using, for example, a roll (230), A stress is applied to the organic semiconductor film (210) between the stamp (220) and the substrate (250), in particular, a cutting stress is applied. Thereby, it is considered that the aromatic ring of the organic semiconductor material of the organic semiconductor film (210) maintains a configuration in which the stamp is substantially vertically erected, as shown in Fig. 6(b), for a specific direction, such as an arrow. The rotation direction (261) of the drum shown by the number (231), or its vertical direction ( 262) For the alignment. At this time, by forming the transfer temperature into the liquid crystal phase temperature range of the organic semiconductor film, the organic semiconductor film becomes a liquid crystal phase, and molecular alignment can be easily performed for a slight cutting stress.
關於在本發明之方法中所被使用的有機半導體材料，可參照關於本發明之有機半導體膜的記載。 Regarding the organic semiconductor material used in the method of the present invention, the description about the organic semiconductor film of the present invention can be referred to.
本發明之方法中所被使用的有機半導體溶液所含有的溶媒亦可為可使有機半導體材料溶解及/或分散的任意溶媒。以如上所示之溶媒而言，係可列舉甲苯、二甲苯、四氫奈、十氫萘、氯仿、一氯苯、二氯苯、三氯苯、及該等之組合等。 The solvent contained in the organic semiconductor solution used in the method of the present invention may be any solvent which can dissolve and/or disperse the organic semiconductor material. Examples of the solvent as described above include toluene, xylene, tetrahydronaphthalene, decalin, chloroform, monochlorobenzene, dichlorobenzene, trichlorobenzene, and the like.
在本發明之方法中，係可將有機半導體層由印模轉印至基材或膜。如上所示之基材或膜亦可為意圖將有機半導體膜配置在其上的任意基材或膜。因此，例如以如上所示之基材而言，可列舉如矽晶圓、玻璃般的無機材料、聚合物薄膜般的有機材料。 In the method of the present invention, the organic semiconductor layer can be transferred from the stamp to the substrate or film. The substrate or film as shown above may also be any substrate or film on which the organic semiconductor film is intended to be disposed. Therefore, for example, the substrate shown above may be an organic material such as a ruthenium wafer, a glass-like inorganic material, or a polymer film.
此外，該基板或膜亦可為對水的接觸角為50度以上、60度以上、70度以上、80度以上、90度以上、或100度以上。亦即，該基板或膜可為表面能量小的基板或膜。如上所示在表面能量小的基板或膜，藉由本發明之方法轉印有機半導體膜時，藉由構成有機半導體材料的芳香環所 形成的面容易取得相對基板呈大致垂直豎立的構形。 Further, the substrate or film may have a contact angle with respect to water of 50 degrees or more, 60 degrees or more, 70 degrees or more, 80 degrees or more, 90 degrees or more, or 100 degrees or more. That is, the substrate or film may be a substrate or film having a small surface energy. As described above, in the substrate or film having a small surface energy, when the organic semiconductor film is transferred by the method of the present invention, the aromatic ring constituting the organic semiconductor material is used. The formed face is easily configured to be substantially vertically erected with respect to the substrate.
此外，本發明之方法中適用有機半導體溶液的印模係可為在其上形成有機半導體膜，接著自該處將有機半導體膜轉印在基材等的任意印模，亦即用以形成有機半導體膜的接觸印刷用印模。如上所示之印模係可在印刷面被配置印模而安裝在滾輪，一面使滾輪旋轉一面將印模推壓在基材等來進行轉印。 Further, the stamper to which the organic semiconductor solution is applied in the method of the present invention may be any stamp on which an organic semiconductor film is formed, and then the organic semiconductor film is transferred from a substrate or the like, that is, to form an organic A stamp for printing contact of a semiconductor film. The stamper shown above can be attached to a roller by being placed on a printing surface, and can be transferred by pressing the stamp on a substrate or the like while rotating the roller.
在本發明之方法中適用有機半導體溶液的印模亦可具有對水的接觸角較大的表面，亦即例如對水的接觸角為40°以上、50°以上、60°以上、70°以上、80°以上、90°以上、100°以上、或105°以上的表面。如上所示，基材表面之對水的接觸角較大意指該表面較具疏液性，亦即該表面的表面能量較小。 The stamp suitable for the organic semiconductor solution in the method of the present invention may also have a surface having a large contact angle with water, that is, for example, a contact angle to water of 40° or more, 50° or more, 60° or more, 70° or more a surface of 80° or more, 90° or more, 100° or more, or 105° or more. As indicated above, a larger contact angle to the surface of the substrate means that the surface is more lyophobic, i.e., the surface energy of the surface is less.
