JP2992910B2 - Information processing device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an information processing apparatus for recording or reproducing information, and more particularly, to a recording medium disposed between at least a pair of electrodes, one of which is a probe electrode, in the presence of an electrolyte. The present invention relates to an information processing apparatus using a reversible state change by an electrochemical oxidation-reduction reaction.

[0002]

2. Description of the Related Art In recent years, the use of memory materials is at the core of the electronics industry such as computers and related equipment, video disks, digital audio disks, and the like, and the development of such materials has been very active. The performance required for the memory material varies depending on the application, but in general, a material having a high density and a large recording capacity is required.

Conventionally, semiconductor memories and magnetic memories using a magnetic material or a semiconductor as a material have been mainly used. However, with the recent development of laser technology, inexpensive optical memories using organic thin films such as organic dyes and photopolymers have been used. High-density recording media have appeared.

In optical memories, high-density recording / reproducing on the order of μm has become possible by utilizing the unevenness of the surface of a recording medium and the difference in reflectance. As such a recording medium, a metal or metal compound thin film, an organic dye thin film, or the like is used,
Using the heat of laser light, information is recorded by drilling holes and changing the reflectance by evaporation and melting, and in such a method, the spot diameter of the laser light used defines the recording density. I have. Furthermore, at present, the use of video information is rapidly progressing, and there is an increasing demand for the development of smaller and larger-capacity high-density memories.

On the other hand, recently, a scanning tunneling microscope (hereinafter abbreviated as STM) capable of directly observing the electronic structure of surface atoms of a conductor has been developed [G. Binning et a
l. , Helvetica Physica Act
a, 55 , 726 (1982)], real-space images can be measured with high resolution regardless of whether they are single crystal or amorphous.
In addition, it has the advantage that it can be observed with low power without causing damage to the medium by current damage, and furthermore, it operates in the atmosphere and can be used for various materials, so that a wide range of applications is expected.

[0006] This STM utilizes the fact that when a voltage is applied between a metal probe and a conductive substance to approach a distance of about 1 nm, a tunnel current flows between them. This current is very sensitive to the change in distance between the two, and by scanning the tip to keep the tunnel current constant,
At the same time as drawing the surface structure of the real space, it is also possible to read various kinds of information on the total electron cloud of surface atoms.

As an application of the STM to the recording / reproducing technique, there are a method of recording by changing the surface state of the recording medium by an electromagnetic wave such as an electron beam, an ion beam, X-rays or light, and reproducing the information by the STM. A method has been proposed in which recording and reproduction are performed using an STM by using a material having a memory effect in voltage-current characteristics, for example, a thin film layer of a chalcogenide or a π-electron organic compound.

Attempts have also been made to produce cone-shaped protrusions by applying a voltage that causes field emission to the STM probe electrode and locally melting the Rh-Zr alloy sample surface [U. See Stafer et al. , Appl. P
hys. Lett. 51 (4) 27 July 198
7].

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to produce a reversible state change in a very small area on a recording medium by an oxidation-reduction reaction. Another object of the present invention is to provide an information processing apparatus which can be erased.

[0010]

As a structure for achieving the above object, first, at least one probe electrode and a working electrode opposed to the probe electrode are provided to supply movable ions. An electrolyte and a recording medium capable of easily controlling a reversible change between an oxidized state and a reduced state by application of an external voltage in the presence of the electrolyte are disposed between the probe electrode and the working electrode. An apparatus provided with a means for applying a voltage between the probe electrode and the working electrode and a means for controlling a distance between the probe electrode and the recording medium, wherein an oxidation reaction or a change in state of the recording medium is performed. An information processing apparatus provided with a reaction compensation region for compensating a reaction to the reduction reaction on or near the probe except for the tip of the probe, or near the surface of the recording medium. There is a point.

That is, the first feature of the present invention is that, as shown in FIG. 1, a bias voltage is applied between the probe electrode 3 and the working electrode 4 so that the recording medium (the working electrode 4 and the recording Reaction compensation region 6 for compensating the charge of the oxidation reaction or reduction reaction caused by the layer 5).
In this configuration, a dedicated electrode is provided on the probe electrode except for the tip of the probe electrode 3, or a dedicated electrode is newly provided near the probe electrode 3 and the surface of the recording medium.

A second feature of the present invention is that the reaction compensation region 6 is formed of the same material as the recording medium, and in the initial state, the oxidation-reduction state of the compensation region is set to the opposite state of the recording medium. Is to be.

In general, in an electrode reaction in an electrochemical reaction system, charge is compensated between two electrodes, so that the reaction proceeds without accumulation of charge. For example, when an oxidation reaction involving emission of electrons occurs at one electrode, a reduction reaction involving addition of electrons proceeds at the other electrode, and the balance of electrons is canceled to compensate for the charge. In the reaction system in the electrolyte cell for measurement, a noble metal such as Pt, Au, Ir or the like which does not react by itself but has strong catalytic action is used as a counter electrode with respect to the working electrode on which the target measurement material is formed. Is used. In this case, as a counter-reaction generated on the counter electrode side as a compensation reaction of an oxidation reaction or a reduction reaction that proceeds at the working electrode 4, a reaction accompanied by generation of gas or deposition of a reaction product is almost performed. It is an irreversible reaction system. In the case of a measurement cell, the surface area of the counter electrode is much larger than that of the working electrode, and at the same time, the gas adsorbed on the counter electrode surface or the reaction product can be desorbed by replenishment, stirring, or washing of the electrolyte. It does not matter that the reaction system is a reversible reaction system.

However, when considered as an STM memory system, the generation of gas and the deposition of reaction products at the probe electrode corresponding to the counter electrode, particularly at the tip thereof,
STM operations such as distance control and reproduction using the tunnel current involving the tip of the probe electrode will be hindered. At the same time, an irreversible system has problems in film peeling, durability, deterioration of characteristics, etc. due to gas generation, and a reversible reaction system in which gas generation and reaction product precipitation do not occur as a whole system is desirable.

Therefore, in the present invention, in order to prevent an unnecessary side reaction from occurring at the tip of the probe electrode 3 which is a key to the STM operation, the reaction of the oxidation reaction or the reduction reaction which proceeds on the reaction medium side near the tip of the probe is performed. It is proposed to provide a region for compensating the reaction and establish a reversible reaction system as a whole.

The reaction in the reaction compensation region 6 is required if the reaction potential is smaller than the gas generation potential or the by-product deposition potential at the tip of the probe electrode, and reversible as a whole reaction system including the balance of mobile ions. I just need.

In particular, the present invention proposes to use a reverse reaction of a reaction that proceeds in a recording medium as an ideal compensation reaction, which is a second feature of the present invention. By forming the reaction compensation region from the same material as the recording medium and setting the oxidation-reduction state of the reaction compensation region to the opposite state of the recording medium in the initial state, the reaction compensation region has the same reaction potential and reaction equivalent as the recording medium. Thus, an ideal reversible reaction system in which the same mobile ions are added and desorbed can be realized.

