JP2003218361A - Organic transistor element, active driving element and display medium comprising it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the arrangement of a TFT element capable of obtaining various utilization forms of thin rewritable digital paper, and its manufacturing method. <P>SOLUTION: In an organic transistor element, a channel of an organic semiconductor coupling a source electrode and a drain electrode intersects a gate electrode coated with an insulation layer through the insulation layer wherein the gate electrode coated with the insulation layer is stringy. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active driving device having an electric field driving type organic transistor device which is easy to manufacture and advantageous for use in digital paper.

[0002]

2. Description of the Related Art With the spread of information terminals, there is an increasing need for flat panel displays as displays for computers. In addition, with the progress of computerization, there is an increasing opportunity to digitize the information that was previously provided on paper media, and as a mobile display medium that is thin, light, and easily portable, electronic paper or digital The need for papers has increased, and practical application of thin liquid crystal display devices, electrochromic displays, electrophoretic display devices described in U.S. Pat. No. 6,262,833, JP 2000-171839A, 2001-201770, etc. has been studied. There is.

For practical use of such a display medium, use of an active driving element (TFT element) as an image driving element has been studied in order to secure uniformity of screen brightness and screen rewriting speed.

[0004]

In the current ordinary computer display, the above-mentioned TFT element is formed on a glass substrate and liquid crystal, organic EL, etc. are sealed. This T
The FT element is mainly a-Si (amorphous silicon),
A semiconductor such as p-Si (polysilicon) is used, and these Si semiconductors (and a metal film if necessary) are multilayered, and source, drain, and gate electrodes are sequentially formed on the substrate to form a TFT element. Is manufactured. Such TF
The manufacture of T-elements usually requires sputtering and other vacuum-based manufacturing processes.

In this manufacturing process, a vacuum system manufacturing process including a vacuum chamber has to be repeated many times to form each layer, resulting in a huge amount of equipment cost and running cost. For example, TF as shown in FIG.
In the T element, it is usually necessary to repeat steps such as vacuum deposition, doping, photolithography, and development many times for forming each layer, and the element is formed on the substrate through dozens of steps. . As for the semiconductor portion that is required for the switching operation, a plurality of types of semiconductor layers such as p-type and n-type semiconductor layers are stacked. In the figure, 1 is a substrate, 2 is a gate electrode,
Reference numeral 3 is a source electrode, 4 is a drain electrode (2 to 4 are each made of Al or the like), and 5 is a conductive film.

In such a conventional manufacturing method using Si semiconductor, it is not easy to change the equipment, for example, a large design change of the manufacturing apparatus such as a vacuum chamber is required to meet the need for a larger screen.

On the other hand, in recent years, along with research on organic semiconductors, it has been considered to replace organic materials with Si materials and incorporate them into such circuits. However, the conventional circuit configuration is mainly replaced, and problems in the manufacturing process such as repeating the vacuum manufacturing process have not been solved. Various organic thin film transistors based on organic semiconductors have been proposed. In particular, 2001 Society of Polymer Science, Proceedings, Vol. 50, No. 13, p. 3175, describes that a normally-on type organic thin film transistor can be prepared by a very simple method. There is.

As an application of thin and rewritable digital paper, a thin and light flexible and rewritable display medium for displaying contents such as electronic newspapers and electronic publications, and an event that can be repeatedly used by changing the display Various forms of use are conceivable, such as banners and flags used, banners used for buildings, numbering for competitions, etc., but it is currently difficult to realize due to restrictions on the manufacturing process of TFT elements.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a structure of a TFT element and a manufacturing method thereof, which can realize various usage forms of a thin and rewritable digital paper.

[0010]

In a Si semiconductor material used for a normal switching element, a channel is formed by combining a gate electrode with a source portion and a drain portion, and ON / OFF of a current between the source and the drain is controlled. .

On the other hand, if an organic semiconductor material that exhibits a special behavior in which conductivity decreases when an electric field is applied, a transistor that cuts off a current when an electric field is applied can be formed, and is an organic material. Focusing on its excellent workability, the present inventor has come up with the idea of manufacturing a matrix circuit for forming a TFT by forming a source line and a gate line into a thread and weaving them into a woven fabric.

That is, the above objects of the present invention are as follows: 1) A gate electrode in which a channel made of an organic semiconductor connecting a source electrode and a drain electrode is covered with an insulating layer,
An organic transistor element which is crossed via the insulating layer and has a thread-shaped gate electrode covered with the insulating layer, 2) an active driving element controlled to be driven by the organic transistor element of 1), 3) an element The matrix circuit to be formed is woven into a woven fabric made of a thread made of an insulating material, and the thread forming the source line and the thread forming the gate line and the thread forming the gate line are contacted and crossed with each other. An active drive element having a channel made of an organic semiconductor that connects a drain electrode and a thread forming a source line, 4) a display medium display-controlled by the active drive element of 2) or 3), 5) active The matrix circuit that forms the drive element
A yarn that is woven into a woven fabric made of an insulating material and forms a source line and a gate line that intersect with each other, and a yarn that contacts and intersects with the yarn that forms the gate line to form a source line. And a display medium which has a channel made of an organic semiconductor connecting the display electrodes and is display-controlled by the element, 6) a sheet-shaped display medium of 4) or 5), and 7) an insulating material. A step of forming a woven fabric in which the yarn forming the source line and the yarn forming the gate line intersect each other using the yarn, the yarn forming the source line and the yarn forming the gate line; forming a display electrode on the woven fabric Forming a source line by contacting and crossing a channel made of an organic semiconductor with a thread forming a gate line, and connecting the display electrode with a thread forming a source line. And active drive element display medium is manufactured through the step of sealing the matrix circuit for forming a is accomplished by.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

FIG. 2 schematically shows the structure of the organic transistor element of the present invention. In the figure, in an organic transistor element 20 of the present invention, a channel 21 made of an organic semiconductor that connects a source electrode and a drain electrode, which will be described later, has an insulating layer 2
The gate electrode 22 covered with 3 intersects with the insulating layer. The channel 21 need only be in contact with the insulating layer 23 in part, but is preferably formed so as to cover the surface as shown in the drawing.

