JPS63161552A - Method and device for recording - Google Patents

Abstract

PURPOSE:To attain high density recording by applying a voltage in excess of a threshold voltage causing an electric memory effect from a probe electrode to a recording medium having the electric memory effect. CONSTITUTION:The voltage in excess of a threshold voltage causing the electric memory effect is applied to a recording medium 1 having the electric memory effect from the probe electrode 102. That, is while an XY stage 114 is moved at a prescribed interval, a pulse voltage having a level of a threshold voltage is applied and the ON-state is written, a probe voltage for write is applied between the probe electrode 102 and an opposed electrode 103 to read directly the change in the current quantity flowing to the ON-state region and the OFF- state region or read it via a servo circuit 106. Thus, high density recording is attained.

Description

[Detailed description of the invention] (Technical breakdown) The present invention relates to a recording device.

More specifically, the present invention relates to a recording device using a recording medium that has a layered structure of an organic compound between a pair of electrodes, one of which is a probe electrode, and has a memory effect on voltage and current switching characteristics.

(Background Art) In recent years, the use of memory materials has become the core of the electronics industry, such as computers and related equipment, video disks, digital audio disks, etc.
The development of these materials is also progressing very actively. The performance required of memory materials varies depending on the application, but in general, ■
High density and large recording capacity; ■Fast response speed for recording and playback; ■Low power consumption; ■High productivity and low price.

Until now, semiconductor memory and magnetic memory were mainly made of magnetic materials and semiconductors, but with the recent advances in laser technology, inexpensive and high-density optical memory using organic thin films such as organic dyes and photopolymers has been developed. recording media have appeared.

On the other hand, recently, a scanning tunneling microscope (hereinafter abbreviated as STM) that can directly observe the electronic structure of surface atoms of a conductor has been developed.
tica Physica Acta, 55°72
6 (1982)] It has become possible to measure real space images with high resolution regardless of whether they are single crystal or amorphous, and it also has the advantage of being able to observe with low power without damaging the medium due to current. It is expected to have a wide range of applications because it can operate in the atmosphere and can be used with various materials.

STM involves applying a voltage between a metal tip and a conductive material.
It takes advantage of the fact that a tunnel current flows when brought close to a distance of about nm. This current is very sensitive to changes in the distance between the two, and by scanning the probe upward while keeping the tunneling current constant, it is possible to draw the surface structure in real space and at the same time draw various information about the total electron cloud of surface atoms. Information can also be read. Analysis using STM is limited to conductive samples, but it is beginning to be applied to structural analysis of extremely thin monomolecular films formed on the surface of conductive materials, making use of differences in the states of individual organic molecules. It is also possible to consider application as a reproduction technology for high-density recording.

On the other hand, the conventional method of forming a latent image by discharging or energizing using needle-shaped electrodes is known as an electrostatic recording method, and has been applied to many recording papers etc. (Japanese Patent Laid-Open No. 49-3
Publication No. 435).

The film thickness used in this electrostatic recording medium is on the μ order, and there have been no reports yet of an example in which a latent image on the medium is electrically read and reproduced.

Meanwhile, a proposal for a molecular electronic device in which a single organic molecule has functions such as a logic element or a memory element was announced, and a Langmuir-Prodgett film (hereinafter referred to as LB film), which is considered to be one of the construction technologies for molecular electronic devices, was announced. Research on (abbreviated) is also becoming more active. The LB film arranges organic molecules in an orderly manner.
It is made by laminating molecular layers, and the film thickness can be controlled in units of molecular length, making it possible to form a uniform and homogeneous ultra-thin film. Many attempts have been made to use the LB film as an insulating film to create devices that take full advantage of this feature. For example, a tunnel junction element with a metal-insulator-metal (MIM) structure [G.

L, Larkins at al, Th1nSo
lid Films, 99. (1983)] and metals.
Light emitting elements [G, G, R
oberts et at,.

Electronics Letters.

20.489 (1984)] or switching elements [N. J. Thomas et at.

Electronics Letters.

Idan, 838 (1984)]. Although device characteristics have been investigated through a series of these studies, the lack of reproducibility and stability, such as variations in characteristics between devices and changes over time, remain unsolved problems.

Conventionally, the above studies have focused on fatty acid LB membranes, which are relatively easy to handle. However, recently, organic materials have been created one after another that overcome the heat resistance and mechanical strength, which were previously thought to be inferior. As a result of intensive research to create MIM devices with excellent reproducibility and stability using LB films made of these materials as insulators, we have now been able to create thinner and more uniform dye insulating films than ever before. Ta. Furthermore, as a result, an MIM element that exhibits a switching phenomenon and has a completely new memory function has been discovered.

