JPS61113232A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve the characteristics of a film, the speed of film formation and reproducibility as well as to contrive to make uniform the quality of a film by a method wherein an activating seed, to be grown by decomposing the compound containing carbonic acid and halogen, and the nitrogen compound which chemically interacts with the activating seed are introduced into film-forming space where a deposited film is formed, and the nitrogen compound is excited and reacted using photo energy. CONSTITUTION:As a nitrogen compound is excited using photo energy, the deposition film to be formed is not subjected to the adverse effect generated by an etching action and other abnormal discharge action and the like. Also, a more stabilized CVD method can be performed by arbitrary controlling the atmospheric temperature of a film- forming space and the temperature of a substrate. The photo energy can be applied uniformly or selectively to the raw material reached at the point in the vicinity of the substrate. A deposition film can be formed by selectively irradiating the photo energy on the entire substrate or the desired part only using a suitable optical system, or it is made to irradiate on the prescribed pattern part only using a resist and the like. The film-forming speed can be increased remarkably by using an activating film, and the substrate is brought into the state of low temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to deposited films containing nitrogen, particularly functional films, particularly amorphous or amorphous films used in semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, imaging devices, etc. relates to a method suitable for forming deposited films containing crystalline nitrogen.

[Prior art]

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

Deposited films composed of amorphous silicon for 100 years have improved 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. 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 with electrical, optical, photoconductive, or mechanical properties that can sufficiently satisfy various uses, it is currently considered best to form it by plasma CVD. ing.

According to Hyakunen et al., depending on the application of the deposited film, it is necessary to satisfy the requirements of large area, uniform film thickness, and uniform film quality, and also achieve reproducible mass production through high-speed film formation.
Forming an amorphous silicon deposited film 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 complex, the management tolerance is narrow, and equipment adjustments are delicate. For these reasons, 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.

[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 introduce active species generated by decomposing compounds containing carbon and halogen into a film formation space for forming a deposited film on a substrate, and nitrogen compounds that chemically interact with the active species. This is achieved by the deposited film forming method of the present invention, which is characterized in that a deposited film is formed on the substrate by introducing each of these nitrogen compounds separately and irradiating them with light energy to excite the nitrogen compound and cause it to react. Ru.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film-forming space for forming a deposited film, light energy is used to excite the nitrogen compound and cause it to react. There is virtually no adverse effect due to abnormal discharge action.

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.

Furthermore, excitation energy is applied uniformly or selectively to the raw material that has reached the vicinity of the substrate, but if optical energy is used, the entire substrate is irradiated using an appropriate optical system to form a deposited film. Alternatively, it is possible to selectively control and irradiate only the desired area to form a partially deposited film, or use a resist etc. to irradiate only a predetermined graphic area to form a deposited film. It is advantageously used because it has the convenience of being able to be formed.

One of the differences between the method of the present invention and the conventional CVD method is that active species activated in advance in a space different from the film forming space (hereinafter referred to as the decomposition space) are used. This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and in addition, it is possible 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 a species that chemically interacts with the nitrogen compound or its excited decomposition product to impart energy or cause a chemical reaction to form a deposited film. Refers to something that has a stimulating effect. Accordingly, the active species may or may not contain constituent elements constituting the deposited film to be formed, and correspondingly, The nitrogen compound used in the present invention may be a nitrogen compound that can serve as a raw material for forming a deposited film by containing constituent elements constituting the deposited film to be formed, or may be a nitrogen compound that can serve as a raw material for forming the deposited film to be formed. It may also be a nitrogen compound that does not contain any constituent elements and can only serve as a raw material for film formation.
Alternatively, a nitrogen compound that can be a raw material for forming these deposited films and a nitrogen compound that can be a raw material for film formation may be used together.

It is preferable that the nitrogen compound used in the present invention is already in a gaseous state before being introduced into the film forming space, or is introduced in a gaseous state. For example, when using liquid and solid compounds, the compound can be vaporized by connecting an appropriate vaporizer to the compound supply source and then introduced into the film forming space.