可在本發明之方法中使用的接觸印刷用印模係轉印部比周緣部更具疏液性的接觸印刷用印模。在此，疏液性意指表面能量小，因此該接觸印刷用印模可指轉印部的表面能量小、而且周緣部的表面能量大之具有轉印部-周緣部構形的接觸印刷用印模。 The contact printing stamp transfer portion which can be used in the method of the present invention is more lyophobic than the peripheral portion to contact the printing stamp. Here, the lyophobic property means that the surface printing energy is small, and therefore the contact printing stamp can refer to a contact printing stamp having a transfer portion-circumferential portion configuration in which the surface energy of the transfer portion is small and the surface energy of the peripheral portion is large. .
在該接觸印刷用印模的轉印部上，若由有機半導體溶液形成有機半導體膜時，由於親液性的周緣部存在於疏液性的轉印部的周圍，而在較不易潤濕的轉印部的表面保持有機半導體溶液的膜，可促進在轉印部的表面上由有機半 導體溶液形成有機半導體膜。亦即，藉由該印模，即使在較不易潤濕的轉印部的表面上，亦可形成有機半導體膜。 When the organic semiconductor film is formed of the organic semiconductor solution on the transfer portion of the contact printing stamp, the lyophilic peripheral portion exists around the lyophobic transfer portion, and is less likely to be wetted. The surface of the printing portion maintains a film of the organic semiconductor solution, which promotes the organic half on the surface of the transfer portion The conductor solution forms an organic semiconductor film. That is, with the stamp, an organic semiconductor film can be formed even on the surface of the transfer portion which is less wettable.
此外，在該接觸印刷用印模的轉印部上，由有機半導體溶液形成有機半導體膜時，所得的有機半導體膜與轉印部的附著較弱，因此可在較具疏液性的基材的表面，亦即例如對水的接觸角為50°以上的基材的表面，轉印有機半導體膜。 Further, when the organic semiconductor film is formed of the organic semiconductor solution on the transfer portion of the contact printing stamp, the adhesion between the obtained organic semiconductor film and the transfer portion is weak, so that it can be used in a liquid-repellent substrate. The surface, that is, the surface of the substrate, for example, having a contact angle with water of 50 or more, transfers the organic semiconductor film.
其中，一般的接觸印刷用印模的轉印部，一般而言形成為親液性，俾以改良對於在其上的有機半導體溶液的潤濕性，藉此可安定地形成有機半導體溶液的膜。因此，在習知的接觸印刷用印模的轉印部上，由有機半導體溶液形成有機半導體膜時，所得的有機半導體膜與轉印部的附著較強，因此在較具疏液性的基材的表面，亦即例如對水的接觸角為50°以上的基材的表面，不易轉印有機半導體膜。 Among them, the transfer portion of a general contact printing stamp is generally formed into a lyophilic property to improve the wettability with respect to the organic semiconductor solution thereon, whereby a film of the organic semiconductor solution can be stably formed. Therefore, when an organic semiconductor film is formed from an organic semiconductor solution on a transfer portion of a conventional contact printing stamp, the obtained organic semiconductor film has a strong adhesion to the transfer portion, and thus is more lyophobic. The surface, that is, the surface of the substrate having a contact angle with water of, for example, 50° or more is difficult to transfer the organic semiconductor film.
關於本發明，對水的接觸角係可在25℃下，在測定接觸角的表面上滴下50μL的水，由側面觀察所滴下的液滴形狀，藉由計測液滴與表面所成角度來決定。 About the present invention, the contact angle of water may be based at 25 ℃, 50 μ L of water dropped on the surface of the measurement of contact angle, a droplet by dropping shape in side view, by measuring the angle formed by the droplet with the surface To decide.
如上所示，若在本發明之方法中適用有機半導體溶液的印模具有低表面能量表面時，有機半導體膜中的有機半導體材料係在與印模相接的面，亦不易受到印模表面影響，因此容易藉由有機半導體材料本身的結晶性等來進行再配列。 As described above, if the printing mold to which the organic semiconductor solution is applied in the method of the present invention has a low surface energy surface, the organic semiconductor material in the organic semiconductor film is not easily affected by the surface of the stamp on the surface which is in contact with the stamp. Therefore, it is easy to re-arrange by the crystallinity of the organic semiconductor material itself.
