JPS61138236A - Display element - Google Patents

Abstract

PURPOSE:To obtain the titled element having a high density, a high resolution display, a high speed and sensitivity display by constituting the titled element with a monomolecular film or a built-up film composed of a polydiacetylene derivative having a hydrophilic and a hydrophobic groups in a molecule. CONSTITUTION:An indium-tin oxide film (ITO) having about 2,000Angstrom in thickness is formed on a surface of a glass substrate 13 by a sputtering method. A down side electrode 14 is prepared by coating the obtd. film with a photoresist, and by backing a stripped wiring pattern followed by etching the obtd. pattern to remove selectively a surplus ITO film. A tantalum nitride film having about 1,000Angstrom in thickness is laminated on the layer 14 according to the sputtering method. By repeating the above described treatment, the heating layer 15 is formed by laminating a lattice dot pattern on the obtd. film. An upper side electrode is formed by providing a stripped wiring on the layer 15 intersecting perpendicularly to the layer 14. The display layer 17 is formed on the substrate of the upper side layer.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Technical Field The present invention relates to a display element that performs display using chemical or physical changes in a monomolecular film of a diacetylene rust conductor compound or a cumulative film thereof.

(2) Background technology Conventional 1 display elements include LEDs, CRTs, liquid crystal devices (hereinafter referred to as LCDs), and electrochromic devices (hereinafter referred to as ECDs).
- Electroluminescent devices (hereinafter referred to as ELDs) are known. Among these, LC is a small and high-density element.
Examples include DΦECD-ELD.

However, these devices had a number of drawbacks as shown below.

1. The film is thick and has a complicated layer structure.

2. Electrode wiring is complicated.

3. Not suitable for ultra-high density/large area.

Furthermore, The LCD is There is a perspective bond.

Response speed is slow.

ECD is Since electrolyte is used, cells must be assembled.

This is an oxidation-reduction reaction in the electrolyte and easily reacts with impurities.

Lack of safety.

E.L.D. Brightness is low.

Each of these has their own problems.

The drawbacks of such conventional examples are solved, and 1) various functional films can be produced relatively easily. 2) At that time, various functions of functional molecules are not lost or 3) In the above-mentioned thinning process, the membrane constituent molecules can be formed into a film in such a way that the film can be expressed at a high level in the in-plane direction without any special a-operation. As a result of various studies on how to orient the material with an ordered structure, the present invention was completed. Moreover, by using such a film forming method, it has become possible to easily provide a display element with high sensitivity and high resolution with high quality.

(3) Disclosure of the Invention An object of the present invention is to provide a high-density display element that causes chemical or physical changes in molecular units or molecular groups due to external factors.

Another object of the present invention is to provide an element that is superior to conventional examples with regard to molecular orientation within the plane of the element, which is an important factor when performing high-density recording in units of molecules or groups of molecules. A further object of the present invention is to provide elements having various properties by relatively simple operational changes in manufacturing the display element.

The above object is achieved by the present invention as described below.

The substance constituting the display layer of the present invention has a woody site in its molecule,
It consists of a molecule having at least one hydrophobic site and at least one diacetylene site (hereinafter referred to as a diacetylene derivative compound).

General formula Horse-CmiC-CmiC-R,,-XX
;! l Aqueous site, R2; Hydrophobic site C-C-C; Represented by diacetylene site, examples of hydrophilic sites include hydroxyl group, carboxyl group, amine group, nitrile group, thioalcohol group, imino group , a sulfone group, a sulfinyl group, or a salt thereof. As hydrophobic sites, horse and L
! L7) A long-chain alkyl group having a total number of carbon atoms of 10 to 30 is preferred.

