JP2732887B2 - Rectifier - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a rectifier in the field of integrated circuits.
More specifically, by using an oxidation-reduction substance as a constituent material of the element, the size can be brought close to an ultra-fine size (tens to hundreds of square meters) at the molecular level, and high density and high speed can be achieved. The present invention relates to a rectifying element that can be used.

[Related Art] Conventionally, rectifiers used in integrated circuits include:
There was a MOS structure shown in FIG. In FIG. 4, (11) is a p-type silicon substrate, (12) is an n-type region,
(13) is a p-type region, (14) is an n-type region, and (15) is SiO
_Two films, (16) and (17) are electrodes, and a pn junction (p-type region (13) -n-type region (14) junction) is formed between these two electrodes (16) and (17). As a result, rectification characteristics are realized.

[Problems to be Solved by the Invention] Since the conventional rectifying element having the MOS structure is configured as described above, it can be finely processed, and at present, the rectifying element having the above structure or a transistor element having a similar structure. 1 Mbit LSIs have been put to practical use as LSIs using.

By the way, in order to increase the memory capacity and operation speed of an integrated circuit, miniaturization of the element itself is indispensable.
In an element using, the mean free path of electrons and the element size are almost equal in an ultra-fine pattern of about 0.2 μm, and there is a limit that the independence of the element cannot be maintained. In this way, silicon technology, which continues to evolve every day, is expected to eventually hit the wall in terms of miniaturization, and is an electric circuit element based on a new principle, 0.2 μm
There is a need for something that can break the m wall.

The present invention has been made in view of such circumstances,
It is an object of the present invention to provide an electric circuit element whose size can be reduced to an ultra-fine size on a molecular level by using a redox substance film as a constituent element of the electric circuit element, and in particular, to provide a rectifying element among them.

[Means for Solving the Problems] By the way, there are several kinds of proteins having the ability to transfer electrons in a predetermined direction in the living body (hereinafter referred to as electron transfer proteins). For example, it is embedded in a biological membrane with a certain orientation, and has a specific intermolecular arrangement so that electron transfer occurs between molecules.

This electron transfer protein involves an oxidation-reduction (redox) reaction during electron transfer, allowing electrons to flow from the negative level to the positive level of the redox potential of each electron transfer protein. It is thought that the movement of electrons can be controlled at the molecular level.

According to recent findings, it is possible to form an electron transfer complex capable of electron transfer by combining an electron transfer protein other than the electron transfer protein complex present in a living body. (Nature, volume 301, 169
1983 (Nature, Vol. 301, P169, 1983).

Therefore, if two types (A and B) of electron transfer materials having appropriate redox potentials are used and two layers are bonded and bonded to AB, it is possible to form a junction that produces rectification characteristics by utilizing the difference in the redox potentials. it is conceivable that. The present inventor has focused on this fact and created the present invention.

Therefore, a rectifying element according to the present invention is a rectifying element including a rectifying unit that performs a rectifying operation using a redox potential difference, and at least a pair of electrodes electrically connected to the rectifying unit. First consisting of flavin derivative
It is characterized by comprising a redox substance film and a second redox substance film made of a porphyrin derivative.

[Operation] In the present invention, rectification characteristics are generated by at least two types of redox substances having different redox potentials.
In other words, using the schematic diagram of the AB-type redox substance complex in FIGS. 3A and 3B and the relationship between the redox potentials thereof, two redox substances having different redox potentials will be described.
In the complex formed by joining A and B, electrons easily flow from the negative level of the redox potential to the positive level as shown by the solid arrow in the figure, but in the opposite direction (the direction of the broken arrow in the figure). ), Which exhibits a rectifying characteristic and has a rectifying characteristic. By using this composite, a rectifying element having properties similar to a pn junction formed by joining an n-type semiconductor and a p-type semiconductor can be obtained.

EXAMPLES Hereinafter, an example of the present invention will be described with reference to the drawings, but the present invention is not limited to only such an example.

FIG. 1 is a cross-sectional view schematically showing a rectifying element according to one embodiment of the present invention. In FIG. 1, (1) is a substrate having insulating properties, which is made of, for example, glass, quartz, SiO ₂ or the like. (2a) and (2b) are a pair of electrodes, and (9) is a rectification unit, which is composed of a first redox material film (3) and a second redox material film (4).