具有對水的接觸角較大的表面的印模係可例如藉由以 疏液性材料處理印模表面而得。以如上所示之疏液性材料而言，可列舉例如矽烷、矽氮烷、氟化合物、聚醯亞胺、聚酯、聚乙烯、聚苯硫醚、聚對二甲苯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚二甲基矽氧烷、及該等之組合。 An impression having a surface having a larger contact angle to water can be, for example, The lyophobic material is obtained by treating the surface of the stamp. The lyophobic material as shown above may, for example, be decane, decane, fluorine compound, polyimine, polyester, polyethylene, polyphenylene sulfide, parylene, polyterephthalic acid. Ethylene glycol ester, polyethylene naphthalate, polydimethyl oxa oxide, and combinations thereof.
在製造有機半導體膜之本發明之方法中，為了將有機半導體溶液適用在印模，可使用澆鑄法、旋塗法、浸漬法等任意方法。 In the method of the present invention for producing an organic semiconductor film, any method such as a casting method, a spin coating method, or a dipping method can be used in order to apply the organic semiconductor solution to the stamp.
在製造有機半導體膜之本發明之方法中，係將適用在印模上的有機半導體溶液乾燥，在印模上獲得有機半導體膜。在此，該乾燥係例如可藉由使印模上的有機半導體溶液，露出於超過40℃、超過50℃、超過70℃或超過100℃的氣體環境來進行。而且，該乾燥亦可藉由減壓，由有機半導體溶液去除溶媒來進行。 In the method of the present invention for producing an organic semiconductor film, an organic semiconductor solution suitable for use on a stamp is dried to obtain an organic semiconductor film on a stamp. Here, the drying can be performed, for example, by exposing the organic semiconductor solution on the stamp to a gas atmosphere exceeding 40 ° C, exceeding 50 ° C, exceeding 70 ° C, or exceeding 100 ° C. Further, the drying can be carried out by removing the solvent from the organic semiconductor solution by pressure reduction.
製造有機半導體膜之本發明之方法係包含以有機半導體材料呈液晶化的溫度，將印模上的有機半導體層進行轉印的步驟，例如轉印至基材或其他印模的步驟。 The method of the present invention for producing an organic semiconductor film includes a step of transferring an organic semiconductor layer on a stamp at a temperature at which the organic semiconductor material is liquidified, for example, a step of transferring to a substrate or other stamp.
亦即例如可將印模上的有機半導體膜，直接轉印至矽 晶圓、聚合物薄膜等基材上。此外，可將印模上的有機半導體膜轉印至其他印模，接著由該其他印模轉印至基材。 That is, for example, the organic semiconductor film on the stamp can be directly transferred to the crucible. On substrates such as wafers and polymer films. Further, the organic semiconductor film on the stamp can be transferred to other stamps, and then transferred to the substrate by the other stamp.
其中，由印模對基材或其他印模的有機半導體膜的轉印，係可藉由使保持有有機半導體膜的印模與基材或其他印模相接觸來達成。在此，接觸時間、印模及基材的溫度等轉印條件係可以有機半導體材料呈液晶化且可轉印的方式來任意決定。 Here, the transfer of the organic semiconductor film of the substrate or other stamp by the stamp can be achieved by bringing the stamp holding the organic semiconductor film into contact with the substrate or other stamp. Here, the transfer conditions such as the contact time, the temperature of the stamp, and the substrate can be arbitrarily determined by allowing the organic semiconductor material to be liquid crystallized and transferable.
具體而言，該轉印係可使基材或其他印模的溫度高於印模的溫度來進行。此外，該轉印係可藉由：處理印模的表面，減小對有機半導體膜的附著性、及/或處理基材或其他印模的表面，加大對有機半導體膜的附著性來達成。此外，該轉印係可藉由上述之組合來達成。 In particular, the transfer system can be carried out at a temperature above the temperature of the stamp by the temperature of the substrate or other stamp. In addition, the transfer system can be achieved by treating the surface of the stamp, reducing the adhesion to the organic semiconductor film, and/or treating the surface of the substrate or other stamp, and increasing the adhesion to the organic semiconductor film. . Further, the transfer system can be achieved by the combination described above.
其中，在該本發明之方法所使用的其他印模亦可為被轉印在印模上所形成的有機半導體膜，接著可自該處將有機半導體膜轉印至基材等的任意印模，亦即接觸印刷用印模。如上所示之其他印模係可以例如聚矽氧烷等來製作。此外，由其他印模對基材的有機半導體膜的轉印係可如關於由印模對基材或其他印模的有機半導體膜的轉印所作說明般來進行。 Wherein, the other stamp used in the method of the present invention may be an organic semiconductor film formed by being transferred onto a stamp, and then the organic semiconductor film may be transferred from any place to the substrate or the like. That is, contact with the printing impression. Other stamps as shown above may be produced, for example, by polyoxyalkylene or the like. Further, the transfer of the organic semiconductor film of the substrate by other stamps can be carried out as described with respect to the transfer of the organic semiconductor film of the substrate to the substrate or other stamp.
