JP2011064945A - Method for manufacturing printing plate, printing plate, and organic thin film transistor using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing plate to be used for printing an organic semiconductor, the printing plate capable of imparting high characteristics regardless of a substrate surface. <P>SOLUTION: A method for manufacturing a printing plate including at least a support body and a resin is provided, characterized by forming a self-assembled monomolecular film on the printing surface of the printing plate. Otherwise, the printing surface of the printing plate is subjected to a surface treatment by rubbing. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a plate used for printing, a printing plate for the plate, and an organic thin film transistor produced using the plate.

  Due to the remarkable development of information technology, information is frequently sent and received at notebook computers and portable information terminals. It is a well-known fact that in the near future, a ubiquitous society that can exchange information regardless of location will come. In such a society, a lighter and thinner information terminal is desired.

  At present, the mainstream of semiconductor materials is silicon-based, and as a manufacturing method, one using photolithography is generally used.

  On the other hand, attention has been focused on printable electronics for manufacturing electronic members using printing technology. By using the printing technique, there are advantages that the apparatus and manufacturing cost are lower than those of photolithography, and that a plastic substrate can be used because no vacuum or high temperature is required.

  In this case, an organic semiconductor soluble in an organic solvent is used as the semiconductor material. For example, in patent document 1, the organic-semiconductor layer is formed using the inkjet method.

  However, when using an organic semiconductor, it is known that the characteristics to be obtained vary greatly depending on the substrate surface on which the organic semiconductor layer is formed. For example, Non-Patent Document 1 describes that characteristics obtained by depositing organic semiconductors on different surfaces greatly change. Further, for example, Non-Patent Document 2 describes that the properties obtained are greatly different when the surface of the insulating film is modified with various self-assembled monolayers. These are considered to be caused by the change in the orientation state and crystal state of the organic semiconductor due to the difference in surface free energy and functional group on the substrate surface.

Japanese Patent Laid-Open No. 2005-210086

Journal of American Chemical Society 2006, 128, 12851 MaterialsToday, March 2007, Vol. 10, No. 3, 47

  However, for example, it is actually difficult to use a laminated structure as described in Non-Patent Document 1, and in order to use a material used for an interface with an organic semiconductor in a single layer, insulation and solvent resistance are required. There is a problem.

In addition, the surface modification method as described in Non-Patent Document 2 does not generally have a reaction site with a material for forming a self-assembled monolayer in an organic polymer insulating film formed by a coating method. Therefore, it is difficult to apply. Even if a material having such a reaction site is temporarily used, there is a problem that the process becomes complicated.

  An object of the present invention is to provide a printing plate used when printing an organic semiconductor capable of obtaining high characteristics regardless of the substrate surface.

  The invention according to claim 1 of the present invention is characterized in that, in the method for producing a printing plate comprising at least a support and a resin, a self-assembled monolayer is formed on the surface of the printing surface of the printing plate. This is a method for producing a printing plate.

  In the invention according to claim 2, the self-assembled monolayer is formed of hexamethyldisilazane, alkyltrimethoxysilane, alkyltriethoxysilane, alkyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, or phenyltrichlorosilane. The method for producing a printing plate according to claim 1, comprising at least one of them.

  According to a third aspect of the present invention, in the method for producing a printing plate comprising at least a support and a resin, the surface of the printing surface of the printing plate is subjected to a surface treatment using a rubbing treatment. It is a manufacturing method.

  The invention according to claim 4 is the method for producing a printing plate according to any one of claims 1 to 3, wherein the printing plate is either a relief plate or a flexographic plate. .

  A fifth aspect of the present invention is a printing plate manufactured using the manufacturing method according to any one of the first to fourth aspects.

  The invention according to claim 6 is the printing plate according to claim 5, wherein a metal oxide is contained in either or both of the resin and the resin of the printing plate. .

  The invention according to claim 7 is the printing plate according to claim 5 or 6, wherein the support is a metal.

  The invention according to claim 8 is an organic thin film transistor formed by using the printing plate according to any one of claims 5 to 7.

  According to the method for producing a printing plate of the present invention, the surface of the printing plate is subjected to surface treatment by a wet method for forming a self-assembled monomolecular film or a dry method such as rubbing, thereby inking the printing plate. It is possible to optimize the orientation state and crystal state of the formed organic semiconductor.

  In addition, when the printing plate is a relief plate or a flexographic plate, the state of the optimized organic semiconductor can be easily transferred, the throughput is high, and the ink consumption can be suppressed.

  Moreover, it becomes easy to perform the surface treatment using the self-assembled monomolecular film by including a metal oxide in the resin of the printing plate or on the resin.

  Further, when the support is made of metal, the dimensional stability of the printing plate can be increased, and as a result, the dimensional stability of the printing pattern can also be improved.

