JPS63241176A - Formation of functional deposited film by microwave plasma cvd method - Google Patents

Abstract

PURPOSE:To efficiently form the title functional deposited film having excellent characteristics by producing plasma with the microwave having specified energy, and decomposing the raw gas contg. a specified amt. of gaseous Si2F6 with the plasma under specified pressure. CONSTITUTION:A supporting body is arranged in the deposited film forming device capable of being depressurized, and the raw gas for forming the deposited film such as SiH4 is introduced. Plasma is produced therein by microwave energy to decompose the raw gas, and the functional deposited film of amorphous Si, etc., is formed on the supporting body. In the formation of the deposited film, <=10vol.% gaseous Si2F6 is mixed into the raw gas. The microwave energy of >=1.1 times the microwave energy when the depositing rate is saturated is imparted to the raw gas. Besides, the internal pressure during film deposition is controlled to <=10mTorr. By this method, the generation of polysilane powder due to the polymerization of the raw gas is prevented, and the functional deposited film of a semiconductor alloy, etc., having excellent optical and electrical characteristics and capable of being widely used is efficiently and stably formed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of non-crystalline materials such as amorphous silicon, amorphous germanium, amorphous silicon germanium, amorphous silicon carbide, amorphous silicon, and amorphous silicon oxide. The present invention relates to a method for forming a functional deposited film that can be formed as a crystalline semiconductor U and can be suitably used as a semiconductor element such as an electrophotographic photoreceptor, a solar cell, a thin film transistor, or an optical sensor.

More specifically, the present invention relates to an improved method for forming a functional deposited film, which efficiently forms the functional deposited film through a microwave plasma CVD method.

[Description of prior art]

＃〃 type deposited films have been proposed, and their formation is carried out using the microwave plasma CVD method (hereinafter referred to as "MW-P").
Several methods have been proposed, such as in US Pat. No. 4,504,518, for example.

According to the conventionally proposed method for forming a functional deposited film using the MW-PCVD method, the utilization efficiency of raw material gas and the film deposition rate can be satisfied to a certain degree, and the formation of an amorphous silicon deposited film is possible. It is possible.

However, the amorphous silicon deposited film obtained by such conventional methods has drawbacks such as having a columnar structure in terms of film quality, as well as drawbacks in optical and electrical properties, which limits its applications and thus limits its versatility. There is a scarcity problem.

That is, when used in photoreceptors for electrophotography or laser beam printers, although the dark conductivity and photoconductivity themselves are somewhat satisfactory,
There are problems such as slow response speed of photoconductivity and many afterimages.

These problems become particularly noticeable when obtaining an electrophotographic photoreceptor with a large film thickness and area, and are unsuitable in any case.

In addition, when used in solar cells, thin film transistors, optical sensors, etc., as in the case mentioned above, the response speed of photoconductivity is slow, so it is required to have high efficiency and high speed. It is insufficient to serve as a semiconductor element for those devices.

In addition to the problem that it is difficult to maintain stable microwave plasma discharge for a long time with the conventional method of forming a deposited film using the MW-PCVD method, there is also the problem that the microwave plasma discharge The main reason for this is that there is a problem in that the electrical characteristics of the deposited film that is formed change significantly even when subjected to severe disturbances.

[Purpose of the invention]

An object of the present invention is to provide a method for efficiently forming a functional deposited film such as a semiconductor alloy that has excellent optical and electrical properties and is versatile.

Another object of the present invention is to provide a method for efficiently generating polysilane powder by polymerizing raw material gas using the MW-P CVD method.

Still another object of the present invention is to provide a method for efficiently forming a film using the MW-P CVD method.

Another object of the present invention is to provide stable microwave plasma over long periods of time, even in the case of devices with large layer thicknesses or in the case of devices made by successively depositing multiple types of layers. M to maintain and enable efficient formation of those desired elements.
An object of the present invention is to provide a method for forming a deposited film using the W-PCVD method.

Still another object of the present invention is to perform MW-PCV in which even if the discharge state of microwave plasma is disturbed during film formation, it does not affect the optical and electrical properties of the deposited film.
An object of the present invention is to provide a method for forming a deposited film by a method.

[Structure of the invention]

The present inventors have obtained the above-mentioned findings as a result of intensive research to solve the problems in the conventional deposited film formation method using the MW-PCVD method and achieve the object of the present invention.
Based on this knowledge, we conducted further research and completed the present invention.

That is, the present inventors solved the various problems in the conventional deposited film formation method using the MW-PCVD method described above from the viewpoint of the raw material gas used, the microwave energy applied to the raw material gas in the film forming operation, and the internal pressure conditions. We explored possible solutions.

The inventors first repeatedly attempted to form a deposited film by changing the type and amount of raw material gas used, through trial and error.

