JPH0528548A - Information processing equipment - Google Patents

Abstract

(57) [Abstract] [Purpose] By producing a reversible state change in a very small area on a recording medium by a redox reaction,
An object of the present invention is to provide an erasable information processing device that has a memory property and has a higher density than conventional ones. A probe electrode 3 and a working electrode 4 arranged opposite thereto are provided, and an electrolyte 1 for supplying mobile ions and a reversible state between an oxidized state and a reduced state by an external voltage application in the presence of the electrolyte. Recording media 4 and 5 capable of controlling various changes are arranged between the probe electrode 3 and the working electrode 4,
Furthermore, in an apparatus provided with a means for applying a voltage between the probe electrode 3 and the working electrode 4 and a means for controlling the distance between the probe electrode and the recording medium, a reaction to an oxidation reaction or a reduction reaction in the state change of the recording medium is performed. The information processing device is provided with the reaction compensation region 6 for compensating for the above, on or near the probe excluding the probe tip portion.

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 specifically, a recording medium arranged 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 device using a reversible state change caused by an electrochemical redox reaction.

[0002]

2. Description of the Related Art In recent years, the use of memory materials has become the core of the electronics industry for computers and related equipment, video discs, digital audio discs, etc., and the development of such materials is extremely active. The performance required for the memory material varies depending on the application, but generally, high density and large recording capacity are required.

Up until now, semiconductor memories and magnetic memories made of magnetic materials or semiconductors have been mainly used, but with the recent progress of laser technology, optical memories using organic thin films such as organic dyes and photopolymers have become inexpensive. High-density recording media have appeared.

In an optical memory, high density recording / reproducing on the order of μm has become possible by utilizing the unevenness of the surface of the recording medium and the difference in reflectance. As the recording medium, a thin film of a metal or a metal compound, an organic dye thin film, or the like is used,
Information is recorded by using the heat of laser light to make holes or change the reflectance by evaporation / melting, and in such a method, the spot diameter of the laser light used determines the recording density. There is. In addition, at the present time, video information is rapidly advancing, and there is an increasing demand for the development of a small-sized, large-capacity, high-density memory.

On the other hand, recently, a scanning tunneling microscope (hereinafter abbreviated as STM) has been developed which allows direct observation of the electronic structure of surface atoms of a conductor [G. Binning et a
l. , Helvetica Physica Act
a, 55 , 726 (1982)], real-space images can be measured with high resolution regardless of single crystal or amorphous.
Moreover, it has the advantage that it can be observed at low power without damaging the medium with electric current, and also operates in the atmosphere, and can be used for various materials, so wide-ranging applications are expected.

This STM utilizes the fact that when a voltage is applied between a metal probe and a conductive substance to bring them closer to a distance of about 1 nm, a tunnel current flows between them. This current is very sensitive to changes in the distance between the two, and by scanning the probe to keep the tunnel current constant,
It is possible to draw the surface structure in real space, and at the same time, read various information about the total electron cloud of surface atoms.

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

Further, it has been attempted to apply a voltage that causes field emission to the probe electrode of the STM and locally melt it on the sample surface of the Rh-Zr alloy to form a cone-shaped protrusion [U. Staffer et al. , Appl. P
hys. Lett. 51 (4) 27 July 198
7].

[0009]

DISCLOSURE OF THE INVENTION The object of the present invention is to achieve a higher density than the conventional one having a memory property by causing a reversible state change in a very small area on a recording medium by a redox reaction. And providing an erasable information processing device.

[0010]

Means and Actions for Solving the Problems As a constitution for achieving the above-mentioned object, firstly, at least one probe electrode and a working electrode arranged to face the probe electrode are provided, and mobile ions are supplied. An electrolyte and a recording medium capable of easily controlling a reversible change between an oxidized state and a reduced state by applying an external voltage in the presence of the electrolyte are disposed between the probe electrode and the working electrode, and A device provided with a means for applying a voltage between the probe electrode and the working electrode and a means for controlling the distance between the probe electrode and the recording medium, which is an oxidation reaction in a change in the state of the recording medium or An information processing device provided with a reaction compensation region for compensating the reaction to the reduction reaction, on or near the probe excluding the probe tip, or near the recording medium surface. There is a point.

That is, the first feature of the present invention is to apply a bias voltage between the probe electrode 3 and the working electrode 4 as shown in FIG. Reaction compensation region 6 for charge compensation of oxidation reaction or reduction reaction caused by (layer 5 laminated)
The probe electrode 3 is provided on the probe electrode excluding the leading edge, or a new dedicated electrode is 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 area 6 is formed of the same material as the recording medium, and the redox state of the compensation area is set to the reverse state of the recording medium in its initial state. To be there.

Generally, in an electrode reaction in an electrochemical reaction system, the charge proceeds between the two electrodes so that the reaction proceeds without accumulating the charge. For example, when an oxidation reaction accompanied by electron emission occurs at one electrode, a reduction reaction accompanied by electron addition proceeds at the other electrode, the balance of electrons is offset and the charge is compensated. Further, in the reaction system of the measuring electrolyte cell, a noble metal or carbon such as Pt, Au, Ir or the like which does not itself react but has a strong catalytic action as a counter electrode with respect to the working electrode on which the measurement material of interest is formed. Is used. In this case, as a counter reaction that occurs on the counter electrode side as a compensating reaction for the oxidation reaction or the reduction reaction that proceeds at the working electrode 4, most of the reactions involving the generation of gas or the deposition of reaction products, and as a whole system It is an irreversible reaction system. In the case of the measurement cell, the surface area of the counter electrode is much larger than that of the working electrode, and at the same time, the adsorbed gas on the surface of the counter electrode or the reaction product can be desorbed by replenishing, stirring or washing the electrolyte. It does not matter that it is a reversible reaction system.

