JPS61228615A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To make the improvement of film productivity and mass production easy while contriving to improve the properties of a film, a film forming speed and reproducibility and the uniformity of film quality by chemical reaction affecting heat energy, making the coexistence of a compound containing carbon and a halogen and an active species made from a compound containing silicon for forming film. CONSTITUTION:A compound containing carbon and a halogen and an active species made from a silicon containing compound which reacts chemically with the compound and is made a material for forming a deposition film are each introduced in a film forming space 101 and a deposition film is formed on a substrate 103 by a chemical reaction affecting heat energy. For example, the substrate 103 made of a polyethylene terephtalate film is placed on a susceptor 102, the film forming chamber 101 is exhausted, then Si5H10 is introduced in an activation chamber 123 from a cylinder 106 for gas supply, is activated by a microwave plasma generation equipment 122 and introduced in the film forming chamber 101. Whereas, CF4 gas is introduced in the film forming chamber 101 from a supply source 112 and an amorphous silicon film containing carbon is formed maintaining within the film forming chamber 101 at 190 deg.C by a heat energy generation equipment.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention is directed to silicon-containing deposited films, particularly functional films, particularly semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, imaging devices, The present invention relates to a method suitable for forming an amorphous, polycrystalline, or other non-single-crystal silicon-containing deposited film for use in photovoltaic devices and the like.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using vacuum evaporation, plasma CVD, CVD 1 reactive sputtering, ion blasting, photo-CVD, etc. Generally, plasma CVD is the most popular method. Widely used and commercialized.

Deposited films composed of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility.
In terms of mass production, there is room for further improvement in overall characteristics.

The reaction process in forming an amorphous silicon deposited film by the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, which often has a significant negative effect on the deposited film formed. Moreover, parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions. On the other hand, in order to develop an amorphous silicon film that fully satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. There is.

According to Katori et al., depending on the application of the deposited film, it is possible to fully satisfy the requirements of large area, uniform film thickness, and uniform film quality, and also at high speed.
Since it is necessary to achieve mass production with reproducibility depending on the film, the formation of amorphous silicon deposited films using the plasma CVD method requires a large amount of capital investment in mass production equipment, and the management items for mass production are also complicated. As a result, the permissible management range has become narrower, and the adjustment of the equipment has become more delicate, so these have been pointed out as problems that should be improved in the future. On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to provide a deposited film with practically usable characteristics.

As mentioned above, it is strongly desired to develop a method for forming an amorphous silicon film that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity. The same can be said of other functional films, such as silicon nitride films, silicon carbide films, and silicon oxide films.

The present invention eliminates the drawbacks of the plasma CVD method described above, and provides a new method for forming a deposited film that does not rely on conventional forming methods.

[Object of the invention and summary of disclosure]

The purpose of the present invention is to improve the characteristics, film formation speed, and reproducibility of the film to be formed, and to make the film uniform in quality. The object of the present invention is to provide a deposited film forming method that can be easily achieved.

The above purpose is to form a compound containing carbon and halogen in a film forming space for forming a deposited film on a substrate, and a silicon-containing compound that chemically interacts with the compound and becomes a raw material for forming a deposited film. This is achieved by the method for forming a deposited film of the present invention, which is characterized in that a deposited film is formed on the substrate by introducing active species such as the active species and applying thermal energy to them to cause a chemical reaction.

[Embodiment]

In the method of the present invention, instead of generating plasma in the IR and WA chamber spaces for forming deposited films, compounds containing carbon and halogen coexist with active species generated from silicon-containing compounds for film formation. By applying thermal energy to these components, chemical interactions are caused, promoted, and amplified, so that the deposited film that is formed is not susceptible to etching effects or other abnormal discharge effects, for example. According to the present invention, it may be adversely affected by, etc.
A more stable CVD method can be achieved by arbitrarily controlling the atmospheric temperature in the film-forming space and the substrate temperature as desired.