Examples of nitrogen compounds include simple nitrogen (N2), and compounds whose constituent atoms are nitrogen and one or more atoms other than nitrogen. The atoms other than nitrogen include hydrogen (H), halogen (X=F, C1, Br or
, sulfur (S), carbon (C), oxygen (0), phosphorus (P)
, silicon (Si), germanium (Ge), boron (B
), alkali metals, alkaline earth metals, transition metals, etc. In addition, any atom of an element belonging to each group of the periodic table that can be combined with nitrogen can be used.

Incidentally, 1.For example, compounds containing N and H include NH3,
Compounds containing N and X, such as N2 NNN2 , primary to tertiary amines, halides of these amines, and hydrozylamine, include NX3. NOX, NO2X,
As a compound containing N and S, such as N O3Xa, N4S
a, N2. Compounds containing N and C, such as S5, include H
Compounds containing N and 0, such as CN and cyanide, HOCN and its crucible, H5CN and its salt, are N20. N
o, No2, N203, N20a, N20S, N
Compounds containing N and P such as O3 include P3N5. P2
Nitrogen compounds used in the present invention include N3, PN, etc., but are not limited thereto.

These nitrogen compounds may be used alone or in combination.
You may use more than one species in combination.

In the present invention, the active species from the decomposition space introduced into the film forming space has a lifespan of 5 seconds or more, more preferably 15 seconds or more, and optimally 30 seconds or more from the viewpoint of productivity and ease of handling. Some are selected and used as desired.

In the present invention, the compound containing carbon and halogen introduced into the decomposition 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, and specifically, For example, CY (
u is an integer u 2u+2 number greater than or equal to 1, and Y is F, C1, Br, or I. ), CY (v is an integer of 3 or more and v 2v , Y has the above meaning). X+y=2u or 2u+2. ), and the like.

Specifically, for example, CF4, (CF2)s, (CF2)6
, (CF2)4, C2F6, C3FB, CHF3
, CH2F2 , CC14(CC12)5 , CBr
Examples include those that are in a gaseous state or can be easily gasified, such as a, (CBrz)s, C2C16, and C2Cl3F3.

Furthermore, in the present invention, in addition to the active species generated by decomposing the compound containing carbon and halogen, active species generated by decomposing the compound containing silicon and halogen can be used in combination. 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, Si Y (u is 1 or more Integer, Y is F, u
2u+2 C1, Br or engineering. ) Chain silicon halide represented by Si
y Y has the above meaning. x+y=2u or 2u+2. ), and the like.

Specifically, for example, S i Fa, (SiF2)s, (S
iF2)6. (SiF2)a, Si2 Ft+, Si3
FB, SiHF3,5fH2F2.5tC1, (Si
C12)5.5iBra, (SiBr2)c,,Si2
Examples include those in a gaseous state or those that can be easily gasified, such as C16, Si2 C13F3.

In order to generate active species, in addition to the above-mentioned compounds containing carbon and halogen (and compounds containing silicon and halogen), if necessary, carbon compounds such as simple carbon (and other silicon compounds such as simple silicon) are added. , hydrogen, halogen compounds (
For example, F2 gas.

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

In the present invention, the method for generating active species in the 5-resolved space is based on the discharge energy,
Excitation energies such as thermal energy and light energy are used.

Active species are generated by adding decomposition energy such as heat, light, and discharge to the above-mentioned materials in one decomposition space.

In the present invention, the ratio of the amount of nitrogen compounds in the film formation space to the active species from the decomposition space is determined as desired depending on the deposition conditions, the type of active species, etc., but is preferably 1.
A ratio of 0:1 to 1:10 (introduction flow rate ratio) is appropriate.

