JPS61194822A - Deposited film forming method - Google Patents

Abstract

PURPOSE:To improve the various characteristics of a film, a high speed film formation, reproducibility and uniformity of film quality by feeding an active seed made of carbon and halogen and an active seed made of a germanium- containing compound, and making thermal energy act to chemically react them. CONSTITUTION:A polyethylene terephthalate film base 103 is placed on a supply base 102, and a film forming chamber 101 is evacuated. Mixture gas of GeH4 and PH3 is fed from a gas supply system 106 to an activating chamber 123, a hydrogenated germanium active seed and active hydrogen are formed by a microwave plasma generator, and fed to the chamber 101. Solid Si particles 114 are filled in the chamber 112, an active seed SiF2 is formed by blowing SiF4 from a guide tube 115 while heating, and fed from a guide tube 116 into the chamber 101. The pressure in the chamber 101 is held at 0.4 Torr, held at 220 deg.C by a thermal energy generator 117 to form an amorphous deposited film.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention relates to deposited films containing germanium, 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 a deposited film containing amorphous or crystalline germanium for use in photovoltaic devices and the like.

[Prior art]

For example, vacuum evaporation, plasma CVD, CVD, reactive sputtering, ion blasting, photo-CVD, and other methods have been tried to form deposited films such as amorphous germanium and amorphous silicon. Specifically, the plasma CVD method is widely used and commercialized.

These deposited films have been improved in terms of electrical and optical properties, fatigue properties due to repeated use, use environment properties, productivity including uniformity and reproducibility, and mass production. There is room for improvement in its characteristics.

The reaction process in forming deposited films of amorphous germanium and amorphous silicon using the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and the reaction mechanism is still unclear. It wasn't much. In addition, there are many formation parameters for the deposited film (e.g., substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, plasma generation method, etc.). Due to the combination of these parameters, 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 a film of amorphous germanium or amorphous silicon that satisfies electrical, optical, photoconductive, or mechanical properties, it is currently necessary to form it by plasma CVD. considered to be the best.

According to Hyakunen et al., depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniform film thickness, and uniform film quality, and to achieve mass production with high reproducibility through high-speed film formation.
Forming a deposited film of amorphous germanium or amorphous silicon using the plasma CVD method requires a large amount of equipment investment for mass production equipment, and the management items for mass production are also complicated, with a narrow management tolerance. As the car's equipment is delicately adjusted, these issues have been pointed out as issues that need to be improved in the future. On the other hand, normal CVD
Conventional techniques based on this method require high temperatures and have not been able to provide deposited films with practically usable properties.

As mentioned above, it is strongly desired to develop a method for forming amorphous germanium or amorphous silicon films that can be mass-produced using low-cost equipment while maintaining practical properties and uniformity. These things are
The same can be said of other functional films 1, such as silicon nitride films, silicon carbide films, and silicon oxide films.

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

[Purpose and outline of the invention]

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 create an active species (A) generated by decomposing a compound containing carbon and halogen in a film formation space for forming a deposited film on a substrate, and a chemical reaction between the active species (A) and the active species (A). A deposited film is formed on the substrate by separately introducing active species (B) generated from germanium-containing compounds for film formation that interact with each other, and applying thermal energy to them to cause a chemical reaction. This is achieved by the deposited film forming method of the present invention, which is characterized by the back side being formed.

□ [Embodiment] In the method of the present invention, instead of generating plasma in a film forming space for forming a deposited film, active species (A) generated by decomposing a compound containing carbon and halogen are used to form a film. In coexistence with the active species (B) generated from the germanium-containing compound used, by applying thermal energy to the active species (B), chemical interactions are caused, or promoted and amplified. The deposited film formed is not adversely affected by etching effects or other adverse effects such as abnormal discharge effects.

Further, according to the present invention, 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.

Further, according to the present invention, 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 that acts on the active species (A) and/or the active species (B) and causes a chemical reaction between them acts on at least a portion of the film forming space near the substrate or the entire film forming space. It is something that will be done. There is no particular restriction on the heat source used, and 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 addition to 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 the formation position and thickness of the deposited film on the substrate can be controlled. It is possible to control and make things worse.

