JP3421083B2 - Method for producing oxotitanium phthalocyanine thin film - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thin film of oxotitanium phthalocyanine (hereinafter abbreviated as TiOPc), which is particularly useful for electrophotographic photoreceptors, laser printer photoreceptors, photoelectric conversion materials, sensor materials and the like. The present invention relates to a method for producing an oxotitanium phthalocyanine thin film having high orientation.

[0002]

2. Description of the Related Art Phthalocyanines are compounds useful as paints, printing inks, colorants and electronic materials. Among them, TiOPc is a compound which has been actively used in recent years as an electrophotographic photoreceptor or a laser printer photoreceptor. Is. This thin film is useful as an electrophotographic photosensitive member, and various studies have been made.

First, according to Japanese Patent Application Laid-Open No. 59-166959, the vapor deposition film of TiOPc is brought into contact with the vapor of a soluble solvent so that the Bragg angle (2θ) in an X-ray diffraction pattern.
Is 7.5 degrees, 12.6 degrees, 13.0 degrees, 25.4 degrees, 2
It is disclosed that a thin film having strong diffraction peaks at 6.2 degrees and 28.6 degrees is obtained and used as a charge generation layer in an electrophotographic photoreceptor. This TiOPc vapor-deposited film is manufactured by using phthalonitrile and titanium tetrachloride.
Using iOPc as a raw material, 10 ^-5 to 10 ^-6 torr (tor)
r) 0.05-0.5 on aluminum substrate under vacuum
This is a method of contacting with a vapor of a soluble solvent such as tetrahydrofuran or methanol after 1 μm vapor deposition for 1 to 24 hours.

According to JP-A-59-49544, the amorphous TiOPc thin film obtained by vapor deposition is treated with a solvent such as toluene, xylene, chloroform or dichloroethane to obtain a Bragg angle (2θ). 9.2
A TiOPc vapor-deposited film giving strong diffraction peaks at 13.1, 20.7, 26.2, and 27.1 degrees can be obtained. In the examples, only the vapor-deposited film vapor-deposited at 10 ⁻⁵ Torr is described, and the details of the vapor deposition conditions are not described.

Further, in JP-A-1-120564, TiOPc is 300 ^-60 at 10 ^{-4 -10 -6} torr.
A Bragg angle (2θ) of 27.0 is obtained by heating the deposited film to 0 ° C. to form a deposited film and treating the deposited film with alcohol.
It is disclosed that a vapor-deposited film having a diffraction peak at a position near a degree can be obtained. In Japanese Patent Laid-Open No. 4-81860, TiOPc obtained by heating to 450 to 500 ° C. at 10 ⁻⁴ to 10 ⁻⁷ Torr.
It is disclosed that a vapor deposition film having a diffraction peak at a Bragg angle (2θ) of 27.3 degrees can be obtained by bringing the vapor deposition film into contact with a mixed vapor containing an aromatic solvent and water.

In all of the above-mentioned manufacturing methods, a solvent treatment is carried out in which the TiOPc vapor-deposited film is brought into contact with a solvent.
A thin film obtained by such a manufacturing method was reported by Enoda et al. (Joun
al of Imaging Science, 34 (6), 234 (1990)) and the like, the thin film obtained by the method is considered to be α type, and the thin film obtained by the method is considered to be β type. Since the Bragg angle (2θ) has many strong diffraction peaks at a Bragg angle (2θ) of 7.5 ° to 28.6 ° in the line diffraction diagram, these thin films are not particularly oriented. In the method, the Bragg angle (2θ) is 27.0 degrees or 2 only after the solvent treatment.
A diffraction peak is shown at a position of 7.3 degrees, and it is described as an amorphous state before the treatment. Further, even after the solvent treatment, the X-ray diffraction pattern is not a single diffraction peak, but other diffraction peaks are described. Therefore, the thin film is not oriented.

