JPH0328706B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a method for manufacturing an electrophotographic photoreceptor.

(Prior art) Conventional electrophotographic photoreceptors are made of Se, a typical chalcogen element, on a conductive substrate such as aluminum.
(Selenium) film is deposited by vacuum evaporation method, and this Se photoreceptor has a spectral sensitivity of 500nm.
It is unstable and easily crystallized. To improve the stability of this Se photoreceptor, a small amount of As (arsenic) is added to Se-
There is an As chalcogen alloy photoreceptor. In addition, there is a Se-Te photoreceptor that has extended spectral sensitivity to long wavelengths, and this is a chalcogen alloy made by adding Te (tellurium) to Se. The electrical resistance of the photoreceptor decreases, and as a result, the surface charge retention properties deteriorate, making it practically unusable as a photoreceptor. Furthermore, Bi (bismuth) in Se
There is a Se-Bi chalcogen alloy photoreceptor which has spectral sensitivity even at 800 nm. Furthermore, I (iodine) is added to this Se-Bi alloy to form a Se-Bi-I chalcogen alloy film. Photoreceptors made of materials such as this Se-Bi-I alloy film in which a halogen element such as I is added to a chalcogen alloy have higher sensitivity and lower residual potential than those without the addition. well known.

Conventionally, electrophotographic photoreceptors use aluminum as a conductive substrate, and a chalcogen or chalcogen alloy, such as a Se film, Se-As alloy film, Se-Te alloy film, Se-Bi-I alloy film, etc., is coated on this substrate. It is formed by depositing any one of the photoresist films using a vacuum evaporation method. Here, deposition of binary alloys such as Se-Te alloy film is relatively easy, but Se-Bi-
Since the I alloy film has a ternary composition, it is very difficult to form a film with a desired composition on a substrate, and a special method must be used.

FIG. 1 shows one of these special methods, which is the first conventional example, the flash vapor deposition method. In the figure, 1 is an aluminum substrate, 2 is a crucible, 3 is a material supply device, and 4 is a vacuum chamber. That is, in advance,
Create a mixture of Se-Bi-I, grind it into fine particles to make the particle size uniform, and feed this little by little into a heated crucible 2 from a material feeder 3,
This method evaporates the supplied amount in a short time and vacuum-deposit it on the aluminum substrate 1.

However, this method requires a material with a uniform composition of Se-Bi-I alloy and a very uniform grain size, and it is also very difficult to control the material feed rate.
Furthermore, I replaced I in Se-Bi-I alloy with F.
When forming a Se-Bi-F alloy film by this method, it is difficult to produce the ternary material itself, and this method is not possible.

Next, FIG. 2 shows a second conventional example, in which reference numeral 5 denotes a shutter, and the same reference numerals as in FIG. 1 denote the same parts. In other words, the second conventional example is a three-temperature method using a vacuum evaporation method, and Se, Bi, and
Three types of BiF ₃ materials are placed separately in three crucibles 2, and the temperature of each crucible 2 is controlled to a separate optimum temperature while being measured using a thermocouple (not shown) to determine the amount of evaporation of each. control. However, in this case, it takes a considerable amount of time for the temperature of each of the three crucibles 2 to become constant and, as a result, for the amount of evaporation to become constant, and during that time, all of the material placed in the crucibles 2 evaporates. Sometimes it happens. Furthermore, since the composition of the deposited film cannot be strictly controlled by controlling the temperature of the crucible 2 alone, it is necessary to control the amount of evaporation by adjusting the opening of the shutter 5 provided in the crucible 2. Therefore, this method has some difficult problems to be solved in practice.

(Disclosure of the Invention) Therefore, as a result of extensive studies, the present inventors found that
Instead of the conventional vacuum evaporation method, F, which was difficult to add in the past, can be easily added to chalcogen or alloys containing selenium (Se) using a reactive sputtering method using SF ₆ gas. , obtained the knowledge that forming a chalcogen or chalcogen alloy film containing F is a method for stably and inexpensively manufacturing a desired high-sensitivity electrophotographic photoreceptor,
We have arrived at the present invention.

That is, the present invention comprises a step of preparing a conductive substrate and a photoresist film forming step of forming a photoresist film on the conductive substrate, and the photoresist film forming step uses argon as a sputtering gas and SF ₆ as a reactive gas. A reactive sputtering method using a gas (sulfur hexafluoride) is used, and a chalcogen or chalcogen alloy containing selenium (Se) is used as the sputtering target. This is a method for producing an electrophotographic photoreceptor, which is characterized by forming a thin film in which F (fluorine) and S (sulfur) are added to a chalcogen alloy. The purpose is to manufacture it at low cost.

(Example) Examples of the present invention will be described in detail below with reference to the drawings.

First, a first embodiment is shown in Fig. 3. Fig. 3 shows a high frequency sputtering device, in which 1a is an aluminum substrate, 6 is a sputtering target (Se ₉₈ Bi ₂ chalcogen alloy target), 4 is a vacuum chamber, and 7 is a sputtering target. is a variable leak valve, 8 is an Ar gas container, 9 is SF ₆
It's a gas container.