However, when considering it as an STM memory system, the generation of gas and the deposition of reaction products at the tip of the probe electrode corresponding to the counter electrode, especially at the tip thereof,
This will hinder the STM operation such as distance control and reproduction using the tunnel current involving the tip of the probe electrode. At the same time, in the irreversible system, there are problems in film peeling, durability, characteristic deterioration, etc. due to gas generation, and a reversible reaction system in which gas generation and reaction product precipitation do not occur is desirable for the entire system.

Therefore, in the present invention, a pair of oxidation reaction or reduction reaction that progresses on the reaction medium side near the probe tip is prevented so that an unnecessary side reaction does not occur at the tip of the probe electrode 3 which is the key to the STM operation. It is proposed to establish a reversible reaction system as a whole system by providing a region for compensating the reaction.

The reaction in the reaction compensation region 6 should be such that the reaction potential is smaller than the gas generation potential or the side reaction product deposition potential at the tip of the probe electrode, and the reaction system as a whole including the balance of mobile ions is reversible. Good.

In particular, the present invention proposes to use the reverse reaction of the reaction proceeding in the recording medium as an ideal compensation reaction, which is the second feature of the present invention. By forming the reaction compensation region with the same material as the recording medium and setting the oxidation-reduction state of the reaction compensation region to the reverse state of the recording medium in the initial state, the same reaction potential and reaction equivalence as those of the recording medium can be obtained. It is possible to realize an ideal reversible reaction system in which the same mobile ions are added and desorbed.

In the present invention, at least one probe electrode is used for one electrode, and the probe electrode is
By using M to bring it close to the recording medium, approximately 1 nm, to limit the region where the redox reaction takes place, and to generate molecules or molecular groups with different electronic states in an extremely minute region, high density recording is possible. Has achieved.

The distinction between the regions having different electronic states is as follows.
It is impossible with the reading conventionally used for optical recording, and it becomes possible only by using the STM which is extremely sensitive to the spread of the electron cloud near the molecule. Specifically, it is detected by the change in the 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 to keep the tunnel current value constant, and the detection is performed by the control signal at that time. Good.

Materials used for the recording medium and the reaction compensator according to the present invention include organic compounds and inorganic compounds capable of a wide range of reversible redox reactions, and typical examples include electrochromic materials. .

The electrochromism means a phenomenon in which one or both of the electron transfer bodies are colored by an electrochemical redox reaction, and the electronic state and its band structure are caused by the change of the valence of a metal ion or an organic molecule. Is changed, the physical characteristics such as absorption spectrum or conductivity reversibly switch. In view of such a memory property, application as a recording medium is expected to be promising in addition to display. For organic substances, viologen polymers, styryl compounds, rare earth diphthalocyanines, TTF-modified polystyrene, etc., or conductive polymer groups such as polythiophene, polyaniline, polypyrrole, polychenylene, etc., which are easily obtained mainly by doping an electropolymerized film, and for inorganic substances, WO ₃ , Transition metal oxides such as IrO _x are typical.

Next, a second structure capable of achieving the above object has at least one probe electrode and a working electrode arranged to face the probe electrode, and in the presence of an electrolyte supplying mobile ions and the electrolyte. A recording medium capable of easily controlling a reversible change between an oxidized state and a reduced state by applying a voltage from the outside 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 the electrons involved in the change between the oxidized state and the reduced state of the recording medium, The information processing device is supplied by a tunnel current generated between the probe electrode and the recording medium.

Here, the electrolyte is an electrolytic solution, and a standard reference electrode for regulating potential is provided near the surface of the recording medium.
Moreover, the point that the portion immersed in the electrolytic solution excluding the tip end portion of the probe electrode is coated with an inert insulating material, and the electrolyte is a gel or solid electrolyte, Gel or solid electrolyte is arranged between the recording medium and the working electrode, further,
It is also configured to dispose an electron blocking layer between the recording medium and the working electrode, and the recording medium and the working electrode are semiconductor materials having different conductivity types, and the bonding interface between them is A point having a diode characteristic,
Further, the present invention is also characterized by an information processing device satisfying the point that a second counter electrode other than the probe electrode is provided so as to face the working electrode, and the like.

The structure and operation of the present invention will be described in more detail below.

In the present invention, the electrons involved in the reversible redox reaction in the recording medium, which are caused by the voltage applied between the probe electrode and the working electrode, are generated between the probe electrode and the recording medium at least during recording. Is to be supplied by the tunnel current generated in the. According to this, since the electrons involved are tunnel electrons from only a few atoms at the leading edge of the probe, the redox reaction caused in the recording medium is also limited to the effective tunnel current region, and it is extremely small with a dozen Å to 100 Åφ or less. It is possible to control the reversible state change limited to a large area.

The features of the present invention described above will be described in more detail with reference to FIG. Generally, reversible redox reactions involving addition and desorption of mobile ions are carried out by cations (Kati
on) K ⁺ and anion (Aion) A ⁻ , they can be represented by Chemical Formula 1 or Chemical Formula 2.

[0027]

[Chemical 1]

[0028]

[Chemical 2] Here, consider the case of a general system in which the electrolyte is an electrolytic solution. As shown in FIG. 2 (a), the reaction medium 5 formed on the working electrode 4 and the probe electrode 3 having a sharp tip in the electrolytic solution containing the movable cation K ⁺ filled in the electrolytic cell container 2.
Biasing the probe electrode 3 side in the positive direction with respect to the working electrode 4 in the reaction system facing each other, positive ions K ⁺ are forcibly drifted into the reaction medium 5 and simultaneously injected from the working electrode 4 side. The electron causes the forward reaction shown in the chemical formula 1 to proceed to produce the product MK.

