JPH10226883A - Manufacture of phthalocyanine crystalline thin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain crystalline oriented films which are uniformly crystalline, are stable and have optical anisotropy and magnetic anisotropy by depositing phthalocyanine molecules or particulates on a substrate consisting of glass, resins, etc., to form thin films, then subjecting the thin films to a heat treatment. SOLUTION: The examples of the phthalocyanine to be used include iron phthalocyanine or iron phthalocyanine, etc., contg. K or Na. The method for depositing the films may be executed by vacuum vapor deposition, etc. The heat treatment temp. of the thin films is specified to about 100 to 400 deg.C. The heat treatment time is preferably specified to >=1 hours. The pressure at the time of the heat treatment is preferably confined to about <=1/10atm. pressure in order to suppress the unnecessary chemical reaction. While the optical characteristics, magnetic characteristics, film quality, etc., of the thin films may be improved by such deposition treatment and heat treatment, the effect of the improvement may be more additionally enhanced by executing such treatments in a magnetic field.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phthalocyanine crystalline thin film and a method for producing the thin film.

[0002]

2. Description of the Related Art A phthalocyanine polymer alignment film is prepared by the LB method (for example, JP-A-63-44963 and JP-A-63-4570013), and an intermediate product obtained by alkali-treating phthalocyaninato silicon dichloride is deposited. Obtaining oriented phthalocyaninato silicon dichloride polymer thin film by vacuum evaporation method as raw material
-64710), a phthalocyaninato silicon dichloride is vacuum-deposited on a substrate, and then heat-treated in a vacuum to obtain a silicon phthalocyanine polymer thin film having orientation (Japanese Patent Publication No. 5-64711). After providing a recording layer composed of an organic dye thin film thereon, the recording layer is externally heat-treated at a temperature of 150 to 280 ° C.
It is known to obtain an optical recording medium with improved recording and reproduction sensitivity (Japanese Patent Laid-Open No. 2-106390). However, a method for producing a uniform and stable phthalocyanine crystal orientation film has not been known.

[0003]

SUMMARY OF THE INVENTION Phthalocyanine has an extremely large number of crystalline states, and it is difficult to obtain a uniform crystalline film. In addition, there are many unstable crystal phases, which change over time, change due to heat, and change due to mechanical external force. Various methods for producing phthalocyanine thin films are known, but it has been difficult to obtain uniform crystalline and stable thin films. These cause deterioration of characteristics and reliability when a device using a phthalocyanine thin film is manufactured. SUMMARY OF THE INVENTION An object of the present invention is to obtain a crystalline alignment film that is uniform and stable and has optical anisotropy and magnetic anisotropy.

[0004]

According to the present invention, there is provided a phthalocyanine crystalline thin film comprising the steps of: depositing phthalocyanine molecules or fine particles on a substrate such as glass or plastic to form a thin film; By providing a manufacturing method, the above problem could be solved.

A feature of the present invention is that a thin film formed by depositing phthalocyanine molecules or fine particles is subjected to a heat treatment to obtain a stable crystalline material (e.g., a stable crystalline material) having uniform optical characteristics, magnetic characteristics, and the like, which hardly change with time. β-phthalocyanine) is to easily obtain a thin film.

The phthalocyanine used in the present invention includes iron phthalocyanine, metal-free phthalocyanine, copper phthalocyanine, zinc phthalocyanine, lead phthalocyanine,
Examples include silicon phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine, and iron phthalocyanine containing potassium or sodium.

As a method of depositing the film, there are a vacuum deposition method, a micellar electrolytic method and the like. The vacuum evaporation method can be performed by a general resistance heating method, an EB evaporation method, or the like, but the resistance heating method tends to form a more stable film. Further, the fine particles in the micellar electrolysis method are often in the form of α-type, X-type, or other crystals. However, the phthalocyanine molecules or fine particles that can be used in the present invention are not limited to those having a specific crystal system. Although the thickness of the deposited film varies depending on the use of the thin film, it is usually 0.1 to 10
It is about μm.