As the organic semiconductor material used in the channel 21 connecting the source electrode and the drain electrode in the present invention and exhibiting the above-mentioned special behavior, a conductive polymer compound having a basic skeleton such as chemical formula 1 can be mentioned. Examples are shown in Chemical formulas 2 to 8, but the π-conjugated polymer compound of Chemical formulas 2 to 6 is particularly preferable.

[0016]

[Chemical 1]

[0017]

[Chemical 2]

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

An organic semiconductor using a π-conjugated polymer compound has a three-dimensional π-electron cloud such as fullerene or carbon nanotube for the purpose of carrier transfer and carrier trap between a plurality of π-conjugated polymer compounds. It is preferable to add the compound having.

These compounds are, for example, fullerene C-
60, fullerene C-70, fullerene C-76, fullerene C-78, fullerene C-84, fullerene C-
240, fullerene C-540, mixed fullerene, fullerene nanotube, multi-walled nanotube (Mu
lti Walled Nanotube, single walled nanotube
be). Further, a fullerene or carbon nanotube may have a substituent introduced for the purpose of imparting compatibility with a solvent.

Lewis acid (iron chloride, aluminum chloride, antimony bromide, etc.), halogen (iodine, bromine, etc.), sulfonate (polystyrenesulfonic acid sodium salt (PSS), p-) is added to the π-conjugated polymer compound. Those doped with potassium toluene sulfonate etc.) perform good switching drive. Specifically, there is a complex of PEDOT (polyethylenedioxythiophene) and PSS (polystyrene sulfonic acid). The conductivity of the organic semiconductor channel of the transistor is preferably 10 ^-2 s / cm or more.

The source electrode, the drain electrode and the gate electrode 22 may be made of a metal material such as Al, Cu, Cr or the like, or a conductive material. In order to obtain good characteristics, it is preferable to use a metal, an alloy, an electrically conductive compound or a mixture thereof having a low work function as an electrode substance. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al). ₂ O ₃ ) mixtures, indium, lithium / aluminum mixtures, rare earth all-genus and the like.

The insulating layer 23 is made of SiO ₂ , TiO ₂ or the like, a photocurable resin of a photo-radical polymerization type or a photocationic polymerization type, or a copolymer containing an acrylonitrile component, polyvinylphenol, polyvinyl alcohol, novolac resin, and It is also possible to use cyanoethyl pullulan or the like.

When forming an insulating layer of SiO ₂ or TiO ₂ , a composition containing at least one selected from metal alkoxides and hydrolysates thereof and an organic solvent is applied to the gate electrode by dip coating or the like, Active energy rays,
For example, by applying energy such as heat rays or ultraviolet rays,
It can be cured, for example, Japanese Patent Laid-Open No. 2000-327.
310 and JP 2000-344504 can be referred to.

As the alkoxide, Al (OC)
_{H 3) 3, Al (OC} 2 H 5) 3, Al (O-i-C
_{3 H 7) 3, Al (} O-n-C 4 H 9) 3; Si (OC
_{H 3) 4, Si (OC} 2 H 5) 4, Si (O-i-C
₃ H ₇ ) ₄ , Si (Ot-C ₄ H ₉ ) ₄ ; Ti (OC
_{H 3) 4, Ti (OC} 2 H 5) 4, Ti (O-n-C
_{3 H 7) 4, Ti (} O-i-C 3 H 7) 4, Ti (O-n-C
_{4 H 9) 4, Ti (} O-n-C 3 H 7) 4 2-10 mer, T
_{i (O-i-C 3} H 7) 4 2-10 mer, Ti (O-n
-C ₄ H ₉ ) ₄ dimer, VO (OC ₂ H ₅ ) ₃ ; Zn
(OC ₂ H ₅ ) ₂ ; Y (OC ₄ H ₉ ) ₃ ; Zr (OCH ₃ ) ₄ ,
_{Zr (OC 2 H 5) 4} , Zr (O-n-C 3 H 7) 4, Zr
_{(O-i-C 3 H} 7) 4, Zr (O-i-C 4 H 9) 4, Zr
_{(O-n-C 4 H} 9) 4 2-10 mer; In (O-n-
_{C 4 H 9) 3; Sn} (O-n-C 4 H 9) 4, Ta (OC
_{H 3) 5, Ta (O} -n-C 3 H 7) 5, Ta (O-i-C 3
_{H 7) 5, Ta (O} -n-C 4 H 9) 5; W (OC 2 H 5) 6;
Ce (OC ₃ H ₇ ) _{3 and the} like can be mentioned. These can be used alone or in combination of two or more. Above all, T
_{i (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, T
_{i (O-n-C 4} H 9) 4, Ti 2 of _{(O-n-C 3 H} 7) 4
10-mer, Ti (O-n-C 4 H 9) 4 2-10 mer; Zr (O-i-C 3 H 7) 4, Zr (O-n-C
_{4 H 9) 4; Si (} OC 2 H 5) 4, Si (O-i-C 3 H 7)
₄ is particularly preferred.