[0007]

[Problems to be Solved by the Invention]
In the method for producing an iOPc vapor deposition film, the crystal form in the vapor deposition film can be controlled to α type, β type, etc. depending on the type of solvent, but the molecular orientation could not be controlled.

Further, Maruyama et al. Aim at a non-linear optical material, and sapphire R whose orientation is regulated by an organic molecular beam deposition method.
1 substrate under ultra high vacuum of 3 × 10 ^-10 Torr on the surface
By heating to 00 ° C., the thin film X-ray diffraction shows a strong diffraction peak only when the Bragg angle (2θ) is 7.550 degrees.
A b-axis oriented polycrystalline film of iOPc has been obtained.
MD92-112, OME92-65 (1993)).

However, this method requires a special vacuum device for obtaining an ultrahigh vacuum, and further, the orientation property is obtained under the condition that a film is formed on a substrate whose orientation is specifically controlled under heating. This is a method for producing a thin film, which is difficult to industrialize, and the film forming apparatus is inevitably expensive.

[0010]

In view of the above situation, the present inventors have aimed to obtain a highly oriented TiOPc thin film without using a special vacuum device or a limited substrate.
As a result of diligent studies, an important factor that regulates the orientation of TiOPc crystals is the vapor deposition rate, and by controlling this vapor deposition rate to a certain value or less, a glass substrate that does not have the ability to control the orientation in a normal vacuum device is obtained. A highly oriented TiOPc thin film can be obtained even when vapor-deposited on a substrate such as
Line diffraction shows a strong diffraction peak only in the range of Bragg angle (2θ) of 6.8 ± 0.2 degrees, and by further crystallizing this oriented thin film with an organic solvent, the orientation of the thin film can be improved. The crystallinity of the thin film is improved, and the strong Bragg angle (2θ) shows a strong diffraction peak only in the range of 7.6 ± 0.2 degrees in the thin film X-ray diffraction, and the photoconductivity of the oriented thin film. Was found to be higher than that of a non-oriented thin film, and the present invention was completed.

That is, the method for producing an oxotitanium phthalocyanine thin film according to claim 1 is to deposit oxotitanium phthalocyanine on a substrate or the like at a deposition rate of 0.8 Å / sec or less under a vacuum of 10 ⁻⁴ to 10 ⁻⁸ Torr. To form a thin film. In the method for producing an oxotitanium phthalocyanine thin film according to a second aspect, oxotitanium phthalocyanine is vapor-deposited, and then the thin film is crystallized using an organic solvent. In the method for producing an oxotitanium phthalocyanine thin film according to claim 3, tetrahydrofuran or dichloromethane is used as the organic solvent. The method for producing an oxotitanium phthalocyanine thin film according to claim 4,
The vapor deposition rate is set to 0.15 to 0.8 angstrom per second. In the method for producing an oxotitanium phthalocyanine thin film according to a fifth aspect, an oxotitanium phthalocyanine having a halogen atom content of 0.1% by weight or less is used as a vapor deposition raw material which is a raw material of the thin film. The method for producing an oxotitanium phthalocyanine thin film according to claim 6, wherein the oxotitanium phthalocyanine produced by the reaction of phthalonitrile and tetraalkoxytitanium in the presence of a compound having a urea or amide group as a vapor deposition raw material for the thin film. Is used.

The present invention will be described in detail below. The thin film obtained by the method of the present invention will be described with reference to FIG. Figure 1
Is an X-ray diffraction diagram (Cu-Kα) of TiOPc oriented vapor deposition film
In the figure, a) is an untreated vapor-deposited film, and b) or c) is an X-ray diffraction diagram of the vapor-deposited film subjected to the crystallization treatment with vapor of dichloromethane or tetrahydrofuran, respectively. As shown in FIG. 1, the Bragg angle (2θ) of the thin film X-ray diffraction was 6.8 ± 0.2 or 7.6 ± 0.2.
Only a strong diffraction peak is shown. Here, the vapor deposition rate is controlled to 0.8 angstroms per second or less for vapor deposition. As shown in FIG. 1a), the untreated thin film deposited at a rate of 0.8 angstroms or less is only at the position where the Bragg angle (2θ) is 6.8 ± 0.2 degrees by thin film X-ray diffraction. A diffraction peak is shown. The thin film after the crystallization treatment with the organic solvent has a Bragg angle (2) as shown in FIGS.
The diffraction peak is shown only at a position where θ) is 7.6 ± 0.2 degrees.