[Purpose of the invention]

That is, an object of the present invention is to provide a recording device and a recording method using a novel high-density recording medium that has memory properties in terms of voltage and current switching characteristics.

[Summary of the invention]

The present invention provides a recording device having a probe electrode, a recording medium having an electric memory effect, and a write voltage applying means for applying a voltage from the probe electrode to the recording medium, and a recording medium having an electric memory effect from the probe electrode. The recording method is characterized by applying a voltage that exceeds the generated threshold voltage.

Since most organic materials generally exhibit insulating or semi-insulating properties, there is a wide variety of organic materials having a group having a π-electron level that can be applied to the present invention.
'Structures of dyes having a π-electron system suitable for the present invention include, for example, dyes having a porphyrin skeleton such as phthalocyanine and tetraphenylporphine, azulene dyes having squarylium groups and croconic methine groups as bonding chains, quinoline, and benzene. Cyanine-based similar dyes in which two nitrogen-containing heterocycles such as thiazole and benzoxazole are bonded by squarylium group and croconic methine group, or cyanine dyes, fused polycyclic aromatics such as anthracene and pyrene, and aromatic rings and heterocycles. Chain compounds formed by polymerization of ring compounds and polymers of diacetylene groups, derivatives of tetraquinodimethane or tetrathiafulvalene, analogs thereof and charge transfer complexes thereof, and metal complexes such as ferrocene and trisbipyridine ruthenium complexes. Examples include compounds.

Regarding the formation of organic recording media, it is possible to specifically apply vapor deposition methods, cluster ion beam methods, etc., but among the known conventional techniques, L
Method B is extremely preferred.

According to this 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 has a thickness on the order of a molecule. , and can stably supply a uniform and homogeneous ultra-thin organic film over a large area.

The LB method is a molecule with a structure that has a hydrophilic site and a hydrophobic site, and when the balance between the two (amphiphilic balance) is maintained appropriately, the molecule lowers the hydrophilic group on the water surface. This is a method of creating a monomolecular film or a cumulative film thereof by utilizing the fact that monomolecular layers form toward

Examples of the group constituting the hydrophobic moiety include various hydrophobic groups such as generally widely known saturated and unsaturated hydrocarbon groups, condensed polycyclic aromatic groups, and deformed polycyclic phenyl groups. Each of these constitutes a hydrophobic portion singly or in combination. On the other hand, the most typical constituent elements of the hydrophilic moiety are, for example, carkiphoxyl group, ester group,
Examples include hydrophilic groups such as acid amide groups, imide groups, hydroxyl groups, and amino groups (1, 2, 3, and 4). These also constitute the hydrophilic portion of the above molecule either singly or in combination.

If a dye molecule has a well-balanced combination of these hydrophobic groups and hydrophilic groups and a π-electron system with an appropriate size, it is possible to form a monomolecular film on the water surface, and this is It is an extremely suitable material for the invention.

As a specific example, the following molecules may be used as [I]croconic methine dyes.

4)e 5)e ,6) R,R.

R, R.

R, R.

Here, R is a long-chain alkyl group that corresponds to the group with 0 electron index mentioned above and is introduced to facilitate the formation of a monomolecular film on the water surface, and its carbon number n is 5≦ n≦
30 is preferred.

The compounds mentioned above as specific examples are only basic structures,
Needless to say, various substituted forms of these compounds are also suitable in the present invention.

[+1 Cosquarylium dye] A compound in which the croconic methine group of the compound listed in 11 is replaced with a squarylium group having the following structure.

[Ill] Porphyrin-based pigment compound M=H2, Cu
, Ni, Al-Cl, and the rare earth metal ion R are introduced to facilitate the formation of a monomolecular film, and are not limited to the substituents listed here. Also, R
1 to R4, R are the aforementioned σ electron [IV] condensed polycyclic aromatic compound R OOH [v] diacetylene compound CH3 (-CH2). C=C-C:=C(-CH2)-
m XO≦n, m≦20, where n+m>10

[Vl] Other CHa (CH2) 4beφ (NarakutoCN6)
R It goes without saying that pigment materials other than those mentioned above are suitable for the present invention as long as they are suitable for the LB method.

For example, biomaterials (for example, bacteriorhodopsin and cytochrome C) and synthetic polypeptides (PBLG), which have been actively researched in recent years, can also be applied.

