JPS6328984B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vapor deposition method, particularly to a vapor deposition method for forming a multilayered vapor deposited film.

Vapor-deposited films having a multilayer structure are used in various fields such as photocells, integrated circuits, antireflection layers using interference effects, and electrophotographic photoreceptors.

Conventionally, in order to form a multilayered vapor deposition film, vapor deposition materials forming each layer have been placed in different vapor deposition containers and heated in sequence in each vapor deposition container. Therefore, it has been necessary to install a plurality of vapor deposition containers in the vapor deposition apparatus and further to control the temperature of each vapor deposition container. For example, in the case of an electrophotographic photoreceptor, there is a
When stacking vapor deposition materials such as AS ₂ Se ₃ and Sb ₂ Se ₃ that have a higher melting point than Se, conventional methods
Usually, As ₂ Se ₃ or Sb ₂ Se ₃ is evaporated from separate evaporation boats to obtain a laminated evaporation film, but this method requires the same number of evaporation boats as evaporation containers for the number of layers to be laminated, resulting in a multilayer structure. The more complicated the deposition becomes, the more difficult it becomes to increase productivity.

Therefore, the main object of the present invention is to provide a vapor deposition method that solves this problem. The vapor deposition method according to the present invention is a vapor deposition method in which vapor deposition materials with different melting points are sequentially vaporized to form a multilayered vapor deposition film, in which the vapor deposition materials with different melting points are housed in one vapor deposition container, and the temperature of the vapor deposition container is adjusted stepwise. This method is characterized by forming a multilayered deposition film by sequentially depositing the deposition materials starting from the lowest melting point.

Therefore, in the vapor deposition method according to the present invention, 1
It is possible to form a multilayer film using one vapor deposition container, and is also excellent in terms of equipment and operation, and can be expected to improve productivity. As the vapor deposition material, materials having different melting points and which do not cause compositional variations among the vapor deposition materials are preferably used.

Examples will be explained below.

Example 1 As shown in FIG. 1, an Al substrate 2 was placed at a predetermined position in a vapor deposition tank 1. Next, 40g of Se powder with a purity of 5nine and 40g of Se powder with a purity of 5nine were placed in the quartz deposition boat 3.
1 g of AS ₂ Se ₃ powder was mixed and filled. Next, a chromel/alumel thermocouple 5 for monitoring the temperature of the evaporation source is fixed in the quartz vapor deposition boat 3.
A tungsten spiral heater 4 is installed in the deposition boat 3 to exhaust the air in the deposition tank 1 and make the degree of vacuum approximately 5×10 ⁻⁵ torr. Next, the substrate heating heater 6 was ignited to raise the temperature of the Al substrate 2 to 70°C and keep it constant. The relationship between temperature control inside the deposition boat 3 and time will be explained below with reference to Fig. 2.The tungsten spiral heater 4 on the deposition boat 3 is ignited, the temperature inside the deposition boat 3 is raised to 300°C, and Se is deposited. It started. Tungsten spiral heater 4 at point t-1 where Se completely disappears.
The current was increased to raise the temperature inside the deposition boat 3 to 450°C, and the deposition of As ₂ Se ₃ was started. At point t-2, when As ₂ Se ₃ has completely disappeared, the current of the tungsten spiral heater 4 is cut off, and the deposition is completed, and the vacuum is broken.
The Al substrate 2 was taken out into the atmosphere. The thickness of the deposited film was 41μ. As a result of analyzing the composition of this deposited film in the film thickness direction using an X-ray microanalyzer and non-dispersive Se and As elements were detected in
61wt% and As was 39wt%.

Example 2 The same vapor deposition equipment as in Example 1 was used, and 40 g of Se powder with a purity of 5 nines and 1 g of Sb ₂ Se ₃ with a purity of 5 nines were mixed in the quartz vapor deposition boat 3, and the vacuum level at the time of vapor deposition was maintained except for filling. The substrate temperature was the same as in Example 1.
The temperature control and time relationship inside the deposition boat 3 will be explained below with reference to FIG. 3. The tungsten spiral heater 4 on the deposition boat 3 is ignited, the temperature inside the deposition boat 3 is raised to 300°C, and Se is deposited. It started. The point where Se completely disappeared t-
In Step 3, increase the current of the tungsten spiral heater 4 and raise the temperature inside the deposition boat 3 to 650℃.
Vapor deposition of Sb ₂ Se ₃ was started. Inside the deposition boat 3
At point t-4, when Sb ₂ Se ₃ was completely exhausted, the current in the tungsten spiral heater 4 was cut off to complete the vapor deposition, and then the vacuum was broken and the Al substrate 2 was taken out into the atmosphere. The thickness of the deposited film was 41μ. The composition of this deposited film in the film thickness direction was analyzed using an X-ray microanalyzer and a non-dispersive X-ray analyzer.
Only Se element was detected up to a film thickness of less than 40 μm, and Se and Sb elements were detected in a film thickness range of 40 μm to 41 μm, with the proportions of Se being 49 wt% and Sb being 51 wt%.