In the present invention, at least one probe electrode is used for one of the electrodes, and the probe electrode is set to ST.
By using M to approach the recording medium very close to about 1 nm, the area where the oxidation-reduction reaction occurs is limited, and molecules or molecular groups having different electronic states are generated in extremely small areas, thereby achieving high-density recording. Have achieved.

The identification of the regions having different electronic states is as follows.
This is not possible with reading conventionally used for optical recording, but is only possible with the use of STM, which is extremely sensitive to the spread of electron clouds near molecules. Specifically, the detection is performed based on a change in a tunnel current value flowing between the probe electrode and the counter electrode, but the distance between the probe electrode and the recording medium is controlled so as to keep the tunnel current value constant, and the detection is performed based on a control signal at that time. Is also good.

As a material used for the recording medium and the reaction compensator according to the present invention, there is a wide range of organic compounds and inorganic compounds capable of reversible oxidation-reduction reaction, and a typical example is an electrochromic material. .

The electrochromism is a phenomenon in which one or both of the electron carriers are colored by an electrochemical oxidation-reduction reaction. The change in the valence of a metal ion or an organic molecule causes the electronic state and its band structure to change. Changes, the physical characteristics such as the absorption spectrum and the electrical conductivity are reversibly switched. In view of such a memory property, application as a recording medium in addition to display use is also expected. Viologen polymer is organic, styryl class compounds, rare earth diphthalocyanine, TTF polystyrene or the like, or mainly easily polythiophene obtained by doping electrolytic polymerization film, polyaniline, polypyrrole, etc. conductive polymer groups such as polythienylene, WO ₃ is an inorganic substance , transition metal oxides such as IrO _X is typical.

Next, a second configuration which can achieve the above object has at least one probe electrode and a working electrode opposed to the probe electrode, and is provided with an electrolyte for supplying mobile ions and an electrolyte in the presence of the electrolyte. A recording medium capable of easily controlling a reversible change between an oxidized state and a reduced state by applying an external voltage is disposed between the probe electrode and the working electrode, and further, the probe electrode and the working electrode A device provided with a means for applying a voltage between and a means for controlling the distance between the probe electrode and the recording medium, wherein electrons involved in the change between the oxidized state and the reduced state of the recording medium, An information processing apparatus provided by a tunnel current generated between the probe electrode and the recording medium.

Here, the electrolyte is an electrolytic solution, and a reference electrode for regulating potential is provided near the recording medium surface.
In addition, the portion of the probe electrode immersed in the electrolytic solution except for the foremost portion is coated with an inert insulating material, and the electrolyte is a gel or solid electrolyte, A point in which a gel or solid electrolyte is arranged between the recording medium and the working electrode, further,
A point that an electron blocking layer is also arranged between the recording medium and the working electrode, and the recording medium and the working electrode are semiconductor materials having different conductivity types from each other, and a bonding interface between the two is different. A point having a diode characteristic,
Further, the present invention is also characterized by an information processing apparatus which satisfies, for example, a configuration having a second counter electrode other than the probe electrode opposite to the working electrode.

Hereinafter, the structure and operation of the present invention will be described in more detail.

According to the present invention, electrons involved in a reversible oxidation-reduction reaction in a recording medium caused by a voltage applied between the probe electrode and the working electrode are used at least during recording between the probe electrode and the recording medium. Is supplied by the tunnel current generated in According to this, since the participating electrons are only tunneling electrons from a few atoms at the tip of the probe, the oxidation-reduction reaction caused in the recording medium is also limited to the effective tunnel current region, and is extremely small in the range of tens to several hundreds Å or less. It is possible to control a reversible state change limited to a specific region.

Hereinafter, the features of the present invention will be described in more detail with reference to FIG. Generally, a reversible oxidation-reduction reaction involving addition and desorption of mobile ions is carried out by using a cation (Kati)
on) K ⁺ and Anion A ⁻ can be represented by Chemical Formula 1 or Chemical Formula 2.

[0027]

Embedded image

[0028]

Embedded image Here, the case of a general system in which the electrolyte is an electrolyte is considered. As shown in FIG. 2A, a reaction medium 5 formed on a working electrode 4 and a probe electrode 3 having a sharp tip are placed in an electrolytic solution containing mobile cations K ⁺ filled in an electrolytic cell container 2.
Are biased in the positive direction with respect to the working electrode 4 with respect to the working electrode 4 so that the positive ions K ⁺ drift forcibly into the reaction medium 5 and are simultaneously injected from the working electrode 4 side. The forward reaction shown in Chemical Formula 1 proceeds by the electrons to produce a product MK.

When a voltage is applied in a direction in which mobile ions are forcibly drifted into the medium in order to cause an oxidation-reduction reaction, electrons involved in this reaction are always applied to the working electrode 4 on which the reaction medium 5 is formed. Supplied by On the other hand, with the reverse bias, the cations K ⁺ gather around the probe electrode 3 and are not introduced into the reaction medium 5, so that the reaction does not proceed. The situation is the same in the case of the reverse reaction of Formula 1 (FIG. 2 (b)), the forward reaction of Formula 2 (FIG. 2 (c)), and the reverse reaction of Formula 2 (FIG. 2 (d)). When a bias is applied between the working electrode 4 and the probe electrode 3 in a direction in which mobile ions are injected or ejected into the reaction medium 5 in a direction in which each reaction proceeds, electrons involved in each reaction are always applied to the working electrode 4. Since it is supplied from the side, tunnel electrons generated between the probe electrode 3 and the working electrode 4 cannot participate in the reaction. On the other hand, the application of the bias in the reverse direction does not involve mobile ions, and thus the reaction does not proceed.

However, the reaction region in the reaction involving the injected and injected electrons from the working electrode 4 side has a comparison area of several hundred nmφ or more corresponding to a widening electric field generated between the probe electrode 3 and the working electrode 4 by bias application. It is not suitable for the purpose of the present invention.

Therefore, as a structural feature for realizing the present invention, an electron blocking layer 19 is provided between the working electrode 4 and the reaction medium 5.
Alternatively, the reaction medium 5 and the working electrode 4 are formed by using semiconductor materials having different conductivity types for the reaction medium 5 and the working electrode 4 and forming an electron barrier layer when a bias is applied.
It is proposed to block electron transfer between them. As shown in FIG. 2A, first, in order to cause a forward reaction of Formula 1, the potential of the probe electrode 3 is biased in a positive direction with respect to the working electrode 4 so that cations in the electrolytic solution are reacted with the reaction medium 5. Force to drift inside. However, at this time, since the electrons from the working electrode 4 are blocked by the electron blocking layer 19, the reaction does not proceed. Immediately after the supply of cations, a pulse voltage of the opposite polarity is applied, and tunnel electrons are supplied from the tip of the probe before the cations in the reaction medium 5 diffuse or drift into the electrolyte. The reaction can proceed. In this case, the reaction region is limited to the tunnel current region, and a reversible oxidation-reduction reaction can be realized in a very small region of more than tens of Åφ to 100Åφ. It is possible to provide an information processing device capable of recording and reproducing.