In the present invention, in addition to nitrogen compounds, hydrogen gas, /\ rogene compounds (e.g. F2 gas,
C12 gas, gasified Br2,12, etc.), argon,
Introducing and using an inert gas such as neon, a silicon compound, a carbon compound, a germanium compound as a raw material for forming a deposited film, and an oxygen compound as a raw material for forming a deposited film and/or a film forming material into a film forming space. You can also do it. When using a plurality of these raw material gases, it is possible to mix them in advance and introduce them into the film forming space, or to supply each of these raw material gases individually from independent supply sources at a certain l/'ti.
It can also be introduced into the film forming space.

Silanes, siloxanes, etc. in which hydrogen, norogen, or hydrocarbon groups, etc. are bonded to silicon can be used as the silicon compound serving as a raw material for forming the deposited film. Particularly suitable are chain and cyclic silane compounds, and compounds in which part or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with /\logen atoms.

Specifically, for example, SiH4, Si2 H6, S I
3 HB, SI4 H+. ,Si,H1□,5
s i, F2, +2 (P'±
It is an integer of 1 or more, preferably 1 to 15, more preferably 1 to 10. ) linear silane compound, SiH
3SiH(SiH3)SiH3,5iH3SiH(Si
H3) Si3H7,5i2H5SiH(SiH・)Si
- Chain silane compounds having a branch represented by Si, H2, +2 (p has the above-mentioned meaning) such as H, etc., and one hydrogen atom of these linear or branched chain silane compounds. Compounds partially or entirely substituted with halogen atoms,
5i3H6, S l4 HB, S I5 Hl
. , 5i6H1□, etc., cyclic silane compounds represented by SiH (q is an integer of 3 or more, preferably 3 to 2q6), in which some or all of the hydrogen atoms of the cyclic silane compound are replaced with other cyclic silanyl groups. Examples of compounds substituted with and/or 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 SiH
3F, SiH3CI, SiH3Br, SiH3I, etc. siHr5xt (x is a halogen atom, r is 1 or more, preferably 1 to
10, more preferably an integer from 3 to 7, S+t=2r+2
Or 2r. ) and halogen-substituted linear or cyclic silane compounds.

These compounds may be used alone or in combination of two or more.1 In addition, carbon compounds that serve as raw materials for forming deposited films include:
Chain or cyclic saturated or unsaturated hydrocarbon compounds, organic compounds whose main constituent atoms are carbon and hydrogen, and in which one or more of silicon, halogen, sulfur, etc. are used as a stratifier;
Among organosilicon compounds having a hydrocarbon group as a constituent, those in a gaseous state or those that can be easily vaporized are preferably used. Among these, examples of hydrocarbon compounds include, for example, saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, etc. As a hydrocarbon, methane CCH3
), ethane (C2Hr, ), propane (C3H8
), n-butane (n-C4H1O), pentane (C5
H12), ethylene (C2
H4), propylene (C3H6), butene-t
(C4H8), butene-2 (C4Ha), inbutylene (C4H8), pentene (CsH+o), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3Ha), butyne (C4H6), and the like.

In addition, as organosilicon compounds, (CH3)4S i, CH3S ic 13, (CH
3) 25iC12, (CH3)35tC1, C2H55
Organochlorocitene such as iC13, CH35iFz
C1, CH35iFC12, (CH3)25iFC1,
C2H5SiF,,C1,C2H55tFC12,C3
Organochlorofluorosilane such as H7SiF2 C1, C3H75iFC12, [(CH3)3Si12,
Organodisilazane such as [(C3H7)3S i]z and the like are preferably used.

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

In addition, as a germanium compound that is a raw material for forming a deposited film, an inorganic or organic germanium compound in which hydrogen, halogen, or a hydrocarbon group is bonded to germanium can be used.For example, GeH (a is an integer of 1 or more) , b=2a+2b or 2a), a polymer of this germanium hydride, a compound in which some or all of the hydrogen atoms of the germanium hydride are replaced with halogen atoms. , organic germanium compounds such as compounds in which some or all of the hydrogen atoms of the germanium hydride are replaced with an organic group such as an alkyl group or an aryl group, and optionally a halogen atom, sulfides of germanium hydride, imides, etc. can be mentioned.