As a result, Si2F6 gas in an amount of about 10% by volume or less was mixed with the raw material gas for forming the deposited film introduced into the film forming chamber, and the MW
- When performing a deposition operation using the PCVD method, even if the plasma discharge fluctuates and is disturbed, all of these gases are smoothly decomposed and the plasma discharge in the film forming area is maintained in a constant state. In addition, it is possible to maintain the electron density in the plasma at a high level, thereby promoting the decomposition and excitation of the film-forming raw material gas, allowing the film-forming to proceed efficiently and to obtain the desired deposited MI film. understood. In addition, especially when using S i Ha gas as the raw material gas for film formation,
It has been found that the effect of such a gas is extremely efficiently exerted, and an excellent functional deposited film can be efficiently obtained.

The present inventors further attempted to form a deposited film using a deposited film forming apparatus using the MW-P CVD method shown in FIGS. 2 and 3, which will be explained later. Regarding the microwave energy applied to the film-forming raw material gas, the relationship with the film deposition rate was variously investigated using the film-forming raw material gas as a parameter, using the apparatus shown in FIGS. 2 and 3, 5iHa gas is used as the raw material gas for film formation, and the flow rate is 250 sec +
m, and Corning Glass Works (
A 1lh7059 glass plate manufactured by USA) was installed tightly in a groove dug on the surface of a cylindrical AI cylinder, and the internal pressure was raised to 50 mTo.
A-5r:HlfJ was formed as rr, and the relationship between the film deposition rate and microwave energy during the film formation was investigated, and the results shown in Fig. 4 were obtained.Then, the flow rate of the raw material gas was changed and the same procedure was performed as above. The relationship between the film deposition rate and the microwave energy was investigated, and the same trends as shown in FIG. 4 were obtained, and all the results are summarized and schematically shown in FIG. 1.

In FIG. 1, the flow rate of the film-forming raw material gas is the flow rate (11
Three cases are shown in which flow rate (2) is the largest and flow rate (3) is decreased in that order.

From the results shown in FIG. 1, the following findings were obtained.

In other words, when the flow rate of the raw material gas for film formation is the highest, the film deposition rate increases linearly with respect to the increase in microwave energy, and reaches a certain point, that is, point A1 (hereinafter referred to as " S
tationary). The flow rate of the raw material gas for film formation is less than the flow rate (11).
In the case of , the trend of film deposition rate with increasing microwave energy is Flow! Although it is the same as the case of (1), it reaches the saturation point At, that is, the critical point A2 earlier than the case of the flow N(11), and after that, it remains constant even if the microwave energy is increased. The flow rate of the raw material gas for film formation is smaller than the flow rate (2), that is, the flow rate (3).
), the trend of film deposition rate with increasing microwave energy is the same as in the above case,
The saturation point A, that is, the critical point A, is reached earlier than in the case of flow rate (2), and thereafter it remains constant even if the microwave energy is increased.

Next, from the viewpoint of the transition state of the film deposition rate based on the relationship between the flow rate of the raw material gas for film formation and the microwave energy, the present inventors found that the film deposition rate is Three regions are selected: the rn region (i.e., region l) that is proportional to the increase in energy, the region near the critical point (i.e., region 2), and the region where the film deposition rate is saturated (i.e., region 3). The relationship between the film formation conditions and the properties of the resulting deposited film was comprehensively investigated as follows using the case of a hydrogenated amorphous M(A-5r:H) film as an example.

That is, first, three types of A-3i:H films were deposited with silane gas using a deposited film forming apparatus using the MW-PCVD method shown in FIGS. (SiHJ was used as the raw material gas for film formation, and the film formation process was observed and the obtained film was evaluated in each case. As a result, the flow rate i (11
, Flow rate (2), and Flow rate (3) all have the following findings in common.

That is, first, in the case of region l, under the film forming conditions of region l, SiH" (silane decomposing active species) is produced during the film forming process.
The luminescence of H" (hydrogen active species) was observed to be stronger than that of H" (hydrogen active species) (according to the analysis results of plasma luminescence), and the silane gas was not sufficiently decomposed.
If the film is formed at a speed of 2 seconds or more, the silane gas will not be decomposed sufficiently, and a large amount of decomposed species that have not been activated will be deposited on the support, resulting in a surface reaction on the support surface. It was found that three-dimensional silicon-to-silicon bonds are less likely to occur in the deposited film because there is less Hl which affects the silicon. In addition, the obtained film has a characteristic that the ratio of photoconductivity to dark conductivity is small, and the results of the infrared absorption spectrum show that the absorption based on (SiHl) is higher than the absorption based on (S i H). It was found that the film was very large and contained a considerable amount of polysilicon. Furthermore, the results of electron spin resonance revealed that the spin density was extremely high and the film contained many silicon atoms with dangling bonds.

