JPH03237435A - Bidirectional nonlinear resistance element and active matrix liquid crystal panel using bidirectional nonlinear resistance element and production thereof - Google Patents

Abstract

PURPOSE:To lower the specific dielectric constant of the insulating layer of MIM (metal insulator metal) elements and to obtain stable quality with ease of production by using an electrolyte contg. an org. compd. and forming the bidirectional nonlinear resistance element. CONSTITUTION:After an org. film having a high insulating characteristic is formed on a conductor, the same conductor as this conductor or the conductor of a different kind is formed on the org. thin film. This org. this film is synthesized by an electrolytic polymn. using at least a supporting electrolyte for the electrolyte or an electrolyte contg. the org. compd. soluble in the electrolyte. Namely, electrodes 2 having prescribed patterns are formed on one transparent substrate and thereafter the electrolytically polymerized films 1 having the high insulating characteristic are formed on the electrodes 2 by the electrolytic polymn. method; thereafter, a transparent electrode 3 is formed over the entire surface of the transparent substrate. The transparent electrode 3 is patterned to the prescribed patterns. The bidirectional nonlinear resistance element of a high yield and low cost having the image quality equiv. to the image quality of thin-film transistors is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The nonlinear resistance element of the present invention can be applied to any element requiring nonlinear resistance. For example, M I M is used as a switch reflex element for liquid crystal displays.
It can be applied as a (metal-insulator-metal) element, and can be used as a switching element for a liquid crystal display such as a display for a computer or a television.

[Conventional technology]

Currently, the image display methods of LCD televisions can be roughly divided into two types: simple matrix method and active matrix method. In the simple matrix method, a liquid crystal is sandwiched between two groups of strip-shaped electrodes arranged so that their directions are perpendicular to each other, and a drive circuit is connected to each of these strip-shaped electrodes. Since this method has a simple structure, it is difficult to realize a system with low 1ilfiI8, and there is a problem that the contrast is low due to crosstalk. In comparison, the active matrix method has a switch for each pixel to maintain the voltage, and even when driven in time division, the voltage at the time of selection is maintained, increasing the display capacity and offering better image quality characteristics such as contrast. On the other hand, the disadvantage is that the structure is complex and the manufacturing cost is high. For example, T P T (Thinrilo+ Tr
It is difficult to increase the yield by stacking 5 to 6 layers of groove films using 5 or more photomasks. Therefore, recently, the yield of active devices has been improved, and two-terminal devices with low manufacturing costs have become available. A typical two-end element is MI~1 (MeLal In
5ulator Metal). Its general +
The manufacturing process is shown in Figures 1 and 2. Conventional element insulating film (here, TaOx with anodized lower electrode) was used, but its dielectric constant is about 26, so under the conditions of general element size of 5 μm x 4 μm and anodic oxide film thickness of 600 A, the device cannot be used. The capacitance was as large as 0°1 pF, which was about 1/3 of the liquid crystal capacitance of one general pixel (200×20 (1 μm)).

However, when a voltage is applied to a 7-day product panel, the capacitance ratio between the product and the element is about 3, so the voltage is applied to 1 element, which deteriorates the voltage characteristics, and as a result, the panel The display quality also had the problem of being inferior to TPT panels.

Also, as can be seen from the manufacturing process in Figure 2, M I
The M element side substrate is manufactured by repeating photolithography and etching steps.

Therefore, although the manufacturing process is shorter than that of TPT, it causes a decrease in yield.

Further, as a film forming apparatus, a vacuum apparatus such as a sputtering apparatus is repeatedly used, resulting in a process with poor productivity.

[Problem to be solved by the invention]

As described above in the related art, (1) the display quality of the MIM panel is inferior to that of the TPT panel.

(2) ~i The IM manufacturing process is simpler than TPT, or more likely to result in a low yield due to the photolithography/etching process.

(3) Productivity is poor due to film formation process or vacuum process.

There are three issues.

An object of the present invention is to obtain an active matrix product panel having an image quality comparable to that of a TFT, a high yield, and a low cost nonlinear resistance element.

