JPS61248417A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve a film formation speed and the reproducibility and obtain a uniform film quality by a method wherein a compound containing carbon and halogen and an activation species produced from a germanium compound for film formation are introduced into a film formation space and subjected to a chemical reaction by the application of a thermal energy to form deposited films on a substrate. CONSTITUTION:A compound containing carbon and halogen and an activation seed which is produced by activating a gaseous germanium containing compound and, if necessary, an activation species which is produced by activating gaseous materials such as a silicon containing compound, hydrogen, a halogen compound, an inert gas and a compound containing impurities as its components are separately, or after being properly mixed together if necessary, introduced into a film formation space in which a substrate 11 is provided. Then a thermal energy is applied to the atmosphere to form an intermediate layer 12 on the substrate 11. With this constitution, a film formation speed and the reproducibility of the film formation are improved and an improved and uniform film quality can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to deposited films containing germanium, particularly functional films, particularly semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, The present invention relates to a method of forming a deposited film containing amorphous or crystalline germanium for use in imaging devices, photovoltaic elements, etc.

[Description of prior art]

Conventionally, several types of amorphous germanium (hereinafter simply referred to as r a -(:, e J and ) membranes have been proposed, some of which have been put into practical use, and along with such a-Qe membranes, they are
- Several methods have been proposed for forming the Q6 film.
Vacuum deposition method, ion plating method, so-called CVD
method, plasma CVD method, photo-CVD method, etc. Among them, plasma CVD method has been put into practical use as the most suitable method and is generally widely used.

By the way, although the conventional a-Q6 film obtained by, for example, plasma CVD method is said to be satisfactory for the time being due to its rich characteristics, even so, there is still a lack of certainty regarding the establishment of the product. The electrical, optical, and photoconductive properties required for Is it a challenge to satisfy people as a whole? There is still a long way to go before it can be resolved.

The reason for this is that the desired a-Qek cannot be obtained by a simple layer deposition operation, not to mention the materials used, and the particular process operations require skilled ingenuity. big.

Incidentally, for example, in the case of the so-called CVD method, C-based and G-based
Since the e-based gas material is diluted, so-called impurities are mixed in, and then thermally decomposed at a high temperature of 500 to 650°C, precise process operations and control are required to form the desired a-Qe film. Therefore, the equipment becomes complicated and the cost increases considerably, but it is extremely difficult to regularly obtain a homogeneous a-Qe film product having the desired characteristics as described above. Therefore, it is difficult to adopt it on an industrial scale.

Furthermore, even with the plasma CVD method, which is generally widely used as the optimal method, there are some problems in process operation and problems in equipment investment. Regarding process operations, the conditions are as described above for CVD.
Law and Shi are even more complex, and are extremely difficult to translate into film. That is, for example, there are already many parameters such as substrate temperature, flow rate and flow rate ratio of introduced gas, pressure during layer formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, and plasma generation method. In addition to these parameters, there are also other parameters, and in order to obtain the desired product, it is necessary to select the exact parameters, and because the parameters are strictly selected, there are If one of the constituent factors, especially plasma, becomes unstable, the formed film will be severely affected and cannot be used as a product. As for the equipment, as mentioned above, strict selection of parameters is required.
The structure naturally becomes complex, and as the scale and type of equipment changes, it must be designed to accommodate carefully selected parameters. For these reasons, although the plasma CVD method is considered to be the most suitable method at present, it is difficult to achieve the desired a-Qe as described above.
Mass production of membranes requires a large capital investment in equipment, and the process control items for mass production are many and complex, the process control tolerance is narrow, and equipment adjustments are delicate. So, in the end, is it a product? There are problems such as making the cost considerably high.

On the other hand, the various devices mentioned above are becoming more diverse, and the requirements for element materials, such as the various characteristics mentioned above, are increasing. I am satisfied overall and it is appropriate for the applicable target and use.
In some cases, there is a social demand for a steady supply of stable a-Ge film products in the form of large-area gold product stocks, and the development of methods and equipment to meet this demand is in progress. There are situations where it is desperately needed.

These matters also apply to other element members such as germanium nitride films, germanium carbide films, and germanium baride films.