When the deposition rate is higher than 0.8 angstroms per second, for example, a thin film formed at a rate of 5 angstroms per second, a thin film X-ray diffraction diagram (Cu-Kα) of an untreated thin film is shown in FIG. 2a). As described above, it is considered that a diffraction peak is not shown, a broad state occurs, and an amorphous state is obtained. When this thin film is crystallized with an organic solvent, the Bragg angles (2θ) are 7.5 degrees, 12.7 degrees, 22.6 degrees, and 2 degrees, as shown in FIGS.
It becomes a thin film that gives a strong diffraction peak at 8.5 degrees (± 0.2 degrees in each case), and becomes a non-oriented film in which crystals are clearly arranged randomly. At present, it is not clear that molecules or microcrystals are oriented at 0.8 angstroms or less, and random at higher angles, but if the deposition rate is 0.8 angstroms per second or less, an oriented thin film can be obtained.

The vapor deposition rate is not particularly limited as long as it is 0.8 angstroms per second or less, but 0.15 to 0.8 angstroms per second is preferable because it takes a lot of time to form a film if it is slow. Further, the vapor deposition rate can be easily controlled by controlling the heating of TiOPc while monitoring the vapor deposition rate using a film thickness monitor or the like.

In the method of the present invention, the type of substrate is not selected,
The film can be formed on any substrate. Examples of the substrate include Ti on a substrate having no orientation control ability such as glass, quartz, plastic, metal, amorphous silicon, and a metal film deposited on plastic or glass.
An OPc alignment film can be formed. Of course, crystalline silicon, mica, potassium chloride single crystal, or the like having a fixed crystal orientation may be used as the substrate.

The degree of vacuum during vapor deposition is usually in the range of 10 ^-4 to 10 ^-8 Torr. The distance between the evaporation source of the evaporation device and the substrate is not particularly limited, but when the substrate is located near the evaporation source, the orientation of TiOPc is disturbed by the influence of the heat of the evaporation source, and when the influence of heat is particularly strong. Is mixed with β-type crystals. Further, if the substrate is located far from the evaporation source, a large vacuum chamber is required, or sublimated TiOPc does not reach the substrate (mean free path is determined by the degree of vacuum). Therefore, the distance between the evaporation source and the substrate is generally preferably in the range of 5 to 50 cm.

The heating range of the vapor deposition source depends on the degree of vacuum. In the case of low vacuum, high temperature is required, and in high vacuum,
The sublimation temperature becomes lower. For example, 10 ^-5 to 10 ^-6
The temperature is about 350 to 500 ° C. at about torr. When the vapor-deposited film was crystallized with an organic solvent, the peak at which the Bragg angle (2θ) was 6.8 ± 0.2 in the thin film X-ray diffraction was 7.
Shift to 6 ± 0.2 degrees. This peak is α type TiO 2.
It is shown that the b-axis of Pc is oriented almost perpendicular to the substrate, that is, the phthalocyanine ring is oriented almost perpendicular to the substrate.

As the organic solvent, ethers such as tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and chlorobenzene, alcohols such as methanol, ketones such as acetone, amines such as pyridine can be used. Of these, tetrahydrofuran and dichloromethane are particularly preferable. For crystallization with an organic solvent, the deposited film may be immersed in the organic solvent, but if soaked, the deposited film may slightly dissolve depending on the type of the solvent. Therefore, contact the vaporized film with the vapor of the organic solvent. . When the vapor of the organic solvent is used, crystallization proceeds in an extremely short time, but in order to perform crystallization completely, the range of 30 minutes to 24 hours is preferable. When using the vapor of the organic solvent, heating is not necessary, but it can be performed in a temperature range from room temperature to the boiling point of the organic solvent.