In the present invention, the thermal energy for exciting and reacting the deposited film forming raw material is applied to at least a portion of the film forming space near the substrate or the entire film forming space, and there is no particular restriction on the heat source used. Conventionally known heating media such as heating by a heating element such as resistance heating, high frequency heating, etc. can be used. Alternatively, thermal energy converted from light energy can be used. Furthermore, if desired, light energy can be used in combination with thermal energy. Light energy can be applied to the entire substrate using an appropriate optical system, or can be selectively applied to only desired areas, so that the formation position and thickness of the deposited film on the substrate can be controlled. etc. can be easily controlled.

Futomaki nF1171 Susha is a follower's CvD Tsuji - Takashi's fortune 1
One is to use activated species that have been activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and also to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

In the present invention, the active species refers to the compound that is the raw material for forming the deposited film or its excited decomposition product, and causes a chemical interaction with it to impart energy or cause a chemical reaction, thereby causing the deposition. It refers to something that has the effect of promoting the formation of a film. Therefore, the active species may include constituent elements that constitute the deposited film to be formed, or may contain such constituent elements. It is not necessary.

In the present invention, the active species from the activation space introduced into the film forming space has a lifetime of 0.1 seconds or more, more preferably 1 second or more, and optimally 10 seconds or more, from the viewpoint of productivity and ease of handling.
A length longer than 1 second is selected and used as desired. The silicon-containing compound for film formation is activated by activation energy in the activation space to generate active species, and when the active species are introduced into the film formation space and form a deposited film, At the same time, carbon and halogen-containing compounds introduced into the film forming space chemically interact with each other due to the action of thermal energy. As a result, a desired deposited film can be easily formed on a desired substrate.

The silicon-containing compound used as a raw material for forming a deposited film used in the present invention is already in a gaseous state before being introduced into the activation space, or is preferably introduced in a gaseous state. For example, it is a liquid compound. When using a compound supply source, an appropriate vaporization device can be connected to the compound supply source to vaporize the compound before introducing it into the activation space. As the silicon-containing compound, silanes, siloxanes, etc. in which hydrogen, halogen, or hydrocarbon groups are bonded to silicon can be used.

Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with halogen atoms.

Specifically, for example, SiH4, Si2H6゜5i3H
B, 5iaHtO, 5i5H12, 5i6H14, etc.
ipH2p+2 (p is an integer of 1 or more, preferably 1-15, more preferably 1-10), 5iH3SiH(SiH3)SiH3
゜5iH3SiH (SiH3)Si3H7゜5i2H5
5ipH2p+z such as SiH (SiH3) Si2H5
(p has the above-mentioned meaning), a chain silane compound having a branch represented by (p has the above-mentioned meaning), a compound in which part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with a halogen atom, 5i3H6, 5i4HB.

S i 5 H10, S i 6 H12, etc. (7) Si
A cyclic silane compound represented by qH2q (q is an integer of 3 or more, preferably 3 to 6), a part or all of the hydrogen atoms of the cyclic silane compound are replaced by other cyclic silanyl groups and/or
Examples of compounds substituted with chain silanyl groups and compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are substituted with halogen atoms include SiH3F, 5iH3C1
.

S i rH5X t(
or a halogen atom, r is 1 or more, preferably 1-10,
More preferably an integer from 3 to 7, S+t=2r+2 or 2
It is r. ) and halogen-substituted linear or cyclic silane compounds. These compounds may be used alone or in combination of two or more.

In the present invention, the compound containing carbon and halogen introduced into the film forming space is, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon are replaced with halogen atoms.

Specifically, 1, for example, chain halogenated carbon represented by CuY2u+2 (u is an integer of 1 or more, Y is at least one element selected from F, CI, Br, and I), CVY2V (V is Cyclic halogenated carbon, CuHX, represented by an integer of 3 or more, Y has the above meaning
YY (u and Y have the meanings given above.

) (+y=2u or 2u+2), and the like.

Specifically, for example, CF4. (CF2)s.

(CF2)e, (CF2)4, C2F6, C3F
B, CHF3. CH2F2. CC14 (CCl2)5
, CB C4, (CBr2)5 , C2C16,C2
Br6. CHCl3. CHBr3゜CHI3. C2Cl
Examples include those in a gaseous state or easily gasified, such as 3F3.