The heat treatment temperature of the thin film is 100
In general, the treatment time may be shorter at higher temperatures, but some types of phthalocyanines are likely to cause unnecessary chemical reactions. In such a case, the treatment is performed at a lower temperature. There is a need. The heat treatment time is about 10 minutes to 10 hours, preferably 1 hour or more. Also,
The pressure at the time of the heat treatment is preferably about 1/10 atm or less, more preferably 1/10 atm, in order to suppress unnecessary chemical reaction.
/ 100 atm.

As described above, there is a risk that unnecessary chemical reaction may occur in the heat treatment of the thin film. To suppress this, it is effective to lower the pressure during the heat treatment. Depending on the relationship between the pressure and the vapor pressure of the phthalocyanine, the deposited phthalocyanine may evaporate. The type of the phthalocyanine is not particularly limited. However, it is preferable to perform the reaction in an inert gas, for example, He or Ar gas. As the heat treatment means, a general electric furnace may be used, but care must be taken to prevent contamination of the target thin film.

By performing the deposition and / or heat treatment in a magnetic field, an oriented film can be formed by diamagnetic anisotropy for most phthalocyanines and paramagnetic anisotropy for iron phthalocyanines and the like. it can. Thereby, the optical characteristics, magnetic characteristics, film quality, and the like of the thin film can be improved. By performing both the deposition process and the heating process in a magnetic field, the effect of the improvement can be further enhanced. When the deposition is carried out in a vacuum, the substrate is placed in a magnetic field, and when the film is deposited by micelle electrolysis or the like, the whole cell is placed in a magnetic field.

The magnetic field intensity needs to be at least 0.1T or more. In particular, when an alignment film is obtained by utilizing the diamagnetic anisotropy of phthalocyanine molecules, 1 T or more is required. Examples of the magnetic field generator include a magnetic circuit using a permanent magnet, a general electromagnet, and a superconducting magnet. Especially,
When processing at 2T or more, a superconducting magnet is required.

A preferable thin film obtained by the present invention is an iron phthalocyanine thin film containing ferromagnetic potassium and / or sodium. The iron phthalocyanine thin film containing ferromagnetic potassium is (C ₃₂ H ₁₆ Fe
N ₈ ) · K, and the iron phthalocyanine thin film containing sodium is represented by (C ₃₂ H ₁₆ FeN ₈ ) · Na.
Is preferably 1: 0.5 to 8.

The iron phthalocyanine thin film containing ferromagnetic potassium or sodium can be obtained by simultaneously depositing iron phthalocyanine and potassium or sodium.
In this case, since it is difficult to control the composition of the thin film, it is preferable to prepare the thin film by a method of periodically depositing potassium or sodium and iron phthalocyanine.

The iron phthalocyanine thin film containing potassium and / or sodium obtained as described above was stable and extremely excellent in magnetic properties.

A shorter lamination cycle is preferable because a uniform film can be easily obtained by heat treatment for a shorter time. The period is suitably about 10 nm to 500 nm. However, a magnetic thin film can be obtained by performing the heat treatment for a long time even if it is thicker than the above period.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

Example 1 A β-type iron phthalocyanine powder was used as a raw material on a glass substrate.
An iron phthalocyanine thin film having a thickness of 1 μm was prepared by vacuum evaporation. The thin film at this stage was a thin film mainly containing α-type iron phthalocyanine and a plurality of crystalline and non-crystalline materials. Put this in a glass container, 300 ℃ in an electric furnace,
Heat treatment was performed for 2 hours, and then the furnace was cooled. As a result, β
As a result, a homogeneous crystalline film of single-phase iron phthalocyanine was obtained.

Example 2 A metal-free phthalocyanine alignment film was prepared by micellar electrolysis in a magnetic field. At this point, it is presumed that the crystal is of the X type, but the crystal was almost at a level at which no crystal could be confirmed by X-ray diffraction. Put this in a glass container and place it in an electric furnace for 30 minutes.
Heat treatment was performed at 0 ° C. for 2 hours, followed by furnace cooling. As a result, a β-type iron phthalocyanine single-phase crystal orientation film was obtained.