Further, as a raw material for forming this thin film, T produced from phthalonitrile and titanium tetrachloride known in the related art.
iOPc can be used. In addition, the TiOPc produced by this method contains partially chlorinated TiOPc. To make the effect of the present invention more effective,
TiOPc containing less than 0.1% by weight of halogen atoms
Is more preferably used. As a method for synthesizing high-purity TiOPc containing no halogenated TiOPc, a method of reacting a phthalonitrile with a titanium tetraalkoxide in the presence of a urea or amide compound, which the present inventors have already applied, is disclosed in Japanese Patent Application No. 25455/1993. No.) or a known method such as a method of reacting 1,3-diiminoisoindoline with titanium tetraalkoxide.

On the other hand, in the visible absorption spectrum of the vapor-deposited film, the oriented TiOPc vapor-deposited film was 720 in the untreated state.
Although the absorption maximum at nm is exhibited, the absorption maximum shifts to a long wavelength in the thin film subjected to the crystallization treatment with an organic solvent, and the absorption maximum is about 830 n.
The absorption maximum is shown in m. Therefore, the oriented vapor deposition film obtained by crystallization with an organic solvent becomes highly sensitive to near-infrared light such as laser, laser printer photoreceptor,
It is useful for sensors and photovoltaic devices.

When the TiOPc alignment film obtained by the method of the present invention is used as an electrophotographic or laser printer photosensitive member, TiOPc vapor-deposited on the aluminum substrate by the method of the present invention is used as a charge generation layer, and then, Ti
A charge transfer layer is formed on the OPc vapor deposition film in the form of a charge transfer substance alone or a resin in which the charge transfer substance is dissolved or dispersed.
Furthermore, when configuring a sensor using photoconductivity,
The sensor can be constructed by forming a comb-teeth electrode on the vapor deposition film, or by forming a comb-teeth electrode on the substrate in advance and then forming a TiOPc alignment film.
Moreover, a sensor or a photoelectric conversion element can be constructed by sandwiching a TiOPc alignment film between a transparent conductive film such as NESA and ITO and a semitransparent metal electrode. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0022]

【Example】

(Example 1) 128 g of phthalonitrile, 89.6 g of titanium tetrabutoxide, 58 g of urea and 380 ml of n-octanol were placed at room temperature in a 4-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas introduction tube, and While stirring, the flask was immersed in an oil bath at 160 ° C. under a nitrogen atmosphere and reacted at that temperature for 6 hours. After the reaction was completed, the formed precipitate was filtered off, washed with dimethylformamide, acetone, and methanol, dried in vacuum, and dried with Ti.
121.6 g of OPc was obtained. The elemental analysis of the product was in agreement with the calculated value within an error range, and the reaction basically contained no halogen atom. This TiOPc was heated to 500 to 510 ° C. under a pressure of 2 mmHg in an argon gas stream for sublimation purification. This purified TiOPc was used as a raw material for vapor deposition.

Using an evaporation apparatus having a vacuum system constructed by an oil rotary pump and an oil diffusion pump, the purified TiOPc was charged in an alumina crucible and vapor deposition was performed under a vacuum of 2 × 10 ^-6 Torr. The substrate is made of Pyrex glass with a length and width of 20 mm and a thickness of 1 mm.
Three pieces were installed at a distance of m. The vapor deposition rate was measured by a film thickness monitor using a crystal oscillator. The deposition rate was set to 400-4 for the alumina crucible while observing with the film thickness monitor.
It was controlled to 0.5 angstroms per second by heating to 50 ° C. Thus, a vapor deposition film having a film thickness of 1500 angstrom was formed on the three substrates. One of the vapor-deposited films was left as it was, and the other two were left in saturated steam of dichloromethane and tetrahydrofuran for 12 hours to perform crystallization treatment with an organic solvent.