Example 3 Using the same vapor deposition apparatus as in Example 1, 40 g of Se powder with a purity of 5 nines, 1 g of As ₂ Se ₃ with a purity of 5 nines, and 1 g of Sb ₂ Se ₃ with a purity of 5 nines were mixed in the quartz vapor deposition boat 3. The degree of vacuum and substrate temperature during vapor deposition were the same as in Example 1 except for filling. Deposition boat 3 below
The relationship between temperature control and time inside the vessel will be explained with reference to FIG. 4. The tungsten spiral heater 4 on the deposition boat 3 is ignited to raise the temperature inside the deposition boat 3 to 300° C. and the deposition of Se is started. Se
At the point t-5 when the tungsten spiral heater 4 completely disappears, the current of the tungsten spiral heater 4 is increased to raise the temperature inside the deposition boat 3 to 450° C., and the deposition of As ₂ Se ₃ is started.
At point t-6 when As ₂ Se ₃ is completely gone, the current of the tungsten spiral heater 4 is increased to raise the temperature inside the deposition boat 3 to 650° C. and the deposition of Sb ₂ Se ₃ is started. At point t-7, when Sb ₂ Se ₃ was completely exhausted, the current in the tungsten spiral heater 4 was cut off to complete the vapor deposition, and then the vacuum was broken and the Al substrate 2 was taken out into the atmosphere. The thickness of the deposited film was 42μ. The composition of this deposited film in the film thickness direction was analyzed using an X-ray microanalyzer and a non-dispersive X-ray analyzer.
In the range less than 40μ from the substrate, only Se element is detected, and in the film thickness range of 40 to 41μ, Se element is 61wt.
%, As element is 39wt%, in the film thickness range of 41~42μ
49wt% of Se element and 51wt% of Sb element were detected.

Example 4 The same vapor deposition equipment as in Example 1 was used, and 40 g of Se powder with a purity of 5 nines and 40 g of Se powder with a purity of 5 nines were placed in the vapor deposition boat 3.
Example 1 except that 7g of As ₂ Se ₃ was mixed and filled.
Vapor deposition conditions were set in the same manner as above. The relationship between the temperature inside the deposition boat 3 and time will be explained with reference to FIG.
The temperature rose to 300°C and Se deposition started. Se on the substrate
At point t-8, when the film thickness of the layer reaches 38μ, the temperature inside the deposition boat 3 is raised to 450℃ by increasing the current of the tungsten spiral heater 4, and Se and
Deposition of a mixed layer of As ₂ Se ₃ was started. At point t-9, when the As ₂ Se ₃ material was completely exhausted, the current to the tungsten spiral heater 4 was cut off to complete the vapor deposition, and then the vacuum was broken and the Al substrate 2 was taken out into the atmosphere.
The thickness of the deposited film was 47μ. As a result of analyzing this deposited film using an X-ray microanalyzer and a non-dispersive X-ray analyzer, it was found that up to a film thickness of 39μ from the substrate, Se was the only element, while in the film thickness range of 39 to 47μ, Se was present.
The element As is detected, and the Se percentage is 39μ to 42μ in film thickness.
The percentage of Se gradually decreases in the range of 93wt% to 61wt% between 42μ and 47μ.
It remained constant at 61wt%.

[Brief explanation of the drawing]

FIG. 1 shows one embodiment of a vapor deposition apparatus used to carry out the vapor deposition method according to the present invention. Figure 2, Figure 3, Figure 4
The figure and FIG. 5 each show one mode of temperature control of a vapor deposition boat by the vapor deposition method of the present invention. 1... Vapor deposition tank, 2... Al substrate, 3... Vapor deposition boat, 4... Tungsten spiral heater.

Claims (1)

[Claims] 1. In a vapor deposition method in which vapor deposition materials with different melting points are sequentially vaporized to form a multilayered vapor deposition film, the vapor deposition materials with different melting points are housed in one vapor deposition container, and the temperature of the vapor deposition container is raised stepwise. A vapor deposition method characterized by forming a multilayered vapor deposited film by sequentially vapor depositing materials.