Example 3 Using a β-type iron phthalocyanine powder as a raw material, a 1 μm-thick iron phthalocyanine thin film was formed on a glass substrate by a vacuum evaporation method. This was placed in a glass container, and heated at 300 ° C. for 2 hours by an infrared heater in a magnetic field of 8 T, and then gradually cooled at a constant rate. As a result, a crystalline alignment film of β-type iron phthalocyanine single phase was obtained.

Example 4 Iron phthalocyanine and potassium were co-deposited at a ratio of 1: 4, placed in a glass container, heated at 300 ° C. for 2 hours in an electric furnace, and then cooled in the furnace. In the vapor deposition, the β-type iron phthalocyanine is controlled by the resistance heating method, and the potassium is controlled by the EB heating method so as to have the above-mentioned ratio.
Was prepared. As a result, in the β-type crystal, 15 emu /
A thin film having a magnetization of g was obtained.

Example 5 Iron phthalocyanine and potassium were alternately vapor-deposited for 10 cycles at a cycle of 500 nm in a ratio of 1: 4, placed in a glass container, and heated at 300 ° C. for 2 hours in an electric furnace. Thereafter, the furnace was cooled. As a result, a thin film of β-type crystal having a thickness of 5 μm and having a magnetization of 15 emu / g was obtained.

[0022]

【effect】

1. Claim 1 A uniform crystalline and stable phthalocyanine thin film can be obtained. 2. Claim 2 A phthalocyanine organic magnetic thin film having excellent magnetic properties can be obtained. 3. Claim 3 In addition to the effect of the invention of claim 2, it is possible to shorten the heat treatment time or perform heat treatment at a low temperature, thereby reducing the manufacturing cost or improving the uniformity of the film without unnecessary chemical reaction. The effect of is obtained. 4. Claims 4 and 5 A phthalocyanine thin film having a crystal orientation is obtained. As a result, a thin film having magnetic anisotropy or a thin film having large saturation magnetization can be obtained in the case of a magnetic film, and a thin film having optical anisotropy can be obtained in the case of an optical thin film. 5. Claim 6 Unnecessary chemical reaction does not occur, and is effective in improving the uniformity of the film. 6. Claim 7 In addition to the effect of the invention of claim 6, evaporation during heat treatment is suppressed, and the yield is improved. 7. Claim 8 It is stable and excellent in magnetic characteristics, optical characteristics, etc., and can improve the performance or reliability of the device.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Ujiie, 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd. (72) Yasuo Miyoshi 1-3-6 Nakamagome, Ota-ku, Tokyo Share Inside the company Ricoh

Claims (8)

[Claims] 1. A method for producing a phthalocyanine crystalline thin film, comprising: depositing phthalocyanine molecules or fine particles on a substrate to form a thin film; and heat-treating the thin film. 2. The method for producing a phthalocyanine crystalline thin film according to claim 1, wherein potassium and / or sodium are deposited in addition to iron, cobalt or nickel phthalocyanine molecules or fine particles. 3. The method for producing a phthalocyanine crystalline thin film according to claim 2, wherein potassium and / or sodium are periodically deposited with iron, cobalt or nickel phthalocyanine molecules or fine particles. 4. The method according to claim 1, wherein the deposition is performed in a magnetic field. 5. The method according to claim 1, wherein the heat treatment of the thin film is performed in a magnetic field.
5. The method for producing a crystalline phthalocyanine alignment film according to 2, 3, or 4. 6. The method according to claim 1, wherein the heat treatment of the thin film is performed in a vacuum.
The method for producing a phthalocyanine crystalline thin film according to 2, 3, 4, or 5. 7. The method for producing a phthalocyanine crystalline thin film according to claim 1, wherein the heat treatment of the thin film is performed in an inert gas. 8. The method of claim 1, 2, 3, 4, 5, 6, or 7.
A phthalocyanine crystalline thin film produced by the method described in the above.