製造有機半導體膜之第2本發明之方法係包含：在基板或膜上提供由具有芳香環的有機半導體材料所構成的有機半導體膜的步驟；及以有機半導體材料呈液晶化的溫度 ，對有機半導體層，由外部施加應力，使有機半導體材料在有機半導體膜的面內作配向的步驟。在此，對基板或膜上提供有機半導體膜，係可以任意方法進行，可使用例如澆鑄法、旋塗法、接觸印刷法般的印刷法、浸漬法等溶液法、及使有機半導體材料蒸鍍在基材的蒸鍍法來提供。 The second method of the present invention for producing an organic semiconductor film includes a step of providing an organic semiconductor film composed of an organic semiconductor material having an aromatic ring on a substrate or a film, and a temperature at which the organic semiconductor material is liquid crystallized The organic semiconductor layer is subjected to a stress applied from the outside to align the organic semiconductor material in the plane of the organic semiconductor film. Here, the organic semiconductor film may be provided on the substrate or the film by any method, and a solution method such as a casting method, a spin coating method, a contact printing method, a dipping method, or the like may be used, and an organic semiconductor material may be evaporated. It is provided by a vapor deposition method of a substrate.
藉由製造有機半導體膜之本發明之方法，可藉由以有機半導體材料呈液晶化的溫度，對有機半導體層由外部施加應力，尤其施加切斷應力，例如對基材推壓印模，在印模與基材之間，對液晶狀態的有機半導體膜施加應力，藉此可使有機半導體材料在有機半導體膜的面內作配向。 By the method of the present invention for producing an organic semiconductor film, stress can be externally applied to the organic semiconductor layer by a temperature at which the organic semiconductor material is liquidified, in particular, a cutting stress is applied, for example, a stamp is pressed against the substrate, Between the stamp and the substrate, stress is applied to the organic semiconductor film in a liquid crystal state, whereby the organic semiconductor material can be aligned in the plane of the organic semiconductor film.
尤其藉由製造有機半導體膜之該本發明之方法，可製造本發明之有機半導體膜。 The organic semiconductor film of the present invention can be produced, in particular, by the method of the present invention for producing an organic semiconductor film.
其中，關於可在該方法中使用的有機半導體材料、印模、基板等，可參照第1本發明之方法之上述記載。 Among them, the organic semiconductor material, the stamp, the substrate, and the like which can be used in the method can be referred to the above description of the method of the first aspect of the invention.
使用以下之例，詳加說明本發明，但是本發明並非限定於此。此外，在以下之例中，均作成底部閘極/頂部接觸型(BGTC型)的電晶體。 The present invention will be specifically described using the following examples, but the present invention is not limited thereto. Further, in the following examples, a bottom gate/top contact type (BGTC type) transistor was fabricated.
水接觸角係使用協和界面科學製水接觸角計CA-X型，以25℃的純水來進行測定。 The water contact angle was measured using a Concord Interface Scientific Water Contact Angle Meter Model CA-X and purified water at 25 °C.
有機半導體膜的電荷移動度係使用Keithley公司製4200-SCS型半導體評估裝置來進行評估。此外，電荷移動度的標準偏差係評估10個以上的元件特性而算出。 The charge mobility of the organic semiconductor film was evaluated using a 4200-SCS type semiconductor evaluation device manufactured by Keithley. Further, the standard deviation of the charge mobility is calculated by evaluating ten or more element characteristics.
使用Rigaku製SmartLab，以CuK α線、管電壓45kW、管電流200mA的條件，以入射角0.2°對轉印方向，由平行方向及垂直方向入射X線而進行測定。 Using a SmartLab manufactured by Rigaku, the X-ray was incident from the parallel direction and the perpendicular direction with respect to the transfer direction at an incident angle of 0.2° with a CuK α line, a tube voltage of 45 kW, and a tube current of 200 mA.
使矽酮橡膠(信越化學工業製SIM-260)硬化成平板狀，將使用己烷而將寡聚物去除者提供作為印模材料。 The fluorenone rubber (SIM-260 manufactured by Shin-Etsu Chemical Co., Ltd.) was hardened into a flat plate shape, and oligo remover was used as an impression material using hexane.