In the case of region 2, although silane gas is almost 100% decomposed under the film formation conditions of region 2, active species that are not suitable for high-speed film deposition or do not have sufficient internal energy are generated. However, if you try to form a film at a film deposition rate of 50 people/see or higher, the structure of the deposited film will not be sufficiently relaxed due to the surface reaction on the support surface, and there will be dihedral angles in the formed film. angl
e) fluctuations (d i 5 order) and weak coupling (we
It was found that 5i-3i of ak bond) increased and many traps were formed.

Regarding the obtained film, as far as the ratio of photoconductivity to dark conductivity is concerned, it is somewhat satisfactory if used as an electrophotographic photoreceptor, but the response of photoconductivity to light irradiation is It turned out that the speed was slow, and there were many traps in one mock.

On the other hand, in the case of region 3, under the film forming conditions of region 3, most of the silane gas is sufficiently decomposed, and the silane gas is not given the microwave energy on the plate that is necessary to decompose it. 50 people/se
Silane gas is decomposed into a state suitable for high-speed film formation as shown in c.
# It was found that the action of electrons activates it to a state with high internal energy. Furthermore, when plasma emission was observed during the film formation process, it was found that the emission of H'' was much stronger than that of S i 11'', indicating that hydrogen was highly activated. In addition, the obtained film has an extremely favorable ratio of the light λ gummy rate to the dark conductivity, and the light i
It was found that the response speed of electric conductivity to light irradiation was extremely fast, and there were extremely few traps in the film.

From the above results, the first
When film formation is performed by setting film formation conditions in region 3 from the graph in the figure, that is, the region where the film deposition rate is saturated, the desired functional deposited film can be efficiently formed at a high film deposition rate. It turned out that. Next, the present inventors experimentally investigated the amount of microwave energy applied to the flow rate of the film-forming raw material gas in order to normalize the film-forming conditions in Region 3, and found the following. did. That is, the amount of microwave energy applied to the film-forming raw material gas to form the desired functional deposited film is 1.1 times or more and 5 times the amount of microwave energy required to saturate the film deposition rate. It has been found that it is necessary to keep it below, preferably 1.15 times but not more than 4 times, optimally 1.2 times or more and not more than 3 times.

If the amount of microwave energy applied to the film-forming raw material gas is less than 1.1 times the amount of microwave energy required to saturate the film deposition rate, the desired high-speed film formation cannot be achieved. This is unsuitable because the deposited film that is formed at the same time will have insufficient properties, and if it exceeds 5 times, collisions of ions in the generated plasma will occur, and the film will be formed. Each method was found to be unsuitable because it resulted in a deposited film with inferior properties.

The present inventors have confirmed the fact as a fact experimentally,
That is, during the film forming operation, 5ilF is added to the film forming raw material gas.
A desired functional deposited film can be obtained by mixing a predetermined amount of i gas and applying a predetermined amount of microwave energy to the film-forming raw material gas, but a functional deposited film with better characteristics can be obtained. We explored the possibility of constantly, stably and efficiently obtaining this by focusing on the internal pressure during film formation.

The present inventors first studied the important points to keep in mind regarding controlling the internal pressure during the film-forming operation in order to obtain the desired functional deposited 4n film by the MW-PCVD method, and as a result, they came to the following knowledge. . That is, (i) in order to form a film with high speed deposition and high utilization efficiency of raw material gas, and to obtain a deposited film with better electrical properties, the active species decomposed and excited by microwave energy must be brought into a more highly excited state. It is necessary to transport the product onto a support. (ii) For this purpose, it is essential that the mean free path of the active species (excluding collisions with II particles) is long. (iii) A long mean free path means that the active species once decomposed and excited Not only can it exist for a long time, but also the active species can collide with electrons again and become more excited, (iv) Therefore, it is a practical MW-P CV.
For a deposited film forming apparatus using the D method, the mean free path of the active species is required to be approximately 1 cm or more. (V) And if we replace this part with the numerical value of internal pressure, preferably lQmT
or less, more preferably 3 mTorr or less, optimally 1 mTorr or less to 0.1 mTorr or less.

By conducting the process under these conditions, it is possible to suppress the polymerization reaction in the gas phase, maintain the ion and electron density necessary to maintain the plasma, and also prevent plasma damage to the deposited film and plasma sandwiching. It is possible to achieve the best balance with promotion of body surface reactions.

Incidentally, the above points are verified from the experimental results obtained by the present inventors shown in FIG.

That is, the experimental results shown in FIG.
Using the apparatus shown in the figure, S I
Using H4 gas, 3ilFi gas was mixed with it at a volume ratio of 1.0%, and the S i Ha gas flow rate was set at 250 sec.
m, and Corning Glass Works (
Corning Glass Works, tl, s,
A.) Using a ceramic 7059 glass plate, the internal pressure during film formation was controlled under the following conditions: microwave energy (2.45 GHz) 5.5 kW, support temperature 270°C, deposition rate 110 people/sec. The response speed (relative ratio) and attractive conductivity/
Dark conductivity (relative ratio) was measured and the results are summarized and shown in a logarithmic graph.