The same applies to the reverse reaction of the chemical formula 1 and the forward reaction and the reverse reaction of the chemical formula 2 (FIG. 2B). Taking advantage of the fact that the time is much shorter than the time, the injection and injection of tunnel electrons between the probe electrode 3 and the reaction medium 5 before the ions reversely diffuse or drift in the reverse direction can be performed. The reaction can proceed. In FIG. 2, the polarity of the probe electrode 3 is switched to perform injection / injection of mobile ions and injection / injection of tunnel electrons. However, an opposing flat electrode for injection / injection of mobile ions is separately provided. Only the control electrode may be used. FIG.
(C) and (d) show that the conductivity type of the reaction medium 5 and the working electrode 4 are made different to form a pn junction. If a reverse bias is applied in the direction in which the reaction proceeds, the electron blocking layer is formed. Electron supply from the working electrode 4 side can be cut off without providing 19.

As described above, in order to cause an oxidation-reduction reaction in a very small area by the tunnel electrons, that is, to perform recording, the distance between the probe electrode 3 and the recording layer 5 of the recording medium (corresponding to the above-described reaction medium 5) is set. 0.1Å within a distance of 10Å
It can be realized by controlling with the following accuracy, detecting a tunnel current generated when a voltage is applied between the probe electrode 3 and the recording medium, and applying the aforementioned STM analysis technology. The same applies to the case of reproducing recorded bits, in which the tunnel current reflecting the difference in the electronic state corresponding to the difference in the physical state such as the conductivity, surface work function, intermolecular bonding state, molecular group size, etc. of the recorded bit is measured. Detecting and realizing in-plane direction resolution of the order of Å by STM technology.

Now, it is more difficult to discriminate between a faradic current generated by the movement of mobile ions and a tunnel current as compared with that in the air or vacuum, in the STM analysis in the electrolyte. In order to solve this problem, the potentials of the surface of the recording layer 5 and the surface of the probe electrode 3 of the recording medium should be kept below the reaction potential at which a surface reaction occurs during distance control and reproduction. It is important to minimize the reaction area so that the effect is minimized even if it occurs.

Therefore, as a next feature of the present invention, in a system in an electrolytic solution, a reference electrode 7 for regulating the potential on the surface of the recording layer 5 and the surface of the probe electrode 3 is provided near the recording medium surface (FIG. 1). Further, the immersion part in the electrolytic solution excluding the region of 1 nm to several hundred nmφ of the tip part of the probe electrode 3 which is the tunnel electron generation part is covered with an inert insulating material such as a polymer or glass, so that unnecessary parts are unnecessary. It is proposed to minimize the area where the surface reaction occurs, and satisfies the above requirements.

The next feature of the present invention is that a solid or gel electrolyte is used as the electrolyte, the electrolyte is disposed between the recording layer 5 and the working electrode 4, and a unidirectional electrolyte is provided between the probe electrode 3 and the working electrode 4. It is an object of the present invention to propose a configuration in which a bias voltage is applied to simultaneously inject and eject movable ions between an electrolyte and a recording medium and tunnel electrons between a recording medium and a probe electrode.

As the recording layer 5 according to the present invention, an electrochromic material is listed as a typical example of an organic compound and an inorganic compound capable of performing a wide and reversible oxidation-reduction reaction. Electrochromism is a phenomenon in which one or both of the electron movers is colored by an electrochemical redox reaction.The change in the electronic state and its band structure due to a change in the valence of a metal ion or an organic molecule. Accordingly, physical characteristics such as an absorption spectrum and conductivity can be reversibly switched and have a memory property, so that it is expected to be used not only for display but also as a recording medium. Examples of organic substances include viologen polymers, styryl compounds, rare earth diphthalocyanines, TTF-modified polystyrene and the like, and conductive polymers such as polythiophene, polyaniline, polypyrrole, and polyphenylene which are easily obtained mainly by doping of an electropolymerized film.
₃ , transition metal oxides such as IrO _x are typical.

As the electron blocking layer 19, various oxide films such as Al ₂ O ₃ or inorganic materials such as a nitride film, etc .;
Polyimide-based materials are preferred.

As the solid or gel electrolyte, Si
O, MgF ₂ , Cr ₂ O ₃ , ZrO ₂ , Ta ₂ O _5, etc., or a hydrous dielectric, β-alumina, RbAg ₄ I ₅ , Li ₃ N, acrylamidomethyl, propanesulfonic acid polymer, N
A solid electrolyte containing mobile ions suitable for a reaction medium such as afion, PbF ₂ , LiF, and CaCl ₂ , or a gel formed by impregnating various electrolytes with a polymer such as a polyether-based polymer can be considered.

When analyzing a sample with low conductivity by STM,
It must be formed very thinly on the surface of the conductive material with a thickness of several tens angstroms or less. Regarding the formation of such an ultra-thin recording layer, specifically, a vapor deposition method, an electrolytic polymerization method,
Although the plasma polymerization method, MBE method, cluster ion beam method, and the like can be applied, if it is limited to organic substances, Langmuir-Blodget method (LB) is a known conventional technique because of its controllability, easiness, and reproducibility. Method) is very suitable.

According to the LB method, when a molecule having a structure having a hydrophilic site and a hydrophobic site in a molecule and a balance between them (an amphiphilic balance) is appropriately maintained, the molecule is placed on the water surface. This is a method of forming a monomolecular film or a cumulative film thereof by utilizing the fact that the hydrophilic group is turned downward to form a monomolecular layer.

According to the LB method, a monomolecular film of an organic compound having a hydrophobic portion and a hydrophilic portion in one molecule or a cumulative film thereof can be easily formed on a substrate, and the thickness on the order of molecules can be obtained. And a uniform and homogeneous organic ultrathin film can be stably supplied over a large area. Therefore, an ultrathin film required for analysis by STM can be easily formed. Further, regarding the response speed, which is a weak point of electrochromism, the factor that determines the response speed is the drift speed of free charge, which is not a problem in the state of such an ultrathin film.

In the present invention, the substrate for supporting the thin film on which the inorganic and organic materials are laminated may be any of metal, glass, ceramics, plastic materials and the like. The substrate as described above may have any shape and is preferably flat, but is not limited to a flat plate. That is, this is because the film formation method has an advantage that a film can be formed according to the shape of the surface of the substrate regardless of its shape.