Further, in the present invention, as the compound containing carbon and l\logehalogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used.

For example, S IxZ2v+ 2 (v is 1
or above, Z is F, CI, Br, or I. ) chain/\ silicon halide, cyclic silicon halide, S i uH) (Zy (v and Y are as defined above), 5ivZ2v (v is an integer of 3 or more; It has the meaning: x+y=2y or 2v+2
It is. ), and the like.

Specifically, for example, siF4. (S 1F2)s.

(SiF2)s, (SiF2)4,5i2Fe.

5i3FB, SiHF3. SiH2F2゜5iC14(
5iC12)s, SiBr4゜(SiBr2)5,5i
2C16,512Br6゜5iHC13,5IHBr3
, 5iHI3°5i2CI3F3 and the like, which are in a gaseous state or can be easily gasified.

Furthermore, in addition to the above-mentioned compounds containing carbon and halogen (and compounds containing silicon and halogen), other silicon compounds such as simple silicon, hydrogen, and halogen compounds (for example, F2 gas) may be added as necessary.

C12 gas, gasified Br2. I2 etc.) can be used in combination.

In the present invention, methods for generating active species in the activation space include microwave, R
Activation energy such as electrical energy such as F, low frequency, and DC, thermal energy such as heater heating, infrared heating, and light energy is used.

Activated species are generated by adding excitation energy such as heat, light, electricity, etc. in the activation space to the above.

In the present invention, the amount of active species generated from a compound containing carbon and halogen and a silicon-containing compound serving as a raw material for forming a deposited film in the film forming space.

The ratio can be determined as desired depending on the film forming conditions, the type of active species, etc., but it is preferably lO:1-1:10 (introduction flow rate ratio), and more preferably 8:2-4:1.
It is desirable to set it to 6.

In the present invention, in addition to the silicon-containing compound, hydrogen gas and/or no\mouth M y A-A are used as chemical substances for I & membranes.
&/ 4M -' 1-FT: 41 C1riH2-
Gasified Br2. I2, etc.), argon, neon, and other inert gases can also be introduced into the film forming space.

When using multiple of these film-forming chemicals, they can be mixed in advance and introduced into the activation space in a gaseous state, or each of these film-forming chemicals can be supplied from an independent source. They can be supplied individually from each other and introduced into the activation space, or they can be introduced into independent activation spaces and activated individually.

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. The impurity element used is 1 as a p-type impurity.
Group Ⅰ A7) elements of the periodic table, such as B, AI, Ga, I
Suitable examples include n, TI, etc., and examples of the n-type impurity include elements 1 of group V A of the periodic table, such as P.

Preferred examples include As, Sb, Bi, etc.
In particular, B, Ga, P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical properties.

The substance containing such an impurity element as a component (substance for introducing impurities) is in a gaseous state at room temperature and normal pressure, or at least under the conditions for forming a deposited film, and can be easily vaporized using an appropriate vaporization device. Preferably, a compound is selected,
Such compounds include PH3, P2H4, PF3
.

PF5. PCl3. AsH3, AsF3. AsF5. A
sCl3. SbH3,5bFs, SiH3, BF3. B
Cl3. BBr3. B2He, B4O10, B5H9,
B2O33, B6O10, B6O12, AlCl3, etc. can be mentioned. The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity introducing substance may be introduced into the film forming space directly in a gaseous state, or may be introduced into the film forming space by mixing a compound containing silicon and a halogen, or it may be activated in an activation space and then introduced into the film forming space. It can also be introduced into In order to activate the impurity-introducing substance, the above-mentioned activation energy can be appropriately selected and employed. Active species (PN) generated by activating the impurity introducing substance are mixed with the active species in advance or are introduced independently into the film forming space.

Next, the present invention will be described with reference to typical examples of electrophotographic image forming members formed by the method of the present invention.

FIG. 1 is a schematic diagram for explaining an example of the structure of a typical electrophotographic image forming member and photoconductive member obtained by the present invention.