One of the differences between the method of the present invention and the conventional CVD method is that it uses active species 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 chemical interaction with the compound or excited active species of the raw material for forming the deposited film, for example, by imparting energy or causing a chemical reaction. 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. In the present invention,
Active species from the activation space (A) introduced into the film forming space (
A) has a lifespan of 0.1 seconds or more, more preferably 1 second or more, and optimally 1 second or more from the viewpoint of productivity and ease of handling.
Those with a length of 0 seconds or more are selected and used as desired.

The constituent elements of this active species (A) constitute the components constituting the deposited film formed in the film forming space. In addition, the germanium-containing compound for film formation is activated by activation energy in the activation space (B) and forms active species (B).
), and the activated species CB) are introduced into the film forming space, and when forming a deposited film, chemically generated by the action of the active species (A) introduced from the activation space (A) and thermal energy. interact. the result.

A desired deposited film is easily formed on a desired substrate. The active species (B) generated from the germanium-containing compound constitutes the components constituting the deposited film formed in the film forming space, as in the case of the active species (A).

The germanium-containing compound introduced into the activation space (B) used in the present invention is already in a gaseous state before being introduced into the activation space (B), or is introduced in a gaseous state. For example, when using a liquid compound, the compound can be vaporized by connecting an appropriate vaporizer to the compound supply system and then introduced into the activation space (B).

As the germanium-containing compound, an inorganic or organic germanium compound in which hydrogen, halogen, or a hydrocarbon group, etc. are bonded to germanium can be used.
A chain or cyclic germanium hydride represented by ezHb (cL is an integer of 1 or more, b=2a+2 or 2a), a polymer of this germanium hydride, a part of the hydrogen atom of the germanium hydride, or Compounds in which all hydrogen atoms are substituted with halogen atoms, organic germanium compounds such as compounds in which some or all of the hydrogen atoms of the germanium hydride are substituted with organic groups such as alkyl groups and aryl groups, and optionally with halogen atoms, etc. and other germanium compounds.

Specifically, for example, QeH4, Ge2H6, Ge3HB.

n-Ge4H1(1, tert-Ge4H10゜G
e3H6, ce5Hto, ceH3F.

GeH3CI, GeH2F2, H6Ge6F6.

Ge (CH3)4, Ge (C2H5)4.

Ge (CaH2) 4 , Ge (CH3) 2
F2.

CH3GeH3, (CH3) 2GeH2.

(CH3) 3GeH, (C2H5)2GeH2.

GeF2. GeF4. Examples include GeS.

These germanium compounds may be used alone or in combination of two or more.

In the present invention, as the compound containing carbon and halogen introduced into the activation space (A), for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound is replaced with a halogen atom is used, Specifically, for example, c
uy2U+2 (U is an integer greater than or equal to 1, Y is F, CI.

It is at least one element selected from Br and I. ) chain I＼rogenated carbon, CVY2V
(V is an integer of 3 or more, Y has the above-mentioned meaning), CuHxYy (u and Y
has the meaning given above. z+y=2u or 2u+2. ), and the like.

Specifically, for example, CF4. (CF2)5.

(CF2)6, (CF2)4, C2F6.

C3FB, CHF3, CH2F2, CCl4゜(CC12)5, CB r4. (CB r 2)
5.

Examples include those that are in a gaseous state or can be easily gasified, such as C2C16 and C2Cl3F3.

Furthermore, in the present invention, in addition to the active species (A) generated by decomposing the compound containing carbon and halogen, active species (SX) generated by decomposing the compound containing silicon and halogen are also used. Can be used together.

As the compound containing silicon and halogen, 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, and specifically,
For example, 5iuY2u+2 (U is an integer greater than or equal to 1, Y is F
, C1, Br, and at least one element selected from ) chain silicon halide, 5
Cyclic silicon halide represented by ivY2v (v is an integer of 3 or more, Y has the above meaning), S i uH
xYy (u and Y have the above meanings. x+y=
2u or 2u+2. ), and the like.

Specifically, for example, SiF4. (SiF2)5゜(SiF
2) e, (SiF2)4,5i2Fe.

5i3FB, SiHF3. SiH2F2゜5iC14,
(SiC12)5. SiBr4゜(SiBr2)5,5
i2C16,5i2Brs.

5iHCu3, 5iHBr3, 5iHI3゜5i2C1
Examples include those in a gaseous state or easily gasified, such as 3F3.