On the other hand, the electrode material used in the present invention also has to have high conductivity and does not cause unnecessary reaction with the electrolyte. For example, Au, Pt, Ag, Pd, A
metals such as 1, In, Sn, Pb, W and alloys thereof;
Furthermore, graphite and silicide, and even IT
Numerous materials, including conductive oxides such as O, can be cited, and these can be applied to the present invention. As a method for forming an electrode using such a material, a conventionally known thin film technique is sufficient.

The tip of the probe electrode 3 needs to be as sharp as possible in order to increase the resolution of recording / reproducing / erasing. In the present invention, the tip of platinum having a thickness of 1 mmφ is 90
°, mechanically polished to a cone and applying an electric field in an ultra-high vacuum to evaporate surface atoms,
It is not limited to this.

The portion of the probe electrode 3 immersed in the electrolytic solution except for the leading edge is coated with an insulating inert material such as a polymer or glass to minimize the Faradic current due to a side reaction on the probe electrode surface. , Distance control,
The S / N ratio of the tunnel current signal at the time of reproduction is guaranteed.

[0047]

Embodiments of the present invention will be described below.

(First Embodiment) FIG. 1 is a block diagram showing an information processing apparatus according to a first embodiment of the present invention. In this figure, reference numeral 23 denotes a current-voltage conversion amplifier, and reference numeral 22 denotes a fine movement driving mechanism 9 using a piezoelectric element so that the probe current becomes constant.
Is a servo circuit that controls 27 is a potential regulating circuit for controlling the surface potential of the probe electrode 3 and the working electrode 4 and the bias voltage between both electrodes with reference to the potential of the reference electrode 7;
Reference numeral 26 denotes a pulse application circuit for applying a pulse voltage for recording / erasing between the probe electrode 3 and the working electrode 4.

Here, since the probe current changes abruptly when the pulse voltage is applied, the servo circuit 22 turns on the HOLD circuit so that the output voltage becomes constant during that time.
It is controlled to be.

Reference numeral 25 denotes an XY scanning drive circuit for controlling the movement of the probe electrode 3 in the XY directions. Coarse movement drive mechanism 1
0 and the coarse drive circuit 24 are connected to the probe electrode 3 and the recording layer 5 such that a probe current of about 10 ⁻⁹ A is obtained in advance.
And coarse movement control. All of these functions are centrally controlled by the computer 21.

In this embodiment, a platinum probe electrode is used as the probe electrode 3. This probe electrode 3
The distance (Z) is finely controlled by a piezoelectric element so as to keep the tunnel current flowing between the recording layer 5 and the surface constant. Further, the fine movement driving mechanism 9 is designed so that the fine movement can be controlled in the in-plane (X, Y) direction while keeping the distance Z constant.

The reaction compensating region 6 according to the present invention may be arranged and fixed on a flat electrode facing the recording layer 5 in the vicinity of the probe electrode 3 and the surface of the recording layer 5. Drive control is performed independently or in conjunction with the probe electrode 3.

The reaction compensation area 6 is formed of the same material as the recording layer 5. In this example, the t- of lutetium diphthalocyanine [LuH (Pc) ₂ ] was determined using the LB method.
A monomolecular film of the butyl derivative was formed. The details are shown below.

After cleaning the optically polished glass substrate with a neutral detergent and trichlene, the IT substrate is sputtered.
O was vacuum-deposited to form an electrode. Next, [LuH (P
c) The t-butyl derivative of ₂ ] was dissolved in a mixed solvent of chloroform / trimethylbenzene / acetone (1/1/2) to obtain a solution having a concentration of 0.5 mg / ml. After the above-mentioned substrate was submerged in a pure aqueous phase at 20 ° C., the above solution was developed on the aqueous phase to form a monomolecular film on the water surface. Waiting for the evaporation of the solvent, increasing the surface pressure of the monolayer to 20 mN / m, and while keeping this constant, slowly pull up the substrate across the water surface at a speed of 3 mm / min. Formed. The recording layer 5 is formed in exactly the same manner.

The potential of the reaction compensation area 6 is
7 may be controlled independently, but in this embodiment, it is set to the same potential as the probe electrode 3.

When the reaction compensation region 6 is formed of the same material as the recording layer 5 as in this embodiment, the reaction compensation region 6
Is set to a state of reaction with the recording layer 5. That is, after being previously formed in another electrolytic cell using KCl as an electrolytic solution and initially set to an oxidation state [LuH (Pc) ₂ ] · 2Cl opposite to the initial reduction state [LuH (Pc) ₂ ]. , Probe electrode 3, working electrode 4 and reaction compensation area 6
Is closed by relaying the potential regulating circuit 27. Electrolyte 1 is 1MK
A Cl aqueous solution was added until each electrode was immersed.

The recording / reproducing operation will be described below in order. The distance between the probe electrode 3 and the recording layer 5 is set by applying a voltage of -0.3 V to the surface potential of the recording layer 5 to the probe electrode 3 while regulating the potential of each electrode by the electronic regulation circuit 27 (potentiometer). In the state where the voltage is applied, the recording layer 5 is gradually moved to the probe electrode 3 by the coarse movement driving mechanism 10 including a piezoelectric piezo element or the like via the coarse movement driving circuit 24.
To approach. At the same time, while monitoring the current flowing between the probe electrode 3 and the working electrode 4, the coarse drive is stopped at a distance of 10 ° at which a tunnel current starts to be generated between the two electrodes, and then the fine drive mechanism 9 stops the coarse drive. The probe electrode 3 is drawn through the servo circuit 22 so as to have a corresponding tunnel current value. Thereafter, the XY scanning drive circuit 25
The servo circuit 22 is operated so that the tunnel current is constant while performing X and Y scanning by the fine movement driving mechanism 9 via the micro-movement driving mechanism 9. At this time, the Z-direction to the fine movement driving mechanism 9 which is the output voltage of the servo circuit 22 is applied. By monitoring the control signal, an uneven state or an electronic state of the surface of the recording layer 5 can be detected.