Such amphipathic molecules form a monomolecular layer on the water surface with the parent group facing downward. At this time, the monomolecular layer on the water surface has the characteristics of a two-dimensional system, and when the molecules are sparsely dispersed, the two-dimensional ideal gas equation is expressed between the area A per molecule and the surface pressure π. πA=KT holds true, resulting in a "gas film". Here, is the Boltzmann constant and T is the absolute temperature. If A is made sufficiently small, the intermolecular interaction becomes stronger, resulting in a two-dimensional solid "condensation film (or solid film)." The condensed film can be transferred layer by layer onto the surface of arbitrary objects having various materials and shapes, such as glass and resin. Using this method, a monomolecular film or a cumulative film thereof can be formed and used as a recording layer.

As a specific manufacturing method, for example, the method shown below can be mentioned.

Chloroform and benzene for the desired organic compound.

Dissolve in a solvent such as acetonitrile. Next, using a suitable apparatus as shown in FIG. 7 of the accompanying drawings, the solution is spread on the aqueous phase 81 to form an organic compound in the form of a film.

Next, a partition plate (or float) 83 is provided to prevent this spread layer 82 from spreading freely on the aqueous phase 81 and spreading too much, and by limiting the spread area of the spread film 82, the state of aggregation of the film substance is controlled. , we obtain a surface pressure π proportional to its collective state. By moving the partition plate 83, the developed area can be reduced to control the aggregation state of the membrane material, and the surface pressure can be gradually increased to set the surface pressure π suitable for membrane production. While maintaining this surface pressure, the monomolecular film of the organic compound is transferred onto the substrate 84 by gently raising or lowering the clean substrate 84 vertically. Such a monomolecular film 91 is a film in which molecules are arranged in an orderly manner as schematically shown in FIG. 8a or 8b.

The monomolecular film 91 is manufactured as described above, and by repeating the above operations, a desired number of cumulative films can be formed. In order to spread the monomolecular film 91 on the substrate 84, in addition to the above-mentioned vertical dipping method, methods such as a horizontal deposition method and a rotating cylinder method can also be used. The horizontal deposition method is a method in which a monomolecular film is transferred by bringing the substrate into horizontal contact with the water surface, and the rotating cylinder method is a method in which a cylindrical substrate is rotated above the water surface to transfer the monomolecular film onto the substrate surface. It's a method.

In the above-mentioned vertical immersion method, when a substrate with a hydrophilic surface is lifted out of water in a direction across the water surface, a single molecule l1i91 of an organic compound is formed on the substrate 84 with the hydrophilic site 92 of the organic compound facing the substrate 84 side. (Figure 8b). When the substrate 84 is moved up and down as described above, the monomolecular films 91 are stacked one by one in each step, forming a cumulative film 101.

Since the direction of the film-forming molecules is reversed during the pulling process and the dipping process,
According to this method, a Y-shaped film is formed between each layer of the monomolecular film in which hydrophobic sites 93a and 93b of the organic compound face each other (FIG. 9a). On the other hand, in the horizontal adhesion method, a single molecule 11i9 with the hydrophobic part 93 of the organic compound facing the substrate 84 side is used.
1 is formed on a substrate 84 (FIG. 8a). In this method, even if the monomolecular film 91 is accumulated, the direction of the film-forming molecules does not change, and an X-shaped film is formed in which the hydrophobic parts 93a and 93b face the substrate 84 in all layers (No. 9b figure). On the contrary, the cumulative film 101 in which the hydrophilic parts 92a and 92b of all the layers face the substrate 84 side is called a Z-type film (9th
c).

The method of applying the monomolecular film 91 onto the substrate 84 is not limited to the above method; when a large-area substrate is used, a method of extruding the substrate from a roll into an aqueous phase may also be used. Further, the directions of the hydrophilic groups and hydrophobic groups described above toward the substrate are in principle, and can be changed by surface treatment of the substrate, etc.

As described above, a potential barrier layer consisting of the organic compound monomolecular film 91 or its cumulative film 101 is formed on the substrate 84.

In the present invention, the substrate 84 for supporting the thin film in which the above-mentioned inorganic and organic materials are laminated may be metal, glass,
Any material such as ceramics or plastic material may be used, and biomaterials with extremely low heat resistance may also be used.

The substrate 84 as described above may have any shape and is preferably flat, but is not limited to a flat plate. That is, the film forming method has the advantage that a film can be formed in accordance with the shape of the surface of the substrate, regardless of the shape.