When a voltage is applied in a direction in which mobile ions are forced to drift into the medium in order to cause a redox reaction, the electrons involved in this reaction are always on the side of the working electrode 4 on which the reaction medium 5 is formed. Supplied by. On the other hand, in the reverse bias, the positive ions 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 the chemical formula 1 (FIG. 2 (b)), the forward reaction of the chemical formula 2 (FIG. 2 (c)), and the reverse reaction of the chemical formula 2 (FIG. 2 (d)). When a bias is applied between the working electrode 4 and the probe electrode 3 in the direction in which mobile ions are injected or extracted in the reaction medium 5 in the direction in which each reaction proceeds, the electrons involved in each reaction are always 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, when the bias is applied in the reverse direction, mobile ions cannot participate, and therefore the reaction does not proceed.

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

Therefore, as a structural feature for realizing the present invention, the electron blocking layer 19 is provided between the working electrode 4 and the reaction medium 5.
Or the reaction medium 5 and the working electrode 4 are formed of semiconductor materials having different conductivity types, and an electron barrier layer is formed when a bias is applied.
It is proposed to block the electron transfer between them. As shown in FIG. 2A, first, in order to cause the forward reaction of Chemical formula 1, the potential of the probe electrode 3 is biased in the positive direction with respect to the working electrode 4, and the cations in the electrolytic solution are mixed with the reaction medium 5. Forced to drift in. However, at this time, the electrons from the working electrode 4 are blocked by the above-mentioned electron blocking layer 19, so that the reaction does not proceed. Immediately after supplying the cations, a pulse voltage of opposite polarity is applied to supply tunnel electrons from the probe tip before the cations in the reaction medium 5 diffuse or drift into the electrolytic solution. The reaction can proceed. In this case, the reaction area is limited to the tunnel current area, and a reversible redox reaction can be realized in a microscopic area of a dozen Åφ to a hundred Åφ. 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, the forward reaction and the reverse reaction of the chemical formula 2 (FIG. 2 (b)). First, mobile ions are poured in and out in the reaction direction, and the tunneling time of electrons moves the ions. By taking advantage of the fact that the time is much shorter than the time, the tunneling electrons take part in and out between the probe electrode 3 and the reaction medium 5 before the ions undergo reverse diffusion or backward drift, and thus the redox involving the tunneling electrons is performed. The reaction can proceed. In FIG. 2, the polarities of the probe electrode 3 are switched to inject and inject mobile ions and inject and inject tunnel electrons. However, a counter flat electrode for pouring and injecting mobile ions is separately provided, and the probe electrode 3 is used when tunnel electrons are generated. Only the control electrode may be used. Figure 2
(C) and (d) are for forming a pn junction by making the conductivity types of the reaction medium 5 and the working electrode 4 different from each other. If a reverse bias is applied in the reaction progressing direction, the electron blocking layer is formed. The electron supply from the working electrode 4 side can be cut off without providing 19.

As described above, the distance between the probe electrode 3 and the recording layer 5 (corresponding to the reaction medium 5) of the recording medium is set to cause the redox reaction in the microscopic region by the tunnel electrons, that is, for recording. 0.1 Å within a distance of 10 Å
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 STM analysis technique described above. The same applies to the case of reproducing the recorded bit. The tunnel current that reflects the difference in the electronic state corresponding to the difference in the physical state such as the conductivity, surface work function, intermolecular bonding state, and molecular group size of the reacted recording bit is calculated. Detecting and STM technology can realize Å-order in-plane direction resolution.

Now, as compared with the atmosphere and the vacuum, the STM analysis in the electrolyte is particularly problematic because it is difficult to discriminate the faradic current and the tunnel current generated by the movement of the mobile ions. In order to solve the problem, it is necessary to control the distance and suppress the potential of the surface of the recording layer 5 and the surface of the probe electrode 3 of the recording medium to the reaction potential or less at which the surface reaction occurs at the time of reproduction. It is important to keep the reaction area to the necessary minimum so that the effect is minimized even if it occurs.

Therefore, as a next feature of the present invention, the system in the electrolytic solution has a reference electrode 7 for regulating the potentials of the surface of the recording layer 5 and the surface of the probe electrode 3 near the surface of the recording medium (see FIG. 1). Further, the probe electrode 3 that is the tunnel electron generating part, the tip part of the probe electrode 3 except for the region of 1 nm to several hundred nmφ is immersed in the electrolytic solution and is covered with an inert insulating material such as a polymer or glass, which is unnecessary. It proposes to limit the area where surface reaction occurs to the minimum, 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 arranged between the recording layer 5 and the working electrode 4, and the one direction is provided between the probe electrode 3 and the working electrode 4. It is another object of the present invention to propose a configuration in which mobile ion extraction and extraction between the electrolyte and the recording medium and tunnel electron injection and extraction between the recording medium and the probe electrode are simultaneously established by applying a bias voltage.

The recording layer 5 according to the present invention covers a wide range of organic and inorganic compounds capable of reversible oxidation-reduction reaction, and typical examples include electrochromic materials. Electrochromism is a phenomenon in which one or both of electron carriers are colored by an electrochemical redox reaction, and the electronic state and its band structure change due to the change in valence of a metal ion or an organic molecule. As a result, the physical properties such as absorption spectrum and conductivity can be reversibly switched, and since it also has a memory property, it is expected to be applied as a recording medium in addition to display applications. For organic substances, viologen polymers, styryl compounds, rare earth diphthalocyanines, TTF-modified polystyrene, etc., or conductive polymer groups such as polythiophene, polyaniline, polypyrrole, polychenylene, etc., which are easily obtained mainly by doping an electropolymerized film, and for inorganic substances, WO
Typical examples are transition metal oxides such as ₃ and IrO _x .