As described above, an area of several hundred nm square is scanned first, and it is confirmed that the area is sufficiently flat within a range of several to ten and several degrees. 3A by applying a +1.5 V pulse voltage to the surface of the recording layer 5 to the probe electrode 3 and the reaction compensation electrode after holding the probe electrode 3 by holding the XY scanning signal. Thus, in the recording layer 5, the anion (A
⁻ , Here, Cl ⁻ ) is injected, and at the same time, electrons are released to the working electrode 4 and the chemical formula 3

[0059]

Embedded image Oxidation reaction progresses, and minute recording bits of several tens nm to one hundred and several tens nm nm corresponding to the spread of the electric field depending on the distance between the probe electrode 3 and the working electrode 4 are formed. here,
If there is no reaction compensating electrode, a reduction reaction of K ⁺ + e ⁻ → K proceeds on the probe electrode surface as a counter reaction to the oxidation reaction in the recording layer 5, and potassium is deposited on the probe electrode. When HCl is used as the electrolytic solution, 2H ⁺ +2
e ⁻ → The reduction reaction of H ₂ proceeds, and H
₂ gas is generated. In any case, the STM operation such as the distance control reproduction by the probe electrode 3 may be seriously hindered. On the other hand, in the configuration according to the present invention, when HCl is used as the electrolytic solution, the reaction compensation region 6 is formed in parallel with the oxidation reaction in the recording layer 5 as shown in FIG.
At anion Cl ^- Formula 4 due to the release

[0060]

Embedded image Since the reduction reaction proceeds, there is no need to worry about side reactions such as reaction product analysis and gas generation, and good reversibility can be maintained in the entire reaction system, thereby achieving the object of the present invention.

Reproduction is performed by re-scanning a region of several hundred nm around the periphery which was scanned before recording, while keeping the probe electrode 3 at -0.3 V with respect to the surface of the recording layer 5. In the [LuH (Pc) ₂ ] .2Cl oxidized region where the recording bit was formed, a conspicuous state or a remarkable change in the electronic state was recognized corresponding to the region of 20 to 150 nmφ, and a three-digit signal in terms of tunnel current was detected. A change is detected.

On the other hand, erasing is performed by applying a pulse voltage of -1.5 V to the surface of the recording layer 5 to the probe electrode 3 and the reaction compensating electrode. At the same time, an oxidation reaction which is a counter-reaction proceeds in the reaction compensation region, and mobile ions and electrons are compensated between the two. After the pulse application, the recording bit was reduced to the initial state, and it was confirmed that the recording bit was erasable.

FIG. 3B is a principle diagram when the electron blocking layer 19 is provided between the recording layer 5 and the working electrode 4. In this case, since the movement of electrons between the recording layer 5 and the working electrode 4 is blocked, even during recording, the electrons involved in the oxidation-reduction reaction on the recording layer 5 are not absorbed by the probe electrode 3 and the recording layer 5.
It is supplied by the tunnel current generated between them. Therefore, the formed recording bit is 1n corresponding to an effective tunnel current region in which only the top few atoms of the probe electrode 3 are involved.
Very small recording bits of m to 10 nmφ can be formed. Recording is performed in two stages. First, in the first stage, the potential of the probe electrode and the reaction compensation electrode is biased to -1.5 V (relative to the surface of the recording layer).
^- is injected, while in the reaction compensation electrode side progresses reduction reaction. Here, as a second stage, a reverse polarity pulse +2.5
By applying V (with respect to the working electrode 4) to the probe electrode 3, a tunnel current is generated between the probe electrode 3 and the recording layer 5, and excess electrons in the recording layer are emitted as tunnel electrons. The oxidation reaction proceeds in.

(Embodiment 2) In Embodiment 1, the case where the material of the reaction compensation region 6 is the same as that of the recording layer 5 has been described. However, the material is not particularly limited to the same material. Any material can be used as long as it is capable of performing a reversible oxidation-reduction reaction lower than the reaction product deposition potential and has a suitable electrolyte capable of supplying the opposite mobile ions. For example,
In a system in which [LuH (Pc) ₂ ] is used as the recording layer 5, tungsten trioxide WO ₃ which is a typical inorganic electrochromic material can be used as a reaction compensation region material.

Here, when the electrolytic solution is a 0.5M HCl aqueous solution, the oxidation reaction that proceeds in the recording layer 5 during recording,

[0066]

Embedded image In the reaction compensation region, the chemical formula 6

[0067]

Embedded image Of the electrolytic solution proceeds, the decomposition reaction of the electrolytic solution, the chemical formula 7

[0068]

Embedded image The balance of mobile ions and electrons accompanying the above can be compensated, and good reversibility without gas generation or reaction product precipitation can be maintained as a whole system.

(Embodiment 3) In Embodiment 1, the reaction compensation area 6
Is formed on a newly provided compensating electrode different from the probe electrode 3 and the recording layer 5, but the present invention is not necessarily limited to this. FIG. 4A shows a case where a reaction compensation region 6 is formed on the electrode surface except for the tip end portion of the probe electrode 3 instead of providing an inert insulating film, which is an ideal arrangement closest to the tip of the probe electrode. At the same time, there is an advantage that it is not necessary to newly provide an electrode.

FIG. 4B shows the case where the reaction compensation area 6 is formed integrally on the same support as the recording medium. When the reaction compensation area 6 is made of the same material as the recording layer 5, the reaction compensation area 6 is simply formed on the support. When the working electrode 4 and the recording layer 5 are formed thereon, it is only necessary to divide them into two regions that are insulated from each other by wet processing or dry etching. The wiring can be used as the reaction compensation area 6 by wiring with the same potential.

FIGS. 5 (a) to 5 (c) are conceptual diagrams showing a system in which a plurality of systems according to the present invention are integrated and formed by applying micromechanics technology applying a semiconductor process.
On the same Si substrate 18, a cantilever type actuator 1 for fine movement driving by a piezoelectric thin film bimorph structure such as ZnO
Dozens to hundreds of electrodes 2 are formed on each cantilever. In addition to the driving electrode 14 as shown in the drawing, the reaction compensation is formed on the probe electrode 3 and the electrode 13 formed so as to surround the probe electrode. An area 6 is provided. The reference electrode 7 is fixed on the supporting Si substrate 18, but may be provided on each cantilever or near the probe electrode. In addition, the drive electrode 14 and the wiring electrode 1
5 and 16 need to be coated with an inert insulating coating film 17 in order to prevent unnecessary side reactions.

(Embodiment 4) In all of the embodiments 1 to 3, a system using an electrolytic solution as an electrolyte is used. In this embodiment, a gel or solid electrolyte is used as an electrolyte, as shown in FIG. As described above, the solid electrolyte 1 is formed on the working electrode 4 so as to be sandwiched between the recording layer 5 and the reaction compensation region (layer) 6, and is characterized by being integrated as a recording medium portion.

For example, when the [LuH (Pc) ₂ ] t-butyl derivative described in Example 1 is used as the recording layer 5 and the reaction compensation layer 6, lead difluoride PbF is used as the solid electrolyte layer.
It can be used ₂ F _2. First, a [LuH (Pc) ₂ ] t-butyl derivative monomolecular film is formed on the ITO working electrode 4 by the above-described LB method, and then oxidized in a fluoride aqueous solution electrolysis cell to form [LuH (Pc) ₂ ] · 2F. And continued Pb
Heating the molybdenum boat to 550-600 ° C. with F ₂ ,
Vacuum degree before vapor deposition 5 × 10 ^-6 torr, vapor deposition rate 5Å / sec
Vacuum deposition under the condition of c.
Similarly, by forming the uH (Pc) ₂ ] t-butyl derivative in a monomolecular layer, an integrated recording medium portion is obtained.