In order to generate the active species (A), in addition to the above-mentioned compound containing carbon and halogen (and compound containing silicon and I\halogen), if necessary, a carbon-containing compound with the same ability as simple carbon (and simple silicon). other silicon-containing compounds), hydrogen,
Norogen-containing compounds (e.g. F2 gas, C12 gas,
Gasified Br2. I2 etc.) can be used in combination.

In the present invention, methods for generating activated species (A) and (B) in activation spaces (A) and (B), respectively, include microwave, RF high frequency, low frequency, Excitation energies such as electrical energy such as DC, thermal energy such as resistance heating and infrared heating, and optical energy such as laser and xenon lamp light are 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 active species (B) and the active species (A)
The ratio of the amount of 1 to 1 is determined as desired depending on the film forming conditions, the type of active species, etc., but is preferably 10:1-1:1.
0 (introduction flow rate ratio) is appropriate, more preferably 8:2
A ratio of ~4:6 is desirable.

In the present invention, in addition to germanium-containing compounds, hydrogen gas and/or halogen compounds (for example, F2 gas, CI2 gas, gasified Br2,
2), an inert gas such as argon or neon, or a silicon-containing compound, a carbon-containing compound, etc. as a raw material for forming the active species (B) can also be introduced into the activation space (B). When using a plurality of these film-forming chemicals, they can be mixed in advance and introduced into the activation space (B) in a gaseous state, or each of these film-forming chemicals can be supplied independently. Supply each individually from the source and activate the space (B)
It can also be introduced into

As the silicon-containing compound introduced into the activation space (B), silanes and siloxanes in which hydrogen, halogen, hydrocarbon groups, etc. 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, S
i 3HB, S i 4H10, S i 5H12,5
A linear silane compound represented by S i pH2p+2 (P is an integer of 1 or more, preferably 1-15, more preferably 1-10) such as i6H14.

S 1H3s iH(S 1H3)SiH3゜5iH3
SiH(SiH3)Si3H7,5i2H5SiH(S
iH3) A chain silane compound having a branch represented by 5ipH2p+2 (p has the above-mentioned meaning) such as Si2H5.

Compounds in which part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with halogen atoms, 5i3H6, Si 4H9, 5isHxo, 5ie
5 iq H2q such as H12 (q is 3 or more, preferably 3 to
It is an integer of 6. ), a compound in which some or all of the hydrogen atoms of the cyclic silane compound are substituted with other cyclic silanyl groups and/or chain silanyl groups,
As an example of a compound in which some or all of the hydrogen atoms of the silane compounds exemplified above are replaced with halogen atoms, SiH3F
, 5ir such as 5iH3C1, 5iH3Br, 5iH3I, etc.
HsXt (or halogen atom, r is an integer of 1 or more, preferably 1 to 1O2, more preferably 3 to 7, s + t = 2r
+2 or 2r. ) are halogen-substituted linear or cyclic silane compounds. These compounds may be used alone or in combination of two or more.

Further, as the carbon-containing compound introduced into the activation space CB), a chain or cyclic saturated or unsaturated hydrocarbon compound,
Among organic compounds whose main constituent atoms are carbon and hydrogen and one or more constituent atoms such as silicon, halogen, and sulfur, and organosilicon compounds whose constituent constituents are hydrocarbon groups, gaseous A substance that can be easily vaporized is preferably used.

Among these, examples of hydrocarbon compounds include carbon atoms of 1 to
Examples of saturated hydrocarbons include methane (CH3), ethane (C2
H6), propane (C3H8), n-butane (n-C4
H1o), pentane (C5Br2), x Tyrenic hydrocarbons include ethylene (C2H4), propylene (C
3H6), butene-1 (C4H8), butene-2 (C4
He), isobutylene (C4H6), pentene (C
5H10), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4), butyne (C4H6), and the like.

Also, as an organosilicon compound.

(CH3) 43 i, CH3S ic 13.

(CH3) 2stc12. (CH3) 3siC1,
Organochlorosilane such as C2H55iC13, CH3
5iF2C1, CH35iFC12, (CH3)25i
FC1, C2H55iF2CI, C2H55iFC12
, C3H75iF2C1, C3H75iFC12, organochlorofluorosilane, ((CH3)3S t)
Organodisilazane such as 2, ((C3H7)3Si)2, etc. are preferably used.