[Purpose of the invention]

The purpose of this invention is to solve the above-mentioned problems and to satisfy the above-mentioned requirements regarding conventional element members used in devices, photovoltaic elements, etc. and their manufacturing methods.

That is, the main object of the present invention is to provide electrical, optical, and photoconductive properties that are virtually always stable regardless of the usage environment, and excellent light fatigue resistance. It has excellent durability and moisture resistance, and does not deteriorate even after repeated use. Do you have a residual potential problem? An object of the present invention is to provide an improved a-Qee element member that is uniform and free of uniformity.

Another object 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 quality uniform and homogenized. The above-mentioned improved a-Q that can be easily improved and mass-produced
The object of the present invention is to provide a new method of manufacturing an e-membrane element member.

[Structure of the invention]

The above-mentioned object of the present invention is to contain a compound containing carbon and a halogen in a film forming space for forming the entire deposited film on a substrate, and a germanium-containing compound for film forming that chemically interacts with the compound. By introducing the active species generated by the oxidation and the active species, and applying thermal energy to them to cause a chemical reaction,
This is accomplished by forming a deposited film on the substrate.

Does the method of the present invention involve plasma? In the coexistence of a compound containing carbon and halogen and an active species generated from a germanium-containing compound for film formation that chemically interacts with the compound, By applying thermal energy, a desired deposited film is formed by causing, or further promoting and amplifying, the chemical interaction between them, and in the method of the present invention, the formation The resulting deposited film is not adversely affected by etching effects or by abnormal discharge effects of the pond.

Further, the method of the present invention can achieve a more stable CvD method by arbitrarily controlling the atmospheric temperature in the film-forming space and the substrate temperature as desired.

In the method of the present invention, carbon and halogen? Thermal energy that acts on the contained compound and/or the active species that chemically interacts with the compound and causes a chemical reaction between them is applied to at least a portion of the film-forming space near the substrate or a film-forming space. It acts on the whole. 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, appropriate optical system? It is possible to irradiate the entire substrate using the irradiation method, or to selectively irradiate only desired areas, making it easier to control the formation position and thickness of the deposited film on the substrate. .

One of the points that distinguishes the method of the present invention from conventional CVD methods is that it uses activated species that have been activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). As a result, the film formation speed of the conventional CVD method can be dramatically increased, and the substrate temperature during deposition film formation can be further lowered, resulting in stable film quality. Deposited film? It can be provided industrially in large quantities and at low cost.

In the method of the present invention, a germanium-containing compound is used as a raw material for forming a deposited film. It is activated in the activation space and generates active species. Then, the generated activated species are introduced from the activation space into the film forming space, and a deposited film is formed in the film forming space. Therefore, the constituent elements of the active species constitute the components constituting the deposited film formed in the film forming space. In the method of the present invention, active species are selected and used as desired, but from the viewpoint of productivity and ease of handling, those with a lifespan of 1 second or more are usually used; It is preferable to use a time period of 1 second or more, most preferably 10 seconds or more.

Further, the compound containing carbon and 710 gen used in the method of the present invention is introduced into the film forming space, is excited by the action of thermal energy, and is simultaneously introduced into the film forming space from the activation space. For example, energy can be generated through chemical interactions with seeds. Addition or chemical reaction? I woke you up,
Formation of deposited film? A stimulating effect? exhibited in the system.

Therefore, carbon and norogen? The components of the compound include:
The constituent elements of the deposited film to be formed may be the same or different.

It is preferable that the germanium-containing compound introduced into the activation space in the method of the present invention is already in a gaseous state or is in a gaseous state before being introduced into the activation space. For example, when using a liquid compound, an appropriate vaporizer can be connected to the compound supply source to vaporize the compound before introducing it into the activation space.

As the germanium-containing compound, an inorganic or organic germanium compound in which hydrogen, nitrogen, or a hydrocarbon group, etc. are bonded to germanium can be used, such as Ge, ) (b (a is an integer of 1 or more, b = 2a+2 or 2a), a polymer of this germanium hydride, a compound in which some or all of the hydrogen atoms of the germanium hydride are substituted with halogen atoms, the above-mentioned Some or all of the hydrogen atoms of hydrogenated germanium ram are replaced with organic groups such as alkyl groups and aryl groups σ, and optionally dihalogen atoms, and organic germanium compounds such as nitrogen compounds, and other germanium compounds can be prepared. can be mentioned.