A voltage of -0.3 V (the working electrode 4
STM operation was performed in the same manner as in Example 1 while monitoring the tunnel current generated at that time, and the distance between the probe electrode 3 and the recording layer 5 was controlled to several Å. By applying a pulse of 0.0 V (to the working electrode 4), the solid electrolyte layer 1 causes the anion F ⁻
At the same time, tunnel electrons are emitted from the recording layer 5 toward the topmost atoms of the probe electrode 3. In a micro-region corresponding to the effective tunnel current region, the chemical formula 8

[0075]

Embedded image Oxidation reaction progresses, and a very small recording bit of tens to several tens of φ can be formed. On the other hand, in parallel with the reaction compensating layer 6,

[0076]

Embedded image The reduction reaction proceeds, and good reversibility without gas generation or reaction product precipitation can be maintained as a whole system,
It is possible to achieve high reliability without characteristic deterioration due to interface peeling or the like due to gas generation.

For reproduction, a voltage of -0.3 V (with respect to the working electrode 4) is applied to the probe electrode 3, and for erasing, a pulse voltage of -2.0V (with respect to the working electrode 4) is applied to the probe electrode 3. This can be performed similarly to the first embodiment.

As a combination of another recording layer material, a compensation layer material and a solid electrolyte, for example, when the same material is used for the recording layer and the compensation layer, WO ₃ or IrO _x, which is famous as an inorganic electrochromic material, is used. A combination of Ta ₂ O ₅ which is a good proton conductor as a solid electrolyte layer, or polyaniline which is a doping film electrolytically polymerized from a perchloric acid aqueous solution containing an aniline monomer as a material for a recording layer and a compensating layer; LiBF ₄ or L as electrolyte
Various material configurations can be considered, such as a combination of a gel obtained by mixing an iClO ₄ / propylene carbonate solution with a polymer, or a case where these recording layer and compensation layer materials are used in different combinations.

(Embodiment 5) FIG. 7 is a block diagram of an information processing apparatus according to the present embodiment. In the figure, the distance (Z) of the probe electrode 3 is finely controlled by a piezoelectric element so as to keep the tunnel current flowing between the probe electrode 3 and the surface of the recording layer 5 constant. Further, the fine movement driving mechanism 9 is designed so that the fine movement can be controlled in the in-plane (X, Y) direction while keeping the distance Z constant.

In this embodiment, recording, reproduction,
The probe electrode 3 used for erasing is to minimize the faradic current due to side reactions on the electrode surface and to increase the S / N ratio of the tunnel current signal at the time of distance control and reproduction. The middle immersion portion is covered with an inert insulating coating film 8 such as a polymer or glass. Ag · A is near the probe electrode 3.
A simple reference electrode 7 such as a gCl type or Pt, Au wire or the like is provided. As a potential reference for the electrolyte system, a probe electrode 3 and a recording layer 5 are connected via a potential regulating circuit (potentiometer) 27. The potential on each surface is regulated, and the potential fluctuation accompanying the electrode reaction at the time of recording or the electric double layer near the electrode is corrected. The recording medium portion includes a working electrode 4 formed on a support, an electron blocking layer 19 formed thereon,
Further, it is constituted by a recording layer 5 formed thereon, so that electron transfer between the working electrode 4 and the recording layer 5 is blocked. In this embodiment, a monolayer film of a t-butyl derivative of lutetium and diphthalocyanine [LuH (Pc) ₂ ] is used as the recording layer 5, and a two-layer film of Kapton-type polyimide is used as the electron blocking layer 19. Formed.

The details will be described below. First, the optically polished glass substrate was washed with a neutral detergent and trichlene, and then ITO was vacuum-deposited by a sputtering method to form a working electrode 4. The Kapton type polyimide film uses pure water as an aqueous phase, has a surface pressure of 35 mN / m, and has a cumulative speed of 5 mm.
At a rate of / min, two layers of PAAD, which is a precursor of polyimide, were laminated in a Y type on the ITO electrode 4 by a vertical immersion method, and then subjected to an imidization treatment. The imidation treatment was performed by a chemical treatment using a mixed solution of acetic anhydride, pyridine, and benzene.

Next, a 0.5 mg / ml solution of [LuH (Pc) ₂ ] t-butyl derivative in a mixed solvent of chloroform / trimethylbenzene / acetone (1/1/2) was used, and the aqueous phase was similarly used. [LuH (Pc) ₂ ] on the above-described polyimide two-layer film under the conditions of pure water, vertical immersion method, surface pressure of 20 mN / m and cumulative speed of 3 mm / min.
A monomolecular film of the t-butyl derivative was formed.

The recording medium portion formed as described above is
It was fixed on the bottom surface of the electrolytic cell container 2, and then an aqueous solution of potassium chloride (KCl) was added as the electrolyte 1 until the recording layer 5, the probe electrode 3, and the reference electrode 7 were immersed.

Hereinafter, the recording and reproducing operations will be described in order. The distance between the probe electrode 3 and the recording layer 5 is set in a state where a voltage of −0.3 V with respect to the recording layer surface potential is applied to the probe electrode 3 while regulating the respective electrode potentials by the potential regulating circuit 27. The recording layer 5 is gradually approached to the probe electrode 3 by the coarse movement mechanism 10 including a piezoelectric piezo element or the like via the coarse movement drive circuit 24. At the same time, while monitoring the current flowing between the probe electrode 3 and the working electrode 4, a tunnel current starts to be generated between the two electrodes to 10 °.
The coarse drive is stopped at a distance of, and then the fine drive mechanism 9 sets a tunnel current value corresponding to the set distance,
The probe electrode 3 is pulled in via the servo circuit 22. Thereafter, while performing X and Y scanning by the fine movement driving mechanism 9 via the XY scanning driving circuit 25, the servo circuit 22 is operated so that the tunnel current becomes constant.
By monitoring the Z-direction control signal to the fine movement driving mechanism 9 which is the output voltage of No. 2, it is possible to detect the unevenness state or the electronic state of the recording layer surface.