FIG. 1 is an X-ray diffraction diagram of these three kinds of vapor-deposited films. In the figure, a) is an untreated vapor-deposited film, and b) or c) is an X-ray of a crystallized vapor-deposited film. It is a diffraction diagram.
3 (1), (2) and (3) are diagrams showing the angle dependence of the polarization absorption spectra of these three kinds of vapor deposition films, (1) is an untreated vapor deposition film, and (2) Or (3)
FIG. 3 is a diagram showing the angle dependence of a polarized light absorption spectrum of a vapor-deposited film crystallized with dichloromethane or tetrahydrofuran vapor. In the figure, 0), 30), 60)
Shows polarization absorption spectra at incident angles of 0 degree, 30 degrees, and 60 degrees, respectively. The plane of polarization of the incident light was set parallel to the plane of incidence of the light on the vapor deposition substrate.

As is apparent from FIG. 1a), the Bragg angle (2θ) is 6.85 in the X-ray diffraction diagram of the untreated vapor-deposited film.
A diffraction peak is shown only at a degree (12.99 Å), indicating that the TiOPc molecules are oriented. Figure 3
By the angle dependence of the incident light of the polarization absorption spectrum of (1),
When the incident angle is changed from 0 degree to 30 degrees and 60 degrees, 720
Although the absorption maximum in nm hardly changes, the absorption near 640 nm increases, which indicates that the TiOPc molecules are oriented in substantially the same direction.

As shown in FIGS. 1b) and 1c), when the vapor-deposited film is crystallized with vapor of dichloromethane or tetrahydrofuran, crystallization proceeds, and in the X-ray diffraction pattern, the Bragg angle (2θ) is 7.6. A diffraction peak is observed only at a degree (11.61 angstrom). This is α type Ti
It corresponds to the (010) plane of OPc. Therefore, the b-axis of the α-type crystal is oriented substantially perpendicular to the substrate, that is, Ti
It indicates that the phthalocyanine ring of OPc is oriented substantially vertically to the substrate, and the orientation of the microcrystals forming the deposited film is aligned. In addition, when crystallization treatment with solvent vapor is performed,
The absorption maximum of the visible absorption spectrum shifts from 720 nm in the untreated case shown in FIG. 3 (1) to 830 nm shown in FIGS. 3 (2) and 3 (3). Due to the angle dependence of the incident light of the polarization absorption spectrum, as the incident angle increases, 60
Since the absorption near 0 to 640 nm increases, Ti
It can be seen that OPc molecules or fine crystals are oriented.

(Comparative Example 1) Using the same apparatus as in Example 1, the deposition rate was 5.0 angstroms per second and the film thickness was 150.
Thin films of 0 angstrom were formed on three substrates, and similarly, one was left untreated and the other two were crystallized with saturated vapor of dichloromethane or tetrahydrofuran. The X-ray diffraction patterns of the obtained thin films are shown in FIG.
a) to c), the angle dependence of the polarization absorption spectrum is shown in FIG.
It showed in (1)-(3). 4 (1), (2), (3)
Is an untreated amorphous TiOPc vapor-deposited film,
It is a figure of the angle dependence of the polarization absorption spectrum of the unoriented TiOPc vapor deposition film which performed the crystallization process by the dichloromethane or the tetrahydrofuran vapor.

As is clear from FIG. 2a), the X-ray diffraction pattern of the untreated vapor-deposited film shows no peak and is amorphous. When the incident angle is changed from 0 degree to 30 degrees and 60 degrees due to the angle dependence of the incident light of the polarization absorption spectrum of FIG. 4A, the absorption maximum of 720 nm and 640 nm.
The absorption in the vicinity does not show the incident angle dependency as in Example 1, but tends to decrease as the incident angle increases. Like the X-ray diffraction diagram, the molecules or fine crystals are oriented in the thin film. Indicates that there is no.