On the other hand, the electrode material used in the present invention may be any material as long as it has high conductivity, such as Au.

Pt, Ag, Pd, Aj! , In, Sn, Pb, W, and other metals and their alloys, as well as graphite, silinide, and even conductive oxides such as ITO. is possible.

As a method for forming electrodes using such materials, conventionally known thin film techniques are sufficient. However, when forming the LB film on the surface of the electrode material directly formed on the substrate, it is preferable to use a conductive material that does not form an insulating oxide film, such as a noble metal or an oxide conductor such as ITO.

Note that the metal electrode of the recording medium is necessary because the recording layer of the present invention is insulative, but if the recording layer exhibits semiconductor properties of MΩ or less, the metal electrode is unnecessary.

That is, the recording layer itself can be used as a counter electrode to the probe electrode.

Further, the tip of the probe electrode needs to be as sharp as possible in order to improve the recording/reproducing/erasing resolution. In the present invention, a 1φ thick platinum tip is mechanically polished into a 90° cone and an electric field is applied in an ultra-high vacuum to evaporate the surface atoms. The shape and processing method are not limited to these.

When an element with the MIM structure shown in FIG. 4 is created using the materials and film formation method described above, a memory switching element exhibiting current-voltage characteristics as shown in FIGS. 5 and 6 is obtained. It has already been found that two states (ON state and OFF state) each have memory properties. These memory switching characteristics range from several Å to several tens of Å.
However, as a recording medium using the probe electrode of the present invention, a layer thickness in the range of several Å to 500 µm is preferable, and most preferably a layer thickness in the range of 10 Å to 200 µm. It is better to have

In FIG. 4, reference numeral 84 represents a substrate, 41 an Au electrode, 42 an A1 electrode, and 43 the aforementioned monomolecular cumulative film.

FIG. 1 is a block diagram showing a recording apparatus of the present invention. In FIG. 1(A), 105 is a probe current amplifier;
06 is a servo circuit that controls the fine movement mechanism 107 using a piezoelectric element so that the probe current is constant. 10
8 is a power source for applying a pulse voltage for recording/erasing between the probe electrode 102 and the electrode 103;

Since the probe current changes rapidly when the pulse voltage is applied, the servo circuit 106 controls the HOLD circuit to be turned on so that the output voltage remains constant during that time.

109 is an XY scanning drive circuit for controlling the movement of the probe electrode 102 in the XY directions.

110 and 111 are used to coarsely control the distance between the probe electrode 102 and the recording medium 1 so that a probe current of about 10-'A is obtained in advance. All of these devices are centrally controlled by a microcomputer 112.

Further, 113 represents a display device.

In addition, the mechanical performance in movement control using piezoelectric elements is shown below.

Z direction fine movement control range i: o, 1 layer m to 1 μm Z direction coarse movement control range: 10 nm to IQmm XY direction scanning range:
0. 1 nm to l μm measurement, control tolerance: <O,
inn Hereinafter, the present invention will be explained according to examples.

(Example 1) A recording/reproducing apparatus shown in FIG. 1 was used. Probe electrode 10
As No. 2, a platinum probe electrode was used. This probe electrode 102 is used to control the distance 111 (Z) from the surface of the recording layer 101, and the distance 11 (Z) is controlled by a piezoelectric element to finely move it so as to keep the current constant. Furthermore, the fine movement control mechanism 107 is designed to be able to perform fine movement control also in the in-plane (x, y) directions while keeping the distance @2 constant. However, these are all conventionally known techniques.

Further, the probe electrode 102 can be used for direct recording, reproduction, and erasing. Furthermore, the recording medium is placed on a high-precision XY stage 114 and can be moved to any position.

Next, squaryryum bis-6-octyl azulene (hereinafter 5O
The details of the recording/reproducing/erasing experiment using the LB film (8 layers) of AZ (abbreviated as AZ) are described below.

Recording medium 1 having a recording layer 101 in which 5 OAZ 8 layers are accumulated
XY Stage 114 no Kamifi! l. First, the position of the probe electrode 102 was determined visually and firmly fixed. Au electrode (earth side) 103 and probe electrode 102
A voltage of -3.0 V was applied during this period, and the distance (Z) between the probe electrode i-pole 102 and the surface of the recording layer 101 was adjusted while monitoring the current. Thereafter, by controlling the fine movement control mechanism 107 to change the distance between the probe electrode 102 and the surface of the recording layer 101, current characteristics as shown in FIG. 2 were obtained. Note that the probe current Ip for controlling the distance mz between the probe electrode 102 and the surface of the recording layer 101 is 10-'
A≧Ip≧10-+2A1 preferably 1O-8A≧Ip≧
The probe voltage needs to be adjusted to be 10-''A.