將印模材料切成20mm見方，使與轉印部相對應的遮罩載置於該印模材料，將轉印部遮蔽，對如上所示轉印部被遮蔽的印模材料，經30分鐘進行UV(紫外線)-臭氧處理。亦即，在轉印部未進行UV-臭氧處理，而且在周緣部進行UV-臭氧處理。藉由該UV-臭氧處理，在周緣部提供親液性的表面。 The stamp material was cut into 20 mm squares, and a mask corresponding to the transfer portion was placed on the stamp material, and the transfer portion was shielded, and the stamp material was shielded from the transfer portion as shown above for 30 minutes. UV (ultraviolet)-ozone treatment. That is, the UV-ozone treatment was not performed on the transfer portion, and the UV-ozone treatment was performed on the peripheral portion. By the UV-ozone treatment, a lyophilic surface is provided at the peripheral portion.
未進行UV-臭氧處理的轉印部的水接觸角為110°，將UV-臭氧處理進行30分鐘後的周緣部的水接觸角為44°。此外，在印模上存在12個轉印部，各個轉印部的大小為100μm×2mm。 The water contact angle of the transfer portion not subjected to UV-ozone treatment was 110°, and the water contact angle of the peripheral portion after the UV-ozone treatment was performed for 30 minutes was 44°. Further, there are 12 transfer portions on the stamp, and the size of each transfer portion is 100 μm × 2 mm.
將聚〔雙(3-十二烷基-2-噻吩基)-2,2’-二噻吩-5,5’-二基〕(「PQT」)(American Dye Source公司製，ADS12PQT，MW=18,000)0.5質量份，加熱溶解為甲苯99.5質量份，而得作為有機半導體溶液的PQT溶液。將該PQT溶液旋塗(1800rpm、20秒鐘)在經圖案形成的印模材料上。之後，照原樣放置10分鐘左右，而將PQT溶液進行熟成及乾燥，藉此在印模上形成有機半導體膜。 Poly[bis(3-dodecyl-2-thienyl)-2,2'-dithiophene-5,5'-diyl] ("PQT") (manufactured by American Dye Source, ADS12PQT, MW= 18,000) 0.5 parts by mass, heated and dissolved to 99.5 parts by mass of toluene, and obtained as a PQT solution of an organic semiconductor solution. The PQT solution was spin coated (1800 rpm, 20 seconds) onto the patterned impression material. Thereafter, the PQT solution was aged and dried as it was for about 10 minutes, whereby an organic semiconductor film was formed on the stamp.
使用300nm之附熱氧化膜的n型矽晶圓(面方位〈100〉、比電阻0.05Ω)，以熱濃硫酸進行30分鐘處理後，使用純水、丙酮、甲苯、己烷，分別進行數次超音波洗淨。另外以UV臭氧洗淨裝置進行30分鐘洗淨後，以十八烷基三氯矽烷(OTS)進行表面處理。 Using an n-type 矽 wafer (surface orientation <100>, specific resistance 0.05 Ω) with a thermal oxide film of 300 nm, the mixture was treated with hot concentrated sulfuric acid for 30 minutes, and then purified using pure water, acetone, toluene, and hexane. The ultrasonic is washed. Further, it was washed with a UV ozone cleaning apparatus for 30 minutes, and then surface-treated with octadecyltrichloromethane (OTS).
其中，藉由OTS所為之基材處理係如下進行。 Among them, the substrate treatment by OTS was carried out as follows.
製作OTS的20mM甲苯溶液。在所得的OTS溶液中浸漬上述矽基材，保持7天。浸漬後，將基材以甲苯及乙醇洗淨，在乙醇中經30分鐘進行超音波洗淨。至此為止的工程係全部在被控制成濕度為3%以下的手套箱中進行。之後，將基材以純水洗淨，以100℃進行5分鐘熱處理，而得OTS處理基材。 A 20 mM toluene solution of OTS was prepared. The above ruthenium substrate was immersed in the obtained OTS solution for 7 days. After immersion, the substrate was washed with toluene and ethanol, and ultrasonically washed in ethanol for 30 minutes. All the engineering projects up to this point were carried out in a glove box controlled to have a humidity of 3% or less. Thereafter, the substrate was washed with pure water and heat-treated at 100 ° C for 5 minutes to obtain an OTS-treated substrate.
將具有有機半導體膜的印模固定在滾筒，而得附印模的滾筒。將矽基材加熱/保持為135℃，使上述附印模的滾筒接觸其上，使其旋轉，而將有機半導體膜全體轉印在基材。 A stamp having an organic semiconductor film is fixed to the drum to obtain a cylinder to which the stamp is attached. The base material was heated/maintained at 135 ° C, and the roller of the above-mentioned stamp was brought into contact with it to be rotated, and the entire organic semiconductor film was transferred onto the substrate.