One example of a method for creating a monomolecular film or a monomolecular cumulative film of such a diacetylene derivative compound is I,
The Langmuir-Blodgett method (hereinafter referred to as LB method) developed by Langmuir et al. is used. In the LB method, for example, in a molecule with a structure that has a lignophilic site and a hydrophobic site, when the balance between the two (amphiphilic balance) is maintained appropriately, the molecule has a hydrophilic group on the water surface. This is a method of creating a monomolecular film or a cumulative film of monomolecular layers by utilizing the fact that the monomolecular layer forms downward. When the monomolecular layer on the water surface has the characteristics of a two-dimensional system and zero molecules are sparsely dispersed, the two-dimensional ideal gas equation, πA=kT, is established between the area per molecule A and the surface pressure π. where k is Portzmann's constant and T is the absolute temperature. If A is made sufficiently small, the intermolecular interaction will be strengthened, resulting in a two-dimensional solid "solid film (or solid film)." The condensed film can be transferred one by one onto the surface of carriers having various materials and shapes, such as glass substrates. As a specific method for producing a monomolecular film or a cumulative film of monomolecular layers of the diacetylene derivative compound of the present invention using this method, for example, the following method can be mentioned.

The desired diacetylene derivative compound is dissolved in a solvent such as chloroform. This solution of the diacetylene derivative compound is spread on the aqueous phase 10 using the apparatus shown in FIGS. 1(a) and 1(b) to form the diacetylene derivative compound in the form of a film.

Next, in order to prevent this spread layer from spreading freely on the water phase and spreading too much, a partition plate (or float) 3 is provided to limit the spread area and control the aggregation state of the membrane material. Obtain the surface pressure. This partition plate 3 is moved to reduce the developed area to control the state of aggregation of the film material, gradually increasing the surface pressure, and setting the surface pressure suitable for producing a cumulative film.

By gently raising and lowering the clean carrier 11 vertically while maintaining this surface pressure, a single molecule of diacetylene derivative compound IN! (hereinafter referred to as a diacetylene monolayer) is transferred onto the carrier 11. A diacetylene monomolecular film is produced as described above, and by repeating the above operations, a desired cumulative number of diacetylene monomolecular cumulative films can be formed. In order to transfer the diacetylene monomolecular film onto the carrier, in addition to the vertical seeding method described above, methods such as the horizontal deposition method and the rotating cylinder method can be used. The horizontal attachment method is a method in which the carrier is transferred by contacting it horizontally with the water surface.
The rotating cylinder method is a method in which a cylindrical carrier is rotated on the water surface and transferred to the carrier surface. In the vertical seeding method described above, when a carrier with a wood-philic surface is lifted out of water in a direction across the water surface, a diacetylene monomolecular film with the hydrophilic groups of the diacetylene derivative compound facing the carrier is formed on the carrier. .

As mentioned above, when the carrier is moved up and down, diacetylene monolayers are piled up one by one in each process.The direction of the film-forming molecules is reversed in the pulling process and the seeding process, so this method A Y-shaped film is formed between the layers, in which the parent group and the hydrophobic group of the diacetylene derivative compound face each other.In contrast, in the horizontal adhesion method, a diacetylene monomolecular film with the hydrophobic group of the diacetylene derivative compound facing the carrier is formed on the carrier. is formed.

in this way.

Even when accumulated, there was no change in the orientation of the film-forming molecules, and in all cases, an X-shaped film was formed with the hydrophobic group facing the carrier side.On the contrary, in all layers, the parent group was facing the carrier side. The cumulative film is called a Z-type film.

The method of transferring the monolayer onto the carrier is not limited to these, but when using a large area carrier.

A method may also be used in which the carrier is extruded from a carrier roll into the aqueous phase. Furthermore, the orientation of the aforementioned parent wood group and hydrophobic group toward the carrier is a general rule, and can be changed by surface treatment of the carrier.

The diacetylene monomolecular film and diacetylene monomolecular cumulative film formed on the carrier by the above-mentioned method have high density and a high degree of order, and by composing the display layer with these films, high A recording medium having a high density and high resolution display function can be obtained.