Specifically, for example, GeH, Ge, H6, Ge3H
B, n-Ge, H,, tert-Ge4 Hl
. , Ge3 H6, Ges H+ o,
GeH3F, GeH3C1, GeH2F2
, H6Ge6 F6 , Ge (CH3)
4, Ge (C2Hs) a, Ge
(C6H5) 4 , Ge (c) (3) 2
Examples include F2, GeF2, GeFa, GeS, and the like. These germanium compounds may be used alone or in combination of two or more.

Furthermore, as oxygen compounds, oxygen (02), ozone (
03), etc., as well as oxygen and atoms other than oxygen
Examples include compounds having a species or 2s or more as constituent atoms. The atoms other than oxygen include hydrogen (H), bald 7
(X=F, C1, Br or engineering), sulfur (S), carbon (C), silicon (Si), germanium (Ge),
Phosphorus (CP), boron (B), alkali metals, alkaline earth metals, transition metals, etc., and any atoms of other elements belonging to each group of the periodic table that can be combined with oxygen may be used. I can do it.

Incidentally, examples of compounds containing 0 and H include B20.
Compounds containing 0 and X, such as B202, include HXO, H
Oxygen acids such as XO4, oxides such as x20, x207, and compounds containing 0 and S include B2 so2. H2
Acids such as SO4 and oxides such as S02 and S03, O and C
Compounds containing acids such as B2Co3 and CO, C
Compounds containing O and Si, such as oxides such as O2, include siloxanes such as disiloxane (B3 Si O5iH3) and trisiloxane (B3 SiOs iH20S iH3); compounds containing O and Ge include Ge, oxides, hydroxides, germanic acids, B3 Ge
Organic germanium compounds such as 0GeH3, B3 Ge0G'eH20-GeH3, compounds containing O and P include acids such as H3PO3, H3PO4, and P2O3, P2O.
, etc., and compounds containing 0 and B include H2
Examples include acids such as BO3 and oxides such as P2O2, but the oxygen compound used in the present invention is not limited to these.

These oxygen compounds may be used alone or in combination.
You may use more than one species in combination.

It is also possible to dope the deposited film formed by the method of the invention with an impurity element. The impurity elements to be used include those from periodic table 1II as p-type impurities.
Group A elements 1 eg B, AI.

Preferred examples include G a , I n , T 1 , etc., and preferred n-type impurities include elements of group V A of the periodic table, such as N, P, As, Sb, Bi, etc. , but especially B, Ga, and P.

sb etc. are optimal. The amount of impurity doped is
It is determined as appropriate depending on the desired electrical performance characteristics.

As a compound containing such an impurity element as a component, it is preferable to select a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under deposited film forming conditions, and that can be easily vaporized using an appropriate vaporizing device. . Such compounds include PH3, P2H4, PF3. PF9, PC1
,,AsH3,AgF2,AsF5,AsCt3°SbH3,SbF5. SiH3, BF3, BCl3
, BBr3, B2 H6, Ba Hr
o, B5 B9 ・BSHll, B6H10
- B6H, □, AlCl3, etc. can be mentioned. The compounds containing impurity elements may be used alone or in combination of two or more.

In order to introduce a compound containing an impurity element as a component into the film forming space, it is mixed with the nitrogen compound etc. beforehand and introduced, or these raw material gases are introduced separately on each side from multiple independent gas supply sources. be able to.

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 configuration of a typical 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.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A1. Cr, Mo, Au, Ir, Nb,
Examples include metals such as Ta, V, Ti, Pt, and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually 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, A1.
Cr, Mo, Au, Ir, Nb, Ta, V, Ti, P
L, Pd, In2O3, 5n02゜ITO (I n20
3 +5n02), or a synthetic resin film such as polyester film, NiCr, Al, Ag, Pb, Zn.
, Ni, Au, Cr, Mo, Ir, Nb, Ta, V,
Ti, Pt.