關於該轉印薄膜，實施相對轉印方向呈平行方向及垂直方向的in-plane的X線繞射測定。將結果顯示於第5圖。在第5圖中係顯示出觀察(010)方位的峰值，但是在平行方向A與垂直方向B，X線繞射強度明確不同，PQT薄膜呈單軸配向。此外，在第5圖中可知僅觀測(010)峰值，取得噻吩環相對基板呈垂直豎立的構形。 The transfer film was subjected to X-ray diffraction measurement of in-plane in the parallel direction and the vertical direction with respect to the transfer direction. The results are shown in Figure 5. In Fig. 5, the peak of the observed (010) orientation is shown, but in the parallel direction A and the vertical direction B, the X-ray diffraction intensity is clearly different, and the PQT film is uniaxially aligned. Further, in Fig. 5, it is understood that only the (010) peak is observed, and the configuration in which the thiophene ring is vertically erected with respect to the substrate is obtained.
以遮罩蒸鍍法將金進行真空蒸鍍在所得之有機半導體膜之與轉印部相對應的部位，形成源極電極及汲極電極(L/w=50μm/1.5mm)，將矽基材設為閘極電極，而且將矽基材的表面的氧化膜設為閘極絕緣膜，而得薄膜電晶體。亦即，獲得第4圖的130所示構成的薄膜電晶體。 Gold is vacuum-deposited by a mask vapor deposition method to form a source electrode and a drain electrode (L/w = 50 μ m / 1.5 mm) at a portion of the obtained organic semiconductor film corresponding to the transfer portion. The tantalum substrate is a gate electrode, and an oxide film on the surface of the tantalum substrate is used as a gate insulating film to obtain a thin film transistor. That is, the thin film transistor having the configuration shown at 130 in Fig. 4 is obtained.
此時製作出滾筒的移動方向成為通道長方向的元件(移動度最大)、及與通道方向呈直交方向的元件。將評估結果顯示於表2。 At this time, the moving direction of the drum is made to be an element in the longitudinal direction of the channel (the maximum degree of mobility) and an element that is orthogonal to the direction of the channel. The evaluation results are shown in Table 2.
與例1同樣地，製作PQT膜，接著形成源極電極及汲 極電極而得薄膜電晶體。但是，在該例中，滾筒的移動方向(移動度成為最大的方向，亦即有機半導體材料的主鏈的分子軸方向)、與源極電極與汲極電極之間的電場方向之間的角度成為0°、15°、30°、45°、60°、75°、90°。 In the same manner as in Example 1, a PQT film was formed, followed by formation of a source electrode and germanium. A thin film transistor is obtained from the electrode. However, in this example, the moving direction of the drum (the direction in which the mobility becomes the largest, that is, the molecular axis direction of the main chain of the organic semiconductor material), and the angle between the direction of the electric field between the source electrode and the drain electrode It becomes 0°, 15°, 30°, 45°, 60°, 75°, 90°.
將關於移動度的評估結果顯示於第8圖。 The evaluation results regarding the mobility are shown in Fig. 8.
除了將轉印溫度設為140℃以外，係與例2同樣地實施。將評估結果顯示於表2。 The same procedure as in Example 2 was carried out except that the transfer temperature was changed to 140 °C. The evaluation results are shown in Table 2.
除了將轉印溫度設為130℃以外，係與例1同樣地實施。將評估結果顯示於表2。 The same procedure as in Example 1 was carried out except that the transfer temperature was changed to 130 °C. The evaluation results are shown in Table 2.
此外，關於該轉印薄膜，將實施相對轉印方向呈平行方向及垂直方向的in-plane的X線繞射測定的結果顯示於第6圖。在第6圖中，係顯示出觀察(010)方位的峰值，但是在平行方向A與垂直方向B，X線繞射強度明確不同，PQT薄膜呈單軸配向。此外，在第6圖中，可知僅觀測(010)峰值，取得噻吩環相對基板呈垂直豎立的構形。 Further, as a result of measuring the X-ray diffraction of the in-plane in the parallel direction and the vertical direction with respect to the transfer film, the transfer film is shown in Fig. 6. In Fig. 6, the peak of the observed (010) orientation is shown, but in the parallel direction A and the vertical direction B, the X-ray diffraction intensity is clearly different, and the PQT film is uniaxially aligned. Further, in Fig. 6, it is understood that only the (010) peak is observed, and the configuration in which the thiophene ring is vertically erected with respect to the substrate is obtained.