These carbon-containing compounds may be used alone or in combination of two or more.

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. As the impurity element to be used, as a p-type impurity, an element of Group Ⅰ A of the periodic table, such as B, AI, Ga, In,
Preferred examples include TI, and examples of the n-type impurity include elements of Group V A of the periodic table, such as P.

Preferred examples include As, Sb, Bi, etc.
In particular, g, 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 a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under active species formation conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to select

Such compounds include PH3 and P2H4.

PF3, PF5, PC13, AsH3.

AsF3. AsF5. AsCl3. SbH3゜SbF5
．． SiH3, BF3, BCl3.

BBr 3, B2Hs, B4Hxo, B5H9.

Examples include B5H11, B6H10, B6H12, AlCl3, and the like.

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 activation space (A) and/or the activation space (B) together with each substance that generates the active species (A) and the active species (B) for activation. Alternatively, the impurity-introducing substance, which may be activated in a third activation space (C) different from the activation space (A) and the activation space (B), is subjected to the activation energy described above. can be selected and adopted as appropriate. They are introduced into the film forming space either mixed together or independently.

Next, the present invention will be explained by citing a typical example of a photoconductive member as an electrophotographic image forming member formed by the method of the present invention.

FIG. 1 is a schematic diagram for explaining an example of the configuration of a typical photoconductive member obtained by the present invention.

The photoconductive member 10 shown in FIG. 1 can be applied as an electrophotographic imaging member.

It has a layer structure consisting of a support 11 for a photoconductive member, an intermediate layer 12 provided as necessary, 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 may include a protective layer provided to chemically and physically protect the surface of the photosensitive layer 13, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical withstand pressure. If so, these can also be created by the method of the present invention.

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

A u , I r , N b , T a ,
V, T i, P t.

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

V, T i + P t * P d * I n 2
03*S n O2.

Conductive treatment is performed by providing a thin film such as ITO (In203+5n02), or if it is a synthetic resin film such as polyester film, NiCr, Al, Ag
, Pb, Zn, Ni.

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

The surface is treated with a metal such as Tj, Pt, etc. by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, to make the surface conductive. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined depending on the need. For example, the photoconductive member 10 in FIG. In the case of continuous high-speed copying, it is preferable to use an endless belt or a cylindrical shape.

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

This intermediate layer 12 has germanium atoms as its base material, and silicon (S i ), hydrogen (H), and halogen (
X), amorphous germanium (hereinafter referred to as "amorphous germanium") whose constituent atoms are carbon atoms (C).

A-Ge (denoted as Si, H,
For example, p-type impurities such as boron (B) or phosphorus (P)
Contains n-type impurities such as.

In the present invention, the content of substances governing conductivity, such as B and P, contained in the intermediate layer 12 is preferably 0.
001 to 5X104aL omic ppm, more preferably 0.5 to IX10X104ato ppm, optimally 1 to 5X103 atomic ppm.

When the intermediate layer 12 has similar or the same components as the photosensitive layer 13, the formation of the intermediate layer 12 can be performed continuously from the formation of the intermediate layer 12 to the formation of the photosensitive layer 13. In that case, the active species (A) generated in the activation space (A) and the active species (B) generated from the germanium-containing compound in a gaseous state are used as raw materials for forming the intermediate layer, as necessary. Active species (
B) separately or mixed as necessary and introduced into the film forming space where the support 11 is installed, and by applying thermal energy to the coexistence atmosphere of each introduced active species, the support The intermediate layer 12 may be formed on the body 11.

The compound containing carbon and halogen that is introduced into the activation space (A) to generate active species (A) when forming the intermediate layer 12 is a compound containing carbon and halogen that easily generates active species (A) such as cp2*. The following compounds can be mentioned.

Similarly, as the compound containing silicon and halogen, it is more preferable to select a compound that easily generates an active species such as S i F2)k from among the above-mentioned compounds.

The thickness of the intermediate layer 12 is preferably 30 to 8 Log, more preferably 40 to 8 Log, most preferably 50 to 5 Log.

The photosensitive layer 13 is made of amorphous silicon a-3i (H, X,
Ge, C) or amorphous silicon germanium A containing hydrogen, halogen, carbon, etc. as necessary atoms
- A charge generation function that is composed of 3iGe (H, X, C) and generates photocarriers by laser light irradiation;
It has both the charge transport function of transporting the charge.