Specifically, for example, Gem4, Ge2H1l, Ge, Hs, n-(:,
e, H, , tert-Ge, 1(1o, Ge5Ha,
Ge5T (tob CreHsFs GeH3C4
, GeHsF2, H2Cea Fa, Ge(CH3)+
, Ge'(C2Hs) in Ge(CaHa)+.

Ge(CH3)2Fz, CHsGeH3, (CH3)2
GeH2, (CL)sGeH, (C2Hfi)2GeH
2, ceF', GeF+, GeS, etc.

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

In the method of the present invention, the compound containing carbon and halogen introduced into the film forming space may be, for example, a part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound. A compound substituted with a halogen atom is used, specifically, for example, Cu
Y2u+2 (u is an integer greater than or equal to 1, Y is F, CL, Br
and (9) at least one selected element. ) Chain halide carbon, CvY2v (v
is an integer of 3 or more, and Y has the above meaning. ) Cyclic halogenated carbon, CuHxYy (u and Y have the above-mentioned meanings. x+y=2u or 2u+2)
Examples include chain or cyclic compounds shown in the following.

Specifically, for example, CF4, (cF2)s, (CF2)
6, (CF2) C2F,, C3F8, CHF3,
Examples include those in a gaseous state or those that can be easily gasified, such as CI2Ft, CCt4, (C(,tt)S, CBr(CBr,), C2Cl4, and CzClsFs).

compound source. 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 can be substituted with a halogen atom can be used, and specifically, for example, 5i
uY2u+2 (u is an integer greater than or equal to 1, Y is F%Ct, B
At least one element selected from r and . ) Chain-like silicon fluoride, 5ivY2
Cyclic silicon halogenide, Siu'HxY, represented by v (v is an integer of 3 or more, Y has the above-mentioned meaning).

(U and Y have the above meanings.x+y=2u or 2
It is u+2. ), and the like.

Specifically, for example, s iF4, (SiF2)! , (S
I F2) 6, (SiF2) 5tzFa, si, p
,,SiHF3.5jHzFz,SiO4% (Si
O2)s,3i13r,, (SiBr,),,3t
2 C4s3 i2 B ra, 3iHC4, 5iHB
Examples include those in a gaseous state or those that can be easily gasified, such as rx, 5iHI3.5i2C4Fs.

Furthermore, the carbon and no-rogen mentioned above? In addition to compounds containing silicon (and compounds containing halogen), carbon-containing compounds such as simple carbon (and other silicon-containing compounds such as simple silicon), hydrogen, and halogen-containing compounds (for example, F2 gas) , C4 gas, gasified Br2, I2, etc.)
Such? They can also be used together.

In the method of the present invention, in order to generate active species in the activation space, electric energy such as microwave, RF high frequency, low frequency, DC, resistance heating, infrared heating, etc. (7 ) Excitation energy such as thermal energy, laser, light energy such as xenon lamp light can be used.

That is, active species are generated by applying excitation energy such as heat, light, electricity, etc. to the above-mentioned germanium-containing compound in an activation space.

In the method of the present invention, the above-mentioned carbon and halogen introduced into the film forming space? The ratio of the amount of active species generated from the germanium-containing compound to the above-mentioned germanium-containing compound depends on the film forming conditions,
Although it can be determined as desired depending on the type of active species, it is preferably 10:1 to 1:10 (introduction flow rate ratio), more preferably 8:2 to 4:6.

In the method of the present invention, in addition to the germanium-containing compound, hydrogen gas and/or halogen compounds (for example, F2 gas, C4 gas, gasified Br gas) are used as chemical substances for film formation.
2% I2, etc.), an inert gas such as argon, neon, etc., and a silicon-containing compound, a carbon-containing compound, etc. as a raw material for forming the active species. It can also be used by introducing it into the activation space. When using multiple deposition chemicals, they can be premixed and introduced into the activation space in a gaseous state, or each of these deposition chemicals can be supplied from independent sources. They can also be supplied separately and introduced into the activation space.