The present invention has been completed through further research by the present inventors based on the facts thus discovered.

However, the present invention provides a versatile functional deposited film that eliminates the problems of the conventional deposited film formation method using the MW-PCVD method and has excellent reproducible optical and electrical properties. The purpose is to provide an efficient manufacturing method, which involves introducing a raw material gas for film formation into a deposited film forming apparatus that is capable of reducing the pressure and which is equipped with a support for deposited film formation, and then using microwave energy to produce the film. The method includes generating a plasma to decompose the raw material gas to form a functional deposited film on the support, and adding 5it to the raw material gas in an amount of 10% by volume or less.
Fb gas is mixed, microwave energy 1.1 times or more of the microwave energy at which the film deposition rate is saturated is applied to the mixed gas, and the internal pressure during film deposition is set to 1QmT.
This is a method for forming a functional deposited film, characterized in that the deposited film is formed by the MW-PCVD method while controlling the amount to be less than orr.

The method of the present invention is particularly effective when forming a functional deposited film mainly composed of silicon atoms and containing hydrogen atoms by the MW-PCVD method.

In the method of the present invention, the mixing ratio of S I 2 F b gas to the film-forming raw material gas needs to be set to 10% by volume or less, as described above, and the specific amount is as follows: It is determined by taking into account other related conditions such as the type of film-forming raw material gas used, the plasma generation environment in the film-forming chamber, the film deposition rate, and the optical and electrical properties required for the deposited film. Ru. Generally, the upper limit is 10% by volume, preferably 8.0 to 0.1% by volume, and more preferably 7.0 to 0.5% by volume.

In the method of the present invention, the frequency of the microwave used and the temperature of the support are also important in achieving the object of the present invention;
A range of I 00 GHz can be employed, but preferably 900 MHz to 50 GHz, more preferably 95 GHz.
It is 0MHz to 10GHz.

Regarding the support temperature, a temperature in the range of 50°C to 400°C is possible, but preferably 100°C to 350°C,
More preferably it is 150°C to 300°C.

The method for forming a functional deposited film of the present invention includes A-3i:H:
F, A-Ge:H: F, A-3t:Ge
:II :F.

A-3i:C: IT:F, A-Ge:
C: H: F, A-8i:C; e:C:
H: F, A-3i: N: H: F,
A-3i:Ge:N:H:F,A
-Ge:N:II:F,A-3i
:O: II: F, 8-Ge:O: II: F
, A-3i:Ge:O:H:F, A-5
i:Sn:II:F, A-5i:Pb:H:
F, or A-C: H: Amorphous semi-4 composed of F
It can be applied to the formation of body 4.

Furthermore, the method for forming a functional deposited film of the present invention is extremely effective even when the amorphous semiconductor device is doped with impurities in the semiconductor field, and has excellent semiconductor properties and is versatile. A functional deposited film can be obtained.

Note that the method for forming an 81-functional deposited film of the present invention is A-5i:
Ge:H:X (X represents a halogen atom);
-3i:B:H:It is particularly effective in forming an amorphous semiconductor alloy composed of X.

The raw material gas for film formation in forming a desired functional deposited film by the method of the present invention is appropriately selected and used depending on the type of functional deposited film, that is, the amorphous semiconductor alloy to be manufactured.

These raw material gases include gases whose constituent atoms are silicon atoms, gases whose constituent atoms are germanium atoms, gases whose constituent atoms are tin atoms, gases whose constituent atoms are lead atoms, and gases whose constituent atoms are carbon atoms. A gas selected from gases, gases whose constituent atoms are nitrogen atoms, gases whose constituent atoms are oxygen atoms, gases whose constituent atoms are halogen atoms, etc. can be used.

Specific examples of the raw material gas include the following gases. That is, preferred examples of gases containing silicon atoms include silane-based gases such as 5iHa, 5lzF, and 5i3Hs, and preferred examples of gases containing germanium atoms include G5H4. ，
Examples include germane-based gases such as GetHi-mlh. Further, a preferable example of a gas containing tin atoms as a constituent atom is S n Hf.

Gases such as hS n (CHz) 4 can be mentioned, and a preferable example of a gas having lead atoms as a constituent atom is P
h(CI-14, Pb(CzHs)6, etc.) In addition, suitable examples of gases having carbon atoms as constituent atoms include methane group hydrocarbon gases such as CH4+ C2Ha, C, IH*, etc. Examples include ethylene series hydrocarbon gases such as C2Ha and Cz tl 6, and cyclic hydrocarbon gases such as Cb Hh. Preferred examples of gases containing nitrogen atoms include gases such as N2.NHff, etc. I can do it,
Let oxygen atom be constituent element I! Suitable examples of gas include:
Examples include gases such as Ot, GO, Cot, NOx, and NzO. For gases whose constituent atoms are hexalogen atoms,
5izF used in the method of the invention.