In the rectifying element of the present embodiment, one electrode (2a) is provided on a base material (1), and first and second redox substance films (3) and (4) are formed thereon in this order. The film is formed by the Muir Project method (hereinafter referred to as the LB method). Thereafter, the other electrode (2b) is formed by being disposed on the second redox substance film (4).

The first and second redox substance films (3) and (4) are formed by the LB method because it is suitable for accumulating a monomolecular film. However, the film formation is not limited to the LB method, but may be any film formation method that satisfies the condition that an ultrathin film can be formed. The molecular beam epitaxy method (hereinafter, MBE)
Method), a CVD method can also be suitably used. Also L
The film may be formed by using the B method and the MBE method in combination. That is, for example, the first redox substance film (3) may be formed by the MBE method, and the second redox substance film (4) may be formed by the LB method.

In this embodiment, the first redox substance film (3) is a cumulative monomolecular film of flavin derivative molecules. This monomolecular film is composed of a hydrophilic isoalloxazine ring (5) and a hydrophobic methylene chain (6). The second oxidation lower limit substance film (4) is a cumulative film of a monomolecular film of porphyrin derivative molecules. This monomolecular film is composed of a hydrophilic porphyrin ring (7) and a hydrophobic methylene chain (8).

Here, the porphyrin derivative has the general formula (I): General formula (II): Or the general formula (III): (Wherein m and n are integers of 5 to 20; M is Fe or Ru; X;
Y and Z are ligands for M, and can take the structure of the general formula (I), (II) or (III) depending on the kind and valence of M, and represent a halogen atom, CO, and -OCOC, respectively.
H _3, pyridine, imidazole, P (OR ¹⁾ ₃ or PR ¹ ₃
(R ¹ is a C ₁ -C ₄ lower alkyl group), and X and Y may be the same or different.) Or a porphyrin metal complex represented by the formula:

The flavin derivative has the general formula (IV): (Wherein, R ₁ and R ₂ represent hydrogen or an alkyl group having the following combination: R ₁ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkyl group having 15 to 20 carbon atoms, Or R ₁ is an alkyl group having 6 to 20 carbon atoms, R ₂ is an alkyl group having 6 to 20 carbon atoms, or R ₁ is an alkyl group having 15 to 20 carbon atoms, R ₂ is hydrogen or alkyl having 1 to 5 carbon atoms R ₃ and R ₄ represent hydrogen, an alkyl group having 1 to 5 carbon atoms, a substituent containing a carbonyl group, a methylthioacetic acid group or a methylthiosuccinic acid group).

Such a combination of R _{1 to} R ₄ facilitates control of hydrophilicity and hydrophobicity, arbitrary control of the isotexazine ring in the monolayer, and easy control of the orientation of the isoalloxazine ring in the monolayer. It is for the sake of.

The redox potential difference between the porphyrin derivative and the flavin derivative can take various values depending on the combination of the two, but the redox potential difference is 0.05
It should be between ~ 1.5V, 0.2 ~ 1.2 from the point of rectification ratio
It is preferably between V and particularly preferably between 0.4 and 1.0 V in terms of turn-on and turn-off speed. An example of a combination of a porphyrin derivative and a flavin derivative that satisfies such conditions is a porphyrin derivative in the general formula (I) where m = n = 13 and X = Y
= P (OCH ₃ ) ₃ compound (hereinafter referred to as P1 compound)
And as a flavin derivative, in the general formula (IV), R ₁ = R ₂
= C ₉ H ₁₉ , a combination with a compound in which R ₃ = R ₄ = CH ₃ (hereinafter referred to as F1 compound), and P 1 and a flavin derivative in the general formula (IV), R ₁ = R ₂ = C ₉ H _{19 , R 3 = -CH 2 -S-} CH 2 C
A compound in which m = n = 13 and X = Y = pyridine in the general formula (I) as a porphyrin derivative in combination with a compound (hereinafter, referred to as an F2 compound) in which OOH and R ₄ = CH ₃ (hereinafter, referred to as a P2 compound) ) And a combination of a P2 compound and a P2 compound. Redox potential difference
If the voltage is less than 0.05 V, substantially no rectifying property is obtained, and if the redox potential difference exceeds 1.5 V, the electron transfer speed in the forward direction becomes slow and the rectifying property deteriorates, which is not preferable.