As described above, first, an area of several tens of nm square is scanned, and it is confirmed that the area is sufficiently flat within a range of several to several tens of squares. Z
After holding and fixing the direction fine drive servo signal and the XY scanning signal, first, the potential of the probe electrode 3 is -1.5 V with respect to the Ag / AgCl reference electrode 7 (with respect to the reference electrode 7), and the recording layer surface potential is 0 V (with respect to the reference electrode 7). To the reference electrode 7),
Drift injection of Cl ^- ions in the electrolyte into the recording layer. At this time, if there is no electron blocking layer 19 made of a polyimide bimolecular film, electrons are emitted from the recording layer 5 side to the working electrode 4, and the chemical formula 10

[0086]

Embedded image Oxidation reaction proceeds, and an oxidized region, that is, a recording bit is formed over a relatively large region corresponding to the spread of the electric field depending on the distance between the probe electrode 3 and the working electrode 4. However, in the structure of this embodiment, the electron emission is not performed by the presence of the electron blocking layer 19, thus the oxidation reaction does not proceed, the injected anions Cl ^- is left in the recording layer remains ions. Thereafter, by applying a 2.5 V pulse voltage of opposite polarity between the probe electrode 3 and the recording layer surface, the probe electrode potential (relative to the surface of the recording layer 5) becomes 1.0 V only when the pulse is applied, and the recording is performed. Tunneling electrons are generated from the microscopic region corresponding to the topmost atom of the probe electrode on the layer surface toward the topmost atom of the probe electrode, and [LuH (P
c) The oxidation reaction proceeds only with the ₂ ] molecule. In this case, the reaction region is limited to the effective tunnel current region, and although there is a slight variation depending on the pulse width, a very small recording bit of tens to several tens of φ can be formed. After the pulse application, the probe electrode potential is returned to the initial state of -0.3 V (relative to the surface of the recording layer 5), whereby Cl ^- ions remaining in other regions where the oxidation reaction has not progressed are removed from the electrolytic solution. Re-released to

The reproduction was performed by re-scanning a region of several tens of nm around the periphery which was scanned before recording, while keeping the probe potential at -0.3 V (relative to the surface of the recording layer 5). In the [LuH (Pc) ₂ ] .2Cl oxidized region where the recording bit was formed, a conspicuous state or a remarkable change in the electronic state was observed corresponding to a region of 20 to 50 ° φ, and a signal of three digits in terms of tunnel current was detected. A change was detected.

The erasing is performed by first setting the probe potential to 1.5 V (relative to the reference electrode 7) and the recording layer surface potential 0
In a state of being biased to V (with respect to the reference electrode 7), a pulse voltage of -2.5V of opposite polarity is applied between both electrodes, and the probe electrode potential is instantaneously changed to -1.0V (to the surface of the recording layer 5) Was made by changing to). At the same time as the pulse application, tunnel electrons are injected from the probe electrode side into the recording layer.

[0089]

Embedded image Of the anion C after the pulse voltage application period
l ^- was released from the recording layer, and the recording bit was reduced to the initial state, confirming that it could be erased.

(Embodiment 6) FIG. 8 is a schematic diagram of this embodiment. The present embodiment is characterized in that a second counter electrode 28 other than the probe electrode 3 is provided as an electrode facing the working electrode 4 on which the recording layer 5 is formed. Example 5
Uses the probe electrode 3 as the only counter electrode, and superimposes a pulse of the opposite polarity at the time of recording / erasing, when transitioning from the first stage of injecting and ejecting mobile ions to the second stage of injecting tunnel electrons. In the present embodiment, the bias is applied in the first stage, that is, the bias application for controlling the movable ion injection / injection is performed by using a flat second newly provided counter-parallel to the surface of the recording layer 5. 2 and the probe electrode 3 is used as a control electrode.
By applying a reverse polarity pulse under the bias of the second counter electrode 28, the reaction proceeds by injecting and ejecting tunnel electrons, which is the second stage.

Here, the second counter electrode 13 was formed by vacuum-depositing Au or Pt on a support. The materials used for the recording layer 5, the electron blocking layer 19, etc., the applied bias conditions for recording / reproducing / erasing, and the like are all the same as in the fifth embodiment.

FIGS. 9 (a) to 9 (c) show the application of the micromechanics technology using the above-described semiconductor process.
It is a conceptual diagram which forms a plurality by integrating the above-mentioned system. Fine movement drive cantilever type actuator 1 with piezoelectric thin film bimorph structure such as ZnO on the same Si substrate 18
The probe electrode 3 and the second counter electrode 28 are provided on each cantilever in addition to the drive electrode 14 as shown in the figure. 9A and 9B, the reference electrode 7 is fixed on the supporting Si substrate 18, but may be provided on each cantilever or near the probe electrode. Further, the drive electrode 14 and the wiring electrodes 15 and 16 need to be covered with an inert insulating coating film 17 in order to prevent unnecessary side reactions.

(Embodiment 7) FIG. 10 is a schematic diagram of this embodiment.

The feature of this embodiment is that, instead of providing the electron blocking layer 19, semiconductor layers having different conductivity types are used for the recording layer 5 and the working electrode 4 so that the junction interface has diode characteristics. And an electron barrier generated at the time of reverse bias.

For example, as the working electrode 4,
After forming ITO, which is a type semiconductor, by a sputtering method, as a recording layer 5, an iridium hydroxide Ir showing P-type conduction which is famous as an inorganic electrochromic material is used.
This is achieved by subsequently forming O _x (OH) _nx . IrO _x (OH) _nx is formed by sputtering at a high frequency of 50 to 500 ° in a O ₂ , H ₂ atmosphere using metal Ir as a target.

Using 0.05 MH ₂ SO ₄ as an electrolytic solution, a probe electrode potential was first set to −1.5 V (relative to the surface of the recording layer 5) as a writing bias, and proton H ⁺ was introduced into the recording layer. inject. At this time, a depletion layer is generated at the junction interface between the working electrode 4 and the recording layer 5, and an electron barrier is formed. Therefore, electrons are not supplied from the working electrode 4, and protons H ⁺ are ionized in the film. By continuously superimposing a 2.5 V pulse voltage of the opposite polarity, tunnel electrons are injected from the probe electrode 3 into the recording layer 5, and the chemical formula 12

[0097]

Embedded image Can proceed with the reduction reaction. The reproducing and erasing methods are the same as in the first embodiment.

As the other recording layer 5, for example, a conductive polymer group formed by an electrolytic polymerization method is listed. In these electrolytically polymerized films, the conductivity type can be easily controlled by doping an acceptor or donor type ionic species in the electrolytic solution, which is suitable for the present embodiment.
For example, polyaniline PAn electrolytically polymerized in a perchloric aqueous solution containing an aniline monomer exhibits P-type conductivity. This film is electrochemically active, anionic species ClO ₄ ^- can be repeated doping and dedoping reaction reversible.

(Embodiment 8) In Embodiments 5 to 7 described above, all were in the system using an electrolytic solution as an electrolyte. However, in this embodiment, a solid electrolyte is used as the electrolyte 1 so as shown in FIG. As described above, the solid electrolyte layer 1 is sandwiched between the recording layer 5 and the working electrode layer 4 and is integrated as a recording medium portion. In this system,
The application of unipolar bias between the probe electrode 3 and the working electrode 4 has the advantage that the injection of mobile ions between the solid electrolyte and the recording layer and the injection and tunneling of tunnel electrons between the probe electrode and the recording layer are simultaneously established. There is no need for a two-stage potential control with polarity reversal as in liquid systems.