除了將轉印溫度設為125℃以外，係與例1同樣地實 施。將評估結果顯示於表2。 The same as in Example 1 except that the transfer temperature was set to 125 °C. Shi. The evaluation results are shown in Table 2.
與例1同樣地，在印模上形成PQT薄膜。照原樣放置10分鐘而使溶劑乾燥後，在印模上，將PQT薄膜在減壓下以130℃實施10分鐘熱處理，接著以轉印溫度80℃進行轉印至基板以外，係與例1同樣地實施。將評估結果顯示於表2。 In the same manner as in Example 1, a PQT thin film was formed on the stamp. After allowing the solvent to dry for 10 minutes as it was, the PQT film was heat-treated at 130 ° C for 10 minutes under reduced pressure on a stamp, and then transferred to a substrate at a transfer temperature of 80 ° C in the same manner as in Example 1. Implementation. The evaluation results are shown in Table 2.
除了將轉印溫度設為80℃以外，係與例1同樣地實施。將評估結果顯示於表2。 The same procedure as in Example 1 was carried out except that the transfer temperature was changed to 80 °C. The evaluation results are shown in Table 2.
將在例6中所製作的元件，在真空下以135℃進行5分鐘熱處理。將評估結果顯示於表2。 The element produced in Example 6 was heat-treated at 135 ° C for 5 minutes under vacuum. The evaluation results are shown in Table 2.
除了使用PQT的0.5%甲苯溶液，藉由旋塗法而在基板上直接形成PQT膜以外，係與例7同樣地實施。將評估結果顯示於表2。 The PQT film was directly formed on the substrate by a spin coating method except that a 0.5% toluene solution of PQT was used, and the same procedure as in Example 7 was carried out. The evaluation results are shown in Table 2.
與例8同樣地，製作PQT膜，接著形成源極電極及汲 極電極而得薄膜電晶體。但是，在該例中，滾筒的移動方向(移動度成為最大的方向，亦即有機半導體材料的主鏈的分子軸方向)、與源極電極與汲極電極之間的電場方向之間的角度成為0°、15°、30°、45°、60°、75°、90°。 In the same manner as in Example 8, a PQT film was formed, followed by formation of a source electrode and germanium. A thin film transistor is obtained from the electrode. However, in this example, the moving direction of the drum (the direction in which the mobility becomes the largest, that is, the molecular axis direction of the main chain of the organic semiconductor material), and the angle between the direction of the electric field between the source electrode and the drain electrode It becomes 0°, 15°, 30°, 45°, 60°, 75°, 90°.
將關於移動度的評估結果顯示於第8圖。 The evaluation results regarding the mobility are shown in Fig. 8.
除了使用聚己基噻吩(P3HT：Poly(3-HexylThiophene))(Plextronics Inc.製Plexcore OS1100)作為有機半導體以外，係與例1同樣地進行元件製作。之後，在真空下以100℃進行30分鐘熱處理來測定特性。將評估結果顯示於表2。 A device was produced in the same manner as in Example 1 except that P3HT: Poly(3-HexylThiophene) (Plexcore OS 1100 manufactured by Plextronics Inc.) was used as the organic semiconductor. Thereafter, the properties were measured by heat treatment at 100 ° C for 30 minutes under vacuum. The evaluation results are shown in Table 2.
除了使用聚〔(9,9-二辛基茀基-2,7-二基)-co-聯噻吩〕(「F8T2」)(American Dye Source公司製ADS2008P分子量43000、分散2.8)作為有機半導體，將轉印溫度設為280℃以外，係與例1同樣地實施。將評估結果顯示於表2。 In addition to poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene] ("F8T2") (American Dye Source, ADS2008P molecular weight 43000, dispersion 2.8) as an organic semiconductor, The transfer temperature was changed to 280 ° C, and the same procedure as in Example 1 was carried out. The evaluation results are shown in Table 2.
除了將轉印溫度設為70℃以外，係與例10同樣地實施。將評估結果顯示於表2。 The same procedure as in Example 10 was carried out except that the transfer temperature was changed to 70 °C. The evaluation results are shown in Table 2.
除了使用F8T2的0.5%甲苯溶液，藉由旋塗法而在基板上直接形成F8T2膜以外，係與例10同樣地實施。將評估結果顯示於表2。 The F8T2 film was directly formed on the substrate by a spin coating method except that a 0.5% toluene solution of F8T2 was used, and the same procedure as in Example 10 was carried out. The evaluation results are shown in Table 2.