The photoconductive member 1O shown in FIG. 1 can be applied as an electrophotographic image forming member, and includes an intermediate layer 1 provided as necessary on a support 11 for the photoconductive member.
2 and a photosensitive layer 13.

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13 can be created by the method of the present invention. Furthermore, the photoconductive member 10 is a protective layer provided to chemically and materially protect the surface of the photosensitive layer 13, or a lower layer provided for the purpose of improving electrical withstand pressure.
If wall layers and/or top barrier layers are provided, these can also be made using the method of the invention.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, AI, Cr, Mo.

Au, Ir, Nb, Ta, V, Tf, Pt.

Examples include metals such as Pd and alloys thereof.

Polyester is used as the electrically insulating support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and glass.

Ceramic, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface is NiCr.

AI, Sir, Mo, Au, Ir, Nb, Ta.

V + T i + P t + P d * I n
203 + S n O2 * If it is conductive treated by coating, or if it is a synthetic resin film such as polyester film, NiCr, AI, Ag, Pb, Zn
, Ni.

Au, Cr, Mo, Ir, Nb, Ta, V.

The surface is treated with a metal such as T i or PL by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, so that the surface thereof is conductive. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, as desired.

Its shape is determined, but for example, if the photoconductive member 10 shown in FIG. desirable.

For example, a photosensitive layer 13 is attached to the intermediate layer 12 from the side of the support 11.
This effectively prevents the inflow of carriers into the photosensitive layer 13 and causes the photocarriers generated in the photosensitive layer 13 by the irradiation of electromagnetic waves and moves toward the support 11 from the side of the photosensitive layer 13 to the side of the support ti. It has the function of allowing easy passage.

This intermediate layer 12 has silicon atoms as its base material, carbon atoms, hydrogen atoms (H) and/or /\\rogen atoms (X
) containing amorphous silicon (hereinafter referred to as ra-3i
(C, H, ing.

In the present invention, the content of substances governing conductivity such as B and P contained in the intermediate layer 12 is preferably 0.
．． 0'01~5X104atomic ppm, more preferably 0.5~1X11X104ato PPm
, most preferably 1 to 5×10 3 atomic ppm.

If the components are similar or the same as those of the photosensitive layer 13, the formation of the photosensitive layer 13 can be carried out continuously after the formation of the intermediate layer 12.

In that case, the raw materials for forming the intermediate layer include a compound containing carbon and halogen, a gaseous silicon-containing compound, and, if necessary, hydrogen, a halogen compound, an inert gas, and an impurity element. The activated species generated by activating the gas of the compound contained as middle layer 12
All you have to do is form it.

The layer thickness of the intermediate layer 12 is preferably 30 to 10 JL,
More preferably, it is 40λ to 8 liters, and most preferably 50 to 51 liters.

The photosensitive layer 13 has, for example, an A-3i (H,

The thickness of the photosensitive layer 13 is preferably as follows.

It is desirable that the range is 1-1001L, more preferably 1-aoIL, optimally 2-50IL.

The photosensitive layer 13 is made of non-doped A-3i(H.

x) M, but if desired, the intermediate layer 12 may contain a substance that controls the conduction characteristics with a polarity different from that of the substance that controls the conduction characteristics (for example, n-type), or , the substance that governs the conduction characteristics of the same polarity is added to the intermediate layer 1.
If the actual amount contained in 2 is large, it may be contained in an amount much smaller than the above amount.

In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, it is formed from a compound containing carbon and halogen in the space, and a silicon-containing compound for the film, as in the case of the intermediate layer 12. The photosensitive layer 13 may be formed on the intermediate layer 12 formed on the support by using the active species and, if necessary, an inert gas and impurity sensing energy.

FIG. 2 is a schematic diagram showing a typical example of a PIN type diode device using an a-3i deposited film doped with an impurity element, which is manufactured by carrying out the method of the present invention.

In the figure, 21 is the base, 22 and 27 are thin film electrodes 911+%
Road (Ji, nil i ilh GI n JP+
It is composed of a semi-i[k cancer 741 type semiconductor layer 25 and a p-type semiconductor layer 26.