  In addition, by using the printing plate according to any one of claims 5 to 7, the orientation state and crystal state of the organic semiconductor can be optimized without subjecting the surface of the thin film transistor substrate to surface treatment.

It is a cross-sectional schematic diagram of the printing plate precursor which shows an example of embodiment of this invention. It is a cross-sectional schematic diagram of the printing plate which shows an example of embodiment of this invention. It is a cross-sectional schematic diagram of the printing plate which shows an example of embodiment of this invention. It is a cross-sectional schematic diagram of the printing plate which shows an example of embodiment of this invention. It is a cross-sectional schematic diagram of the organic thin-film transistor which shows an example of embodiment of this invention.

  Hereinafter, examples of embodiments of the present invention will be described with reference to the drawings as necessary. In the present invention, it is desirable that a self-assembled monolayer is formed on the outermost surface of the printing plate. Since the self-assembled monolayer is formed, the outermost surface of the printing plate can have any surface free energy, and can have an appropriate surface free energy according to various semiconductor materials. In addition, since a dense film can be formed, a uniform semiconductor layer can be formed.

  As the self-assembled monolayer used for the outermost surface of the printing plate, a general material can be used. Specifically, hexamethyldisilazane, octyltrimethoxysilane, octadecyltrimethoxysilane, octyltriethoxy Alkylsilane compounds such as silane, octadecyltriethoxysilane, octyltrichlorosilane, octadecyltrichlorosilane, phenyltrimethoxysilane, phenethyltrimethoxysilane, phenoxyoctadecyltrimethoxysilane, phenyltriethoxysilane, phenethyltriethoxysilane, phenoxyoctadecyltriethoxy Phenylsilane compounds such as silane, phenyltrichlorosilane, phenethyltrichlorosilane, phenoxyoctadecyltrichlorosilane, aminopropyltrimethoxy Examples include aminosilane compounds such as lan, aminopropyltriethoxysilane, aminopropyltrichlorosilane, fluorosilane compounds such as perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, and perfluorooctylethyltrichlorosilane. It is not limited to these, It is preferable to select the thing suitable for the semiconductor material to be used.

  In the embodiment of the present invention, the outermost surface of the printing plate may be treated by a dry method. Thereby, the surface suitable for the ink to be used can be obtained. Specifically, surface treatment methods such as corona treatment, plasma treatment, UV ozone treatment, excimer UV treatment, and photo-alignment method can be used, and rubbing treatment that adds alignment performance by rubbing the polymer film with a cloth or the like. Is particularly preferably used for optimizing the alignment state of the semiconductor, but is not limited thereto.

  In the embodiment of the present invention, the printing plate is desirably a relief plate or a flexographic plate. Generally, organic semiconductors have low solubility in solvents, and solutions often have low viscosity. To form patterns with optimized orientation using such solutions, letterpress printing or flexographic printing is used. This is desirable.

In the embodiment of the present invention, as shown in FIGS. 3 and 4, it is desirable that a metal oxide is contained in or on the resin. Examples of the metal oxide include, but are not limited to, silicon oxide, titanium oxide, silver oxide, copper oxide, zirconia oxide, zinc oxide, and indium tin oxide. Further, the metal oxide may be in a state of being contained in the resin as particles or in a state of being formed on the resin as a thin film. When it is contained in the resin, it is convenient because a process is not required after the plate making. When formed on a resin, the process is complicated, but there is an advantage that a denser self-assembled monolayer can be formed. In consideration of the plate making process, it is preferable that the metal oxide layer is formed on the resin after the plate making.

  In the embodiment of the present invention, the support of the printing plate is not particularly limited, but it is desirable that it is made of metal in consideration of dimensional stability. The type of metal is not particularly limited, but stainless steel is preferable from the viewpoint of versatility.

  In the embodiment of the present invention, the ink used for printing is not particularly limited, and examples thereof include a polymer organic semiconductor or a low molecular organic semiconductor dissolved in a solvent. In these inks, additives such as a surfactant, a thickener, a binder, and a poor solvent other than a good solvent may be added as necessary.

  In embodiments of the present invention, it is desirable to dry the ink to some extent on the printing plate. This is because the solute orientation state and crystal state are optimized by drying to some extent.

  In the embodiment of the present invention, the structure of the organic thin film transistor is not particularly limited, and examples thereof include a bottom gate / bottom contact type and a top gate / bottom contact type.