First, the control current was set to the current value in region a in Figure 2 (
10-'A)-(Probe grounding conditions).

1, which is a voltage that does not exceed the threshold voltage that causes an electrical memory effect between the probe electrode 102 and the Au electrode 103.
, 5 V reading voltage was applied and the current value was measured, and it showed an OFF state at less than μA. Next, after applying a triangular wave pulse voltage having the waveform shown in FIG. 3, which is a voltage higher than the threshold voltage Vth ON that causes an on state,
When a voltage of 1.5 μ was applied between the electrodes again and the current was measured, a current of about 0.7 mA flowed, indicating that the device was in an ON state.

Next, the threshold voltage Vth that changes from the on state to the off state
Peak voltage 5V that is higher than OFF, pulse width 1
After applying a triangular wave pulse voltage of μs, 1.5μs is again applied.
When applied, the current value at this time was less than μA and turned off.
It was confirmed that the condition has returned.

Next, the probe current Ip is set to 1O-9A (region b in Figure 2).
was set to control the distance @2 between the probe electrode 102 and the surface of the recording layer 101.

While moving the XY stage 114 at a constant interval (1 μ), the threshold voltage Vth having a waveform similar to that shown in FIG.
A pulse voltage higher than ON (15 layers maX, 1 μs) was applied to write an ON state. Then probe electrode 10
A probe voltage of 1.5 V for reading is applied between the servo circuit 2 and the counter electrode 103 to directly read the change in the amount of current flowing in the ON state region and the OFF state region, or the servo circuit 1
It can be read through 06.

In this example, it was confirmed that the probe current flowing through the ON state region had changed by more than three orders of magnitude compared to before recording (or in the OFF state region).

Furthermore, the probe voltage is set to t higher than the threshold voltage Vth OFF.
As a result of setting it to OV and tracing the recording position again, it was confirmed that all recorded states were erased and the state was shifted to the OFF state.

Next, using the fine movement control mechanism 107, from o, ooiμ to 0
．． The writing resolution of 1μ long stripes at various pitches of 1μ using the above method was 0.01μ.
It was found that the following.

The 5OAZ-LB film used in the above experiment was prepared as follows.

A base electrode in which an optically polished glass substrate (substrate 104) was cleaned using a neutral detergent and trichloride, and then Cr was deposited as an undercoat layer to a thickness of 50 layers by vacuum evaporation, and Au was further deposited by 400 layers by the same method. (Au electrode 103) was formed.

Next, a chloroform solution in which 5OAZ was dissolved at a concentration of 0.2 mg/mu was spread on the water phase at 20°C to form a monomolecular film on the water surface. Waiting for the evaporation of the solvent, the surface pressure of the monomolecular film was increased to 20 mN/m, and while keeping this constant, the electrode substrate was moved across the water surface at a speed of 5 mm.
The sample was gently immersed at a rate of 1/2 min, and then pulled up to accumulate two Y-shaped monolayers. By repeating this operation an appropriate number of times, 6 layers of 2.4, 8, 12, and 20.30 layers are formed on the substrate.
A cumulative film of fiII was formed and a recording/reproduction experiment was conducted.

The evaluation results are shown in Table 1.

The evaluation is comprehensively judged based on the quality of recording and erasing properties after applying the recording write pulse and erasing voltage, as well as the ratio of current values in the recording state and erasing state (ON10FF ratio) and resolution. ◎、Good item ○
, Items with somewhat lower ratings compared to others were marked △.

[Example 2] An experiment was conducted in the same manner as in Example 1 except that a t-butyl derivative of lutetium siphthalodianine [LuH(PC)2] was used instead of the 5OAZ recording medium used in Example 1. The results are summarized in Table 1. It was found that recording could be written and read with a sufficient S/N ratio, similar to the 5OAZ.

Incidentally, the accumulation conditions for the t-butyl derivative of l, uH(PC)2 are as follows.

Solvent: Chloroform/trimethylbenzene/acetone (1/1/2) Concentration H0.5 mg/mj2 Water phase: Pure water, water temperature 20°C Surface pressure: 20 mN/m, substrate vertical speed 3 mmZ (Examples 3 to 9 ] A recording medium was prepared using the substrate electrode materials and dye compounds shown in Table 2, and the control current value of the probe current was set to 10-'
When the same experiment as in Examples 1 and 2 was conducted as A, the results shown in Table 2 were obtained.