The electron blocking layer 19 is an inorganic material such as various oxide films such as Al ₂ O ₃ or a nitride film, and a linear fatty acid based material, which has been reported to have good insulating properties by the LB method in the organic system,
Polyimide-based materials are preferred.

As the solid or gel electrolyte, Si is used.
Hydrous dielectrics such as O, MgF ₂ , Cr ₂ O ₃ , ZrO ₂ , Ta ₂ O ₅ , or β-alumina, RbAg ₄ I ₅ , Li ₃ N, acrylamidomethyl, propanesulfonic acid polymer, N
A solid electrolyte containing mobile ions suitable for the reaction medium such as afion, PbF ₂ , LiF, and CaCl ₂ , or a gel obtained by impregnating various electrolytic solutions with a polymer such as polyether may be considered.

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

In the LB method, in a molecule having a structure having a hydrophilic site and a hydrophobic site in the molecule, when the balance between them (the amphipathic balance) is appropriately maintained, the molecule is This is a method of forming a monomolecular film or a cumulative film thereof by utilizing the fact that a hydrophilic group faces downward to form a monomolecular layer.

According to the LB method, a monomolecular film of an organic compound having a hydrophobic site and a hydrophilic site in one molecule or a cumulative film thereof can be easily formed on a substrate, and a thickness of a molecular order is obtained. It is possible to stably supply a uniform and homogeneous organic ultra-thin film having a large area. Therefore, it is possible to easily form the ultra-thin film necessary for the STM analysis. Further, regarding the response speed, which is a weak point of electrochromism, the factor that controls this is the drift speed of free charges, which does not matter in the state of such an ultrathin film.

In the present invention, the substrate for supporting the thin film in which the inorganic and organic materials are laminated may be any of metal, glass, ceramics, plastic materials and the like. It is preferable that the substrate as described above has an arbitrary shape and is a flat plate, but is not limited to a flat plate. That is, the above-mentioned film forming method has an advantage that a film can be formed in accordance with the shape of the substrate regardless of its shape.

On the other hand, the electrode material used in the present invention may be any one as long as it has high conductivity and does not cause an unnecessary reaction with the electrolyte. For example, Au, Pt, Ag, Pd, A.
Metals such as l, In, Sn, Pb, W and alloys thereof,
Furthermore, graphite and silicide, and even IT
There are many materials including conductive oxides such as O, and their application to the present invention is considered. As a method for forming an electrode using such a material, a conventionally known thin film technique is sufficient.

Further, the tip of the probe electrode 3 needs to be as sharp as possible in order to improve the resolution of recording / reproducing / erasing. In the present invention, the tip of platinum having a thickness of 1 mm is 90
It is mechanically polished so that it becomes a cone of ° and the surface atoms are evaporated by applying an electric field in an ultrahigh vacuum.
It is not limited to this.

The portion of the probe electrode 3 except for the tip of the probe electrode immersed in the electrolytic solution is covered with an insulating inactive material such as polymer or glass to minimize the faradaic current due to a side reaction on the surface of the probe electrode. , Distance control,
The S / N ratio of the tunnel current signal during reproduction is guaranteed.

[0047]

EXAMPLES Examples of the present invention will be described below.

(Embodiment 1) FIG. 1 is a block configuration diagram showing an information processing apparatus showing a first embodiment of the present invention. In the figure, 23 is a current-voltage conversion amplifier, and 22 is a fine movement drive mechanism 9 using a piezoelectric element so that the probe current becomes constant.
It is a servo circuit for controlling. Reference numeral 27 denotes a potential regulation circuit that controls the surface potentials 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 is a pulse application circuit for applying a pulse voltage for recording / erasing between the probe electrode 3 and the working electrode 4.

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.

Reference numeral 25 is an XY scanning drive circuit for controlling the movement of the probe electrode 3 in the XY directions. Coarse drive mechanism 1
0 and the coarse drive circuit 24 are arranged in advance so that a probe current of about 10 ⁻⁹ A can be obtained beforehand and the probe electrode 3 and the recording layer 5
The distance between and is controlled by coarse movement. The respective functions are centrally controlled by the computer 21.

In this example, a platinum probe electrode was used as the probe electrode 3. This probe electrode 3 is
The distance (Z) is finely controlled by the piezoelectric element so that the tunnel current flowing to the surface of the recording layer 5 is kept constant. Further, the fine movement drive mechanism 9 is designed so that the fine movement can be controlled in the in-plane (X, Y) directions 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 surface of the probe electrode 3 and the surface of the recording layer 5, but is preferably fixed. The drive is controlled 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, t- of lutetium diphthalocyanine [LuH (Pc) ₂ ] was used by the LB method.
A monolayer of butyl derivative was formed. The details are shown below.

After the optically-polished glass substrate was washed with a neutral detergent and trichlene, IT was performed by a sputtering method.
O was vacuum-deposited to form an electrode. Next, [LuH (P
c) ₂ ] t-butyl derivative 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. The above substrate was submerged in a pure water phase at 20 ° C., and then the solution was developed on the water phase to form a monomolecular film on the water surface. Waiting for the solvent to evaporate, increase the surface pressure of the monolayer to 20 mN / m, and while keeping it constant, gently pull up the substrate across the water surface at a speed of 3 mm / min to deposit the monolayer on the substrate. Formed. The recording layer 5 is also formed in exactly the same manner.

The potential of the reaction compensating region 6 is the potential regulating circuit 2
Although it may be controlled independently by 7, it is set to the same potential as the probe electrode 3 in this embodiment.