The layer thickness of the photosensitive layer 13 is preferably 1 to toog.
, more preferably from 1 to 80 liters, most preferably from 2 to 50 liters.

The photosensitive layer 13 is/doped c7) A-S i (H,
.

Ge, C) or A-3iGe (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, the amount of the substance that controls the conduction characteristics of the same polarity may be much smaller than the amount. It may be included.

In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, as in the case of the intermediate layer 12, a compound containing carbon and halogen is introduced into the activation space (A),
Active species (A) are generated by decomposing them at high temperatures or by exciting them with discharge energy or light energy, and the active species (A) are introduced into the film forming space.

Separately, germanium-containing compounds and silicon-containing compounds in a gaseous state, as well as gases of compounds containing inert gases and impurity elements as necessary, are excited and decomposed by activation energy, respectively. The active species are generated and introduced into the film forming space where the support 11 is installed, either separately or mixed as appropriate. The active species introduced into the film forming space are caused to chemically interact with each other by using thermal energy, or are promoted or amplified to form a deposited film on the support 11.

FIG. 2 is a schematic diagram showing a typical example of a PIN diode device manufactured by implementing the method of the present invention.

In the figure, 21 is a base, 22 and 271 thin film electrodes, 23 is a semiconductor film, an n-type semiconductor layer 24, an i-type semiconductor layer 25 . It is composed of 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 layer 26 by the method of the present invention. In the case of forming the semiconductor layer 26 using 4, the semiconductor layer 26 is made of an amorphous material (hereinafter referred to as rA-3tGec (hereinafter referred to as rA-3tGec H
, X) (denoted as 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 21 is conductive, the thin film electrode 22 may be omitted. Examples of the semiconductive base include Si.

Examples include semiconductors such as Ge, GaAs, ZnO, and ZnS. As the thin film electrodes 22 and 27, NiCr, A
l, Cr, Mo, Au, Ir.

Nb, Ta, V, Ti, Pt, Pd, In2O3,
Thin films such as SnO2 and ITO (In203+5n02) are vacuum evaporated and electron beam evaporated.

It can be obtained by providing it on the base 21 through a process such as sputtering. The film thickness of the electrode 22.27 is preferably 30 to 5×104, more preferably 100 to 5
It is desirable that the number be 103 people.

In order to make the film forming the semiconductor layer n-type or p-type as necessary, during layer formation, n-type impurity, 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, a compound containing carbon and halogen and a compound containing silicon and halogen are introduced into the activation space (A) according to the method of the present invention, and activated. By exciting and decomposing these under the action of energy, active species (A) such as CF2*, SiF2*, etc. are generated, and the active species (A) are introduced into the film forming space.

Separately, germanium-containing compounds and silicon-containing compounds in a gaseous state, as well as gases of compounds containing inert gases and impurity elements as necessary, are excited and decomposed by activation energy, respectively. The active species introduced into the film-forming space ←→, either separately or in an appropriate mixture, are caused to chemically interact with each other by using thermal energy, or are promoted or amplified to the support 11. A deposited film is formed on top.

The thickness of the n-type and p-type semiconductor layers is preferably in the range of 100 to 104, more preferably 300 to 2000.

Further, the thickness of the i-type semiconductor layer is preferably 50
A range of 0 to 104 people, more preferably 100 to 10,000 people is desirable.

Incidentally, the PIN type diode device shown in FIG. 2 has P,
It is not necessarily necessary to produce all of the i and n layers by the method of the present invention, and the present invention can be practiced by producing at least one layer of p, i, and n by the method of the present invention.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 3, i
Plastic, p-type and nyB A-GeC (H.

X) A deposited film was formed.

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

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity through a conductive wire 105 and generates one heat. The substrate heating temperature is not particularly limited, but when carrying out the method of the present invention, it is preferably 30 to 450°C, more preferably 50 to 350°C.

106 to 109 are gas supply systems.

It is provided depending on the type of gas such as a germanium-containing compound and, if necessary, hydrogen, a halogen compound, an inert gas, a silicon-containing compound, a carbon-containing compound, and a compound containing an impurity element. If these gases are liquid in their standard state, an appropriate vaporizer is provided.