As the silicon-containing compound introduced into the activation space, silanes and siloxanes in which silicon is bonded with hydrogen, rogene, hydrocarbon groups, etc. can be used. In particular, chain and cyclic silane compounds, and some or all of the hydrogen atoms of these chain and cyclic silane compounds.
- Compounds substituted with rogene atoms are preferred.

Specifically, for example, S i K, 312HII,
Si, I(,,814H1゜, Spring--〒Si, H, □
, S16Hu, etc., linear silane compounds represented by Si, H2, -2 (p is an integer of 1 or more, preferably 1 to 15, preferably 1 to 10), Si Mil 5i ((
5iH3) SiH4, S IH3S tH (S 1Hs
) S bH7,5i2H5SiH(S 1ts) S
SiH such as j4Hs (p has the above meaning)
A chain silane compound having a branch represented by p 2p+2, some or all of the hydrogen atoms of these linear or branched chain silane compounds? Substituted compound with halogen atom, 5isH
6, s i, H8, S 15H1Os S '6H12
A cyclic silane/compound represented by Si, H2, etc. (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 with other cyclic silanyl groups and Sim F
, SiKs Ct, 5iH3Br s SiH3I
A halogen-substituted linear or cyclic compound represented by 5irHs Silane compounds, etc. These compounds may be used alone or in combination of two or more.

The carbon-containing compounds introduced into the activation space include chain or cyclic saturated or unsaturated hydrocarbon compounds, carbon and hydrogen? The main constituent atoms are silicon, halogen,
Among organic compounds having one or more constituent atoms such as sulfur, and organosilicon compounds having hydrocarbon groups as constituent atoms, it is preferable to use those in a gaseous state or those that can be easily vaporized.

Among these, examples of hydrocarbon compounds include carbon atoms of 1 to
5 saturated hydrocarbons, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylenic hydrocarbons having 2 to 4 carbon atoms, etc. Specifically, the saturated hydrocarbons include methane (CH
4), ethane (C2Ha), propane (C3H8), n
-Butane (n-C4HIQ)% Pentane (C5HI2)
, ethylene (C2FL) as the ethylene hydrocarbon,
Propylene (C3Ha), butene-1 (C4H11),
Butene-2 (C4H8), inbutylene (C4Ha)
, pentene (CsH+o), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (
Examples include C3H, υ, butyne (C4H6), and the like.

In addition, as organic silicon compounds, (CH3)4Si s CH,5iCz3, (CH3)
zstc4, (CHs)ssic> C2H55iC
Organochlorosilane such as 1-s, CHsSiF, zc
t%CHsS 1FC62゜(CH3)25iFC4C
2H55iF2CjS C2H55iFC62, C,
, H7SiF2C2,C3H? Organochlorofluorosilanes such as 5iFC4 C(CH3)3Si 12
It is preferable to use organodisilates such as s ((CaHt)3Si)z.

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

(9) 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 1 A of the periodic table, such as B, Al, Ga, In,
Preferred examples include Tt, etc., and examples of n-type impurities include elements of group V A of the periodic table, such as P%AJ%S, b
.

13i etc. are mentioned as suitable ones, but especially Blc
a, p% Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical characteristics.

The substance contained as the impurity element gold component (substance for introducing impurities) is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under the deposited film forming conditions, and can be easily vaporized with an appropriate vaporization device. Preferably, the compounds are selected. Such compounds include PH3, P2H4, PF
3. PFs, P C4, AsH2, AsF,, AsF
,,AsC4,SbH3,5bFs,SiH3,BFs
, BC4,BB r3,B2HIl-B4HIQ,B
5H9, B5HII s BaH+os BaHt□
, AlCl3, and the like.

For compounds containing impurity elements, even if one type is used, or two types are used.
You may use more than one species in combination.

These substances for introducing impurities may be introduced into the film forming space directly in a gaseous state, or may be mixed with the above-mentioned compound containing carbon and nitrogen, or may be activated in an activation space. After that, it can also be introduced into the film forming space. To activate the impurity-introducing substance, the above-mentioned activation energy for generating active species can be appropriately selected and employed. Substance for introducing impurities? The active species (PN) generated by activation are mixed with the pre-irradiation active species in advance or are introduced into the film forming space independently.

Let me explain using a typical case.

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 image forming member', and has an intermediate layer 1 provided on a support 11 as required for the photoconductive member.
2. and a photosensitive layer 13.