[Means to solve the problem]

The bidirectional nonlinear resistance element of the present invention is produced by insulating on a conductor in the synthesis of a six-layer thin film by electrolytic polymerization using an electrolytic solution or at least a supporting electrolyte, and an electrolytic solution containing an organic compound that is soluble in the electrolysis. This can be obtained by forming a highly conductive organic film and then forming a conductor of the same or different type as the conductor on the organic thin film. Also, active matrix? The liquid crystal panel uses bidirectional nonlinear resistance elements70,
Furthermore, apart from the basic manufacturing method of active matrix product panels, electrodes with a predetermined pattern are formed on one transparent substrate, and then a highly insulating electrolytic polymer film is formed on the electrodes using an electrolytic polymerization method. After that, a transparent electrode is formed on the entire surface of the transparent substrate, and a conductor/insulator/'conductor nonlinear resistance element is formed by patterning the transparent electrode in a predetermined pattern. It is characterized in that it is formed by bonding a transparent substrate on which electrodes are formed using a n-not-t4-o.

Electropolymerized films have various physical properties, and although diode properties are known, bidirectional nonlinear resistance elements are unknown.

The present invention provides an element having bidirectional nonlinear resistance, which is a characteristic not previously seen as an element using an electrolytic polymer film, and provides a method for manufacturing an active matrix panel using the element.

Next, the present invention will be explained step by step.

■ Forming a substance that becomes a conductor on a transparent substrate. As a conductor, A us A g % CU % N t %
Metals such as Cr-Ta1 and their a gold, 5n02, IT
It may be a transparent conductive film such as O or a semiconductor.

As the method of film formation, methods such as sputtering, vapor deposition, CVD, plating, etc. are used.

A conductor formed on a transparent substrate is formed into a predetermined pattern by photolithography and etching.

(2) Next, a method for forming an organic film on this conductor by electrolytic polymerization will be described.

The electrolytic polymerization solution contains at least Motsuma-1 to be polymerized.
and a supporting electrolyte, and a solvent in which monomers and supporting electrolytes are ij J soluble, such as water, alcohol, acetonitrile, and propylene carbonate, is used. If necessary, add PH buffer solution.

Examples of monomers include aniline, phenol, and other amino groups on the Hensen's ring, aromatic compounds with a hydroxyl group of H, heterocyclic compounds such as virol and thiophene, asuret, and pyrene. There are polycyclic hydrocarbons having more condensed aromatic rings, and h-carbohydrates having an unsaturated f11 ring, and any of these can be applied.

The supporting material has sufficient conductivity for electrolysis.
As long as it can be used as long as it is 2, for example, NaCgo 4,
L r C001, N a B F 4 , N a O
H.

H,SO,+, Na2504 (11,1~1m
.

1, /(I) Add so that it is 4 degrees.

Electrolytic modes for combining h-F8 materials include potential drag electrolysis, constant potential electrolysis, constant temperature current electrolysis, and alternating current electrolysis, but the present invention is not particularly limited thereto.

There are two methods for forming the highly insulating organic film of the present invention.

One method is to form a six-layer membrane by electrolytic polymerization and then remove ions contained in the membrane by detoping. As a dedoping method, after forming an organic film by electrolytic polymerization, ions in the film can be removed by applying a potential of opposite polarity in an electrolytic acid.

Another method is to form an electrochemically inactive film.

An electrochemically inert membrane can be obtained by appropriate combinations of electrolytic conditions, Ryukaku's conditions, electrode materials, etc.

For example, phenol and its dielectric can be electrolytically oxidized in a carbon electrode with an acetonitrile solution (supporting electrolyte NaCN04) to form an electrochemically active polymer film, or electrolytically oxidized in basic methanol to form an inert polyphenylene film. A film of nylene oxide is deposited.

Furthermore, when 1.25-aminobenzene is dissolved in a neutral solution, an electrochemically inactive film is formed.

At this time, the thickness of the white film is preferably 100 Å to 2 μm. 1 (If I CI A or less, the organic film will be porous and the conductor F on the organic film will be prone to short-circuiting. If it is more than 2 μm, even if the resistance is nonlinear, the resistance will be It becomes too large to be used as an active element in finished products or tunnels.

On the organic insulator thus obtained, sputtering,
A metal film having a predetermined thickness by means of vapor deposition, CVD, etc., such as Au, Ag, Cu, Pt, Ni, Co, etc.
Cr, Fe, Ta, Ti.

etc., metal oxides SnO2, In2O,, ZnO.

By forming a compound containing CdO, ZnS, CdS, CdSnO4, etc., a conductor/insulator/conductor nonlinear resistance element (two-terminal element) is formed.

There are several methods for forming active elements in addition to the basic process described above, and each method can manufacture the active matrix liquid crystal panel that is the object of the present invention. The manufacturing methods for each are described below.