In the figure, the gas supply systems 106 to 109 are marked with a for branch pipes, b for flowmeters, C for pressure gauges that measure the pressure on the high pressure side of each flowmeter, and d for gas supply systems 106 to 109. The ones marked with "e" are valves for adjusting the flow rate of each gas. 12
3 is an activation chamber (B) for generating active species (B), and the activation chamber 123 includes an electric furnace that generates activation energy for generating active species CB), an infrared ray A thermal energy generating device 122 such as heating means is provided. The raw material gas for active # (B) production supplied from the gas introduction pipe 110 is activated in the activation chamber CB), and the generated active species (B) are transferred to the film forming chamber 1 through the introduction pipe 124.
01. iit is a gas pressure gauge.

In the figure, 112 is an activation chamber (A), 113 is an electric furnace, and 11
Reference numeral 4 indicates 0 solid particles, 115 indicates an introduction pipe for a compound containing gaseous carbon and halogen, which is the raw material for the active species (A), and the active species (A) generated in the activation chamber (A) 112 are introduced. It is introduced into the film forming chamber 101 via the pipe 116.

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

The heat from the thermal energy generator 117 acts on the active species flowing in the direction S of the arrow 119.

The acted active species undergo a mutual chemical reaction to form A-GeC()(,X
) to form a deposited film.

Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

Substrate 10 made of polyethylene terephthalate film
3 was placed on a support stand 102), and the inside of the film forming chamber 101 was evacuated using an exhaust device to reduce the pressure to about 1 (lGTorr).

GeHa 150SCCM from gas supply cylinder 106
, or a mixture of this gas and 405 CCM of PH3 gas or 82H6 gas (both diluted with 11000 pp hydrogen gas) through the gas introduction pipe 110 into the activation chamber (B) 1.
It was introduced on the 23rd. The GeH4 gas etc. introduced into the activation chamber (B) 123 is activated by the microwave plasma generator 122 and turned into germanium hydride active species, active hydrogen, etc. Fill the film forming chamber l14 with activated hydrogen, etc.
Heating is performed using an FrL air furnace 113.

By maintaining the temperature at approximately 1100°C to bring C into a red-hot state, and blowing CF4 into it from a cylinder (not shown) through the introduction pipe 115, CF2* as an active species (A) is generated, and the CF2* is transferred to the introduction pipe 116. After that, it was introduced into the film forming chamber 101.

While maintaining the internal pressure inside the film forming chamber 101 at 0.4 Torr, the inside of the film forming chamber 101 is heated to 2? -O″C
with undoped or doped A
-GeC(H,X) films (thickness: 700) were respectively formed. The film formation rate was 32 people/sec.

Next, the obtained non-doped or p-type or n-type A-GeC (H, After forming , the applied voltage 1
The dark current was measured at 0 V, the dark conductivity σd was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2-4 GeHac7) Instead of linear cea) (io, branched G
eaH10, or I (other than using eGeeFs,
A-GeC(H) was prepared in the same manner as in Example 1.

X) A film was formed. Measure dark conductivity for each sample,
The results are shown in Table 1.

From Table 1 1 According to the present invention, A-Ge with excellent electrical properties
A C(H,X) film was obtained, and a sufficiently doped A-GeC(H.

X) It was found that a film was 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 Figure 2i'S4, 201 is a film forming chamber, 202 is an activation chamber (A), 203 is an electric furnace, 204 is 0 solid particles, 205 is a raw material introduction tube for active species (A), and 206 is an active species (A)
An inlet pipe, 207 a motor, 208 a heating heater used in the same manner as 104 in FIG. 3, 209 and 210 blowout pipes, 211 an AI cylinder-shaped base, and 212 an exhaust pulp. Further, 213 to 216 are raw material gas supply sources similar to 106 to 109 in FIG.
7 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, a normal electric furnace, high frequency heating device, various heating elements, etc. are used.

Further, the activation chamber (A) 202 is filled with solid particles 204 and heated in the electric furnace 203.

By keeping C at about 1000° C. to make it red-hot, and blowing CFa from a cylinder (not shown) into it through the introduction pipe 206, CF3X as the active species (A) is generated, and the CF2)k is transferred to the introduction pipe 206. After that, it was introduced into the film forming chamber 201.

After being subjected to an activation process such as plasma generation by the microwave plasma generator 221, silicon hydride active species, germanium hydride active species, and active hydrogen were introduced into the film forming chamber 201 through introduction v217-2. At this time, adjust the pH to 3 if necessary.