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

The recording / reproducing operation will be described below in order. To set the distance between the probe electrode 3 and the recording layer 5, a voltage of −0.3 V is applied to the probe electrode 3 with respect to the surface potential of the recording layer 5 while regulating the electrode potential by the electronic regulation circuit 27 (potentiostat). In the applied state, the recording layer 5 is gradually moved to the probe electrode 3 by the coarse movement drive mechanism 10 including a piezoelectric piezo element via the coarse movement drive circuit 24.
Get closer to. At the same time, while monitoring the current flowing between the probe electrode 3 and the working electrode 4, the coarse motion drive is stopped at a distance of -10Å where a tunnel current starts to occur between the two electrodes, and then the fine motion drive mechanism 9 reaches the set distance. The probe electrode 3 is pulled in via the servo circuit 22 so that the corresponding tunnel current value is obtained. After that, the XY scanning drive circuit 25
While the X and Y scanning is performed by the fine movement drive mechanism 9 via the servo circuit 22, the servo circuit 22 is operated so that the tunnel current becomes constant. At this time, the output voltage of the servo circuit 22 is the Z direction to the fine movement drive mechanism 9. By monitoring the control signal, it is possible to detect the uneven state or the electronic state of the surface of the recording layer 5.

As described above, first, a region of several hundred nm □ is scanned, and it is confirmed that the region is sufficiently flat within the range of several Å to ten and several Å. 3A by holding a XY scanning signal and fixing the probe electrode 3 and then 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, as shown in FIG. Similarly, in the recording layer 5, anions (A
^-, wherein the Cl - ^If) is injected, the emitted electrons to the working electrode 4 at the same time, the chemical formula 3

[0059]

[Chemical 3] The oxidation reaction proceeds to form a minute recording bit of tens nm to hundreds of tens nmφ corresponding to the spread of the electric field depending on the distance between the probe electrode 3 and the working electrode 4. here,
If there is no reaction compensation electrode, a reduction reaction of K ⁺ + e ⁻ → K proceeds on the surface of the probe electrode as a counter reaction of the oxidation reaction in the recording layer 5, and potassium is deposited on the probe electrode. When HCl is used as the electrolyte, 2H ⁺ +2
The reduction reaction of e ⁻ → H ₂ proceeds, and H from the probe electrode surface
₂ Gas is generated. In any case, there is a possibility that 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 the anion Cl ⁻ release at chemical formula 4

[0060]

[Chemical 4] Since the reduction reaction of (1) proceeds, there is no fear of side reaction such as reaction generation analysis, gas generation, etc., and good reversibility can be maintained as the entire reaction system, and the object of the present invention can be achieved.

The reproduction is performed by rescanning the peripheral area of several hundred nm scanned before recording with the probe electrode 3 kept at -0.3 V with respect to the surface of the recording layer 5. In the [LuH (Pc) ₂ ] .2Cl oxidation region where the recording bit is formed, a remarkable change in the concavo-convex state or the electronic state is observed corresponding to the region of 20 to 150 nmφ, and a three-digit signal converted into tunnel current is obtained. Changes are 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, so that the recording layer 5 side has a reduction reaction which is a reverse reaction at the time of recording. And at the same time, the oxidation reaction, which is a counter reaction, progresses in the reaction compensation region, and mobile ions and electrons are compensated between the two. After applying the pulse, it was confirmed that the recorded bit was reduced to the initial state and was erasable.

FIG. 3B is a principle diagram in the case where the electron blocking layer 19 is provided between the recording layer 5 and the working electrode 4. In this case, the movement of electrons between the recording layer 5 and the working electrode 4 is blocked, so that even during recording, the electrons involved in the redox reaction on the recording layer 5 are the probe electrodes 3 and the recording layer 5.
It is supplied by the tunnel current generated between them. Therefore, the recording bit to be formed is 1n which corresponds to the effective tunnel current region in which only a few atoms at the tip of the probe electrode 3 are involved.
It is possible to form extremely small recording bits of m to 10 nmφ. Recording is performed in two steps. First, in the first step, the probe electrode and the reaction compensation electrode potential are biased to -1.5 V (relative to the recording layer surface), and the anion Cl is applied on the recording layer side.
^- is injected, while in the reaction compensation electrode side progresses reduction reaction. Here, as the second stage, 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, and the recording layer 5 The oxidation reaction in progresses.

Second Embodiment In the first embodiment, the case where the material of the reaction compensating region 6 is the same as that of the recording layer 5 is described, but the material is not particularly limited to the same material, and the reaction potential may be gas generation or generation. Any material can be used as long as it can undergo a reversible redox reaction lower than the deposition potential of the reaction product and has an appropriate electrolyte capable of supplying the mobile ions of the opposite sides. For example,
In a system having [LuH (Pc) ₂ ] as the recording layer 5, tungsten trioxide WO ₃ , which is a typical inorganic electrochromic material, can be used as the reaction compensation region material.

Here, when the electrolytic solution is an aqueous solution of 0.5 M HCl, the oxidation reaction that progresses in the recording layer 5 at the time of recording, chemical formula 5

[0066]

[Chemical 5] As a counter reaction to

[0067]

[Chemical 6] Reduction reaction progresses, electrolyte decomposition reaction, chemical formula 7

[0068]

[Chemical 7] It is possible to compensate the balance of mobile ions and electrons associated with the above, and maintain good reversibility without generation of gas or precipitation of reaction products in the entire system.

(Example 3) In Example 1, the reaction compensation region 6
Was formed on a compensation electrode newly provided, which is different from the probe electrode 3 and the recording layer 5, but is not necessarily limited to this. FIG. 4A shows a reaction compensation region 6 formed on the electrode surface of the probe electrode 3 excluding the tipmost portion, instead of providing an insulative 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 that the reaction compensation area 6 is integrally formed 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 support is simply used. When forming the working electrode 4 and the recording layer 5 on the upper surface, it is only necessary to divide them into two regions insulated from each other by wet processing or dry etching. After formation, one side is set to a different initial state, and the probe electrode 3 is formed. It can be used as the reaction compensation region 6 by wiring at the same electric potential.