In addition to providing the above-mentioned effects, it also acts as a halogen atom supply source for the deposited film to be formed.

1 Pig S i * F b In addition to gas, S:Fa, 5i
FHx.

SiFzHg, 5iF1H, GeFa, GeHFz+G
eHzFz.

Fluorine compounds such as GeHffF, HF, Fz, 5iCj!
,.

Chlorinated compounds such as GeCA', furthermore, Brt,
[Z, etc. can be exemplified as suitable examples.

Of course, it is possible to make it into a controlled one, and in that case, to make it a p-type, use a raw material gas whose constituent atoms are atoms belonging to group Ⅰ of the periodic table, and use an n-type one. For this purpose, if a raw material gas whose constituent atoms are atoms belonging to Group Ⅰ of the periodic table is introduced into the film forming chamber together with the film forming raw material gas, the desired amorphous material controlled to be p-type or n-type can be formed. A high quality semiconductor alloy can be obtained.

Specific examples of Group Ⅰ atoms include B, A 1. Ga, In
.

T7! Suitable examples of raw material gases for supplying these gases include BFs, BtHb, and B4HI. , BsHw.

Examples include boron hydrides such as BsH++, B6H111, BbH+t, and BiILa. In addition to these, AlC1z
.

GaC1,, GaCCHs>s, I ncI! x, T
1cI! , , etc. can also be mentioned. Specific examples of Group Ⅰ atoms include P, As, Sb, and Bi, and preferable examples of raw material gases for supplying them include PH, P! H,
Examples include phosphorus hydride, AsH3,5bHs, BiHs, etc.

〔Example〕

The deposited film forming method of the present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples in any way.

FIG. 2 is a schematic side cross-sectional view of a deposited film forming apparatus using the MW-P CVD method that can be used to carry out the deposited film forming method of the present invention, and FIG. 3 is a plan cross-sectional view of the apparatus. It is a diagram.

The deposited film forming apparatus shown in FIGS. 2 and 3 used to carry out the deposited film forming method of the present invention is constructed as follows. uU, reactor vessel (201,
301), microwave introduction windows made of alumina ceramics (202, 302), microwave waveguide 303. Exhaust pipe (204, 304), support (cylindrical) (205, 3
05) (When the support is plate-shaped, the plate-shaped support is brought into close contact with the surface of a cylindrical support, for example, an aluminum cylinder to form a deposited film), support Heating heater (207, 307), gas introduction pipe (208, 308), support rotation motor (21)
0). The gas introduction pipe (20
8,308) is 5IHa.

GaHa+H! The exhaust pipe 204 is connected to a cylinder for the raw material gas such as CHa, BzHh, etc. and a cylinder for 5izH & gas via a valve and a mass flow controller (not shown at this point), and the exhaust pipe 204 is connected to a diffusion pump (not shown). It is connected.

The deposited film forming method of the present invention is carried out, for example, as follows using the deposited film forming apparatus.

First, a cylindrical support (205, 305) is installed in a reactor vessel (201, 301), the support is rotated by a support rotation motor (210), and a diffusion pump (not shown) is used to rotate the support.
Reduce pressure to below 10-'Torr. vt, the temperature of the cylindrical support is controlled to a predetermined temperature of 50° C. to 400° C. using a heater (207° 307) for heating the cylindrical support.

When the cylindrical support (205, 305) reaches a predetermined temperature, a predetermined gas is introduced from a gas cylinder (not shown) through the gas introduction pipe (208, 308) into the discharge space (2).
06,306) (III, film forming space). Then, the internal pressure of the discharge space (206, 306) is set to 10. , Tor
The pressure is set to a predetermined pressure of r or less.

After the internal pressure is stabilized, the discharge space (206, 3
06) Introduce microwave energy. At this time, the amount of microwave energy introduced and applied to the film-forming raw material gas is 1.1 times or more and no more than 5 times the amount of microwave energy required to saturate the film deposition rate. controlled by. Further, the internal pressure is controlled to a predetermined pressure of 1QmTorr or less. By performing the film forming operation in this manner, the source gas is decomposed and a predetermined high quality amorphous semiconductor association is formed on the cylindrical support.

Using the deposited film forming apparatus shown in FIGS. 2 and 3, an A-3i (H, F) film was formed according to the deposited film forming method of the present invention.

The protective film was deposited on Corning 7059 glass.

The 7059 glass has a size of 11 nch x 21 nch, and is made by digging a groove in a cylindrical Al cylinder.

I did it.

A cylindrical Al cylinder set with 7059 glass,
It was installed at the position of the cylindrical support 205 shown in FIG.

S 14 gas and Si, F, gas were used as raw material gases for depositing the A-3t(H,F) film. The flow rate of SiH4 gas was 250 seconds.

Cylindrical AI! The temperature of the cylinder was 200°C.