As shown in FIGS. 2b) and 2c), when the vapor-deposited film is crystallized with vapor of dichloromethane or tetrahydrofuran, crystallization proceeds, and in the X-ray diffraction pattern, the Bragg angle (2θ) is 7.42 degrees. , 12.71 degrees, 22.5
Diffraction peaks are shown at 7 degrees and 28.53 degrees, indicating that the crystallites are non-oriented α-type TiOPc oriented in various directions. When the crystallization treatment with the solvent vapor is performed, the absorption maximum of the visible absorption spectrum shifts from 720 nm in the untreated case to 830 nm as in Example 1 (FIG. 4).
(2), (3)).

However, it does not show the incident angle dependency as in Example 1, but when the incident angle is changed to 0 °, 30 ° and 60 °, the absorption tends to be small, and like the X-ray diffraction diagram, It shows that the crystallites are not oriented in the thin film. Further, even if the vapor deposition rate is set to 1, 2, 10, and 15 angstroms per second, the angle dependence of the incident light of the X-ray diffraction and the polarization absorption spectrum shows almost the same tendency, and the molecules or the microcrystals are not oriented. .

(Embodiment 2) In the same manner as in Embodiment 1, the vapor deposition rate is controlled to 0.2 angstrom per second and the film thickness is 2
A vapor deposition film having a thickness of 000 angstrom was formed on three substrates. When processed in the same manner as in Example 1, it was shown that the X-ray diffraction pattern and the angle dependence of the polarization absorption spectrum were similarly oriented. When this operation was performed 10 times, the reproducibility was good.

(Example 3) The same procedure as in Example 1 was performed to form thin films having a thickness of 1500 angstroms on three substrates at a rate of 0.5 angstroms per second. One was untreated and the other two were crystallized with saturated steam of dichloromethane or tetrahydrofuran. These X
The line diffraction pattern was the same as in FIG. 2 on these thin films
A gold comb tooth electrode (gap 0.02 cm, length 3.7 cm) was formed to a thickness of 200 Å under a vacuum of × 10 ^-6 torr. A voltage of 1000 V was applied between the electrodes, and monochromatic light having a wavelength of 716 nm and an intensity of 2.81 mW / cm ² was irradiated, and the photocurrent was measured.

Comparative Example 2 Using the same apparatus as in Example 1, thin films having a thickness of 1500 angstroms were formed on three substrates at a rate of 2, 5, 8 angstroms per second. One was untreated and the other two were treated with saturated steam of dichloromethane or tetrahydrofuran. These X
The line diffraction pattern was similar to that of FIG. With these membranes,
The photocurrent was measured in the same manner as in Example 3.

The results of Example 3 and the results of Comparative Example 2 are shown in FIGS. FIG. 5 is a diagram showing the vapor deposition rate dependence of the photocurrent when the surface-conduction-type devices of the untreated film in Example 3 and Comparative Example 2 were irradiated with 716 nm monochromatic light.
FIG. 6 shows the deposition rate dependence of the photocurrent when 716 nm monochromatic light was irradiated to the surface conductivity type device formed of the deposited film crystallized by dichloromethane vapor in Example 3 and Comparative Example 2. FIG. FIG. 7 shows surface-conduction type devices formed of vapor-deposited films crystallized by tetrahydrofuran vapor in Example 3 and Comparative Example 2,
It is a figure which shows the vapor deposition rate dependence of the photocurrent at the time of irradiating 716 nm monochromatic light. In these figures, ◯ indicates Example 3 and Δ indicates Comparative Example 2. In each case, the photoconductivity (◯) of the TiOPc alignment film deposited at a rate of 0.5 angstroms per second was the same as that of Comparative Example 2 (△) where TiOPc was deposited at a rate of 2, 5, 8 angstroms per second. It can be seen that it is larger than the alignment film. This difference is remarkable especially in the thin film treated with dichloromethane.