The present invention can be applied to the production of any one of the semiconductor layers 24, 25, and 26, but in particular, the conversion efficiency can be increased by producing the semiconductor 26 by the method of the present invention. When the semiconductor layer 26 is created by the method described above, the semiconductor layer 26 is made of an amorphous material (hereinafter rA-3iC) containing silicon atoms, carbon atoms, hydrogen atoms, and/or halogen atoms as constituent elements. (H,X)J).

28 is a conductive wire connected to an external electric circuit device.

The base 21 may be conductive, semiconductive, or electrically insulating. When the base body 21 is conductive, the thin film electrode 22 can be omitted and semiconductors such as GaAs, ZnO, and ZnS can be used. Examples of the thin film electrodes 22.27 include NiCr, AI, Cr, Mo, Au, and Ir.

N l), 7a, V, Ti, PL, Pd, In2O3,
It is obtained by providing a thin film of ITO (In203+5n02) or the like on the substrate 21 through a process such as vacuum evaporation, electron beam evaporation, or sputtering.

The film thickness of the electrode 22.27 is preferably 30 to 5X.
It is desirable that the number of participants be 104 people, more preferably 100 to 5 x 103 people.

In order to make the film body constituting the semiconductor layer n-type or p-type as necessary, during layer formation, an n-type impurity, a p-type impurity, or both impurities are added to the layer to be formed. It is formed by doping while controlling the amount.

In order to form n-type, i-type, and p-type semiconductor layers by the method of the present invention, a compound containing carbon and halogen is introduced into the film formation space, and separately, a compound containing carbon and halogen is introduced into the activation space. Silicon-containing compounds for film formation, and compound gases containing inert gases and impurity elements as necessary.

Each is excited and decomposed by activation energy to generate each active species, and each is introduced separately or appropriately mixed into the film forming space where the support 11 is installed, and thermal energy is used. The thickness of the n-type and p-type semiconductor layers, which may be formed by
A range of 300 to 2000 people is desirable.

The thickness of the i-type semiconductor layer is preferably 500 mm.
A range of 100 to 104 people, more preferably 1000 to 10000 people is desirable.

A specific example of the present invention is shown below.

Example 1 Using the apparatus shown in Figure 3, i
Type, p-type, and n-type a-3i deposited films were formed.

In FIG. 3, 101 is a film forming chamber, and a desired substrate 103 is placed on a substrate support stand 102 inside.

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 105 and generates heat. Although the substrate temperature is not particularly limited, in carrying out the method of the present invention, preferably 5
The temperature is preferably 0 to 450°C, more preferably 100 to 350°C.

106 to 109 are gas supply sources, which are provided depending on the type of gas of a compound containing carbon and halogen, and a compound containing hydrogen, a halogen compound, an inert gas, or an impurity element as a component, which is used as necessary. . When using liquid materials in standard conditions among these raw material compounds, an appropriate vaporization device is provided.

In the figure, the gas supply sources 106 to 109 with the symbol a are branch pipes, and the symbol b is the flowmeter.

C indicates a pressure gauge for measuring the pressure on the high pressure side of each flow meter, and d or e indicates a pulp for adjusting the flow rate of each gas.

123 is an activation chamber for generating active species, and around the activation chamber 123, a radio wave plasma generator 122 for generating active species is provided. Raw material gas for generating active species supplied from the gas introduction pipe 110 is activated in the activation chamber 123, and the generated active species are introduced into the film forming chamber 101 through the introduction pipe 124. ill is a gas pressure gauge.

In the figure, 112 is a compound supply source containing carbon and halogen, and the ae attached to the symbol 112 are 106 to 109.
It shows something similar to the case of . A compound containing carbon and halogen is introduced into the film forming chamber 101 via the introduction pipe 113.

Reference numeral 117 denotes a thermal energy generating device, and for example, a normal electric furnace, a high frequency heating device, various heating elements, etc. are used.

The heat from the thermal energy generator 117 acts on compounds containing carbon and halogen, active species, etc. flowing in the direction of arrow 119, and the heated compounds and active species react chemically with each other. - Form a deposited film of a-5t on the 4kt 03 rest area 9. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

Substrate 10 made of polyethylene terephthalate film
3 is placed on the support stand 102.