The surface is subjected to conductive treatment by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating with the metal. 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. If used as a member, in the case of continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape.

For example, the intermediate layer 12 includes a photosensitive layer 13 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 is made of, for example, amorphous silicon (hereinafter a-5i (H,
X, N)), and contains a p-type impurity such as B or a p-type impurity such as P as a substance that controls electrical conductivity.

In the present invention, the content of the substance controlling the conductivity of B and p4 contained in the intermediate layer 12 is preferably 0.
001 to 5X104ato omi cppm, more preferably 0.5 to IX11X104ato ppm, optimally 1 to 5*103103ato ppm.

When forming the intermediate layer 12, it can be performed continuously up to the formation of the photosensitive layer 13. In that case, the active species generated in the decomposition space, a nitrogen compound in a gaseous state, and optionally hydrogen, a halogen compound, an inert gas, a silicon compound, a carbon compound, and a germanium compound are used as raw materials for forming the intermediate layer. , an oxygen compound, a gas of a compound containing an impurity element as a component, etc. are separately introduced into the film forming space where the support 11 is installed, and by using light energy, an intermediate layer is formed on the support 11. 12 may be formed.

The compound hydrate containing carbon and halogen that is introduced into the decomposition space to generate active species when forming the intermediate layer 12 easily generates active species such as CF2 at high temperatures.

The layer thickness of the intermediate layer 12 is preferably 30A to Log, more preferably 40A to 8L, and optimally 50A to 5 tiles.

The photosensitive layer 13 is made of, for example, a-5i(H,X),
It has both a charge generation function of generating two odocarriers by laser light irradiation and a charge transport function of transporting the charges.

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

The photosensitive layer 13 is made of non-doped a-Si(H.

X) layer, if desired, it may contain a substance that controls the conduction characteristics of a polarity different from the polarity of the substance that controls the conduction characteristics (for example, n-type) contained in the intermediate layer 12, or, The material that governs the conduction characteristics of the same polarity is
If the actual amount contained in No. 2 is large, it may be contained in a much smaller amount than the actual amount.

In the formation of the photosensitive layer 13, similarly to the case of the intermediate layer 12, a compound containing carbon and halogen is introduced into the decomposition space, and by decomposing these at high temperature, active species are generated and introduced into the film forming space. be done. In addition, gases of compounds containing gaseous silicon compounds and, if necessary, nitrogen compounds, hydrogen, halogen compounds, inert gases, carbon compounds, germanium compounds, oxygen compounds, and impurity elements, etc. is introduced into the film forming space where the support 11 is installed,
The intermediate layer 12 may be formed on the support 11 by using light energy.

In addition to this example, the method of the present invention can also be used to form a Si3N4 insulator film, a partially nitrided Si film, etc. by the CVD method that constitutes semiconductor devices such as ICs, transistors, diodes, and photoelectric conversion elements. For example, by controlling the timing and amount of nitrogen compound introduced into the film-forming space, it is possible to form a Si film having a nitrogen concentration distribution in the layer thickness direction. Alternatively, by appropriately combining hydrogen, halogen, silicon compounds, germanium compounds, carbon compounds, oxygen compounds, etc. in addition to nitrogen compounds, N and these HlX, Si, Ge
, C10, etc. as a constituent unit, it is also possible to form a film body with desired characteristics.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Fig. 2, i
Nitrogen-containing amorphous deposited films of type, p-type, and n-type were formed.

In FIG. 2, 101 is a deposition chamber, and a desired substrate 103 is placed on a substrate support 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 150°C, more preferably 100 to 150°C.