The above metal alkoxide may be hydrolyzed (partially or completely hydrolyzed) and used, for example, obtained by hydrolyzing the above metal alkoxide in an organic solvent in the presence of an acidic catalyst or a basic catalyst. To be The acidic catalyst is preferably a mineral acid such as nitric acid or hydrochloric acid or an organic acid such as oxalic acid or acetic acid, and the basic catalyst is, for example, ammonia or the like.

Hydrolyzates of metal alkoxides include
Some or all of the valence of the metal is hydrolyzed
Therefore, Si (OH) is an example of Si._Four, Si
(OCH₃) (OH)₃, Si (OCH₃)₂(OH)₂,
Si (OCH₃)₃(OH), Si (OC₂H_Five)₂(O
H)₂, Si (OC₃H₇(I))₃(OH); with an example of Ti
Then Ti (OH)_Four, Ti (OCH₃) (OH)₃,
Ti (OC₂H_Five)₂(OH) ₂, Ti (OC₃H₇(N))
₃(OH), Ti (OC_FourH₉(N))₂(OH)₂As
, But the degree of substitution is any of 1 to 4.
And the same hydrolyzate for dimers and 10-mers
Can be used.

Specific examples of the metal alkoxide include vinyltrimethoxytitanium, vinyltri (β-methoxy-ethoxy) titanium, divinyloxydimethoxytitanium, glycidyloxyethyltriethoxytitanium, γ-acryloyloxypropyltri-n-propyltitanium. , Γ-methacryloyloxy-n-propyltri-n-propyltitanium, di (γ-acryloyloxy-n-propyl) di-n-propyltitanium, acryloyloxydimethoxyethyltitanium, vinyltrimethoxyzircon, divinyloxydimethoxyzircon , Acryloyloxyethyltriethoxyzircon, γ-acryloyloxy-n-propyltri-n-propylzircon, γ-methacryloyloxy-n-propyltri-n-propylzircon, di (γ-acryloylo) Shi -n- propyl) di -n- propyl zirconate, acryloyloxyethyl dimethoxyethyl zircon, vinyl dimethoxy thallium, vinyl di (beta-
(Methoxy-ethoxy) thallium, divinyloxymethoxy thallium, acryloyloxyethyl diethoxy thallium, γ-acryloyloxy-n-propyl di-n-propyl thallium, γ-methacryloyloxy-n-propyl di-n-propyl thallium, di (γ -Acryloyloxy-n-propyl) -n-propyl thallium, acryloyloxy methoxyethyl thallium, vinyltrimethoxysilane, vinyltri (β-methoxy-ethoxy)
Silane, divinyloxydimethoxysilane, β- (3,4-
Epoxycyclohexyl) -ethyltrialkoxysilane, acryloyloxyethyltriethoxysilane, glycidyloxyethyltriethoxysilane, γ-acryloyloxy-n-propyltri-n-propylsilane, γ-methacryloyloxy-n-propyltri-n
-Propylsilane, di (γ-acryloyloxy-n-
Examples include propyl) di-n-propylsilane and acryloyloxydimethoxyethylsilane.

The layer containing the above metal alkoxide compound is
The metal alkoxide itself self-condenses and crosslinks to form a network bond. A catalyst or a curing agent can be used to accelerate the reaction, and they include a metal chelate compound, an organometallic compound such as an organic carboxylate, an organosilicon compound having an amino group, a photoacid generator, etc. There is. Of these catalysts or curing agents, particularly preferred are aluminum chelate compounds and acid generators by light (photoacid generators). Examples of aluminum chelate compounds include ethyl acetoacetate aluminum diisopropylate and aluminum trisethyl. Acetoacetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, aluminum trisacetylacetonate, etc., and examples of other photoacid generators include benzyltriphenylphosphonium hexafluorophosphate and other Examples thereof include phosphonium salts and salts of triphenylphosphonium hexafluorophosphate.

To a coating composition containing a metal alkoxide and / or its hydrolyzate, a stable coating composition is prepared by reacting with a β-diketone and adding a chelate compound for the purpose of stabilizing the storage of the coating solution. Can be
As a specific example of this β-diketone, methyl acetoacetate,
Examples thereof include ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, and acetylacetone, and ethyl acetoacetate is particularly preferable from the viewpoint of stability. The β-diketone has a molar ratio of 0.1 to the metal alkoxide or its hydrolyzate.
It is used in the range of 5 to 2, but a more preferable range is
It is 0.8 to 1.2.

As the active energy ray-reactive compound, a compound having two or more polymerizable groups such as a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an isopropenyl group and an epoxy group, which can be polymerized by irradiation with active energy rays. What forms a crosslinked structure or a network structure can be used. Of these active groups, an acryloyl group, a methacryloyl group or an epoxy group is preferable in terms of polymerization rate and reactivity, and a polyfunctional monomer or oligomer is more preferable.

Examples of the active energy ray-curable resin include UV-curable acrylic urethane resin, UV-curable polyester acrylate resin, UV-curable epoxy acrylate resin, and UV-curable polyol acrylate resin. .

In order to initiate the photopolymerization or photocrosslinking reaction of the active energy ray-reactive compound, the above-mentioned active energy ray-reactive compound alone is used, but the induction period of the polymerization is long or the initiation of the polymerization is slow. It is preferable to use a photosensitizer or a photoinitiator, which can accelerate the polymerization. Known photosensitizers and photoinitiators can be used. Specifically, acetophenone,
Examples thereof include benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, tetramethyluram monosulfide, thioxanthone and derivatives thereof.