The display element formed as described above changes its absorption wavelength due to light, heat, or solvent, and its apparent color changes.

Ultraviolet heat Heat Heat Colorless - blue -> red - yellow - or solvent When the film is initially colorless and transparent, it turns blue when irradiated with ultraviolet rays, and the maximum absorption wavelength becomes 82G" f180 nm. This change causes the ultraviolet rays to It is caused by irradiation, not by heat or solvent, and is an irreversible change.
Once a film becomes blue, it does not return to a colorless and transparent film.

Next, by heating this blue film to approximately 50° C. or treating it with a solvent such as acetone or ethanol, it becomes a red film, and the maximum absorption wavelength changes to approximately 540 nm. This change is also irreversible.

Furthermore, when this red film is heated to approximately 300° C., a yellow film is obtained, the maximum absorption wavelength of which is approximately 450 nm. The yellow film returns to its original red color at room temperature.

The present invention uses a monomolecular film of polydiacetylene, which has become a red film through the above-mentioned line treatment, or a cumulative film thereof, as a display element.

According to the display element of the present invention, one display image is obtained by heating a predetermined position of the monomolecular film or its cumulative film in accordance with the information signal to cause a color change.

- Since the color-changed portion returns to its original color upon cooling, playback and moving images are possible.

An example using the above-mentioned change in absorption wavelength will be described below.

Example 1 [Manufacture of display element] In FIG. 2, on the surface of a sufficiently clean glass substrate 13,
2000A thick indium tin oxide (I
TO) film was formed by sputtering method. continue,
A photoresist was applied to this film-formed surface, and a striped wiring pattern of 1B wood/-■ was baked. After that, the excess ITO film was selectively removed by etching treatment to form the lower electrode layer 14.

Next, a tantalum nitride film with a thickness of 100 OA was laminated thereon by sputtering, and after the same process, 4
A grid-like dot pattern of 0μ-x 4Gμ layers and 18 dots per layer in the vertical and horizontal directions was formed so as to be laminated on the lower type AI calendar 14 to form one heat generating layer 15.

On top of this heating fi15, use the same method as last time to install an IT
A film of O is formed and photoresist is applied, and striped wiring of 18 lines/■ layer is formed as the lower electrode layer! 4, and
After baking was performed so as to pass over the dot-shaped heat generating layer 15, an etching process was performed to form an upper electrode layer.

Using this as a carrier, there is a display layer made of a diacetylene derivative compound by the LB method! form 7.

(1) After dissolving the diacetylene derivative compound shown in the formula in chloroform to a concentration of 3 x 10-3 mol/l, at pH 8.2, the cadmium chloride concentration, LxlG-3m
Developed on ol/I aqueous phase 10. After removing the solvent chloroform by evaporation, the surface pressure was increased to 20 dyne/am.While keeping the surface pressure constant, the carrier whose surface was sufficiently clean and wood-friendly was moved up and down in the direction across the water surface. The diacetylene monomolecular film was transferred onto the carrier by gently moving it up and down at a speed of 1.0 cm/sin. A display layer 17 was formed.

〔display〕

This display element (FIG. 2(a)) is uniformly and sufficiently irradiated with 254 nm ultraviolet rays 18, and blue Jl! 19 (Fig. 2(b)).

Heat this entire blue 11119 to approximately 50℃ for 20 seconds.
A uniform red color 11121 was obtained (Fig. 2(c)).

Next, a current was applied to the electrodes arranged in a matrix according to a pattern. At this time, when a current flows between the grounded ITO lower electrode 14 and upper electrode 16, tantalum nitride heats up! Heat is generated from IIj15 and ignites display FJ17. When the red display layer is ignited, it changes to red 1 depending on the temperature.
The color changed from lI21 to yellow Ji122, making it possible to display various contrasts. (Fig. 2(d)) When the electricity is turned off, the display layer immediately returns to its original red color.
It was difficult to distinguish from the unheated area, and no afterimage was observed.

