JPS6295849A - Logic electronic circuit device - Google Patents

Abstract

PURPOSE:To produce a film containing a charge-transfer complex compound with simple operations by applying an appropriate material for forming said film on electrodes. CONSTITUTION:A plurality of first electrodes 31 extending in one direction and a plurality of second electrodes 32 extending to intersect said one direction are arranged in lattice. The first electrodes 31 and the second electrodes 32 are connected to each other through films 33 containing a charge-transfer complex compound, at all of or a part of the intersections between them. The films 33 containing the charge-transfer complex compound can be formed by applying an appropriate material on the first electrodes 31 at all of or a part of the intersections with the second electrodes 32.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a device having a programmable logic electronic circuit, and more particularly to a device having a film containing a charge transfer complex compound that can be easily produced. and relates to an electronic circuit device incorporating a matrix electrical element having a programmable logic electronic circuit.

[Conventional technology]

Conventionally, PLA (Program Logic Array) has been known as a method for easily realizing random logic in digital electronic circuits. be.

A typical basic circuit of this PLA is shown in FIG.

FIGS. 4(a) and 4(b) show the circuit of the PLA before programming, and each of the multiple intersections connecting the input terminals A, B, and C and the output terminal, Series combination of diode 41 and fuse 42 (Fig. 4(a))
It has a configuration in which a connection is provided via an oven base transistor 43 or the like. To program the desired content to this PLA, a large current is selectively applied to each intersection during programming, and multiple inputs are made as shown at 44 in FIG. 4(C) depending on the program content to be input. The operation of creating a diode by blowing out the fuse at a predetermined junction of the fuse 42, or by breaking the pace emitter junction at a predetermined throw part as shown at 45 in FIG. 4(d) and short-circuiting it. It was carried out by

(Problems to be Solved by the Invention) However, as mentioned above, in the conventional PLA, in order to perform programming by blowing the fuse or destroying the base-emitter junction using a large current, the PLA
Once it was partially programmed, it was impossible to change it.

However, in order to produce such a PLA device, the main parts are composed of diodes and transistors, so
The production of these requires advanced semiconductor production technology, that is, expensive and complicated semiconductor production equipment and advanced technology, making it difficult to easily produce them with simple operations.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a device having a logic electronic circuit whose contents, once programmed, can be changed.

Another object of the present invention is to provide a device M having a programmable logic electronic circuit that can be easily manufactured with simple operations.

[Means for solving problems]

The above objects can be achieved by the following invention.

A device having a programmable logic electronic circuit according to the present invention includes a plurality of first electrodes extending in one direction and a plurality of second electrodes extending in a direction crossing the first electrodes arranged in a grid pattern,
The first electrode and the second electrode are connected to each other at all or part of the intersections of these plurality of electrodes via a film containing a charge transfer complex compound. The film containing the charge transfer complex compound is formed by applying a layer-forming material to at least all or part of the intersection of the first electrode with the second electrode. It is characterized by being formed.

That is, the present invention has a structure that can be easily produced and is programmable by effectively utilizing the voltage-current characteristics of a thin film containing an organic charge transfer complex compound. This makes it possible to provide a device having a logic electronic circuit that can be changed.

The main component of the matrix electrical element with the programmable logic electronics incorporated into the device of the invention is a thin film containing an organic charge transfer complex consisting of an electron donor and an electron acceptor (hereinafter referred to as complex). (abbreviated as "containing thin film").

The complex-containing thin film that can constitute the matrix electric element incorporated in the device of the present invention has 1f! as an electron donor selected from the group consisting of inorganic cations containing silver and/or copper. With the above; as an electron acceptor, the following general formula: % formula % (), and in these structural formulas, A, B, D, E, F, G,
H and H are each independently hydrogen, a halogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, an ether group having 1 to 3 carbon atoms, or a cyan group. For example, a thin film containing a complex compound composed of one or more kinds of Cu-
TCNQ (copper-tetracyanoquinodimethane complex), C
u-TNAP (Copper-II, II, 12.12-tetracyano-216-nafdoquinodimethane complex), Cu-TC
NQF4 (copper-2,3,5,6-titrafluoro7.
7.8.8~tetracyanoquinodimethane complex), Aq
Suitable examples include thin films containing TCNQ, A9TNAP, A9TCNQF4, and the like.

This complex-containing thin film can be produced, for example, by mixing one or more of the above-mentioned organic charge transfer complexes with a substance having suitable film-forming properties, such as a substance that acts as a binder, and dissolving or dispersing this in a solvent as necessary. A solution for forming a complex-containing thin film is prepared, and this is applied to a predetermined portion of the first electrode, and further, if necessary, it is dried.