1. One method is to form a conductive layer 11 with a predetermined pattern on a transparent substrate as shown in step 1 in Figure 4-a). The second step is to form a Ryukaku'1 monolayer film 12 with high insulating properties, and the third step is to form a conductor 13, which is the same as or different from the electrode material, in a predetermined pattern. A fourth step consists of forming a nonlinear resistance element of an insulator/conductor, and then forming a pixel 14 in the shape of FIG. 4(a)-4 using a transparent conductive film.

Also, by performing the first and fourth steps simultaneously, the fourth
An active element and a pixel having the cross-sectional shape shown in FIG. 3(C) may be provided.

FIGS. 4b) and 4c) are cross-sectional views of active elements formed by the manufacturing process of a), and 11 to 14 of b).
corresponds to number a). In 15 of C), a conductive layer and pixels are first formed using a transparent conductor, an electrolytic polymer film 16 is formed only on the conductive layer, and then a conductor 17 of the same or different type as the conductive layer is coated in a predetermined manner. (It was formed on the turn.

2. As another method, in the manufacturing process of a liquid crystal panel, the first method is to form electrodes with a predetermined pattern on the 16 brackets of -b' as shown in 11 of FIG. 1. This step is to form a transparent insulating film 12 on the entire surface of the transparent substrate or only on the electrode, and to form a contact hole 17 with the electrode in a predetermined portion of the insulating film. By removing the conductor 14, which is the same as or different from the electrode material f1, the third Lf, which forms the electropolymerized film 13 through the contact portion on the electrode, is placed in a predetermined manner.
The fourth king #1 formed in a Z-turn allows the conductor 2/
A nonlinear resistance element T of insulator 7/conductor is formed, and then pixel 1 is formed using a transparent conductive film in the shape shown in FIG. 5(a).
5, the fifth step is to form 5.

Furthermore, by performing the first and fifth steps at the same time and forming contact holes on the electrodes and pixels in the second step, the active element and pixel having the cross-sectional shape shown in FIG. 5(c) can be formed. It's okay.

FIGS. 5b) and 5c) are cross-sectional views of the active element formed by the process of a), and 11 to 15 in b) correspond to the numbers in a).

In C), after forming 16 electrodes and 15 pixels at the same time using a transparent conductor, forming an insulating film of 2, forming 17 contact holes, forming 13 electropolymerized films through these, and forming 14 An active element is formed by forming a conductor.

In this process, a conductor is formed in a predetermined pattern and then a transparent insulating film is coated on the substrate. A contact hole with the conductor layer is formed in a predetermined part of the insulating film (
Figure 5(a)). The insulating layer may be coated over the entire surface, or may be partially coated as shown in FIGS. 5(b) and (C).

As the transparent insulating film +40, for example, Epoquine resin,
Examples include acrylic resin, polyimide resin, polyamide resin, polyvinyl resin, nylon resin, polyester resin, acetate resin, and phenoxy resin. Further, the insulating film may be formed by a dehydration condensation reaction of a standby metal compound. Examples of organometallic compounds include those having central metals such as silico, titanium, tantalum, chromium, atreminium, indium, tungsten, molybdenum, fluoronium, and germanium.

These insulating films may be of a thermosetting type or of an ultraviolet curing type. Methods for forming the insulating film include offset printing, flexible printing 11, and screen printing, in which contact holes are formed on the surface of the coating of the insulating film.

Alternatively, contact holes may be formed by photolithography and etching after forming an insulating film over the entire surface.

The following is a process equivalent to the basic process.

3. In the second process, that is, as shown in FIG. 5, the conductor in the fourth step may be a transparent conductive film, and the conductor/insulator/conductor nonlinear resistance element and pixel may be formed at the same time. .

Next, an explanation will be given using an example.

[Example 1] An electropolymerized membrane was prepared by dissolution using propylene carbonate containing 0.1 moN/Ill of N-methylpyrrole and 0.5 moN/R of sodium perchlorate as a solvent for 7 days. ITO (indium soot oxide) formed by vapor deposition on a glass substrate was used as a base electrode for forming a nonlinear resistance element.

On this ITO electrode, a diameter of 3
The 00 μm hole and the contact portion with the external electrode were covered.

Electrolytic polymerization was carried out using the ITO electrode thus obtained as a test electrode, a platinum electrode as a counter electrode, and a silver oxide electrode as a reference electrode. The electrolytic conditions were as follows: constant potential polymerization was carried out at +0.9 V with respect to the reference electrode, and after forming a poly-N-methylpyrrole film 5000A, sufficient detonation was performed at -0.45 V with respect to the reference electrode. As a result, the electropolymerized film became an insulating film.