In the case of an active energy ray-reactive compound having an epoxy acrylate group, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the active energy ray-reactive compound is 0.1 to 100 parts by mass of the ultraviolet-reactive compound.
15 parts by mass is sufficient to start the photoreaction, and preferably 1 to 10 parts by mass. This sensitizer preferably has an absorption maximum in the near-ultraviolet region to the visible light region.

The metal alkoxide compounds react with each other while undergoing hydrolysis, are incorporated into the metal oxide matrix, bond and crosslink. Further, the active energy ray-reactive group of the metal alkoxide compound and the other active energy ray-reactive compounds can also be polymerized by the active energy ray to form cross-links with each other.

These cross-links have a synergistic effect and the layer containing them has a very high hardness. These crosslinked structures are considered to be in a hybrid state in which the inorganic oxide and the organic polymer are bonded to each other, and unlike the state in which the metal oxide and the organic substance are mixed, the hardness is high because they are integrated, Phase separation hardly occurs. Therefore, it is easy to form a uniform coating film.

Heat or active energy rays are used to cure the resin, but active energy rays such as ultraviolet rays, electron rays, and γ rays are preferable. Ultraviolet rays and electron beams are particularly preferable, and ultraviolet rays are particularly preferable because they are easy to handle and high energy can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a super high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, etc. can be used. Further, ArF excimer laser, KrF excimer laser, excimer lamp, synchrotron radiation light, or the like can also be used. Irradiation conditions differ depending on each lamp, but the irradiation light amount is 20
mJ / m ² or more, preferably 100 mJ / cm ² or more,
Further, it is preferably 400 mJ / cm ² or more. The electron beam is emitted from various electron beam accelerators such as Cockloft-Walton type, Van de Graaff type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type.
An electron beam having an energy of ˜1000 KeV, preferably 100 to 300 KeV can be mentioned.

Solvents include alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene and xylene; ethylene glycol, propylene glycol and hexylene glycol. And the like; glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, and diethyl carbitol; N-methylpyrrolidone, dimethylformamide, water and the like. It is possible to mix and use one or more species. Among them, ketones, for example, acetone, methyl ethyl ketone, a solvent having a carbonyl group such as cyclohexanone, and a combination of an alcohol having a carbon number of 4 or less such as methanol, ethanol, n-propanol, isopropanol, n-butanol, the ultraviolet irradiation dose. It is particularly preferable because it can be reduced and productivity can be improved.

For example, a sol liquid containing SiO ₂ sol and a reactive organosilicon compound can be used to form a SiO ₂ gel film. The SiO ₂ sol is prepared by dissolving silicon alkoxide in an organic solvent suitable for coating and adding a certain amount of water to carry out hydrolysis.

A SiO ₂ sol can be obtained by dissolving the above alkyl silicon alkoxide or silicon alkoxide in a suitable solvent. Examples of the solvent to be used include alcohols such as methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate and butyl acetate, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene. , Or a mixture thereof. Alkyl silicon alkoxide or silicon alkoxide is added to the above solvent so that the concentration becomes 0.1% by mass or more, preferably 0.1 to 10% by mass in terms of SiO ₂ generated as a result of 100% hydrolysis and condensation thereof. Dissolve. If the concentration of SiO ₂ sol is less than 0.1% by mass, the formed sol film cannot sufficiently exhibit desired characteristics, while if it exceeds 10% by mass, it becomes difficult to form a transparent homogeneous film. Further, in the present invention, an organic or inorganic binder may be used in combination as long as the solid content is within the above range.

To this solution is added water in an amount necessary for hydrolysis and the mixture is stirred at a temperature of 15 to 35 ° C., preferably 22 to 28 ° C. for 0.5 to 10 hours, preferably 2 to 5 hours. In the above hydrolysis, it is preferable to use catalysts, and as these catalysts, acids such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid are preferable. About 0.001 to 4 of these acids
It can be added as an aqueous solution of 0.0 mol / L, preferably about 0.005 to 10.0 mol / L, and the water in the aqueous solution can be used as the water for hydrolysis.

The reactive organosilicon compound includes, in addition to the above-mentioned reactive organosilicon compound, a plurality of groups (active energy ray reactive groups) which are reactively crosslinked by heat or ionizing radiation.
For example, an organic reactive compound having a molecular weight of 3000 or less and having a polymerizable double bond group is preferable. Such reactive organosilicon compounds include vinyl-functional polysilanes at one end, vinyl-functional polysilanes at both ends, vinyl-functional polysiloxanes at one end, vinyl-functional polysiloxanes at both ends,
Alternatively, there are vinyl functional polysilanes or vinyl functional polysiloxanes obtained by reacting these compounds.

In addition, vinyltrimethoxysilane,
Vinyltri (β-methoxy-ethoxy) silane, divinyloxydimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, acryloyloxyethyltriethoxysilane, glycidyloxyethyltriethoxysilane, γ-acryloyloxy −
n-propyltri-n-propylsilane, γ-methacryloyloxy-n-propyltri-n-propylsilane, di (γ-acryloyloxy-n-propyl) di-
Examples thereof include n-propylsilane and acryloyloxydimethoxyethylsilane.

The above reactive organosilicon compound is contained in an amount of about 0.1 per 100 parts by mass of the SiO ₂ sol (solid content).
It is preferably used in a proportion of ˜50 parts by mass.

Various additives can be added to the sol solution. As the additive, a curing agent that accelerates film formation is used. Examples of these curing agents include acetic acid of organic acid metal salts such as sodium acetate and lithium acetate, and organic acid solutions such as formic acid. The concentration of the organic solvent solution is about 0.
The amount of addition to the sol solution is preferably about 0.1 to 1 part by mass as the organic acid salt with respect to 100 parts by mass of SiO ₂ present in the sol solution. .