  In the embodiment of the present invention, the printing plate may have an adhesive layer, an antihalation layer, an ablation mask, or the like as necessary.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

<Plate formation for printing>
As shown in FIG. 1, SUS304 having a thickness of 100 μm was used as the support (10). A photosensitive nylon was used as a resin on the support, and a resin layer (11) having a thickness of 150 μm was formed to obtain an original plate. Subsequently, as shown in FIG. 2, the original plate was exposed using a photomask, developed with water, dried at 70 ° C. for 30 minutes, and post-exposed. As a result, a printing plate having a printing pattern was formed. Subsequently, a SiO ₂ film having a thickness of 40 nm was formed on the printing plate by a sputtering method to form a metal oxide layer (12). Subsequently, this printing plate was immersed in a solution of phenyltriethoxysilane diluted to 1% by mass with toluene for 6 hours to form a surface treatment layer (13).
<Thin film transistor substrate formation>
On the other hand, as shown in FIG. 5, glass was used as the organic thin film transistor substrate (20). Aluminum was formed into a film by a 100 nm vapor deposition method as a gate electrode, and the gate electrode (21) was formed by photolithography and etching. Subsequently, a gate insulating film (22) having a thickness of 1 μm was formed by a spin coating method using polyvinylphenol (manufactured by Aldrich) as a gate insulating material. Next, gold was used as a source / drain electrode material, and a film having a thickness of 50 nm was formed by vapor deposition through a shadow mask to obtain source / drain electrodes (23) and (24).
<Organic semiconductor layer formation>
As a printing ink, an ink in which bistriisopropylsilylethynylpentacene was dissolved in tetralin at 1% by mass was used. After inking from an anilox roll, it was dried on a printing plate subjected to surface treatment for 1 minute, and then transferred onto the gate insulating film and the source / drain electrodes to form an organic semiconductor layer (25). As a result, an organic thin film transistor having good transistor characteristics was formed.

  As shown in FIG. 3, as a resin, a material obtained by mixing photosensitive nylon with titanium oxide having an average particle diameter of 50 nm so as to have a weight ratio of 80:20 is used to form a metal oxide layer after the printing pattern is formed. An organic thin film transistor was prepared in the same manner as in Example 1 except that there was no. As a result, an organic thin film transistor having good transistor characteristics was formed.

<Plate formation for printing>
As shown in FIG. 1, SUS304 having a thickness of 100 μm was used as the support (10). A photosensitive nylon was used as a resin on the support, and a resin layer (11) having a thickness of 150 μm was formed to obtain an original plate. Subsequently, as shown in FIG. 4, the original plate was exposed using a photomask and developed with water, and then dried at 70 ° C. for 30 minutes, followed by post-exposure. As a result, a printing plate having a printing pattern was formed. Subsequently, as a surface treatment of the printing plate, a surface treatment layer (13) was formed by performing a rubbing treatment.
<Thin film transistor substrate formation>
On the other hand, as shown in FIG. 5, glass was used as the organic thin film transistor substrate (20). Aluminum was formed into a film by a 100 nm vapor deposition method as a gate electrode, and the gate electrode (21) was formed by photolithography and etching. Subsequently, a gate insulating film (22) having a thickness of 1 μm was formed by a spin coating method using polyvinylphenol (manufactured by Aldrich) as a gate insulating material. Next, gold was used as a source / drain electrode material, and a film having a thickness of 50 nm was formed by vapor deposition through a shadow mask to obtain source / drain electrodes (23) and (24).
<Organic semiconductor layer formation>
After inking from an anilox roll using ink in which Lisicon SP200 is dissolved in tetralin at 1% by mass as a printing ink, it is dried for 1 minute on a surface-treated printing plate, and then a gate insulating film and a source -It transferred on the drain electrode and formed the organic-semiconductor layer (25). As a result, an organic thin film transistor having good transistor characteristics was formed.

DESCRIPTION OF SYMBOLS 10 ... Support body 11 ... Resin 12 ... Metal oxide 13 ... Surface treatment layer 20 ... Thin-film transistor substrate 21 ... Gate electrode 22 ... Gate insulating film 23 ... Source electrode 24 ... Drain electrode 25 ... Organic semiconductor layer

Claims (8)

  In the manufacturing method of the printing plate which consists of a support body and resin at least, the self-assembled monolayer is formed in the surface of the printing surface of the said printing plate, The manufacturing method of the printing plate characterized by the above-mentioned.   The self-assembled monolayer is made of at least one of hexamethyldisilazane, alkyltrimethoxysilane, alkyltriethoxysilane, alkyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltrichlorosilane. A method for producing a printing plate according to claim 1.   In the manufacturing method of the printing plate which consists of a support body and resin at least, the surface of the printing surface of the said printing plate is surface-treated using a rubbing process, The manufacturing method of the printing plate characterized by the above-mentioned.   The method for producing a printing plate according to any one of claims 1 to 3, wherein the printing plate is a relief plate or a flexographic plate.   A printing plate produced using the production method according to claim 1.   6. The printing plate according to claim 5, wherein a metal oxide is contained in either or both of the resin and the resin of the printing plate.   The printing plate according to claim 5 or 6, wherein the support is a metal.   An organic thin film transistor formed using the printing plate according to claim 5.

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