Other conditions were as shown in Table 1.

The comparative example is the condition according to the conventional technology, and the sample size is 101.
-112 are examples in which a halogen atom-containing gas is mixed with the raw material gas.

Samples Na101-112 were deposited with microwave energy 1.1 times higher than the critical point microwave energy as shown in Table 1.

Bright conductivity and dark conductivity were determined by vacuum-depositing an AI gap electrode on 7059 glass with a fat A-3i:H film, and measuring the conductivity with a microcurrent meter (4140B manufactured by YHP). The light source for dark conductivity measurement was a 7 mW He-Ne
I used leather.

The response speed of the photocurrent was measured by causing a 750 nm light emitting diode to emit light in a pulsed manner using a pulse generator, and recording the obtained photocurrent on a storage oscilloscope.

And, 5izF, gas mixing ratio is 10% or less, 8% ~
Good results were obtained according to 0.1%, 7% to 0.5%.

Furthermore, as shown in sample areas 101 and 102, the deposition rate decreased where the mixing ratio of 5iP4 was high.

Under other conditions, the deposition efficiency was nearly 100%.

An A-3i (H, F) film was formed according to the method of forming a deposited film of the present invention using the apparatus for forming a deposited film shown in FIGS. 2 and 3.

The A-S i(H,F) film is 7059 manufactured by Corning.
Deposited on glass. 7059 glass is finchx
A groove with a size of 2 inches was dug in a cylindrical Ae cylinder and a cent was made.

A cylindrical Al cylinder set with 7059 glass,
It was installed at the position of the cylindrical support 205 shown in FIG.

SiH4 gas and SimF&gas were used as raw material gases for depositing the A-5i (HF) film. *7505 ccs of SiH, SiH4 gas was used.

The temperature of the cylindrical Al cylinder was 200°C. Other conditions were as shown in Table 2.

The comparative example in Table 2 is a sample under the conditions of the prior art.

Samples &201 to 203 are samples formed by the deposited film forming method of the present invention.

Bright conductivity and dark conductivity were determined by depositing A-3i:H film.
A gap electrode of Al was vacuum-deposited on the 059 glass, and the 4-electric constant was measured using a microcurrent meter (4140I3 manufactured by YHP). The light source for dark conductivity measurement was a 7 mW He-Ne
I used leather.

The response speed of the photocurrent was measured by causing a 750 nm light emitting diode to emit light in a pulsed manner using a pulse generator, and recording the resulting photocurrent on a storage onoroscope.

Samples 1201 to 20 by the deposited film forming method of the present invention
3) has much improved bright conductivity/dark conductivity and response speed compared to the comparative sample.

Further, the deposition efficiency of the raw material gas was approximately 100%.

Using the deposited film forming apparatus shown in FIGS. 2 and 3, an electrophotographic photoreceptor 505 shown in FIG. 5 was produced according to the deposited film forming method of the present invention.

The electrophotographic photoreceptor 505 is a cylindrical Al cylinder 50
1 to prevent charge injection from the support 502
, a second photosensitive layer, and a third WJ504 as a surface protective layer.

The photoreceptor was manufactured under the manufacturing conditions shown in Table 3. Cylindrical Aj when deposited film is formed! The cylinder temperature was 210°C.

The electrophotographic photoreceptor thus obtained was used in a copying machine (Ki A.
Evaluation was made using Non-manufactured NP7550). The charging ability was improved by 20% and the sensitivity was also improved by 20% compared to the conventional photoreceptor (shown in the comparative example).

Moreover, it had a characteristic that there was almost no afterimage.

[Comparative example]

A conventional electrophotographic photoreceptor was produced using the deposited film forming apparatus shown in FIGS. 2 and 3 under the conditions shown in Table 4.

A-3 was prepared in the same manner as in Example 1 using the deposited film forming apparatus shown in FIGS. 2 and 3 by the deposited film forming method of the present invention.
i: A Ge(H,F) film was deposited.

SiH4 gas was used as a raw material gas for silicon, and Getla gas was used as a raw material gas for germanium, each of which was introduced into the reactor at a rate of 100 sec. Furthermore, S
iz F, gas was introduced at 3 sccm. The substrate temperature was 200°C. Also, the internal pressure during deposition is Q, 4 m
Torr. The microwave energy was 5kW.

In this way, A
-5i: Ge (H,F) film was deposited.

The deposition rate was 81 persons/sec. The response speed was measured in the same manner as in Example 1. A-5i by conventional method
The photocurrent response speed was improved by 50 times compared to the +Ge:H film.

A-5i:Ge(H,F)
A film was deposited.

A-3i: A Ge (H,F) film was deposited on a quartz support by IILm at a support temperature of 200° C. and under the conditions shown in Table 5.

A-5i : Ge (H
.

F) ESR (Electron Spin Resonance, the number of dangling bonds of silicon or germanium atoms can be measured) was measured for the film.