The layer thickness and coating uniformity can be controlled by adjusting the solid content concentration and coating amount in the coating liquid. Further, in order to improve the coatability of the composition, a trace amount of a surfactant or the like may be added to the coating liquid.

The organic transistor element of the present invention is incorporated to form a TFT element to form a display drive circuit for digital paper. FIG. 3 is a block diagram showing the configuration of the entire sheet-shaped display medium.

Each pixel arranged in a matrix on the display section 100 of the sheet-shaped display medium has a flat plate electrode 101 (display pixel section) for accumulating charges and applying an electric field to liquid crystal or the like. In addition, a transistor portion (TFT drive portion 20) for switching ON / OFF of current to the plate electrode 101.
And a capacitor 103 is arranged for each plate electrode 101. The capacitor 103 accumulates and maintains charges at a predetermined timing in order to maintain the electric field of the corresponding plate electrode 101. Driving control of liquid crystal or the like at each of the plate electrodes 101 is executed by the TFT driving section 20, which is controlled by the vertical driving circuit 106 and corresponds to a power supply line (source line 104) and a horizontal line. It is controlled by a control signal line (gate line 105) corresponding to the pixel controlled by the drive circuit 107.

On the display unit 100, a plurality of source lines 104 parallel to each other and a plurality of gate lines 105 parallel to each other are arranged so as to intersect with each other.

The horizontal drive circuit 107 and the vertical drive circuit 106 are controlled by a control circuit 108 according to a required image signal.
Controlled by. The memory 109 is a buffer memory for holding the required image signal, for example, image data for one screen or more, and the control circuit 108 reads the required image signal from the memory 109.

As shown in FIG. 4, a display unit is constructed by having a display element 42 utilizing electrophoresis or the like, a plate electrode 101 and a surface electrode 43 on a support 41. As the display element 42, liquid crystal, organic EL, so-called Eink, or the like can be used. 44 is an adhesive layer and 45 is an insulating layer. Then, an electric field is applied to the display element 42 of the display pixel section under the control of the TFT driving section 20, and the display is controlled in pixel units.

The display element 42 is laminated on the support 41, adhered and sealed with an insulating adhesive, and an insulating layer 45 is further formed. At the time of bonding, an insulating sealing material or an adhesive may be applied, and an insulating thin film may be attached, or a photo-curable material may be applied and then photo-cured to insulate the insulating layer 45 and the adhesive layer. 44 may be cured simultaneously. A TFT element is provided on the insulating layer 45 to form a display medium.

When the display element 42 is made of liquid crystal, either a reflection type or a transmission type can be used, and a deflection film, an alignment film, etc. are laminated. When the scattering mode is used in scattering mode liquid crystal, polymer dispersion mode liquid crystal, liquid crystal gel, etc., the insulating layer can be colored yellow, magenta, cyan, or black depending on the pixel for color display. In this case, the colored layer may be provided on the insulating layer by printing. Cholesteric liquid crystals can also be used.

Here, the surface electrode 43 has a light transmitting property, and specifically, a transparent conductive film is used. The transparent conductive film is, for example, indium tin oxide (ITO), SnO.
₂ , formed using a conductive transparent material such as ZnO.
In forming the transparent electrode film, a thin film can be formed by using a method such as vapor deposition or sputtering. The transparent conductive film preferably has a transmittance of more than 10%, and the sheet resistance is preferably several hundred Ω / □ or less. Although the film thickness depends on the material, it is formed with a thickness of 10 nm or more. This is because when the film thickness is thin, the transparent electrode becomes island-shaped.

The transparent conductive film described above can be applied to the formation of the flat plate electrode 101, in which case a pattern having a desired shape may be formed by a photolithography method, or a desired pattern may be formed at the time of vapor deposition or sputtering of the above electrode substance. You may form a pattern through the mask of this shape.

Further, a predetermined transparent protective layer 46 can be provided further above the surface electrode 43, and a functional film such as an antireflection layer can be formed.

FIG. 5 shows an equivalent circuit 50 of each pixel. S is a source electrode, D is a drain electrode, G is a gate electrode, and S, D, and G form the TFT drive unit 20. Cs is a capacitor for holding an electric field applied to the liquid crystal and other display elements. The source electrode S
Is applied with a source voltage Vs, and the gate electrode G is applied with a gate electrode Vg. The point that the channel from the source electrode to the drain electrode is controlled by the gate electrode and the switching operation is performed is the same as that of the TFT driving unit of a normal Si semiconductor. However, as described above, the organic transistor element of the present invention has completely different switching characteristics from the ordinary Si semiconductor.

The plate electrodes 101 are arranged on the support 41 at equal intervals. The support 41 is composed of a flexible resin sheet, and a plastic film, for example, can be used as the sheet. Examples of the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), polyether imide,
Examples thereof include films made of polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP) and the like.

A plasticizer such as trioctyl phosphate or dibutyl phthalate may be added to these plastic films, or a known ultraviolet absorber such as benzotriazole or benzophenone may be added. In addition, a resin produced by applying a so-called organic-inorganic polymer hybrid method, in which a raw material of an inorganic polymer such as tetraethoxysilane is added, and a high molecular weight is obtained by applying energy such as a chemical catalyst, heat, or light. It can also be used as a raw material.

As the insulating layer 45, an insulating film made of SiO ₂ , TiO ₂ or the like can be used similarly to the insulating layer 23 of the organic transistor element of the present invention. A resin, a copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, a novolac resin, cyanoethyl pullulan, or the like can also be used.