FIGS. 5A to 5C are conceptual diagrams in which a plurality of systems according to the present invention are integrated to form a plurality by applying a micromechanics technique to which a semiconductor process is applied.
On the same Si substrate 18, a fine motion driving cantilever actuator 1 having a piezoelectric thin film bimorph structure such as ZnO.
A plurality of dozens to several hundreds of 2 are formed, and reaction compensation is provided on each cantilever on the electrode 13 formed so as to surround the probe electrode 3 and the probe electrode, in addition to the drive electrode 14 as shown in the figure. Area 6 is provided. Although the reference electrode 7 is fixed on the supporting Si substrate 18, it may be provided on each cantilever or in the vicinity of the probe electrode. In addition, the drive electrode 14 and the wiring electrode 1
In order to prevent unnecessary side reactions, 5 and 16 need to be covered with an inert insulating coating film 17.

(Example 4) Examples 1 to 3 were all in the system using an electrolytic solution as an electrolyte, but in this Example, 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 in that it is 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.
₂ F ₂ can be used. First, a [LuH (Pc) ₂ ] t-butyl derivative monomolecular film was formed on the ITO working electrode 4 by the LB method described above, and then oxidized in a fluoride aqueous solution electrolysis cell to [LuH (Pc) ₂ ] · 2F. And continue to Pb
The F ₂ was heated molybdenum boat 550 to 600 ° C.,
Vacuum degree before vapor deposition 5 × 10 ^-6 torr, vapor deposition rate 5Å / se
50-500Å vacuum evaporation under the condition of c, and finally [L
The uH (Pc) ₂ ] t-butyl derivative is similarly formed into a monolayer to obtain an integrated recording medium portion.

-0.3 V (working electrode 4
STM operation is 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 is controlled to several Å, and then +2 is applied to the probe electrode 3. By applying a pulse of 0.0 V (to the working electrode 4), anions F ⁻ from the solid electrolyte layer 1 are applied.
At the same time as the injection of tunnel electrons, tunnel electrons are emitted from the recording layer 5 toward the most advanced atoms of the probe electrode 3, and in the microscopic region corresponding to the effective tunnel current region, the chemical formula 8

[0075]

[Chemical 8] Oxidation reaction progresses, and it is possible to form a very small recording bit of a dozen Å to several tens Åφ. On the other hand, in parallel, in the reaction compensation layer 6, as a pair reaction,

[0076]

[Chemical 9] The reduction reaction of the above proceeds, and it is possible to maintain good reversibility without generation of gas or precipitation of reaction products as the whole system,
It is possible to achieve high reliability without deterioration of characteristics due to interfacial peeling or the like due to gas generation.

For reproduction, a voltage of -0.3 V (relative to the working electrode 4) is applied to the probe electrode 3, and for erasing, a pulse voltage of -2.0 V (relative to the working electrode 4) is applied to the probe electrode 3. Thus, it can be performed in the same manner as in 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 well known as an inorganic electrochromic material, 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 an aqueous perchloric acid solution system containing an aniline monomer as a recording layer and compensation layer material, and a gel LiBF ₄ or L as electrolyte
Various material configurations can be considered, such as a combination of gelled mixture of an iClO ₄ / propylene carbonate solution with a polymer, or a combination of these recording layer and compensation layer materials different from each other.

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

Now, in this embodiment, recording, reproduction,
The probe electrode 3 used for erasing has the electrolyte solution excluding the tip of the probe in order to minimize the faradaic current due to side reactions on the electrode surface and increase the tunnel current signal S / N ratio during distance control and reproduction. The intermediate immersion portion is covered with an inert insulating coating film 8 such as polymer or glass. Ag · A near the probe electrode 3
A gCl type or a simple type reference electrode 7 of Pt, Au wire or the like is provided, and as a potential reference of the electrolyte system, a potential regulating circuit (potentiostat) 27 is interposed and a probe electrode 3 and a recording layer 5 are provided. The electric potential of each surface is regulated to correct the electric double layer near the electrode or the electric potential fluctuation due to the electrode reaction during recording. The recording medium portion includes a working electrode 4 formed on a support, an electron blocking layer 19 formed on the working electrode 4,
Further, it is constituted by the recording layer 5 formed thereon, and the electron transfer between the working electrode 4 and the recording layer 5 is blocked. In this embodiment, a monolayer film of t-butyl derivative of lutetium and diphthalocyanine [LuH (Pc) ₂ ] is used as the recording layer 5, and a double layer film of Kapton type polyimide is used as the electron blocking layer 19, both of which are formed by the LB method. Formed.

The details will be described below. First, an 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 the water phase and has a surface pressure of 35 mN / m and a cumulative speed of 5 mm.
/ Min, a two-layer Y-type polyimide precursor PAAD was laminated on the ITO electrode 4 by a vertical dipping method, and then imidization treatment was performed. The imidization treatment was a chemical treatment with a mixed solution of acetic anhydride, pyridine and benzene.

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

The recording and reproducing operations will be described below in order. The distance between the probe electrode 3 and the recording layer 5 is set by controlling the potential of each electrode by the potential regulating circuit 27 while applying a voltage of −0.3 V with respect to the surface potential of the recording layer to the probe electrode 3. The recording layer 5 is gradually moved closer to the probe electrode 3 by the coarse movement mechanism 10 composed of 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 occur between both electrodes ~ 10Å
The coarse motion drive is stopped at the distance of, and then the fine motion drive mechanism 9 is set so that the tunnel current value corresponds to the set distance.
The probe electrode 3 is pulled in via the servo circuit 22. After that, the servo circuit 22 is operated so that the tunnel current becomes constant while performing the X and Y scanning by the fine movement driving mechanism 9 via the XY scanning driving circuit 25.
By monitoring the Z-direction control signal to the fine movement drive mechanism 9 which is the output voltage of 2, it is possible to detect the uneven state of the recording layer surface or the electronic state.