This complex-containing thin film has voltage-current characteristics suitable for forming a matrix electrical element incorporated into the programmable logic electronic circuit device of the present invention.

That is, a copper electrode 1 as a positive electrode as shown in FIG.
1 and an aluminum electrode 12, which is a negative electrode, sandwiching the film 13 containing the organic charge transfer complex described above.
When the potential of the copper electrode 11 is increased, as shown by the arrow in FIG. Then, the voltage between the electrodes is a critical voltage v11. If you exceed the
Switching to a low resistance state (approximately 10 Ω to approximately 10 3 Ω). Moreover, this low resistance state has memory properties,
Therefore, by applying a predetermined voltage higher than the critical voltage ve between the two electrodes, a desired resistance state can be imparted to the complex-containing thin film 13. Furthermore, since the complex-containing thin film 13 usually has a high resistance to voltages in the opposite direction to the above, it has a characteristic function as a diode.

〔Example) An embodiment of the present invention will be described below with reference to the drawings.

FIG. 3(a) is a schematic plan view of the main part of the matrix element incorporated in the programmable logic electronic circuit device of the present invention.

This element includes a plurality of linear first electrodes 31 arranged in parallel at equal intervals and extending in the vertical direction, and a plurality of linear second electrodes 32 arranged in parallel at equal intervals and extending in the horizontal direction. A- in FIG. 3(b) and FIG. 3(a) are arranged in a grid pattern.
As shown in the partial cross-sectional view taken along line A, a structure in which at least the first electrode 31 and the second electrode 32 are connected via the complex-containing thin film 33 having the above-described structure at the intersection of each electrode. I have.

Since the complex-containing thin film 33 disposed at each intersection of the electrodes has the voltage-current characteristics as described above, the matrix electric element with such a configuration has a programmable logic similar to the PLA described above. It can have a function as an electronic circuit.

That is, this matrix electric element selectively applies a predetermined voltage higher than the critical voltage vc of the complex-containing thin film to the complex-containing thin film 33 at each intersection of the electrodes according to the content of the program to be stored on the first electrode 31 side. The program is activated by increasing the potential, giving the complex-containing thin film to which this voltage is applied a function as a diode, and maintaining the complex-containing thin film to which this voltage is not applied in a high resistance state. It is possible.

Furthermore, in the matrix element of the device of the present invention, the low resistance state of the complex-containing thin film 33 can be returned to the high resistance state by heating the layer or applying a current pulse to the layer. Since this is possible, the previously programmed contents can be canceled by such an operation, and new contents can be programmed into the circuit by the above-described operation.

A matrix element having such a configuration can be manufactured, for example, as follows.

First, a pattern of the first electrode 31 is formed on a substrate 34 made of an insulator. The first electrode 31 can be formed from materials commonly used for electrodes, such as copper and silver, and the same applies to the second electrode.

Hereinafter, the case where copper is used as the first electrode material and aluminum is used as the second electrode will be further explained.

For example, after depositing copper on a glass plate, a resist pattern of a predetermined shape is formed on the deposited copper layer by pattern exposure and development using a photoresist,
The portions of the deposited copper layer not covered by the resist pattern are etched from the substrate, and finally the resist pattern is peeled off from the substrate to form a copper electrode pattern as the first electrode 31. Alternatively, this copper electrode pattern can be easily formed using, for example, a glass epoxy etching substrate (manufactured by Sanhaseto Corporation).

Next, TCNQ powder (manufactured by Osaka Organic Chemical Co., Ltd.) purified by sublimation is dissolved in distilled and purified acetonitrile at a ratio of 5 Qml of acetonitrile to 19 parts of TCNQ powder. After treating the TCNQ acetonitrile solution prepared in this way by bubbling nitrogen gas for 1 hour, copper powder is added to this solution at a ratio of 0.0289 to TCNQI9. Next, when this solution is stirred for 24 hours, a product containing the Cu-TCNQ complex is formed and precipitated in the solution. The product is filtered from the solution and further treated with Soxhlet extraction using hot acetonitrile to extract and remove unreacted TCNQ from the product, which is then dried.

The Cu-TCNQCN compound thus obtained was pulverized in a benzene solution, a polymer binder (trade name: U-Polymer 800, manufactured by Unitika) was added thereto, and polyethylene glycol (PE) was added as a dispersant.
G) (manufactured by Sanyo Chemical Industries, Ltd.) to prepare a coating solution. At this time, the concentration of each component is Cu-TCNQCN
Compound 10wt, X, polymer binder 10wt, χ
, PEG Iwt, approximately X.