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive plate 13 can be created by the method of the present invention. Furthermore, the photoconductive member 1o is on the surface of the photosensitive layer 13? A protective layer provided for chemical and physical protection, or electrical and electrical pressure resistance? If there is a lower barrier layer and/or an upper barrier layer provided for the purpose of improvement, what about these? It can also be created by the method of the present invention.

Even if the support 11 is conductive,
It may be electrically insulating. Examples of the conductive support include NiCr, stainless steel, At, and CrlMo.
, Au, Ir%Nb, Ta, V, Ti.

Examples include metals such as Pts and Pd, and alloys thereof.

Examples of the electrically insulating support include polyester, polyethylene, polycarbonate, cellulose acetate,
Any film or sheet of synthetic resin such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. can be used. Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the nine-face side that has undergone the conductive treatment.

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

At%Cr, Mo%Au, Ir1Nb, Ta1V, Ti
.

Pt%Pds In2O3,5n02, ITO(
A thin film such as Inzos + S n 02)? NiCr%Al, Ags if it is a synthetic resin film such as a polyester film.
Pb%Zn, NibAu%Cr1Mo,
The surface is treated with a metal such as Ir1Nb, Ta, V, Ti% 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 can be any shape, such as a cylinder, a belt, or a plate. Although its shape can be determined as appropriate depending on the purpose and desire, for example, the photoconductive member 10 shown in FIG. If used as an electrophotographic image forming member, it is desirable to use an endless belt or a cylindrical shape for continuous high-speed copying.

For example, a photosensitive layer 13 is applied to the intermediate layer 12 from the support 11 side.
It effectively prevents the inflow of carriers into the photosensitive layer 13 due to the irradiation of electromagnetic waves and moves the photocarrier from the side of the photosensitive layer 13 toward the side of the support 11. Passage to? Has the ability to easily forgive.

This intermediate layer 12 has germanium atoms as its base material, and contains silicon (Sl)% hydrogen (H), halogen (X
), carbon atom (C) e amorphous germanium (hereinafter referred to as a-Ge(Si)).

It is written as H, X, C). ), and also contains a p-type impurity such as boron (B) or an Xl-type impurity such as phosphorus (P) as a substance that controls electrical conductivity.

In the present invention, the amount of the substance controlling conductivity, such as BIP, contained in the intermediate layer 12 is preferably I x 10
~5 X 10 atomic ppm, more preferably 0.5 ~ I X 10' atomic ppm
m 1 optimally (is 1~5 x 1o atomic P
It is desirable to set it to pm.

When the components of the intermediate layer 12 and the components of the photosensitive layer 13 are similar or the same, the formation of the intermediate layer 12 and the formation of the photosensitive layer 13 can be performed continuously.

In that case, as raw materials for forming the intermediate layer, a compound containing carbon and a halogen, an active species generated from a gaseous germanium-containing compound, and, if necessary, a silicon-containing compound, hydrogen, a halogen compound, an inert The gas and active species generated by activating the gas of a compound containing an impurity element as a component are each separately or mixed as necessary and placed in the film forming space where the support 11 is installed. The intermediate layer 12 may be formed on the support 11 by introducing the heat energy and applying thermal energy thereto.

The layer thickness of the intermediate layer 12 is preferably 3 x 10-3 ~
Preferably it is 10μ, more preferably 4×10−3 to 8μ, optimally 5×10−3 to 5μ.

The photosensitive layer 13 is made of amorphous silicon a-3i (H, X,
(:, e, (:) or if necessary, it is composed of amorphous silicon germanium a-8iGe (H, It has both a charge generation function to transport the charge and a charge transport function to transport the charge.

The thickness of the photosensitive layer 13 is preferably 1 to 100 microns, more preferably 1 to 80 microns, and optimally 2 to 50 microns.

The photosensitive layer 13 is made of non-doped a 3i (H,X)Ge
tc) or a-8iGe (H, Alternatively, if the actual amount of the substance controlling the conductivity contained in the intermediate layer 12 is large, the amount may be made much smaller than the amount of the substance controlling the conductivity of the same polarity. sex? A controlling substance may also be included.

When the photosensitive layer 13 is formed by the method of the present invention, it is formed in the same manner as the intermediate layer 12.