A-5i:Ge(H,F) by the deposited film forming method of the present invention
) membrane has a higher E than that of the conventional membrane as shown in Table 5.
Good characteristics with low SR were obtained. Furthermore, when an infrared absorption spectrum was measured, it was found that A Si : Ge (H) of the deposited film forming method of the present invention.

F) In the film, only absorption of 5i-H and Ge-H was observed.

Furthermore, under the same manufacturing conditions as above, Corning Co., Ltd. 7
20 μm deposited on 059 glass.

In the conventional example, the film peeled off, but in the deposited film according to the present invention, the film did not peel off.

Moreover, no columnar structure was observed in the deposited film.

Furthermore, compared to the conventional example, the plasma discharge was very stable in this example.

A-3i:, C(H,F)
A film was deposited.

A-3ir C05F) films were deposited to a thickness of 1 μm on a quartz support at a support temperature of 290° C. and the conditions listed in Table 6.

A-3i deposited on quartz support '2: CDr,
F) The membrane is IESI? as in Example 5. was measured.

A S +' C(H
JF) membranes were prepared by conventional methods as shown in Table 6.
Is ESI better than 1? Few good characteristics were obtained.

In addition, A-3i:C(H) was produced under the same production conditions as above.

F) Membrane was deposited 30 μm onto AA' support.

In the conventional example, the film peeled off, but in the case of the film according to the present invention,
The i-film did not peel off.

Furthermore, the film thickness and electrical properties on the support were very uniform compared to the conventional example.

EXAMPLE 1 An A-3i:N(H,F) film was deposited by the deposited film forming method of the present invention using the deposited film forming apparatus shown in FIGS. 2 and 3.

A-3i: N (H,F) film on a quartz support
A thickness of 1 μm was deposited at a support temperature of 190° C. and under the conditions shown in Table 7.

The ESR of the A-3i IN (H,F) film deposited on the quartz support was measured in the same manner as in Example 5.

A-3i:N(H) by the deposited film forming method of the present invention.

F) As shown in Table 7, the membrane had good characteristics with less ESR than the membrane produced by the conventional method.

In addition, A-5i:N (Hp>m
was deposited at 30 ttm on the AJ support.

In the conventional example, the film peeled off, but in the deposited film according to the present invention, the film did not peel off.

A-3i (H) was formed by the deposited film forming method of the present invention using the deposited film forming apparatus shown in FIGS. 2 and 3.

F), A-3i s Ge (H, F) film was doped with impurities.

Each doping film was made of Corning 7o59 glass.
1 μ at the support temperature of 250°C and the conditions shown in Tables 8 to 10.
m deposited.

A comb-shaped AI electrode was vacuum-deposited on each doped film, and the dark conductivity was measured using a microcurrent meter (4140B manufactured by YHP).

As shown in Tables 8 to 1θ, the doped films formed by the deposited film forming method of the present invention had higher dark conductivity than the conventional example, and good doping efficiency was obtained.

By using the deposited film forming apparatus shown in FIGS. 2 and 3 and the deposited film forming method of the present invention, A-Si:Ge(H,F)
The crotch was deposited.

A-3i: Ge (HF) film on quartz support
A thickness of 1 μm was deposited at a support temperature of 200° C. and under the conditions shown in Table 11.

A-3i: Ge(II) deposited on a quartz support
F) ESR (Electron Spin Resonance, the number of dangling bonds of silicon or germanium atoms can be measured) was measured for the film.

A-3i;Ge(H,F) by the deposited film forming method of the present invention
) As shown in Table 11, the film had good characteristics with less ESR than the film produced by the conventional method. In addition, when infrared absorption spectra were measured, it was found that in the deposited film forming method of the present invention, 5i-H and Ge-1
(m Si F+ Ce
Almost no absorption of F was observed.

Furthermore, under the same manufacturing conditions as above, Corning Co., Ltd. 7
20 μm deposited on 059 glass.

In the conventional example, the film peeled off, but the fff according to the present invention
The f1 product ff2 did not cause film peeling.

Actually ILL! IL A-si:'c:(H,F
) film was deposited.

A-3i: A C(H,F) film was deposited to a thickness of 1 μm on a quartz support at a support temperature of 290° C. and under the conditions shown in Table 12.

The ESR of the A-3i:C(H,F) film deposited on the quartz support was measured in the same manner as in Example 5.

A-3i:C(I(, F
) As shown in Table 12, the membrane had good characteristics with less ESR than the membrane produced by the conventional method.

In addition, under the same production conditions as above, A-3i:C(H,F)
The membrane was deposited 30 μm onto an AI support.

In the conventional example, the film peeled off, but in the deposited film according to the present invention, the film did not peel off.

An A-3i:N(H,F) film was deposited by the deposited film forming method of the present invention using the deposited film forming apparatus shown in FIG.