For example, when the [LuH (Pc) ₂ ] t-butyl derivative described in Example 5 is used as the recording layer 5, lead difluoride PbF ₂ can be used as the solid electrolyte 1. Such PbF ₂ is obtained by heating a molybdenum board to 550 to 600 ° C. and performing a pre-deposition vacuum of 5 × 10 ⁻⁶ T.
orr, deposition rate 5 ° / sec, 50-500
形成 Formed by vacuum evaporation, and then
A [LuH (Pc) ₂ ] t-butyl derivative monomolecular film is formed by the method B.

The voltage of -0.3 V (the working electrode 4) was applied to the probe electrode 3.
STM operation was performed in the same manner as in Example 5 while monitoring the tunnel current generated at that time, and the distance between the probe electrode 3 and the recording layer 5 was controlled to several Å. By applying a pulse of 0.0 V (to the working electrode 4), the anion F
^- at the same time is injected, the probe electrode 3 from the recording layer 5
Tunneling electrons are emitted toward the few atoms at the forefront of the compound, and in a microscopic region corresponding to the effective tunnel current region, the chemical formula 13

[0102]

Embedded image Oxidation reaction progresses, and a very small recording bit of tens to several tens of φ can be formed.

As in the case of the fifth embodiment, a probe electrode of -0.3 V (with respect to the working electrode 4) is applied for reproduction, and a probe electrode of -2.0 V (for the working electrode 4) is applied for erasing. It can be carried out.

Examples of the combination of the other recording layer 5 and the solid electrolyte 1 include, for example, tungsten trioxide WO ₃ , which is a typical transition metal oxide, as the recording layer 5;
Pentoxide Ta which is a good proton conductor
₂ O ₅ systems can be listed.

A voltage of -1.5 V (working electrode 4
By applying a pulse voltage, Ta ₂
At the same time as the proton H ⁺ is injected from the O ₅ layer, the tunnel electrons are emitted and injected from a few atoms at the tip of the probe electrode, whereby chemical formula 14 is obtained.

[0106]

Embedded image The reduction reaction proceeds, and a very small recording bit of tens to several tens of φ is formed.

[0107]

As described above, the system composed of the probe electrode, the recording layer that performs the reversible oxidation-reduction reaction, and the region for compensating the reaction in the recording layer provides gas generation and reaction accompanying the reaction of the recording layer. By providing an information processing apparatus having reversibility as a whole system without product precipitation or the like, recording at an ultra-high density has become possible as compared with conventional optical and magnetic memory recording. Also, as compared with the recording / reproducing method using the recently proposed various STM techniques, there is a great advantage in that erasing is possible.

[Brief description of the drawings]

FIG. 1 is a block diagram showing an information processing apparatus according to the present invention.

FIG. 2 is a principle diagram illustrating the present invention.

FIG. 3 is a principle diagram illustrating the present invention.

FIG. 4 is a diagram showing a variation of the arrangement of a reaction compensation region according to the present invention.

FIG. 5 is a diagram showing an application example to a multi-probe electrolyte system according to the present invention.

FIG. 6 is a diagram showing an application example to a solid electrolyte system according to the present invention.

FIG. 7 is a block diagram illustrating an information processing apparatus according to the present invention.

FIG. 8 is a conceptual diagram of another embodiment according to the present invention.

FIG. 9 is a diagram showing an application example to a multi-probe electrolyte system according to the present invention.

FIG. 10 is a conceptual diagram of another embodiment according to the present invention.

FIG. 11 is a conceptual diagram of another embodiment according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrolyte 2 Electrolysis cell container 3 Probe electrode 4 Working electrode 5 Recording layer (reaction medium) 6 Reaction compensation area 7 Reference electrode 8 Inactive insulating coating film 9 Fine drive mechanism 10 Coarse drive mechanism 11 X, Y stage 12 Cantilever type Actuator 13 Reaction compensating electrode 14 Drive electrode 15 Probe electrode wiring electrode 16 Reaction compensating electrode wiring electrode 17 Inactive insulating coating film 18 Si substrate 19 Electron blocking layer 21 Computer 22 Servo circuit 23 Current-voltage conversion amplifier circuit 24 Coarse driving Circuit 25 XY scanning drive circuit 26 Pulse applying circuit 27 Potential regulating circuit 28 Second counter electrode

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiko Takeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-4-76840 (JP, A) JP-A-2 −146128 (JP, A)

Claims (8)

(57) [Claims] At least one probe electrode and a working electrode opposed to the probe electrode are provided. An electrolyte for supplying mobile ions and an oxidized state and a reduced state by applying an external voltage in the presence of the electrolyte are provided. A recording medium capable of easily controlling a reversible change between the probe electrode and the working electrode is disposed between the probe electrode and the working electrode, and a means for applying a voltage between the probe electrode and the working electrode, and the probe In an apparatus provided with a means for controlling the distance between an electrode and the recording medium, a reaction compensation region for compensating a reaction for an oxidation reaction or a reduction reaction in a state change of the recording medium, on a probe except for the tip of the probe or its An information processing apparatus provided near or near the surface of a recording medium. 2. The information processing apparatus according to claim 1, wherein the reaction compensation area is formed of the same material as a recording medium, and its initial state is set to a state opposite to that of the recording medium. 3. An oxidizing state and a reducing state by applying at least one probe electrode and a working electrode opposed to the probe electrode and applying an external voltage in the presence of an electrolyte for supplying mobile ions and the electrolyte. A recording medium capable of easily controlling a reversible change between the probe electrode and the working electrode is disposed between the probe electrode and the working electrode, and a means for applying a voltage between the probe electrode and the working electrode, and the probe In a device provided with a means for controlling a distance between an electrode and the recording medium, electrons involved in a change between an oxidized state and a reduced state of the recording medium are generated by a tunnel current generated between the probe electrode and the recording medium. An information processing apparatus characterized by being supplied. 4. The electrolyte is an electrolyte having a reference electrode for regulating potential near the surface of the recording medium, and a portion immersed in the electrolyte except for the foremost part of the probe electrode. 4. The information processing apparatus according to claim 3, wherein the information processing apparatus is covered with an active insulating material. 5. Between the recording medium and the working electrode,
5. An electron blocking layer is provided.
An information processing apparatus according to claim 1. 6. The information processing apparatus according to claim 4, wherein the recording medium and the working electrode are semiconductor materials having different conductivity types from each other, and a junction interface between the two has diode characteristics. 7. An information processing apparatus according to claim 5, further comprising a second counter electrode other than said probe electrode, said second counter electrode facing said working electrode. 8. The method according to claim 3, wherein the electrolyte is a gel or solid electrolyte, and the gel or solid electrolyte is disposed between the recording medium and the working electrode. Information processing device.