As described above, first, the region of several tens nm □ was scanned, and after confirming that the region was sufficiently flat within the range of several Å to several tens of Å, the probe electrode 3 was placed at the center position of the region. Z
After holding and fixing the direction fine drive servo signal and the XY scanning signal, first, the potential of the probe electrode 3 with respect to the Ag / AgCl reference electrode 7 is -1.5 V (with respect to the reference electrode 7) and the recording layer surface potential is 0 V ( (For reference electrode 7),
Cl ⁻ ions in the electrolytic solution are drift-injected into the recording layer. At this time, if the electron blocking layer 19 made of a polyimide bimolecular film is not present, electrons are emitted from the recording layer 5 side to the working electrode 4, and the chemical formula 10

[0086]

[Chemical 10] The oxidation reaction proceeds to form an oxidized region, that is, a recording bit, 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 the present embodiment, electrons are not emitted due to the presence of the electron blocking layer 19, and therefore the above-mentioned oxidation reaction does not proceed, and the injected anion Cl ⁻ remains in the recording layer as ions. Then, by applying a pulse voltage of opposite polarity of 2.5 V between the probe electrode 3 and the surface of the recording layer, the potential of the probe electrode (relative to the surface of the recording layer 5) becomes 1.0 V only when the pulse is applied. Tunnel electrons are generated from the ultrafine region corresponding to the atom at the tip of the probe electrode on the surface of the layer toward the atom at the tip of the probe electrode, and [LuH (P
c) The above-mentioned oxidation reaction proceeds only with the ₂ ] molecule. In this case, the reaction region is limited to the effective tunnel current region, and although it may vary a little depending on the pulse width, it is possible to form a very small number of recorded bits of tens Å to tens Åφ. After the pulse application, the potential of the probe electrode is returned to −0.3 V (relative to the surface of the recording layer 5) in the initial state, so that Cl ⁻ ions remaining in other regions where the oxidation reaction has not progressed remain in the electrolytic solution. Is re-emitted to.

Reproduction was carried out by rescanning the peripheral region of several tens of nm scanned before recording with the probe potential kept at -0.3 V (relative to the surface of the recording layer 5). In the [LuH (Pc) ₂ ] .2Cl oxidation region where the recording bit was formed, a remarkable change in the uneven state or the electronic state was observed corresponding to the region of 20 to 50Åφ, and a three-digit signal converted into tunnel current Changes could be detected.

For erasing, first, the probe potential of 1.5 V (with respect to the reference electrode 7) having the reverse polarity to that at the time of recording, the recording layer surface potential 0
While biased to V (relative to the reference electrode 7), a reverse polarity -2.5V pulse voltage was applied between both electrodes, and the probe electrode potential was instantaneously changed to -1.0V (relative to the surface of the recording layer 5). It was done by changing to. At the same time as the pulse application, tunnel electrons are injected from the probe electrode side into the recording layer, and chemical formula 11

[0089]

[Chemical 11] Of the anion C after the reduction reaction of the
It was confirmed that l ⁻ was released from the recording layer, the recording bit was reduced to the initial state, and erasable.

(Embodiment 6) FIG. 8 shows a schematic view 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
Then, the probe electrode 3 is used as the only counter electrode, and when recording / erasing, a pulse of opposite polarity is superposed at the time of shifting from the first stage of pouring / moving mobile ions to the second stage of injecting tunnel electrons. However, in the present embodiment, the first step, that is, the bias application for controlling the movable ion extraction / injection, was performed by a flat plate newly provided facing the recording layer 5 in parallel. 2 counter electrode 28, the probe electrode 3 is used as a control electrode,
Under the bias of the second counter electrode 28, by applying a reverse polarity pulse, the reaction proceeds by the second stage of injection and extraction of tunnel electrons.

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

9A to 9C show application of the micromechanics technology to which the above-mentioned semiconductor process is applied,
It is a conceptual diagram which integrates the above-mentioned system and forms a plurality. Fine motion drive cantilever type actuator 1 having a piezoelectric thin film bimorph structure such as ZnO on the same Si substrate 18
Several tens to several hundreds of 2 are formed, and 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 drawing. Although the reference electrode 7 is fixed on the supporting Si substrate 18 in FIGS. 9A and 9B, it may be provided on each cantilever or in the vicinity of the probe electrode. Further, the drive electrode 14 and the wiring electrodes 15 and 16 need to be coated with an inert insulating coating film 17 in order to prevent unnecessary side reactions.

(Embodiment 7) FIG. 10 shows a schematic view 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, respectively, so that the junction interface has a diode characteristic. , Which utilizes an electron barrier generated during reverse bias.

For example, as the working electrode 4, an oxygen defect type u
After forming ITO, which is a type semiconductor, by a sputtering method, as the recording layer 5, an aridic acid hydroxide Ir exhibiting P-type conductivity, which is famous as an inorganic electrochromic material, is formed.
It is realized by successively forming O _x (OH) _nx . Such IrO _x (OH) _nx is formed by 50 to 500 Å by high frequency sputtering in an atmosphere of O ₂ and H ₂ with the metal Ir as a target.

0.05 MH ₂ SO ₄ was used as an electrolytic solution, and as a writing bias, the probe electrode potential was first set to −1.5 V (relative to the surface of the recording layer 5) and proton H ⁺ was introduced into the recording layer. inject. At this time, since 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, no electrons are supplied from the working electrode 4, and protons H ⁺ are ionized in the film. The tunnel electrons are injected from the probe electrode 3 into the recording layer 5 by continuously superposing 2.5 V pulse voltage of opposite polarity, and

[0097]

[Chemical 12] It is possible to proceed the reduction reaction of. The reproducing and erasing methods are also in accordance with the first embodiment.