A-Si:N(15F) film was deposited to a thickness of 1 μm on a quartz support at a support temperature of 190° C. and under the conditions shown in Table 13.

A-3i deposited on quartz support: N (H,F)
The ESR of the membrane was measured in the same manner as in Example 5.

A-Si:N (If, F
) As shown in Table 13, the membrane had good characteristics with less ESR than the membrane produced by the conventional method.

In addition, under the same manufacturing conditions as above, A-3i:N(H,F)
The membrane was deposited 30 pm onto an All support.

In the conventional example, the film peeled off, but in the deposited film according to the present invention, the film did not peel off.

A-3i (H) was formed by the deposited film forming method of the present invention using the deposited film forming apparatus shown in FIG. 2 and Part 3.

F), A-3i: Ge (H,F) film was doped with impurities.

Each doping film was made of Corning 7059 glass.
1 at a support temperature of 250°C and the conditions shown in Tables 14 to 16.
μm was deposited.

A comb-shaped Al electrode was vacuum-deposited on each doped film, and the dark conductivity was measured using a microcurrent meter (4140B manufactured by YHP).

The doped film formed by the deposited film forming method of the present invention is
As shown in Tables to Table 16, the dark conductivity is higher than the conventional example,
Results with good doping efficiency were obtained.

[Summary of effects of the invention]

According to the deposited film forming method of the present invention, the high deposition rate is approximately 10
It is possible to form a functional deposited film with 0% raw material gas utilization efficiency and excellent electrical properties. In particular, the photocurrent response speed is greatly improved.

In addition, the high deposition rate means nearly 100% raw material gas utilization efficiency, making it possible to significantly reduce the production costs of various functional devices (electrophotographic photoreceptors, sensors, solar cells, thin film transistors, etc.). .

It is a logarithmic graph showing the relationship.

[Brief explanation of the drawing]

FIG. 1 is a schematic illustration of the principle of the method of the present invention. 2 and 3 show microwave plasma according to the present invention? CV
FIG. 3 is a schematic explanatory diagram of a side sectional view and a plan sectional view of a deposited Mi film forming apparatus using the D method. In the figure, 201.301... Reactor vessel, 202
゜302... Microwave introduction window, 203... Waveguide, 204゜304... Exhaust pipe, 205, 305...
Cylindrical support, 206.306... discharge space, 207
, 307... Heater, 208, 308... Gas introduction pipe, 209... Moving flange, 201... Motor. FIG. 4 is an explanatory diagram of the relationship between deposition rate and microwave energy in the method of the present invention. FIG. 5 is a schematic explanatory diagram of an electrophotographic photoreceptor produced in an example of the present invention. 501... Support, 502... First layer, 503...
- Second layer, 504... Third layer, 505... Photoreceptor for electrophotography. Figure 6 shows the internal pressure during film formation in the method of the present invention, patent applicant Canon Co., Ltd. No. 1! ! l Microwave energy Figure 2 Figure 33

Claims (10)

[Claims] (1) A raw material gas for forming a deposited film is introduced into a deposited film forming apparatus that can be operated at a reduced pressure, in which a support for forming a deposited film is arranged, plasma is generated using microwave energy, the raw material gas is decomposed, and the raw material gas is decomposed. In the deposited film forming method for forming a functional deposited film on a support, Si_2F_6 is added to the raw material gas.
Gases are mixed in an amount of 10% or less by volume, microwave energy 1.1 times or more the microwave energy at which the deposition rate is saturated is applied to the mixed gas, and the internal pressure during film deposition is 10 mTorr or less. A method for forming a functional deposited film characterized by: (2) The method for forming a functional deposited film according to claim 1, wherein the source gas contains at least one of SiH_4 and Si_2H_6. (3) The method for forming a functional deposited film according to claims 1 and 2, wherein the source gas contains at least one of GeH_4 and SnH_4. (4) The raw material gas is CH_4, C_2H_4, C_
The method for forming a functional deposited film according to claims 1 to 3, which contains at least one of 2H_6, C_2H_2, and C_3H_8. (5) The method for forming a functional deposited film according to any one of claims 1 to 4, wherein the source gas contains at least one of N_2 and NH_3. (6) The raw material gas is NO, NO_2, CO, CO_
2. The method for forming a functional deposited film according to claims 1 to 5, which comprises at least one of the following. (7) The raw material gas is an inert gas (He, Ne, Ar,
Claim 1 diluted with Kr, Xe, etc.)
A method for forming a functional deposited film according to items 6 to 6. (8) The method for forming a functional deposited film according to any one of claims 1 to 7, wherein the source gas is diluted with hydrogen gas. (9) The method for forming a functional deposited film according to any one of claims 1 to 8, wherein the internal pressure during deposition is 1 mTorr or less. (10) The method for forming a functional deposited film according to any one of claims 1 to 9, wherein the microwave frequency of the microwave energy applied during film formation is 2.45 GHz.