ITOWA is applied by sputtering onto the electropolymerized film.
was deposited to form a MIM element, and its IV characteristics were evaluated. Figure 6 shows its characteristics. As you can see from the diagram,
Bidirectional resistance nonlinearity was obtained regardless of the polarity of the ground electrode.

[Example 2] Virol C), 2mo (1/p lithium perchlorate 0.2mo17/R) dissolved in propylene carboxylate was used as in-mold IL#1. Same as Example 1. The M I tv1 device was formed using the method described above, but constant current electrolysis was used under the conditions of electrolysis.

FIG. 7 shows the IV characteristics of this MI element.

As can be seen from the figure, bidirectional resistance nonlinearity was obtained regardless of the polarity of the underlying electrode.

[Example 3] 2.6 dimethylphenol 0.05 moi)/'F sodium hydroxide 0. 3 mop/, Q dissolved in methanol was used. Thereafter, an ITO electrode was formed in the same manner as in Example 1, and constant potential electrolysis was performed at +22V. The end point of electrolysis was defined as the point at which current no longer flows.

An ITO film was formed by sputtering on the obtained polymer film to form an MIM element, and its IV characteristics were evaluated. Figure 8 shows its characteristics. As can be seen from the figure, bidirectional resistance nonlinearity was obtained regardless of the polarity of the underlying electrode.

[Example 4] Phenol 0.05 m oQ / (1
A solution of 0.3 mol/1 sodium hydroxide dissolved in methanol was used. Hereinafter, an MIM element was formed in the same manner as in Example 3, and the ■V characteristics were evaluated. As a result, bidirectional resistance nonlinearity was obtained as in the other embodiments.

[Example 5] In the same manner as in Example 4, poly-N-methylvirol was added to 1
A micrometer-sized layer was formed and the IV characteristics were evaluated. Resistance nonlinearity similar to Actual Example 1 was obtained.

[Example 6] ITO (IncHum Tin Oxid) having a plurality of row electrode patterns was formed by sputtering on a glass substrate.
e) Film] 500 A was formed.

As an electrolytic polymerization wave, (however, a solution containing brohylene carbonate) was prepared and nitrogen bubbling was performed. A platinum plate was used as a counter electrode, and a silver oxide electrode was used as a reference electrode. The above-mentioned glass substrate with ITO was immersed in this at a constant potential of +1. OVte1
After performing electrolytic polymerization for 5 minutes to form a poly-N-methylpyrrol film of approximately 4000 layers on ITO, dedoping was performed at -0.8V. Dedoping was carried out until the current reached O.

Thereafter, after washing with pure water and drying at 120° C., an ITO film with a thickness of 500 mm was formed on the entire surface of the glass substrate by sputtering.

This ITO film was photolithographically etched as shown in Figure 3 (
a) Perform patterning to the element shape shown in (b),
Elements were formed at predetermined positions on a plurality of row electrodes.

As a counter substrate to this substrate, a glass substrate provided with a plurality of ITO column electrodes was bonded through a predetermined liquid crystal panel manufacturing process to manufacture an active matrix liquid crystal panel.

When this liquid crystal panel was driven using the same drive circuit as a conventional tvIIM panel and the contrast was determined by DI, it was found that the contrast was increased compared to the conventional panel.

This means that the dielectric constant of poly-N-methylpyrrole is Ta
This is thought to be due to the fact that it is smaller and thicker than 0xllN.

[Example 7] An electrolyte solution dissolved in tutanol was used. Example 1 below
+2,2■ on the ITO electrode on the glass substrate using the same method as above.
Constant potential electrolysis was performed to form an electrolytically polymerized film. The electrolysis completion point was defined as the point where the current became zero.

Hereinafter, one active matrix IL panel was manufactured in the same manner as in Example 6, and as in Example 1, the conventional M
I found that the contrast was amplified compared to the I~1 panel.

[Example 8] When an active matrix liquid crystal panel was manufactured in which the thickness of the electrolytic heavy film was increased to 1000 mm according to Example 6, the same results as in Example 6 were obtained.

[Example 9] A Ta film having a plurality of row electrode patterns was formed on a glass substrate by sputtering into a shape of 15 (10A).

As an electrolytic polymerization wave, 0.1 mol of N-methylpyrrole/0.5 moN/ff of lithium perchlorate (a solution containing propylene carbonate) was prepared, and nitrogen bubbling was performed. A platinum plate was used as a counter electrode, and a silver oxide electrode was used as a reference electrode. The Ta-coated glass substrate was immersed in this solution at a constant potential of +1. Electrolytic polymerization was carried out for 15 minutes in OV to form a poly-N-methylpyrrole film on Ta with a thickness of about 40%.
After forming 0.00 people, dedoping was performed at -0.8V.