In addition, as a result of repeated display, sufficient reproducibility was observed.

Example 2 [Manufacture of display element] After dissolving the diacetylene derivative compound shown in formula (2) in benzene to a concentration of 3 x 10-' mol/l, the pH
Cadmium chloride concentration at 5,8, l x 10-'mat
/1 aqueous phase lO. After removing the solvent benzene by evaporation, the surface pressure was increased to 20 dyne/am, and while maintaining a constant zero surface pressure, a glass substrate with a sufficiently clean and hydrophilic surface was used as a carrier, and the surface was moved up and down in the direction across the water surface. The diacetylene monolayer was transferred onto the carrier 11 by gently moving it up and down at a speed of 1.0c+++/sin, and the diacetylene monolayer and 5, 11, 21, 31, 41F! A diacetylene monomolecular cumulative film was formed on F, and a display element (Fig. 83 (a)) was manufactured.

〔display〕

This display element (FIG. 3(&)) was uniformly and sufficiently irradiated with 254 nm ultraviolet rays 18 to form a blue film 19 (FIG. 3(b)).

The entire blue film 18 was heated to approximately 50° C. for 20 minutes to form a uniform red film 21 (FIG. 3(C)).

Next, an argon laser 23 with an output of 30 mW and a wavelength of 488 nm was irradiated according to the pattern. The exposed area 24 irradiated with the laser 23 changed from red [21] to a yellow film 24, and display was possible (FIG. 3(d)).

When the exposure by the laser 23 was stopped, the display layer immediately returned to its original red color and was indistinguishable from the unexposed area, and no afterimage was observed.

In addition, as a result of repeated display, sufficient reproducibility was observed.

4. Effect The effects of the present invention are listed below.

Since the 1'1 display layer has high density and high orderliness, high density and high resolution display is possible.

2. Since the film is ultra-thin and heat propagates quickly, it has become possible to display images with high speed, high sensitivity, and little afterimage.

3. Contrast was improved because the difference in spectral transmittance was large.

4. A homogeneous display layer can be obtained even with a large-area carrier.

5. The device is easy to manufacture because it requires only a simple layer structure and electrode wiring.

[Brief explanation of drawings]

FIGS. 1 to 3 are diagrams illustrating embodiments of the present invention. FIG. 1 is a schematic diagram showing an example of a display element manufacturing apparatus using the LB method. FIGS. 2 and 3 are schematic diagrams showing how the display element according to the present invention operates. l...Water tank 2・e Frame 3...Float 4φ...Weight 5...Pulley 6Il...Magnet 7 Fist/Pair magnet 80-・Suction pipe 9-・Suction nozzle 10...φ liquid Surface 11...Carrier 12...Carrier upper and lower arms 13...Middle board (carrier) ttS2Ig! J(a) Figure 2(b) Figure 2(d) 3r! ! :1(a) Figure 3(b) wS3 Figure(C) Figure 3(d) Written amendment to the Office procedure Commissioner of the Japan Patent Office Mr. Manabu Shiga L. Indication of the case 1982 Patent Application No. R60180 2 Title of the invention Display element engineering Relationship with the case of the person making the amendment Patent applicant: 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo (114) Director of the Agency of Industrial Science and Technology Tatsu Todoroki 4 Designated agent Spontaneous 6 Number of inventions increased by amendment 0 7, Modification of the scope of claims of the specification to be amended & contents of the amendment (1) The scope of claims will be corrected as shown in the attached document0
Claims: A display element comprising a monomolecular film of a diacetylene derivative compound having a hydrophilic site and a hydrophobic site in the molecule, or a cumulative film thereof.

Claims (1)

[Claims] A display element comprising a monomolecular film of a polydiacetylene derivative compound having a hydrophilic site and a hydrophobic site in the molecule, or a cumulative film thereof.