The insulating layer 4 is made of, for example, SiO ₂ or TiO ₂ .
When forming No. 5, a film can be formed by plasma treatment under atmospheric pressure in addition to the method using the coating liquid described above.

The plasma film forming process under the atmospheric pressure is
Discharged under atmospheric pressure or pressure near atmospheric pressure, plasma-exciting a reactive gas to form a thin film on a substrate, which is described in JP-A-11-133205.
JP-A-2000-185362, JP-A-11-61406
No. 2000-147209 and 2000-121.
804 and the like (hereinafter, also referred to as atmospheric pressure plasma method).

The plasma discharge treatment apparatus discharges between the roll electrode, which is the earth electrode, and the fixed electrode, which is the applying electrode arranged at the opposite position, and introduces a reactive gas between the electrodes to cause a plasma state. By exposing the long film-shaped substrate wound around the roll electrode to the reactive gas in the plasma state, a thin film is formed, but as an apparatus for carrying out the thin film forming method, The present invention is not limited, and any material can be used as long as it stably maintains glow discharge and excites a reactive gas into a plasma state to form a thin film. As another method, there is a jet method or the like in which a base material is placed or transported near the electrodes, not between the electrodes, and the generated plasma is blown onto the base material to form a thin film.

The roll electrode, which is an earth electrode, is formed by a combination of ceramics sprayed on a conductive base material such as metal, and then covered with a ceramic-coated dielectric 25b which is sealed with an inorganic material. Is. Alternatively, a combination may be used in which a conductive base material such as metal is coated with a lining-treated dielectric material provided with an inorganic material by lining. As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. are preferably used. Of these, borate-based glass is more preferably used because it is easy to process. Examples of the conductive base material such as metal include metals such as silver, platinum, stainless steel, aluminum and iron, and stainless steel is preferable from the viewpoint of processing. Alumina and silicon nitride are preferably used as the ceramic material used for thermal spraying. Among them, alumina is more preferably used because it is easy to process. The base material of the roll electrode is
A stainless steel jacket roll base material having a cooling means with cooling water can be used.

As a power source for applying a voltage to the applying electrode,
High frequency power supply (200k
Hz), a high frequency power supply manufactured by Pearl Industry (800 kHz), a high frequency power supply manufactured by JEOL Ltd. (13.56 MHz), a high frequency power supply manufactured by Pearl Industry (150 MHz) and the like can be used.

The distance between the electrodes is determined in consideration of the thickness of the solid dielectric material provided on the base material of the electrodes, the magnitude of the applied voltage, the purpose of utilizing plasma, and the like. The shortest distance between the solid dielectric and the electrode when the solid dielectric is installed on one of the electrodes, and the distance between the solid dielectrics when the solid dielectric is installed on both of the electrodes are uniform in all cases. From the viewpoint of discharging, it is preferably 0.5 mm to 20 mm, and particularly preferably 1 mm ± 0.5 mm.

A high-frequency voltage exceeding 100 kHz and a power of 1 W / cm ² or more are supplied between the electrodes facing each other to excite the reactive gas and generate plasma. By applying such a high-power electric field, it is possible to obtain a dense, highly functional thin film with high film thickness uniformity and high production efficiency.

The upper limit of the frequency of the high frequency voltage applied between the electrodes is preferably 150 MHz or less.
The lower limit of the frequency of the high frequency voltage is preferably 200 kHz or higher, more preferably 800 kHz or higher.

Further, the lower limit value of the electric power supplied between the electrodes is
It is preferably 1.2 W / cm ² or more, and the upper limit value is preferably 50 W / cm ² or less, more preferably 20 W / cm ² or less. The voltage application area (/ cm ² ) at the electrode refers to the area within the range where discharge occurs.

The value of the voltage applied to the electrode fixed by the power source is appropriately determined. Regarding the method of applying the power supply, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF which is intermittently called pulse mode may be adopted, but the continuous mode is more preferable. A dense and high quality film can be obtained.

In order to minimize the influence on the base material during the discharge plasma treatment, the temperature of the base material during the discharge plasma treatment is adjusted to a temperature between room temperature (15 ° C. to 25 ° C.) and less than 200 ° C. Is preferable, and more preferably at room temperature to 10
It is to adjust to 0 ° C. In order to adjust to the above temperature range, the electrode and the base material are subjected to discharge plasma treatment while being cooled by a cooling means, if necessary.

The above discharge plasma treatment is carried out at or near atmospheric pressure. Here, the term "atmospheric pressure" means 20 k.
Represents a pressure of Pa to 110 kPa, preferably 93 k
Pa to 104 kPa.

Further, in the discharge electrode according to the thin film forming method, JIS B on at least the side of the electrode in contact with the base material is used.
Maximum height of surface roughness specified by 0601 (Rma
x) is preferably adjusted to be 10 μm or less, more preferably the maximum value of the surface roughness is 8 μm.
It is below, and particularly preferably, it is adjusted to 7 μm or less.

The center line average surface roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.

In carrying out the thin film forming method, the gas to be used varies depending on the kind of the thin film to be provided on the substrate, but basically it is a mixed gas of an inert gas and a reactive gas for forming the thin film. Is. The reactive gas is preferably contained in the mixed gas in an amount of 0.01 to 10% by volume.

Examples of the inert gas include elements belonging to Group 18 of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc.
Argon is preferably used.