[0035]

As described above, the manufacturing method of the present invention is
The iOPc was placed under a vacuum of 10 ⁻⁴ to 10 ⁻⁸ Torr at 0.
Since a thin film is formed on a substrate by vapor deposition at 8 angstroms or less, a thin film in which molecules or microcrystals are oriented in a certain direction can be manufactured. When this thin film is crystallized with an organic solvent, crystallization proceeds further, and α-type Ti
It becomes a thin film in which OPc crystals are oriented. As described above, a thin film having a higher photoconductivity than a non-oriented thin film and useful as an electrophotographic photosensitive member, a laser printer photosensitive member, a photoelectric conversion material or a photosensor material can be produced.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction diagram of a TiOPc oriented vapor deposition film obtained in Example 1, where a) is an untreated vapor deposition film, and b) and c) are crystallization treatment vapor deposition films. Is.

2 is an X-ray diffraction diagram of a vapor-deposited film of TiOPc in an amorphous or non-oriented state obtained in Comparative Example 1. FIG.

FIG. 3 is a diagram showing the angle dependence of the polarization absorption spectrum of the TiOPc oriented vapor deposition film obtained in Example 1. (1) is a diagram showing an angle dependence of a polarization absorption spectrum of an untreated vapor-deposited film, and (2) and (3) of a vapor-deposited film subjected to a crystallization treatment.

FIG. 4 is a diagram showing the angle dependence of the polarization absorption spectrum of the TiOPc vapor deposition film obtained in Comparative Example 1.

FIG. 5 is a diagram showing the deposition rate dependence of the photocurrent of the untreated film in Example 3 and Comparative Example 2.

FIG. 6 is a diagram showing the vapor deposition rate dependence of the photocurrent of vapor deposited films that were subjected to crystallization treatment with dichloromethane vapor in Example 3 and Comparative Example 2. .

FIG. 7 is a diagram showing vapor deposition rate dependence of vapor deposition films that were subjected to crystallization treatment with tetrahydrofuran vapor in Example 3 and Comparative Example 2.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-719 (JP, A) JP-A-4-232959 (JP, A) JP-A-63-45361 (JP, A) Armstrong NR, et al, PRCEEDINGS, ELEC TROCHEMICAL SOCIETY, 1988, VOL. 88-14, p. 267-279 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C23C 14/00-14/56 C30B 1/00-35/00 CA (STN) JISST file (JOIS)

Claims (6)

(57) [Claims] 1. An oxotitanium phthalocyanine containing 1
A method for producing an oxotitanium phthalocyanine thin film, which comprises depositing a thin film on a substrate or the like at a deposition rate of 0.8 angstroms per second or less under a vacuum of 0 ^-4 to 10 ^-8 Torr. 2. The method for producing an oxotitanium phthalocyanine thin film according to claim 1, wherein after the oxotitanium phthalocyanine is vapor-deposited, the thin film is crystallized using an organic solvent. 3. The method for producing an oxotitanium phthalocyanine thin film according to claim 2, wherein tetrahydrofuran or dichloromethane is used as the organic solvent. 4. The vapor deposition rate is 0.15 to 0.8 per second.
3. Angstroms, characterized in that it is Angstrom.
Or the method for producing an oxotitanium phthalocyanine thin film according to 3 above. 5. The oxotitanium phthalocyanine having a halogen atom content of 0.1% by weight or less is used as a vapor deposition material which is a raw material of the thin film, according to any one of claims 1 to 4. A method for producing the oxotitanium phthalocyanine described. 6. The oxotitanium phthalocyanine produced by the reaction of phthalonitrile and tetraalkoxytitanium in the presence of a compound having a urea or amide group is used as a vapor deposition material which is a raw material of the thin film. The method for producing oxotitanium phthalocyanine according to any one of 1 to 4.