Examples Structural formula (V) as a porphyrin derivative: Using a Ru-porphyrin metal complex represented by the following formula (hereinafter referred to as RPPH) to a film thickness of 30 ° (two layers) and a structural formula (VI) as a flavin derivative: Using 3,10-dinonyl 7,8-dimethylisoalloxazine (hereinafter referred to as DNI) represented by
As a result, a rectifying element having a rectifying portion was prepared. The redox potential difference at this time was about 700 mV (RPPH was the positive direction). The DNI side electrode was grounded to this rectifying element, and a voltage was applied to the RPPH side electrode between -5V and + 5V, and the potential (V) -current (I) characteristics at this time were investigated. The results are shown in FIG. FIG. 2 shows that the rectifying element of the embodiment has rectifying characteristics.

Therefore, a rectifying element having an ultrafine size at the molecular level can be realized by such a configuration, and an integrated circuit capable of high density and high speed can be obtained using this element.

In the present embodiment, a rectifying section (9) is formed by using a monomolecular cumulative film of a flavin derivative and a monomolecular cumulative film of a porphyrin derivative as the first and second redox substance films (3) and (4), respectively. However, these redox substance films may be monomolecular films.

[Effects of the Invention] As described above, in the present invention, since the rectification unit is formed using the redox material films having different redox potentials, it is possible to make the rectification element size close to the ultrafine size at the molecular level. By using this element, an integrated circuit capable of increasing the density and speed of the integrated circuit can be obtained.

Furthermore, since the present invention is formed by the LB method, it is possible to easily accumulate a structure-controlled oxidation-reduction material film regardless of the properties of the substrate. There is also an effect that the configuration of a hybrid device in combination with a compound semiconductor device such as a Si semiconductor or GaAs can be facilitated.

[Brief description of the drawings]

FIG. 1 is a sectional configuration view of a rectifying element according to an embodiment of the present invention,
FIG. 2 is a graph showing voltage-current characteristics of one embodiment of the present invention, FIG. 3A is a schematic diagram showing an AB type redox substance complex, FIG. 3B is a graph showing its redox potential state, FIG. 4 is a sectional view showing an example of a conventional MOS rectifier. (Main symbols in the drawings) (1): Substrate (2a), (2b): Electrode (3): Flavin derivative redox film (4): Porphyrin derivative redox film (9): Rectifying unit

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuo Maeda 8-1-1, Tsukaguchi-Honmachi, Amagasaki-shi, Hyogo Mitsubishi Electric Corporation Central Research Laboratory (56) References JP-A-63-19866 (JP, A) Werner Schmidt, "Bluelight-Induced, Flavin-Mediated Transports of Redox Equivalents acrostics Affairs, 1984. 113-122

Claims (2)

(57) [Claims] 1. A rectifying element comprising a rectifying section that performs a rectifying action using a redox potential difference, and at least a pair of electrodes electrically connected to the rectifying section, wherein the rectifying section is made of a flavin derivative. A first redox substance film, and a general formula (I): General formula (II): Or the general formula (III): (Wherein m and n are integers from 5 to 20; M is Fe or Ru: X,
Y and Z are ligands for M, and can take the structure of the general formula (I), (II) or (III) depending on the kind and valence of M, and represent a halogen atom, CO, and -OCOC, respectively.
H ₃ , pyridine, imidazole, P (OR ¹ ) ₃ , or PR ¹
₃ (R ¹ represents a C ₁ -C ₄ lower alkyl group), and X and Y may be the same or different.) Or a porphyrin derivative which is an alkali metal salt thereof. A rectifying element comprising a second oxidation-reduction film. 2. The flavin derivative of the general formula (IV): (Wherein, R ₁ and R ₂ represent hydrogen or an alkyl group having the following combination: R ₁ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkyl group having 15 to 20 carbon atoms, Or R ₁ is an alkyl group having 6 to 20 carbon atoms, R ₂ is an alkyl group having 6 to 20 carbon atoms, or R ₁ is an alkyl group having 15 to 20 carbon atoms, R ₂ is hydrogen or alkyl having 1 to 5 carbon atoms And R ₃ and R ₄ are hydrogen, an alkyl group having 1 to 5 carbon atoms, a substituent containing a carbonyl group, a methylthioacetic acid group or a methylthiosuccinic acid group. .