Evacuate the inside of the film forming chamber 101 using an exhaust device (not shown),
The pressure was reduced to approximately 1 (16 Torr). At the substrate temperature shown in Table 1, using the gas supply cylinder 106 - (S [5) f
loi50SCCM, or this and PH3 gas or B2H6 gas (both diluted with 11000pp hydrogen gas) 4
A gas mixed with 03CCM was introduced into the activation chamber 123 through the gas introduction pipe 110.

The 5tsHto gas etc. introduced into the activation chamber 123 are
The activated silicon, activated hydrogen, etc. were activated by the microwave plasma generator 122 and introduced into the film forming chamber 101 through the introduction pipe 124.

Further, CF4 gas was introduced from the supply source 112 into the film forming chamber 101 through the introduction pipe 113.

In this way, a non-doped or doped carbon-containing amorphous silicon film (II5I thickness of 700 mm) was formed under the pressure in the film forming chamber 101. The film formation rate is 2
There were 8 people/sec.

Next, the obtained non-doped, P-type, or n-type carbon-containing amorphous silicon film sample was placed in a vapor deposition tank, and a comb-shaped AI gap electrode (gear length: 250 mm, width: 5 mm) was formed at a vacuum level of 1 O-5 Torr. After that, the dark current was measured with an applied voltage of 10 V, and the dark conductivity σd was determined.
The membrane properties of each sample were evaluated. The results are shown in Table 1.

Examples 2 to 4 st51 (linear Si4H10 instead of to, branched 5
Except using i4HtO1 or Has i eFe,
A carbon-containing amorphous silicon film was formed in the same manner as in Example 1. The dark conductivity was measured and the results are shown in Table 1.

Table 1 shows that according to the present invention, a carbon-containing amorphous silicon film with excellent electrical properties, that is, a high σ value, can be obtained, and a-5i (H,
It turns out that M can be obtained.

Example 5 Using the apparatus shown in Fig. 4, the first
A drum-shaped electrophotographic image forming member having a layer structure as shown in the figure was prepared.

In FIG. 4, 201 is a film forming chamber, 202 is a compound supply source containing carbon and halogen, 206 is an introduction pipe, 207 is a motor, 208 is a heater used in the same way as the heater 104 in FIG. 3, and 209, 210 is a blowout pipe, 2
Reference numeral 11 indicates an AI cylinder-shaped body 212 indicates an exhaust valve. Further, 213 to 216 are raw material gas supply sources similar to 106 to 109 in FIG. 3, and 217 is a gas introduction pipe.

An AI cylinder base 211 is suspended in the film forming chamber 201, a heater 208 is provided inside the base, and a motor 20 is installed.
7 so that it can be rotated. 218 is a thermal energy generator.

For example, an ordinary electric furnace, a high-frequency treatment layer, various heating elements, etc. are used.

Further, CF4 gas was introduced from the supply source 202 into the film forming chamber 201 through the introduction pipe 206. , while the inlet pipe 217
S i 2H6 and H2 gas were introduced into the activation chamber 219 from -1.

In the activation chamber 219, the introduced H2 gas undergoes activation processing such as plasma conversion by the microwave plasma generator 221, and becomes activated silicon and activated hydrogen, and is then transferred to the film forming chamber 2 through the introduction pipe 217-2. ．． Introduced into O1.

At this time, impurity gases such as PH3 and 82H6 were also introduced into the activation chamber 219 for activation, if necessary.

While maintaining the internal pressure within the film forming chamber 201 at 1.0 Torr, the inside of the film forming chamber 201 was maintained at 200° C. by a thermal energy generator.

The AI cylinder base 211 is heated to 210°C by a heater, maintained, rotated, and the exhaust gas is passed through the exhaust valve 212.
Exhausted through. In this way, the photosensitive layer 13 was formed.

In addition, a mixed gas of H2/B2H6 (B2H6 gas is 0.2% by volume) is introduced into the intermediate layer from the introduction pipe 217,
The film was formed using a film thickness of 2000.