It was heated, maintained and rotated by a heater 208, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust valve 212. In this way, the photosensitive layer 13 was formed.

Further, the intermediate layer 12 is provided prior to the photosensitive layer 13.

A mixed gas of Si2H6, GeH4°H2 and B2H6 (B2H6 gas is 0.2% by volume) was introduced through the introduction pipe 217-1, and a film was formed to a film thickness of 2000.

Comparative Example l SiF4 and Si 2H6, GeH4, H2 and B2H
A film forming chamber having the same configuration as the film forming chamber 201 was prepared using each of the gases described in No. 6 and equipped with a 13.56 MHz high frequency device, and the layer structure shown in FIG. 1 was formed by a general plasma CVD method. A drum-shaped electrophotographic imaging member was formed.

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 Using GeH4 as a germanium-containing compound, the PIN diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3.

First, a polyethylene naphthalate film 21 on which 1000 ITO films 22 were vapor-deposited was placed on a support stand, and 1 (1
After reducing the pressure to 6 Torr, the active species CF2* and the active species SiF2>IC generated in the same manner as in Example 1 were transferred to the film forming chamber 1.
It was introduced in 01.

Also, S f 2H6 gas, GeH4, PH3 gas (10
00 ppm hydrogen gas dilution) in the activation chamber (B) 12
3 and activated it.

This activated gas is introduced through the introduction pipe 116,
The internal pressure of the film forming chamber 101 was set to 0.4 Torr.

Doped with P while maintaining the substrate temperature at 220°C
A type A-5iGeC (H,X) film 24 (thickness: 700 mm) was formed.

Next, instead of PH3 gas, B2H6 gas (300pp
A non-doped A-31GeC (H,
, X) Film 25 (thickness: 5000) was formed.

Then, B2H6 gas (1000 ppm hydrogen gas dilution)
B-doped p-type under the same conditions as n-type except that
A type A-3iGeC (H,X) film 26 (thickness: 700 mm) was formed. Furthermore, a film thickness of 1 was formed on this p-type film by vacuum evaporation.
000 A1 electrodes 27 were formed to obtain a PIN type diode.

Diode element thus obtained (area alc m2)
The r-v characteristics were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, when light is introduced from the substrate side, a conversion efficiency of 7.0% or more, an open circuit voltage of 0.88 V, and a short circuit current of 11 mA/cm2 are obtained at a light irradiation intensity of AMI C of approximately 100 mW/cm2). It was done.

Example 7-9 Instead of GeH4 as a germanium compound, linear G
e4Hro, branched GeaHIO1 or HeGeeFe
A PXN diode similar to that of Example 6 was manufactured in the same manner as in Example 6 except that . The rectification characteristics and photovoltaic effect were measured and the results are shown in Table 3.

From Table 3, according to the present invention, germanium-containing A-SiGeC has better optical and electrical properties than conventional ones.
It has been found that a (H,X) PIN type diode can be obtained.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible at a relatively low substrate temperature. .

In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. be able to. Furthermore, because relatively low thermal energy can be used as excitation energy, it is possible to form a film even on substrates with poor heat resistance or those that are easily affected by plasma etching, and the process can be shortened by low-temperature treatment. This effect is achieved.

[Brief explanation of drawings]

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 PI ion N-type device produced using the method of the present invention. FIGS. 1 is a schematic diagram for explaining the configuration of a device for 10--An electrophotographic imaging member, 11--A substrate, 12--An intermediate layer, 13--A photosensitive layer. 21---One substrate. 22.27---Thin film electrode, 24---N type semiconductor layer, 25---I type semiconductor layer, 26---P type semiconductor layer, 123, Litigation---Activity Chemical room (B), 106.10
7,108,109,213゜214.215.216
--- Gas supply system, 103, 211 --- Base, 117.218 --- Thermal energy generation device.

Claims (1)

[Claims] Chemically interacts with active species (A) generated by decomposing a compound containing carbon and halogen in a film formation space for forming a deposited film on a substrate. , active species (B) generated from a germanium-containing compound for film formation are separately introduced, and thermal energy is applied to these to cause a chemical reaction, thereby forming a deposited film on the substrate. Characteristic deposited film formation method.