Dedoping was performed until the current became zero.

Thereafter, after washing with pure water and drying at 120° C., a Cr alloy film was formed on the entire surface of the glass substrate by sputtering to a thickness of 50 ()A.

This Cr/1 gold film is photolithographically etched to form a fourth layer.
Patterning was performed to form the element shape shown in Figure (a)-3, and the elements were formed at predetermined positions on a plurality of row electrodes.

Next, I TO (
An indium tin oxide) film was formed to a thickness of 500 mm.

As a counter substrate to this substrate, a glass substrate provided with a plurality of ITO column electrodes was bonded together through a predetermined liquid crystal panel manufacturing process to manufacture an active matrix liquid crystal panel.

When this liquid crystal panel was driven using the same drive circuit as a conventional MIM panel and its contrast was measured, it was found that the contrast was increased compared to the conventional panel.

This is the dielectric constant of poly-N-methylpyrrole or Ta
This is thought to be due to the fact that it is smaller and thicker than the Ox film.

[Example 10] 2.67 methylphenol 0.05rr+og/g sodium hydroxide 0.3 mon/1 dissolved in methanol was used as the electric carp liquid. In the same manner as in Example 1, constant potential electrolysis was performed on a Ta electrode on a glass substrate at +2.2 V to form an electrolytically polymerized film. The electrolysis end point was defined as the point where the current became zero.

An active matrix liquid crystal panel was manufactured in the same manner as in Example 1. As in Example 9, the conventional MI
It was found that the contrast was improved compared to the M panel.

[Example 11] ITO film (Indium Tin Oxide) with multiple row electrode patterns formed by sputtering on a glass substrate
2,000 people formed a membrane.

As electrolytic polymerization solutions, N-methylpyrrole 0.1 mog/i) lithium perchlorate 0°'5 moD/D (dissolved acid containing propylene carbonate) were prepared, and nitrogen bubbling was performed. A platinum plate was used as a counter electrode, and a silver oxide electrode was used as a reference electrode. The above-mentioned glass substrate with ITO was immersed in this at a constant potential of +1. After electrolytic polymerization was carried out for 15 minutes at OV to form a poly-N-methylpyrrole film of about 400 OA on the ITO, dedoping was carried out at -0.8V.

Thereafter, after washing with pure water and drying at 120° C., a Cr alloy film with a thickness of 500 A was formed on the entire surface of the glass substrate by sputtering.

This Cr alloy film is etched by photolithography and etching.
(a) (b) When patterning was performed in the element shape shown in the figures and elements were formed at predetermined positions on a plurality of row electrodes, the same results as in Example 6 were obtained.

[Example 12] A 1500 Ta film having a plurality of row electrode patterns was formed on a glass substrate by sputtering.

On top of this, an epoxy acrylate resin "SO Clear" manufactured by Okuno Pharmaceutical Co., Ltd. was coated with a 2 μm 1v layer as a transparent insulating film using a spin cord, and then U, V was applied through a photomask with a predetermined pattern. , exposure was performed. As a result, a contact hole with the ITo turtle tM was created. The diameter of the contact hole was 1.0 μm.

Next, prepare an electrolytic polymerization solution (a solution containing propylene carbonate),
I did a nitrogen hub link.

A platinum plate was used as a counter electrode, and a silver oxide electrode was used as a reference electrode. The Ta-coated glass substrate was immersed in this solution at a constant potential of +1. Poly-N-
After forming a methyl pyrrole film on ITO with a thickness of about 400 OA, dedoping was performed at -0.8 V. Detoping was carried out until the current became zero.

Thereafter, after washing with pure water, it was dried at 12r1°C, and a C1 film was formed on the entire surface of the glass substrate by sputtering to a thickness of 5 OA.

This Cr film was patterned by photolithography and etching into the element shape shown in FIG. 5, and elements were formed at predetermined positions on a plurality of row electrodes.

Next, ITO was applied onto this element in the shape shown in FIG.
(Indium Tin 0w1de) film at 50C]
A glass substrate having a plurality of ITO column electrodes was bonded thereto as a counter substrate to this substrate through a predetermined manufacturing process of a finished product panel, thereby manufacturing an active matrix liquid crystal panel.