As indicated by Q in the table, all samples could be recorded and reproduced with sufficient resolution and 0N10FF ratio.

Note that the cumulative number of dye LB films is two in all cases. Also p
The t-electrode uses the EB method, and the ITO uses (CH2) 2 OOH *** Highly halophilic bacteria are cultured using a known method, and the purple membrane is extracted.In the examples described above, the LB method was used to form the dye recording layer. However, any film forming method that can form an extremely thin and uniform film is not limited to the LB method, and specific examples include vacuum evaporation methods such as MBE and CVD.

Usable materials include not only other organic compounds but also inorganic materials such as chalcogen compounds.

Furthermore, it is also possible to use a semiconductor as the electrode on the side of the recording medium and to integrate the electrode and the recording layer.

Note that the present invention does not limit the substrate material, its shape, or surface structure in any way.

[Effects of the present invention]

■We have disclosed a completely new recording and reproducing method that allows for much higher density recording than optical recording.

■A new recording medium using the above new recording and reproducing method was disclosed.

■Since the recording layer is formed by the accumulation of monomolecular films, film thickness control on the order of molecules (several angstroms to tens of angstroms) can be easily achieved. Furthermore, since the controllability is excellent, the reproducibility when forming the recording layer is high.

■Since the recording layer can be thin, a highly productive and inexpensive recording medium can be provided.

■The energy required for reproduction is small and the power consumption is low.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram schematically showing an energized recording/reproducing apparatus of the present invention. Figure 2 is a characteristic diagram illustrating the current flowing when 1V is applied to the probe electrode when the distance between the probe electrode and the surface of the sample (recording layer) is changed, and Figure 3 is a pulse voltage waveform diagram for recording. showed that. FIG. 4 is a schematic diagram of the configuration of the MIM element, and FIGS. 5 and 6 are characteristic diagrams showing the electrical characteristics obtained in the element of FIG. 4. FIG. 7 is a schematic diagram of a cumulative film forming apparatus. Figures 8a and 8b are schematic diagrams of monolayers;
Figures 9b and 9c are schematic diagrams of cumulative films.

Claims (14)

[Claims] (1) A recording device comprising a probe electrode, a recording medium having an electric memory effect, and a write voltage applying means for applying a voltage from the probe electrode to the recording medium. (2) The recording device according to claim 1, wherein the recording medium is arranged between the probe electrode and a counter electrode arranged opposite to the probe electrode. (3) Claim 1, wherein the recording medium has a monomolecular film of an organic compound or a cumulative film formed by accumulating the monomolecular layers.
Recording device as described in section. (4) The thickness of the monomolecular film or cumulative film is from several angstroms to several hundred
The recording device according to claim 3, wherein the recording device has a range of 0 Å. (5) The thickness of the monomolecular film or cumulative film is several Å to 500 Å
A recording device according to claim 3, which falls within the scope of. (6) The thickness of the monomolecular film or cumulative film is 10 Å to 200 Å.
3. The recording device according to claim 3, wherein the recording device has a range of Å. (7) The recording device according to claim 3, wherein the monomolecular film or the cumulative film is a film formed by an LB method. (8) The recording device according to claim 3, wherein the organic compound has a group having a π electron level and a group having a σ electron level in the molecule. (9) The recording device according to claim 1, wherein the organic compound is an organic dye compound. (10) The organic compound is a dye having a porphyrin skeleton, an azulene dye, a cyanine dye, a dye having a squarylium group, a dye having a croconic methine group, a fused polycyclic aromatic compound, a fused heterocyclic compound, a diacetylene polymer. At least one compound selected from the group consisting of a metal complex compound, tetraquinodimethane, tetrathiafulvalene, and a metal complex compound.
The recording device according to claim 3, which is a seed compound. (11) The recording apparatus according to claim 1, further comprising an XY scanning drive device for the probe electrode. (12) The recording apparatus according to claim 1, further comprising means for finely controlling the relative position of the probe electrode and the recording medium in three dimensions. (13) A recording method characterized by applying a voltage exceeding a threshold voltage that causes an electric memory effect from a probe electrode to a recording medium that has an electric memory effect. (14) The recording method according to claim 13, wherein a voltage exceeding a threshold voltage that causes an electric memory effect is applied to the recording medium from a probe electrode and a counter electrode.