Comparative Example 1 A film forming chamber with the same configuration as the film forming chamber 201 was prepared using CF4, S i 2H6, H2 and B2H6 gases (13.56M) (equipped with a high frequency device of z, a general An electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by plasma CVD.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 5 and Comparative Example 1.

Example 6 A PIN type diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3 using 5i3H6 as a silicon-containing compound.

First, the polyethylene naphthalate film 21 on which the ITO film 22 of Iooo was deposited was placed on a support stand, and
After reducing the pressure to −6 Torr.

CF4 was introduced into the film forming chamber 101 from the introduction pipe 113 in the same manner as in Example 1, and CF4 was introduced from the introduction pipe 110 to 5i3H.
150 scM of 6 gas and PH3 (diluted with 1000 ppm hydrogen gas) were introduced into the activation chamber 123 for activation.

Next, this activated gas was introduced into the film forming chamber 101 via the introduction pipe 124.

While maintaining the pressure in the film forming chamber 101 at 0.1 Torr and 210°C, P-doped n-type A-3i'C (H
, X) film 24 (film thickness: 700 layers) was formed.

Next, instead of PH3 gas, 82H6 gas (300
n-type A-5iC except that ppm hydrogen gas dilution) was introduced.
i-type A-3i in the same way as in the case of (H,
A C(H,X) film 25 (thickness: 5000) was formed.

Next, B2H6 with H2 gas instead of PH3 gas
B using gas (1000 ppm diluted with hydrogen gas) and under the same conditions as the n-type A-3iC (H,X) film 24.
p-type a-3iC(H,X) film 26 doped with
A film thickness of 700 layers was formed. Furthermore, on this p-type film, an AI electrode 27 with a film thickness of too thick is formed by vacuum evaporation,
A PIN type diode was obtained.

I of the diode element thus obtained (area 1 cm2)
-V characteristics were measured, and rectification characteristics and photovoltaic effects were evaluated. The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, light is introduced from the substrate side, and at the light irradiation intensity AMI (approximately 100 mW/Cm2), the conversion efficiency is 8.5% or more, the open circuit voltage is 0.97 V, and the short circuit current is 10.1 m A/C1112 was obtained.

Examples 7-9 Instead of 5i3H6 as a silicon-containing compound, linear Si4H10, branched 5iaHto, or H6S i
The PIN was set in the same manner as in Example 6 except that 6F6 was used.
A type diode was fabricated.

The rectification characteristics and photovoltaic effect were evaluated and the results are shown in Table 3.

From Table 3, it was found that according to the present invention, an a-SiC (H,

〔Effect of the invention〕

Compilation of the present invention! According to the film forming method, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible. In addition, reproducibility in film formation is improved, film quality can be improved and film quality can be made uniform, and it is advantageous for increasing the area of the film. Improved productivity and mass production can be easily achieved.

Furthermore, relatively low thermal energy can be used as excitation energy, so e.g.

Films can also be formed on substrates that have poor heat resistance or are easily affected by plasma etching. The low-temperature treatment has the effect of shortening the process.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining an example of the configuration of a PIN diode manufactured using the method of the present invention. FIGS. 3 and 4 are configurations of an apparatus for carrying out the method of the present invention used in Examples, respectively. FIG. 2 is a schematic diagram for explaining. 10--An electrophotographic imaging member, 11--One substrate, 12--One intermediate layer, 13--One photosensitive layer, 21--One substrate. 22, 27---A thin film electrode. 24---n-type semiconductor layer. 25----I-type semiconductor layer, 26----P-type semiconductor layer, 101, 201--film formation chamber, 214.215.216----gas supply source, 103
, 211---one substrate, 117.218---one thermal energy generator.

Claims (1)

[Claims] A compound containing carbon and halogen is contained in a film forming space for forming a deposited film on a substrate, and a silicon-containing compound that chemically interacts with the compound and serves as a raw material for forming a deposited film. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing active species generated by the above-mentioned active species and applying thermal energy to them to cause a chemical reaction.