That is, a compound containing carbon and halogen, or a compound containing silicon and halogen, an active species generated from a chemical substance for film formation, and an inert gas and an impurity element as necessary. A gas or the like is introduced into the film forming space where the support 11 is installed, and thermal energy is applied to form the photosensitive layer 1 on the intermediate layer 12 formed on the support 11.
Form 3.

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

In the figure, 21 is a base, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an n-type semiconductor layer 24, an i-type semiconductor layer 2
5. Consisting of a p-type semiconductor layer 26. These semiconductor layers 24.25. One of the 26? It can also be produced by the method of the present invention. In particular, when the semiconductor layer 26 is formed by the method of the present invention, its conversion efficiency can be increased.

When forming the semiconductor layer 26 by the method of the present invention, the semiconductor layer 26 is made of an amorphous material (hereinafter referred to as r a-3iGeC(H
, X) (denoted as J). 28 is a conductive wire connected to an external electric circuit device.

As the base 21, a conductive material, a semiconductive material, or an electrically insulating material can be used. If the base body 21 is conductive, the thin film electrode 22 may be omitted. Examples of the semiconductive substrate include Si, Ge, and GaA.
Examples include semiconductors such as ZnS, ZnO%ZnS, and the like. The thin film electrode 22.27 is made of, for example, NiCr%At%Cr,
Mo, Au, Ir, Nb%Ta.

V 1Tl 1Pts Pds In2O3, sno
, Thin film such as ITO (In203+5n02)? , by providing it on the substrate 21 through a process such as vacuum evaporation, electron beam evaporation, or sputtering. Electrode 22.2
The film thickness of No. 7 is preferably 30 to 5 x 10'X, more preferably 100 to 5 x 103X.

A film that constitutes a semiconductor layer? To make the layer n-type or p-type as necessary, it is necessary to control the n-type impurity, p-type impurity, or both of the impurity elements in the formed layer during layer formation. Formed by doping.

For forming n-type, i-type and p-type semiconductor layers,
According to the method of the present invention, a compound containing carbon and a halogen and a compound containing silicon and a halogen are introduced into a film forming space, and a compound containing silicon and a halogen is separately introduced into an activation space for film forming. Germanium-containing compounds and silicon-containing compounds in gaseous state, inert gas and impurity elements if necessary? Gases of compounds included as components? , each is excited and decomposed by activation energy to generate each active species, and each is introduced side by side or mixed appropriately into the film forming space where the support 11 is installed, and thermal energy is used. Eli chemical interaction? A deposited film is formed on the support 11 by causing, promoting, or amplifying it.

The layer thickness of the n-type and p-type semiconductor layers is preferably 100
-104, but preferably 300-2000
It is desirable to set it in the range of X.

The layer thickness of the fc, i type semiconductor layer is preferably 500 to 500.
1040, preferably in the range of 1000 to 10000.

Note that the PIN type diode device shown in Figure 2 has a 2%
It is not necessarily necessary to fabricate all of the i and n layers, and the desired object can be obtained by fabricating at least one of the p, i, and n layers using the method of the present invention.

〔Example〕

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be explained in detail below according to all embodiments, but the present invention is not limited thereto.

Example 1 Using the apparatus shown in FIG. 3, the following operations were performed to deposit i-type, p-type and n-type a-GeC (H,X) films.
Formed.

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

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 105 to generate heat. The substrate heating temperature is not particularly limited, but in carrying out the method of the present invention, it is preferably 30 to 450°C, more preferably 50 to 350°C.
It is desirable that

106 to 109 are gas supply sources, including germanium-containing compounds, hydrogen, halogen compounds, inert gases, silicon-containing compounds, carbon-containing compounds, and impurity elements, which are used as necessary. It is provided depending on the type of gas such as the compound as a component. Are these gases liquid in standard conditions? When used, a suitable vaporization device is provided.

In the figure, the symbols a'z for gas supply sources 106 to 109 are marked with branch pipes, bl is marked with flow meters, C is marked with pressure gauges that measure the pressure on the high pressure side of each flow meter, and d Or is each gas flow rate marked with e? Pulp for conditioning. 1
23 is an activation chamber for generating active species, and around the activation chamber 123 is activation energy for generating active species. A thermal energy generating device 122-1 such as an electric furnace or infrared heating means is provided. The raw material gas for generating active species supplied through the gas introduction pipe 110 is activated in the activation chamber, and the generated active species are introduced into the film forming chamber Lot through the introduction pipe 124. 111 is a gas pressure gauge.