除了使用〔(9,9-二辛基茀基-2,7-二基)-co-聯噻吩〕(「F8T2」)(American Dye Source公司製ADS2008P、分子量43000、分散2.8)作為有機半導體，將轉印溫度設為280℃以外，係依據非專利文獻7，亦即一面供予強切斷，一面將有機半導體層進行成膜，而作成薄膜電晶體。將評估結果顯示於表2。 In addition to [(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene] ("F8T2") (American Dye Source, ADS2008P, molecular weight 43,000, dispersion 2.8) as an organic semiconductor, When the transfer temperature is 280 ° C, the organic semiconductor layer is formed into a film according to Non-Patent Document 7, that is, a strong cut, and a thin film transistor is formed. The evaluation results are shown in Table 2.
除了使用聚(2,5-雙(3-十四烷基噻吩-2-基)噻吩并〔3,2,b〕噻吩)(「pBTTT-C14」)作為有機半導體，將轉印溫度設為150℃以外，係與《例1》同樣地實施。將評估結果顯示於表2。 In addition to using poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2,b]thiophene) ("pBTTT-C14") as an organic semiconductor, the transfer temperature was set to The procedure was carried out in the same manner as in "Example 1" except for 150 °C. The evaluation results are shown in Table 2.
1‧‧‧有機半導體材料 1‧‧‧Organic semiconductor materials
2、2’‧‧‧藉由構成有機半導體材料的芳香環所形成的面 2, 2'‧‧‧ Surface formed by the aromatic ring constituting the organic semiconductor material
10‧‧‧基板 10‧‧‧Substrate
20‧‧‧有機半導體膜 20‧‧‧Organic semiconductor film
22、24‧‧‧箭號 22, 24‧‧‧ arrows
130、140、150、160‧‧‧薄膜電晶體 130, 140, 150, 160‧‧‧ film transistors
131、141、151、161‧‧‧閘極電極 131, 141, 151, 161‧‧ ‧ gate electrodes
132、142、152、162‧‧‧閘極絕緣膜 132, 142, 152, 162‧‧ ‧ gate insulation film
133、143、153、163‧‧‧半導體膜 133, 143, 153, 163‧‧ ‧ semiconductor film
134、144、154、164‧‧‧源極電極 134, 144, 154, 164‧‧‧ source electrode
135、145、155、165‧‧‧汲極電極 135, 145, 155, 165‧ ‧ 汲 pole electrode
210‧‧‧有機半導體膜 210‧‧‧Organic semiconductor film
220‧‧‧印模 220‧‧‧ impression
230‧‧‧滾筒 230‧‧‧Roller
231‧‧‧箭號 231‧‧‧Arrow
250‧‧‧基材 250‧‧‧Substrate
261‧‧‧旋轉方向 261‧‧‧Rotation direction
262‧‧‧垂直方向 262‧‧‧Vertical direction
第1圖係用以概念性說明本發明中所使用的有機半導體膜的圖。 Fig. 1 is a view for conceptually explaining an organic semiconductor film used in the present invention.
第2圖係用以概念性說明習知之有機半導體膜的圖。 Fig. 2 is a view for conceptually explaining a conventional organic semiconductor film.
第3圖係用以概念性說明本發明中所使用的有機半導體膜的圖。 Fig. 3 is a view for conceptually explaining an organic semiconductor film used in the present invention.
第4圖係說明本發明之薄膜電晶體的圖。 Fig. 4 is a view showing the film transistor of the present invention.
第5圖係顯示關於實施例1中所得之有機半導體膜的in-plane的X線繞射(XRD)分析結果圖。 Fig. 5 is a graph showing the results of X-ray diffraction (XRD) analysis of the in-plane of the organic semiconductor film obtained in Example 1.
第6圖係顯示關於實施例3中所得之有機半導體膜的 in-plane的X線繞射(XRD)分析結果圖。 Fig. 6 is a view showing the organic semiconductor film obtained in Example 3 In-plane X-ray diffraction (XRD) analysis results.
第7圖係用以概念性說明製造有機半導體膜之本發明之方法的圖。 Fig. 7 is a view for conceptually explaining the method of the present invention for producing an organic semiconductor film.
第8圖係顯示關於實施例1A及8A之有機半導體膜的移動度的方向依存性。 Fig. 8 is a graph showing the dependence of the mobility of the organic semiconductor films of Examples 1A and 8A.
1‧‧‧有機半導體材料 1‧‧‧Organic semiconductor materials
2‧‧‧藉由構成有機半導體材料的芳香環所形成的面 2‧‧‧The surface formed by the aromatic ring constituting the organic semiconductor material
10‧‧‧基板 10‧‧‧Substrate
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