When we drove this liquid crystal panel using the same drive circuit as a conventional MIM panel and measured the contrast, we found that
It was found that the contrast was improved compared to conventional panels.

This is the dielectric constant of poly-N-methylpyrrole or Ta
This is thought to be due to the fact that it is smaller and thicker than the Ox film.

[Mitume Example 13] As an electrolytic compound, a solution dissolved in methanol was used. In the same manner as in Example 1, +2.
Constant potential electrolysis was performed at 2V to form an electrolytic polymer film. The electrolysis end point was defined as the point where the current became O.

Below, an active matrix liquid crystal panel was manufactured in the same manner as in Example 12.
I found that the contrast was improved compared to the IM panel.

[Example 14] ITO (Indius Tin) with a plurality of row electrodes and pixel patterns formed by sputtering on a glass substrate
A film of 200 OA was formed. Thereafter, an insulating film and contact holes were created in the same manner as in Example 1.

As an electrolytic polymerization solution, a solution containing propylene carbonate was prepared and subjected to nitrogen huffing. A platinum plate was used as a counter electrode, and a silver oxide electrode was used as a reference electrode. In this, the above I
Immerse the glass substrate with T O at a constant potential of +1°QV.
Electrolytic polymerization was performed for 5 minutes to form a poly-N-methylpyrrol film of about 400 OA on the ITO through the contact hole, and then dedoping was performed at 0.8V. Dedoping is
I continued until the current reached 0.

Thereafter, after washing with pure water and drying at 120° C., a Cr alloy film with a thickness of 500 A was formed on the entire surface of the glass substrate by sputtering.

This Cr alloy film was patterned by photolithography and etching into the element shape shown in FIG. 5, and elements were formed at predetermined positions on a plurality of row electrodes.

An active matrix liquid crystal panel was manufactured using this substrate in the same manner as in Example 12, and similar results were obtained.

[Example 15] A plurality of row electrode patterns were formed on a glass substrate using S/Z ivy.
0xide) Membrane 15 fl (1 person 1 f two sides t2.

On top of this, Okuno Pharmaceutical Co., Ltd.
A 5rs epoxy acrylate resin, "SO Clear" was coated with a spin cord to a thickness of 2 μm, and then UV exposure was performed through a photomask having a predetermined pattern. In this way, a contact hole with the ITO71i electrode was created. The diameter of the collect hole is IC
It was 1um.

Next, as an electrolytic polymerization solution, ((Il, molten acid containing L-brobylene carbonate) was prepared, and nitrogen bubbling was performed.

A platinum plate was used as a counter electrode, and a silver oxide electrode was used as a reference electrode. The glass substrate with ITO was infiltrated into this solution at a constant potential of +1. Electrolytic polymerization was performed in OV for 15 minutes to obtain poly-N
- After a methylpyrrole film was formed on ITO at a strength of approximately 4000 A, detoping was performed at -0.8V. The tax tope went until the current became zero.

Thereafter, it was washed with pure water, dried at 120° C., and an ITO film having a thickness of 500 A was formed on the entire surface of the glass substrate according to the specifications.

This ITO film was patterned into the element shape shown in FIG. 9 by photolithography and etching, and elements were formed at predetermined positions on the row electrodes of several stages.

A glass substrate provided with a plurality of ITO column electrodes was attached as a χ1-oriented substrate of this substrate through a predetermined 7-day panel manufacturing process to manufacture an active matrix liquid crystal panel.

When this liquid crystal panel was driven using the same drive circuit as a conventional MIM panel and its contrast was measured, it was found that the contrast was ablated compared to the conventional Gunelle panel.

This means that the dielectric constant of poly-N-methylpyrrole is Ta
This is thought to be due to the fact that the film is smaller and thicker than the Ox film.

[Example 15] An active element was formed using the same process as in Example 15.

As the electrolyte, 2.6 dimethylphenol and 0. 05m ail /(
1 + sodium oxide 0. 3 mol/I)
was dissolved in methanol and alcohol.

Constant potential electrolysis was carried out at an electrolytic potential of -I-2.2V to conduct electropolymerization and form a film. The electrolysis end point was defined as the point where the current became zero.

Thereafter, an active matrix liquid crystal panel was manufactured in the same manner as in Example 15, and as in Example 1, the conventional Mr.
It was found that the contrast was improved compared to the M panel.

[Example 17] In Example 15, an active matrix liquid crystal panel was manufactured in which the electropolymerized film had a thickness of 100 OA, and the same results as in Example 15 were obtained.