As the other recording layer 5, for example, a conductive polymer group formed by an electrolytic polymerization method is listed. These electropolymerized films can easily control the conductivity type by doping with an acceptor or a donor type ionic species in an electrolytic solution, and are suitable for this example.
For example, polyaniline PAn electrolytically polymerized in an aqueous perchlorine system containing an aniline monomer exhibits P-type conduction. This film is electrochemically active and can reversibly repeat the doping and dedoping reactions of the anion species ClO ₄ ⁻ .

(Embodiment 8) In the above-mentioned Embodiments 5 to 7, all were in the system in which the electrolytic solution was used as the electrolyte, but in this embodiment, by using the solid electrolyte as the electrolyte 1, it is 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,
Application of a unipolar bias between the probe electrode 3 and the working electrode 4 has the advantage that mobile ions can be extracted and extracted between the solid electrolyte and the recording layer and tunnel electrons can be extracted and extracted between the probe electrode and the recording layer at the same time. There is no need for the two-step potential control involving polarity reversal as considered in the liquid system.

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. The PbF ₂ is prepared by heating a molybdenum board to 550 to 600 ° C. and vacuum degree before deposition of 5 × 10 ⁻⁶ T.
orr, vapor deposition rate of 5Å / sec, 50 to 500
Å It is formed by vacuum evaporation, and then the above-mentioned L
A [LuH (Pc) ₂ ] t-butyl derivative monomolecular film is formed by the method B.

-0.3V (working electrode 4
STM operation is 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 is controlled to several Å, and then +2 is applied to the probe electrode 3. By applying a pulse of 0.0 V (with respect to the working electrode 4), the anion F can be removed from the solid electrolyte layer 1.
^- at the same time is injected, the probe electrode 3 from the recording layer 5
Electrons are emitted toward the most advanced atoms of the chemical formula 13 in the microscopic region corresponding to the effective tunnel current region.

[0102]

[Chemical 13] Oxidation reaction progresses, and it is possible to form a very small recording bit of a dozen Å to several tens Åφ.

As in Example 5, regeneration was applied by applying a probe electrode of −0.3 V (with respect to working electrode 4) and erasing was applied with a probe electrode of −2.0 V (with respect to working electrode 4). It can be carried out.

Other combinations of the 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, and the solid electrolyte layer 1.
As a good proton conductor as tantalum pentoxide Ta
A system of ₂ O ₅ can be used.

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

[0106]

[Chemical 14] The reduction reaction proceeds to form a very small number of recorded bits of tens of Å to several tens of Åφ.

[0107]

As described above, the gas generation and reaction accompanying the reaction of the recording layer can be achieved by the system composed of the probe electrode, the recording layer which performs the reversible redox reaction and the region for compensating the reaction in the recording layer. By providing an information processing device that has reversibility in the entire system without product precipitation, etc., it has become possible to perform ultra-high density recording as compared with conventional optical and magnetic memory recording. Further, it has a great advantage in terms of erasability as compared with the recording / reproducing method applying the STM technology which has been recently proposed variously.

[Brief description of 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 reaction compensation region arrangement 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 showing an information processing device of the present invention.

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

FIG. 9 is a diagram showing an example of application 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]

1 electrolyte 2 Electrolysis cell container 3 probe electrodes 4 Working electrode 5 Recording layer (reaction medium) 6 Reaction compensation area 7 Reference electrode 8 Inert insulating coating film 9 Fine movement drive mechanism 10 Coarse drive mechanism 11 X, Y stage 12 Cantilever type actuator 13 Reaction compensation electrode 14 Drive electrode 15 Probe electrode wiring electrode 16 Wiring electrode for reaction compensation electrode 17 Inert insulating coating film 18 Si substrate 19 electron blocking layer 21 computer 22 Servo circuit 23 Current-voltage conversion amplifier circuit 24 Coarse drive circuit 25 XY scanning drive circuit 26 pulse application circuit 27 Potential regulation circuit 28 Second counter electrode

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshihiko Takeda             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation

Claims (8)

[Claims] 1. An electrolyte having at least one probe electrode and a working electrode disposed opposite to the probe electrode, and an oxidizing state and a reducing state by an external voltage application in the presence of an electrolyte supplying mobile ions and the electrolyte. A recording medium capable of easily controlling a reversible change between the probe electrode and the working electrode, and 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 the distance between an electrode and the recording medium, a reaction compensation region for compensating a reaction to an oxidation reaction or a reduction reaction in a state change of the recording medium is provided on the probe or the probe excluding the probe tip. An information processing apparatus, characterized in that it is provided in the vicinity 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 the recording medium, and its initial state is set to a state opposite to the recording medium. 3. An electrolyte having at least one probe electrode and a working electrode arranged to face the probe electrode, and an oxidizing state and a reducing state by an external voltage application 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, and 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 device characterized by being supplied. 4. The electrolyte is an electrolytic solution, which is provided with a reference reference electrode for potential regulation in the vicinity of the surface of the recording medium, and a portion immersed in the electrolytic solution except for the tip end portion of the probe electrode is not formed. 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 arranged.
The information processing device described. 6. The information processing apparatus according to claim 4, wherein the recording medium and the working electrode are made of semiconductor materials having different conductivity types, and a junction interface between the two has diode characteristics. 7. The information processing apparatus according to claim 5, further comprising a second counter electrode other than the probe electrode, the second counter electrode facing the working electrode. 8. The electrolyte according to claim 3, wherein the electrolyte is a gel or solid electrolyte, and the gel or solid electrolyte is arranged between the recording medium and the working electrode. Information processing equipment.