When a titanium compound is used in the mixed gas,
From the viewpoint of forming a uniform thin film on the substrate by the discharge plasma treatment, the content ratio of the titanium compound in the mixed gas is 0.
It is preferably 1 to 10% by volume, and more preferably 0.1 to 5% by volume.

Further, 0.1 to 1 hydrogen gas is added to the mixed gas.
By containing 0% by volume, the hardness of the thin film can be significantly improved, and 0.01 to 5% by volume of a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, and nitrogen. By doing so, the reaction can be accelerated, and a dense and high-quality thin film can be formed.

As the silicon compound and the titanium compound, metal hydrogen compounds and metal alkoxides are preferable from the viewpoint of handling, and metal alkoxides are preferably used because they are free from corrosiveness, generation of harmful gas, and little stains in the process. To be

In order to introduce the silicon compound and the titanium compound between the electrodes which are the discharge space, both may be in a gas, liquid or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, decompression, ultrasonic irradiation or the like. When a silicon compound or a titanium compound is used after being vaporized by heating, it is a liquid such as tetraethoxysilane or tetraisopropoxytitanium at room temperature and has a boiling point of 200.
A metal alkoxide having a temperature of ℃ or less is preferably used. The metal alkoxide may be used by diluting it with a solvent, and as the solvent, an organic solvent such as methanol, ethanol, n-hexane, or a mixed solvent thereof can be used.
Since these diluting solvents are decomposed into molecules and atoms during the plasma discharge treatment, their influence on the formation of a thin film on the substrate and the composition of the thin film can be almost ignored.

Examples of the silicon compound include organometallic compounds such as dimethylsilane and tetramethylsilane, metal hydrogen compounds such as monosilane and disilane, metal halogen compounds such as silane dichloride and silane trichloride, tetramethoxysilane and tetraethoxy. It is preferable to use silane, alkoxysilane such as dimethyldiethoxysilane, or organosilane, but not limited to these. Moreover, these can be used in appropriate combination.

When the above-described silicon compound is used in the mixed gas, the content of the silicon compound in the mixed gas is 0.1 to 10 volumes from the viewpoint of forming a uniform thin film on the substrate by the discharge plasma treatment. %, More preferably 0.1 to 5% by volume.

Examples of the titanium compound include organometallic compounds such as tetradimethylaminotitanium, metal hydrogen compounds such as monotitanium and dititanium, metal halogen compounds such as titanium dichloride, titanium trichloride and titanium tetrachloride, tetraethoxytitanium and tetra. It is preferable to use metal alkoxides such as isopropoxytitanium and tetrabutoxytitanium, but not limited to these.

In the present invention, a yarn made of an insulating material, a yarn forming a source line and a yarn forming a gate line are used, and the yarn forming the source line and the yarn forming the gate line intersect each other. A display electrode is formed in a region surrounded by the source line and the gate line on the woven fabric, and the channel and the display electrode are formed by contacting and intersecting a channel made of an organic semiconductor with a yarn forming the gate line. To form a matrix circuit for forming an active driving element, and sealing the circuit to form a liquid crystal element,
Since a display medium is manufactured by stacking it with a display element such as an electrophoretic element, an organic EL element, an electrochromic element, or an Eink, a sheet-shaped display medium can be easily obtained, and its practicality as a digital paper is guaranteed. it can.

As the yarn made of an insulating material, among the above-mentioned insulating layer materials, a yarn that can be made into a yarn by melt extrusion or the like, a yarn that can be made insulative by coating a yarn that serves as a base material, and a yarn that can be processed into a fibrous shape and can be spun. It can be optionally selected from those that can be made into threads.

As the thread forming the source line, a metal conductive wire, a metal vapor-deposited film or a film coated with metal particles, which is cut into a thread shape, or a thread made of the above-mentioned conductive polymer is used. it can.

The thread forming the gate line relates to the organic transistor element of the present invention, and can be obtained by coating the surface of the thread forming the source line with the above-mentioned insulating layer.

FIG. 6 schematically shows the structure of the TFT element of the present invention corresponding to one pixel. In the figure, the source line 6 woven by a thread 61 made of an insulating material, a thread forming the source line 62 and a thread forming the gate line 63.
2 and the gate line 63 intersect with each other, the display electrode 64 is formed in a region surrounded by the source line 62 and the gate line 63 on the fabric 60, and the channel 6 made of an organic semiconductor is formed.
The source line 62 and the display electrode 64 are connected to each other in such a manner that 5 touches and intersects the gate line 63.

The display electrode 64 may be formed by the above-mentioned photolithography method, vapor deposition or sputtering, or may be formed by patterning a paste of an electrode material, or may be formed by adhering a metal foil or the like.

The channel 65, an example of which is shown in an enlarged view in FIG. 7, can be formed by a photolithography method, an ink jet method or the like. In addition, when a dispersion or solution of a semiconductor channel material is ejected and attached by an ink jet or the like and dried to form a channel 65, it is permeated onto the thread 61 of the insulating material or into the thread 61 as shown in FIG. It is preferably formed by This allows channel 65
The cross-sectional area, width, and length are stabilized, and defects and disconnections can be prevented. In this case, it is preferable to enhance the permeability of the yarn 61 in advance by surface treatment or the like.

The control for driving each pixel of the display medium will be described below. (When the display element has no memory) source line 62,
A drive signal is transmitted to the gate line 63 corresponding to each pixel and applied as a drive current or a drive voltage. The source voltage Vs applied to the source line 62 is turned on before the pixel driving timing, but the gate line 63 is turned on before the source line 62 is turned on.
Has become. The display control corresponding to the unique characteristics of the organic semiconductor is realized by the timing control of the source line 62 and the gate line 63. That is, the current of the organic semiconductor channel 65 is cut off by applying a voltage to the gate line 63 in advance. As a result, electric charges flow into the display electrode 64 (drain electrode side) at the pixel drive timing.