[Example 18] Pyrex 7059 manufactured by Konink, thickness 0°9 mm
on a glass substrate 30 with a thickness of 15 mm using a Svanta apparatus.
An ITO film of 00A was formed. This is etched into a predetermined pattern through a photolithography process, resulting in a width of 15 cm.
A 5 mm wiring was obtained.

On top of this, an epoxy acrylate resin "SO Clear" manufactured by Okuno Pharmaceutical Co., Ltd. was coated as a transparent insulating film (2) to a thickness of 3 μm using a spin cord, and then a predetermined pattern was formed by a photolithography process. This pattern is
Contact holes are formed on the wiring at predetermined intervals. The diameter of the contact hole was 18 μm.

Next, an electrolytic polymer film of poly-N-methylpyrrole was formed on the ITO wiring through this contact hole (not shown, but provided at the position of the electrolytic polymer film 13). The polymerization conditions were as shown in Example 1, and the thickness of the polymerized film was about 5000A.

thus? An ITO film with a thickness of 600 A was formed on the substrate with a thickness of 17 mm on each side using a sputtering device, and etched into a predetermined pattern through a photolithography process.
A pixel electrode 6 of 0 μm was obtained, and an MIM element portion was formed.

Next, an ITO film-32 with a thickness of 1500A was formed on a Pyrex 7 (159 glass substrate manufactured by Konink Co., Ltd.) and a thickness of 0.9mm using a sputtering device as a χ 1-sided substrate to form a predetermined pattern. , 21-sided glass substrate 31
) on the wiring 32 and the pair of pixel electrodes.

The two substrates (MIM elemental f substrate,
21-sided M board) Amionra; 5H602n (Nippon Soda■
(manufactured by) fl, 1? . After dipping in aqueous solution, washing,
After firing at 180'C, rubbing was carried out for orientation treatment.

As a cell gear knob holding material, a thermosetting epoxy resin containing glass fiber with a diameter of 6 μm is used as a sealant 31.
A liquid crystal cell having an MIM element was obtained by bonding the MIM element substrate and its facing substrate together and press-bonding them at 150° C. for 3 hours.

A liquid crystal 33 was sealed in this liquid crystal cell by a vacuum sealing method. For the composition of the ia product, PCH (phenylonclohexane) liquid crystal ZLI-1695 manufactured by Merck II' was used.

A liquid crystal display panel (LCD) was completed by attaching polarizing plates 9 to the upper and lower surfaces of this liquid crystal cell.

When this product display panel was driven with a circuit similar to that of a conventional MIM panel, sufficient display characteristics were obtained at a duty of 1/480.

〔Effect of the invention〕

As explained above, according to the present invention, by forming a bidirectional nonlinear resistance element using an electrolytic ill containing an organic compound, it is possible to lower the dielectric constant of the insulating layer of the MIM element. , and the thickness of the insulating layer is also the same as that of the conventional MI
The thickness can be set to be equal to or thicker than the M element, making it easy to manufacture and providing stable quality.Furthermore, when the liquid crystal panel is closed, the contrast ratio is increased and the image quality is improved.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a conventional MIM element. FIG. 2 is a diagram comparing the conventional process for forming active elements and the basic process of the present invention. (a) A diagram showing a conventional professional system. (b) A diagram showing the basic process of the present invention. FIG. 3 is a diagram showing an active element of the present invention. (a) A sectional view of an active element of the present invention. (b) A front view of an active element and a pixel of the present invention. FIG. 4 is a diagram showing the manufacturing process and structure of the two-terminal R element of the present invention. (a) Manufacturing process diagram of the present invention. (b) A cross-sectional view of the two-terminal element of the present invention. (c) A cross-sectional view of the two-terminal element of the present invention. FIG. 5 is a diagram of a two-terminal element of the present invention. (a) Diagram of the formation process of the two-terminal element of the present invention. (b) A cross-sectional view of the two-terminal element of the present invention. (C) A cross-sectional view of the two-terminal element of the present invention. FIG. 6 is an IV characteristic diagram of the ~11M element of Example 1. FIG. 7 is a ■-■ characteristic diagram of the MIM element of Example 2. FIG. 8 is an IV characteristic diagram of the MIM element of Example 3. In each figure, the broken line shows the IV characteristic when the polarity of the base electrode on the substrate side is negative, and the solid line shows the IV characteristic when the polarity is positive. FIG. 9 shows the active element of the present invention, in which a) is a sectional view and b) is a front view. FIG. 10 shows a cross-sectional view of a liquid crystal panel using the bidirectional nonlinear resistance element of the present invention. 11 ・ 12 ・ 13 ・ 14 ・ 15 ・ 16 ・ 17 ・ 30 ・ Conductor (wiring) Insulator Dragon Kaku q Polymer film conductor ITO (pixel electrode) ITO (wiring) Contact hole glass substrate 31 ・ ・ Sealing agent 32 ・ ・ ・Electrode 33 ・ ・ ・Finished product or better Distributed by Seiko Epnon Co., Ltd.