After applying the solution prepared in this way onto the copper electrode provided on the substrate using, for example, a wire bar coater or a screen printer so that the film thickness after drying is about 2 to 50 μ, This is dried at 80° C. for about 15 minutes to form a film 33 containing Cu-TCNQ.

Finally, a mask corresponding to the pattern of the second electrode 32 is formed using, for example, adhesive tape on the surface of the substrate with the copper electrode pattern on which the Cu-TCNQ complex film is formed, and the substrate is After depositing aluminum, for example, on the substrate, the pattern mask is removed from the substrate and the second electrode 32 is formed.
A matrix element can be manufactured by forming a pattern.

By using the logic electronic circuit device of the present invention incorporating matrix elements having such a configuration, the logic high crab yI:XI stone x 4+ηx2 X3+η-also 1y2 =
X+ Sco X4+X3 ETY3 =XI x3
An example of the configuration of the apparatus of the present invention for obtaining X4 +X, X4 +X, and x3 is shown in FIG. 3(C).

The configuration of such a device is such that six copper electrodes 31-a to 31-f and eleven aluminum electrodes 32-1 to 32-II, which were fabricated according to the method described above, are connected to Cu at their intersections. - at the intersection of the parts circled in FIG.
, 32-1 and 31-f, 32-2 and 31-b, 32-2
and 3l-C232-3 and 31-c, 32-4 and 31-a
, 32-4 and 31-d, 32-5 and 31-c, 32-5
and 31-f, 32-6 and 31-b, 32-6 and 31-e
.

32-7 and 31-a, 32-7 and 31-b, 32-8 and 31-d, 32-8 and 31-0, 32-9 and 31-a,
32-9 and 31-G, 32-9 and 31-d, 32-10
and 31-b, 32-10 and 31-e, 32-II and 3
1-b, 32-II and 31-d and 32-N and 31-f
A voltage higher than the above-mentioned critical voltage ve of the Cu-TCNO complex film is applied to each of the parts between them, and the C of these parts is
It is possible to create the u4CNQ complex film 35 by giving it a diode function.

Note that in order to cancel the programmed contents in this way, the entire matrix element may be heated to, for example, about 50 to 150°C.

〔Effect of the invention〕

A device having a programmable logic electronic circuit configured as described above uses an electric element having a thin film containing an organic charge transfer complex compound, unlike those using conventional diodes or transistors. Because of this structure, the contents once programmed can be further changed as desired, greatly improving functionality.

Moreover, the electric element having the thin film containing the organic charge transfer complex compound of the device of the present invention has a structure that can be easily produced by simple operations, and the present invention allows for easy fabrication. It is now possible to provide a device M with easily programmable logic electronics.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining the function of an electric element incorporated into the electronic circuit device of the present invention, and FIG. 2 is a voltage-current diagram of a thin film containing an organic charge transfer complex compound used in the electronic circuit device of the present invention. A graph showing the characteristics, FIG. 3(a) is a schematic plan view of the main part of an electric element to be incorporated into the electronic circuit device of the present invention, and FIG. 3(b) is a graph showing A-A in FIG. 3(a). 3(c) is a schematic diagram showing an example of the configuration of the device of the present invention, and FIGS. 4(a) to 4(d) are basic circuit diagrams of conventional PLA, respectively. It is. 11.31a to 31-f: Copper electrode 12.32-1 to 32-II Nialuminum electrode 1
3.33: Complex-containing thin film 31: First electrode 32, second electrode 34: Substrate 35: Diode complex-containing thin film 36.46: Inverter 37.47: Resistor 41: Diode 42: Fuse 43: Oven base Transistor 44 = fuse blown part

Claims (1)

[Claims] 1) A plurality of first electrodes extending in one direction and a plurality of second electrodes extending in a direction intersecting the first electrodes are arranged in a grid, and the intersections of these plurality of electrodes are In a logic electronic circuit device configured with an electric element in which the first electrode and the second electrode are connected in whole or in part through a film containing a charge transfer complex compound. , the film containing the charge transfer complex compound is formed by applying a material for forming the film to at least all or part of the intersection of the first electrode with the second electrode. A logic electronic circuit device characterized in that: 2) The film containing the organic charge transfer complex compound,
As an electron donor, one or more selected from the group consisting of inorganic cations containing silver and/or copper; as an electron acceptor, the following general formula: (CN)_2C(=Z=)C(CN
)＿２ [Here, (=Z=) is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and in these structural formulas A, B, D, E, F, G,
H and I each independently represent hydrogen, a halogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, an ether group having 1 to 3 carbon atoms, or a cyano group. 2. The logic electronic circuit device according to claim 1, which is a film comprising an organic charge transfer complex compound composed of one or more selected from the group consisting of compounds represented by the following.