In the figure, 112 is a source of a compound containing carbon and halogen, and the a''-e attached to the reference numeral 112 indicates the same as in the case of 106 to 109.

Compounds containing carbon and halogen are introduced into the inlet pipe 113? The film is introduced into the film forming chamber 101 through the film. 117 is a thermal energy generating device, such as a normal electric furnace, a high frequency heating device,
Use various heating elements.

The heat from the thermal energy generator 117 is transferred to the arrow 116.
It acts on the compound and active species containing carbon and nitrogen flowing in the direction of 119, and the acted compound and active species chemically react with each other to form a-GeC ( Deposited film of H,X)? Form.

By the way, 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 the supply table 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device to reduce the pressure to about 10''-6 Torr.

Gas supply cylinder 106mm GeH4 gas 150S
CCMs or this and PHs gas or B2H6 gas (both diluted with 11000pp hydrogen gas) 508CCM
Gas mixed with? The gas was introduced into the activation chamber 123 via the gas introduction pipe 110. Ge introduced into the activation chamber 123
The H4 gas and the like are activated by the microwave plasma generator 122-2 to become germanium hydride active species, active hydrogen, etc., and the germanium hydride active species, activated hydrogen, etc. are introduced into the film forming chamber 101 through the introduction pipe 124. Introduced, just in case.

On the other hand, supply source 112! 0CF4 gas introduction pipe 11
3? After that, it was introduced into the film forming chamber 101.

While maintaining the internal pressure in the film forming chamber 101 at f 0.4'l'orr, the inside of the film forming chamber 101 is heated to 22
A non-doped or doped a-GeC (H, The film formation rate was 14i/see.

Next, the obtained non-doped or p-type or n-type a-Gee (H,X) film sample? Place the comb-shaped At gap electrode (
After forming a gap length of 250 μm and width of 5 mm, dark current is generated with an applied voltage of 10 V? The film characteristics of each sample were evaluated by measuring and determining the dark conductivity σd. The results are shown in Table 1.

Examples 2 to 4 The same procedure as in Example 1 was carried out except that instead of GeH4 gas, linear Ge, H, gas, branched Ge, H, O gas, and HaGeaFa gas were used. a-GeC(H,
X) A film was formed. Measure dark conductivity for each sample,
result? It is shown in Table 1.

From Table 1, it is clear that according to the present invention, a-Ge has excellent electrical properties.
('(H,X) film was obtained, and it was also found that a sufficiently doped a-GeC(H,X) film was obtained.

Example 5 The device shown in Figure 4? the first one by using the following operations.
A drum-shaped electrophotographic image forming member with a layer structure as shown in the figure? Created.

In Fig. 4, 2 old is a film forming chamber, 202 is a source of a compound containing carbon and nitrogen, 206 is an introduction pipe, 207 is a motor, and 208 is a heating heater used in the same way as 104 in Fig. 3. , 209.210 is a blowout pipe, 211 is At
A cylindrical substrate 212 indicates exhaust pulp.

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 At cylindrical substrate 211 is suspended in the film forming chamber 201, and a heating heater 208 is provided inside the substrate, and a motor 20 is installed.
7 so that it can be rotated. 218 is a thermal energy generating device, which uses, for example, an ordinary electric furnace, a high-frequency heating device, various heating elements, and the like.

First of all, supply source 202, ? CF and gas were introduced into the film forming chamber 201 through the introduction pipe 206.

On the other hand, 512) (6, GeH4, and H2?) were introduced into the activation chamber 219 from the introduction pipe 217-1.
The H6, GeH4, and H2 gases are subjected to activation treatment such as plasma conversion using a microwave plasma generator 220 in the activation chamber 219 to convert them into silicon hydride active species, germanium hydride active species, and active hydrogen through the introduction pipe 217-2'. The film was introduced into the film forming chamber 201 through the film. At this time, P
Impurity gases such as H8 and 82Ha were also introduced into the activation chamber 219 for activation.