Claims (1)

[Claims] 1. A highly insulating organic film formed on a conductor using an electrolytic solution or at least a supporting electrolyte, an electrolytic solution containing an organic compound soluble in the electrolytic solution, and a highly insulating organic film formed on a conductor on the organic thin film. A bidirectional nonlinear resistance element characterized by forming conductors of the same or different type. 2. The bidirectional nonlinear resistance element according to claim 1, wherein the organic film has a thickness of 100 Å to 2 μm. 3. An active matrix liquid crystal panel using a bidirectional nonlinear resistance element, characterized in that the bidirectional nonlinear resistance element according to claim 1 is used. 4. After forming an electrode with a predetermined pattern on one transparent substrate, a highly insulating electrolytic polymer film is formed on the electrode by an electrolytic polymerization method, and then a transparent electrode is formed on the entire surface of the transparent substrate. After forming a conductor/insulator/conductor nonlinear resistance element by patterning a transparent electrode in a predetermined pattern, it is bonded to a transparent substrate on which a transparent electrode with a predetermined pattern is formed using a sealing material. A method for manufacturing an active matrix liquid crystal panel using a bidirectional nonlinear resistance element characterized by: 5. The first step is to form an electrode with a predetermined pattern on the transparent substrate. The second step is to form a highly insulating electrolytic polymer film on the electrode using the electrolytic polymerization method. Alternatively, a third step of forming different conductors in a predetermined pattern forms a conductor/insulator/conductor nonlinear resistance element, and then a fourth step of forming pixels using a transparent conductive film. 5. A method of manufacturing an active matrix liquid crystal panel using a bidirectional nonlinear resistance element according to claim 4, comprising the steps of: 6. The method for manufacturing an active matrix liquid crystal panel using a bidirectional nonlinear resistance element according to claim 5, wherein the first and fourth steps are performed simultaneously to provide an active element and a pixel. . 7. The first step of forming an electrode with a predetermined pattern on one transparent substrate, a transparent insulating film is formed on the entire surface of the transparent substrate or only on the electrode, and the electrode is formed on a predetermined part of the insulating film. The second step is to form a contact hole with the electrode, and the third step is to form an electrolytic polymer film on the electrode through the contact hole using an electrolytic polymerization method. A fourth step of forming a pattern to form a conductor/insulator/conductor nonlinear resistance element, followed by a fifth step of forming pixels using a transparent conductive film. A method of manufacturing an active matrix liquid crystal panel using the bidirectional nonlinear resistance element according to claim 4. 8. The bidirectional nonlinear device according to claim 7, wherein the first and fifth steps are performed simultaneously, and in the second step, a contact hole is formed in the electrode to provide an active element and a pixel. A method for manufacturing an active matrix liquid crystal panel using resistive elements. 9. The bidirectional nonlinear resistance element according to claim 7, wherein the conductor in the fourth step is a transparent conductive film, and the conductor/insulator/conductor nonlinear resistance element and the pixel are simultaneously formed. A manufacturing method of an active matrix liquid crystal panel using the method. 10. A first step of forming an electrode with a predetermined pattern on a transparent substrate. A second step of forming an electrolytic polymer film on the electrode by an electrolytic polymerization method. A transparent insulating film is coated on the entire surface of the transparent substrate. Alternatively, a third step is to form a contact hole with the electrolytic polymer film on the electrode in a predetermined portion of the insulating film, and dedope the electrolytic polymer film through the contact hole to insulate the insulating film. a fourth step of obtaining an electropolymerized film with high resistance; a fifth step of forming a conductor that is the same as or different from the electrode material into a predetermined pattern; the nonlinear resistance of the conductor/insulator/conductor is reduced; 1. A method for manufacturing an active matrix liquid crystal panel using a bidirectional nonlinear resistance element, comprising forming an element and then forming a pixel using a transparent conductive film. 11. Claim 10, wherein the electrode material on the transparent substrate is a transparent conductive film, and the electrode and the pixel are formed at the same time.
A method for manufacturing an active matrix liquid crystal panel using the bidirectional nonlinear resistance element described above.