After that, a predetermined voltage is held in the capacitor structure including the display electrode 64. An electric field is generated on the display electrode 64 by the voltage thus held, and the electric field acts on the display element to visually control the display drive of the corresponding pixel.

On the other hand, when the application of the voltage to the gate line 63 is cut off (OFF) again at the timing of erasing the electric charge of the display electrode 64, the electric charge accumulated in the capacitor structure including the display electrode 64 is released. That is, the display drive control for the display element is completed. The source voltage is OFF at this timing.

The source voltage Vs applied to the source line 62 (when the display element has a memory characteristic) is turned on before the pixel driving timing, but the gate line 63 is turned on. ON from before
Has become. That is, the control for driving a predetermined pixel is common.

On the other hand, when the display driving is finished, the source voltage Vs supplied to the source line 62 is made to have a polarity opposite to that in the driving in advance, and then the gate voltage Vg is turned off. This inverts the polarity of the charge stored in the capacitor structure. As a result, the directions of the electric fields on the display electrodes are opposite, and the state of the display element is changed.

[0101]

According to the present invention, a yarn made of an insulating material, a yarn forming a source line, and a yarn forming a gate line are used to form a woven fabric in which the source line and the gate line yarn intersect with each other. A matrix circuit is formed in which a display electrode is formed in a region surrounded by a source line and a gate line on a woven fabric, and a channel made of an organic semiconductor is brought into contact with the gate line to connect the source line and the display electrode to form an active driving element. A display medium is manufactured by preparing and stacking the circuit and laminating it with a display element such as a liquid crystal element, an electrophoretic element, an organic EL element, an electrochromic element, or an Eink, so that a sheet-shaped display medium is easily obtained. It is possible to guarantee the practicality as a digital paper.

Further, since the display medium itself is a woven fabric, it is possible to rewrite ornaments such as handkerchiefs and stalls in addition to the banners, banners, numbers, etc., which are usually produced by dyeing cloth.

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration corresponding to one display pixel of a TFT element using a Si semiconductor.

FIG. 2 is a model view showing a configuration of an organic transistor element of the present invention.

FIG. 3 is a block diagram showing a configuration of the entire sheet-shaped display medium.

FIG. 4 is a diagram showing a configuration of a display unit.

FIG. 5 is a diagram showing an equivalent circuit of each pixel.

FIG. 6 is a model view showing a configuration of a TFT element of the present invention corresponding to one pixel.

FIG. 7 is an enlarged view of an example channel.

FIG. 8 is a diagram showing another example of channels.

[Explanation of symbols]

1 substrate 2 Gate electrode 3 Source electrode 4 drain electrode 5 Conductive film 20 Organic transistor element (TFT driver) 21 channels 22 Gate electrode 23, 45 Insulation layer 41 Support 42 Display element 43 surface electrode 44 Adhesive layer 46 Transparent protective layer 50 equivalent circuit 60 textiles 61 Thread made of insulating material 62, 104 Power supply line (source line) 63, 105 Control signal line (gate line) 64, 101 Display (plate) electrode (display pixel section) 65 channels 100 display 103 capacitor 106 Vertical drive circuit 107 Horizontal drive circuit 108 control circuit 109 memory

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 29/78 618C 29/28 F term (reference) 2H092 JA24 JB23 JB32 KA09 KA12 KA13 KA18 MA04 MA05 MA13 NA25 PA01 5C094 AA15 AA43 AA48 AA56 BA03 BA21 BA41 CA19 DA06 DA13 DB01 DB04 EA04 EA07 EB10 FA04 FB01 FB14 5F110 AA30 BB01 BB02 CC07 CC10 DD01 EE01 EE02 EE03 EE22 EE50 FF01 FF02 FF21 GG05 QC02 GG02 HK02 HK02 HK02 HK02 HK02 HK02 HK02 HK02 HK02

Claims (7)

[Claims] 1. A gate having a channel made of an organic semiconductor that connects a source electrode and a drain electrode intersects with a gate electrode covered with an insulating layer via the insulating layer and covered with the insulating layer. An organic transistor element characterized in that the electrodes are thread-shaped. 2. An active drive element characterized by being driven and controlled by the organic transistor element according to claim 1. 3. A matrix circuit forming an element is woven into a woven fabric made of a thread made of an insulating material to form a source line and a gate line which intersect with each other, and a gate line. An active driving element characterized in that it has a channel made of an organic semiconductor that connects a drain electrode and a yarn that intersects with the yarn to form a source line. 4. A display medium which is display-controlled by the active drive element according to claim 2. 5. A matrix circuit forming an active driving element is woven into a woven fabric made of a thread made of an insulating material to form a source line and a gate line which intersect each other, and a gate line. A display medium comprising a channel made of an organic semiconductor for connecting a display electrode with a thread forming a source line by intersecting with a thread forming a film, and performing display control by the element. 6. The display medium according to claim 4, which has a sheet shape. 7. A woven fabric in which a yarn made of an insulating material, a yarn forming a source line and a yarn forming a gate line are used and the yarn forming the source line and the yarn forming the gate line intersect each other. A step of forming, 2) a step of forming a display electrode on the woven fabric, 3) a step of contacting a channel made of an organic semiconductor with a thread forming a gate line to connect the thread forming a source line to the display electrode,
A display medium manufactured through a step of sealing a matrix circuit forming an active driving element formed through the steps 1) to 3).