First, with the variable leak valve 7 closed, the vacuum chamber 4 is brought to a high vacuum with a vacuum pump (not shown) to a degree of vacuum of 10 ^-6 Torr or less. Thereafter, SF ₆ gas is introduced into the vacuum chamber 4 by adjusting the variable leak valve 7 so that the degree of vacuum is 1×10 ^-5 Torr. After this, add Ar gas,
The variable leak valve 7 is adjusted and the vacuum is introduced into the vacuum chamber 4 so that the degree of vacuum becomes 5×10 ⁻⁴ Torr. In this way, the proportion of SF ₆ gas in Ar gas was set to 2%. After this, the high frequency of 13.56MHz is
The gas and SF ₆ gas were applied to turn the mixed gas into plasma, and a Se ₉₈ Bi ₂ chalcogen alloy target 6 was sputtered. As a result, Se-Bi
-F-S alloy was sputtered to form a thin film. Here, the diameter of the target 6 is 80 mm, and the substrate 1a is
Distance between target 6 and target 6: 50 mm, high frequency effective output
Deposition speed is approximately 0.15μ at 80W and substrate temperature 50℃
m/min. Furthermore, the reaction mechanism of the reactive sputtering using SF ₆ gas described above, i.e., how SF ₆ decomposes and how F and S are added to the Se-Bi alloy is unknown. , a Se-Bi-F-S alloy film can be formed with good reproducibility.

The composition of the Se-Bi-F-S alloy film prepared by the reactive sputtering method using SF ₆ gas as described above was analyzed and found to be Se _98.1 Bi _1.8 F _0.05 S _0.01 .
It was found that the composition was a Se-Bi alloy with approximately the same composition as the target composition, with small amounts of F and S added. Furthermore, a photoreceptor was fabricated with a 20 μm thick Se-Bi-F-S alloy film formed on an aluminum substrate, and its properties were measured.
Like the I photoreceptor, it also showed high sensitivity at 800 nm. Further, this photoreceptor was stable, did not undergo crystallization or cracking even after repeated use over a long period of time, and had a small residual potential.

In addition, although Se ₉₈ Bi ₂ chalcogen alloy was used as the target in the above example, chalcogen alloy was used instead.
When a photoresist film was formed by sputtering using Se as a target under the same conditions as above, the film formation rate was about 0.2 μm/min. Further analysis of the composition of this photoresist revealed that the composition was Se _99.9.
F _0.08 S _0.02 , and F and S were added to Se.
Moreover, this photoreceptor had almost the same spectral sensitivity as Se.

As described above, according to the present invention, it has become possible to easily add F, which has been difficult to add to chalcogen alloys or chalcogens, with good reproducibility. Note that S (sulfur), which was added at the same time as F, was a chalcogen itself and was in a very small amount, so it had almost no effect on the characteristics of the photoresist film formed.

In the first embodiment, a flat aluminum plate was used as the substrate, whereas in the second embodiment, as shown in FIG. 4, the drum-shaped substrate 10 was rotated at a speed of 10 rpm. The first
A Se-Bi-F-S quaternary chalcogen alloy was uniformly formed to a thickness of 0.2 μm using the same method as in Example 1. Thereafter, the drum 10 on which the Se-Bi-F-S thin film was formed was taken out from the vacuum chamber 4 and coated with a tetrahydrofuran solution of polyvinylcarbazole to a thickness of 20 μm using a spray coating method to form a two-layer photoreceptor drum. Created. and,
When this photoreceptor drum was attached to a laser beam printer using a semiconductor laser as a light source with an emission wavelength of 830 nm and a printing test was performed, -5KV was detected.
Excellent print quality with sufficiently high contrast was demonstrated even when using low corona voltages.

(Effect of the invention) As described above, according to the manufacturing method of the present invention,
Instead of the conventional vacuum evaporation method, a reactive sputtering method using SF ₆ gas is used to easily add F, which was difficult to add in the past, to chalcogen or chalcogen alloys containing selenium (Se). T, F
By forming a chalcogen or chalcogen alloy film containing , a desired high-sensitivity electrophotographic photoreceptor can be produced stably and at low cost.

[Brief explanation of drawings]

Figure 1 is a diagram for explaining the conventional method of manufacturing a Se-Bi-I alloy photoreceptor, and Figure 2 is a diagram for explaining the conventional Se-Bi-I alloy photoreceptor manufacturing method.
3 and 4 are diagrams for explaining the method for manufacturing a Bi-F alloy photoreceptor, and FIGS. 3 and 4 are diagrams for explaining each embodiment of the method for manufacturing an electrophotographic photoreceptor according to the present invention. 1a... Aluminum substrate, 4... Vacuum chamber, 6
...Target, 7...Variable leak valve, 8...Ar gas container, 9...SF ₆ gas container, 1
0...Drum-shaped substrate.

Claims (1)

[Claims] 1. The method consists of a step of preparing a conductive substrate _and a photoresist film forming step of forming a photoresist film on the conductive substrate. It is carried out by a reactive sputtering method using selenium (sulfur chloride), and a chalcogen or chalcogen alloy containing selenium (Se) is used as the sputtering target.
F (fluorine) and S (sulfur) in chalcogen or chalcogen alloy containing selenium (Se)
1. A method for producing an electrophotographic photoreceptor, the method comprising forming a thin film containing.