The At cylindrical base 211 is heated to 220°C by the heater 20.
The tube was heated, held, and rotated as shown in step 8, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust pulp 212. In this way, the photosensitive layer 13 was formed.

In addition, for forming the intermediate layer 12, prior to forming the photosensitive layer 13, 512H6, GeH4
, H2 and B2H6 (BzHa caska 0.21 in capacitance
) mixed gas? It was formed in the same manner as photosensitive layer 13 except that it was introduced. The thickness of the intermediate layer was 2000 mm.

Comparative example l SiF4 gas and 5i2a gas, G eH4 gas, H2
A film forming chamber 201 is formed using gases such as gas and B2H6 gas.
A film forming chamber with the same configuration as above was prepared, equipped with a 13.56 MHZ high frequency device, and using the general plasma CVD method.
A drum-shaped electrophotographic image forming member having the layer structure shown in FIG. 1?
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 Third experiment using GeL gas as a germanium-containing compound
The PIN type diode shown in Fig. 2 was manufactured using the apparatus shown in the figure.

First, 1000X ITO film 22? Vapor-deposited polyethylene naphthalate film 21? Place it on a support stand and
After reducing the pressure to −6 Torr, CF and gas were introduced into the gold film forming chamber 101 through the introduction pipe 113 in the same manner as in Example 1.

Also, from the introduction pipe 110, Si2H6 gas, GeH4 gas,
PH3 gas (1000ppm diluted hydrogen scum)? It was introduced into the activation chamber 123 and activated.

This activated gas is introduced through the introduction pipe 124,
P-doped n-type a-5iGeC (H,
Film 24 (film thickness 700×) *formed.

Then, B2H6 gas (300 p
pm hydrogen gas dilution) 1-n type a-3iG except for introduction
In the same way as in the case of eC(H,X) film, non-doped a
-5iGeC (H,

Then, B2H6 gas (11000pp hydrogen gas dilution)
B-doped p-type under the same conditions as n-type except that
Type B -5iQeC (H-X) film 26 (film thickness 700X
) i formed. Furthermore, a 27-minute At electrode with a film thickness of 1000× was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

I- of the diode element thus obtained (area 1α2)
The V characteristics were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

Also, 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 7.3 inches or more, the open circuit voltage is 0.93 V, and the short circuit current is 10. 3 mA/cyn was obtained.

Examples 7 to 9 In place of GeH4 as a germanium compound, linear G
e, H,, branched Q e4 H+o s or Ha
A PIN type diode similar to that of Example 6 was manufactured in the same manner as in Example 6 except that G ea Fa fl was used. 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 method of the present invention, a germanium-containing a-5iGeC (H,

[Summary of effects 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, relatively low thermal energy can be used as the excitation energy, so for example, substrates with poor heat resistance or the effects of plasma etching can be avoided. The effects of this method include being able to form a film even on substrates that are easily susceptible, and shortening the process through low-temperature treatment.

[Brief explanation of the drawing]

FIG. 1 is the next schematic diagram illustrating 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 a configuration example of a PIN diode manufactured using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the method of the present invention used in Examples, respectively. 10... Electrophotographic image forming member 11... Support 12... Intermediate layer 13... Photosensitive layer 21...
Substrate 22.27...Thin film electrode 24...N-type semiconductor layer 25...I-type semiconductor layer 26...P-type semiconductor layer 28...Conducting wire 101.201... Film forming chamber 112 .202...Compound supply source containing carbon and halogen 123.219...Activation chamber 106, 107, 108, 109, 213,
214, 215, 216... Gas supply source 103, 211... Substrate 117, 218... Thermal energy generator 102...
・Substrate support stand 104, 208...Heater for heating the substrate 105...
・Conductor 110.113.124.206.217-1.
217-2...Introduction pipe 111...Pressure gauge 12
0, 212...Exhaust pulp 121...Exhaust pipe 122.220...Activation energy generator 209
．． 210...Blowout pipe 207...Motor Figure 1 Figure 2

Claims (1)

[Claims] A compound containing carbon and halogen and an active species generated from a germanium-containing compound for film formation that chemically interacts with the compound are placed in a film formation space for forming a deposited film on a substrate. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by applying heat energy to the substrate and causing a chemical reaction.