106 to 109 are gas supply sources, nitrogen compounds,
and hydrogen, a halogen compound, an inert gas, a silicon compound, a carbon compound, a germanium compound, an oxygen compound, a compound containing an impurity element, etc., which are used as necessary. When using a liquid raw material compound, an appropriate vaporization device is provided.In the figure, the gas supplies 8106 to 109 are marked with a for branch pipes, b for flowmeters, C indicates a pressure gauge that measures the pressure on the high pressure side of each flow meter, and d or e indicates a valve for adjusting the flow rate of each gas. 110 is a gas introduction pipe to the film forming space, and 111 is a gas pressure gauge.
In the figure, 112 is a decomposition space, 113 is an electric furnace, 114 is 0 solid particles, and 115 is an introduction pipe for a compound containing gaseous carbon and halogen, which is a raw material for active species. is introduced into the film forming space 10 through the introduction pipe 116.
1.

Reference numeral 117 denotes a light energy generator, for example, a mercury lamp, a xenon lamp, a carbon dioxide laser, an argon ion laser, an excimer laser, or the like.

Light 118 is directed from a light energy generating device 117 onto the entire substrate or a desired portion of the substrate using a suitable optical system.
is irradiated with a raw material gas flowing in the direction of arrow 119 to excite the film forming raw material gas and cause it to react, thereby forming a nitrogen-containing amorphous deposited film on the entire substrate 103 or on a desired portion. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

First step, polyethylene terephthalate film substrate 103
was placed on the support table 102, and the inside of the deposition space 101 was evacuated using an exhaust device, and the temperature was 10-'T.

The pressure was reduced to rr. At the substrate temperature shown in Table 1, NN2150SCC, or a mixture of NN2150SCC and 40SCCM of PH3 gas or BZH6 gas (both diluted with 11000 pp hydrogen gas) was introduced into the deposition space using the gas supply 8106.

Further, one decomposition space 102 is filled with solid 0 grains 114, heated in an electric furnace 113 to melt C, and CF4 is blown therein from a cylinder through a CF4 inlet pipe 115 to generate active species of CF2. , and is introduced into the film forming space lot through the introduction pipe 116.

The atmospheric pressure in the film forming space 101 is set to 0. While keeping it at ITorr
An undoped or doped nitrogen-containing amorphous deposited film (film thickness 700 Å) was formed by irradiating the substrate perpendicularly from a K W The film formation speed is 3
It was 5 people/sec.

Next, each of the obtained non-doped or p-type samples was placed in a vapor deposition tank, and a comb-shaped A1 gap electrode (length 250 mm, width 5 III
) was formed, the dark current was measured at the applied voltage LOV, the dark conductivity σ was determined, and each sample was evaluated.

The results are shown in Table 1.

Examples 2 to 4 The same nitrogen-containing amorphous deposit 81 film as in Example 1 was formed, except that Si2Hb, Ge2H6, or C2H6 was introduced into the film formation space together with N2. The dark conductivity was measured and the results are shown in Table 1.

Table 1 shows that according to the present invention, a nitrogen-containing amorphous deposited film with excellent electrical properties and sufficient doping can be obtained even at low substrate temperatures.

Examples 5 to 8 The same nitrogen-containing amorphous deposited films as in Example 1 were formed except that NH3, NOF, No2, or N2o was used instead of N2.

The nitrogen-containing amorphous deposited film thus obtained had excellent electrical properties and was sufficiently doped.

Example 9 Using the apparatus shown in Fig. 3, the first
A drum-shaped electrophotographic image forming member having a membrane structure as shown in the figure was prepared.

In FIG. 3, 201 is a film forming space, 202 is a decomposition space, 203 is an electric furnace, 204 is 0 solid particles, 205 is an active species raw material introduction pipe, 206 is an active species introduction pipe, 207 is a motor, and 208 is a Heater, 209 is a blowout pipe,
210 is a blowout pipe, 211 is an AI cylinder, 212
indicates an exhaust valve. Further, 213 to 218 are raw material gas supply sources similar to 106 to 109 in FIG. 1, and 217 is a gas introduction pipe.

Lower the AI cylinder 211 into the film forming space 201,
A heating heater 208 is provided inside the motor 207.
Allows for rotation. 218, 218, . . . are optical energy generating devices, and light 219 is irradiated toward a desired portion of the AI cylinder 211.

In addition, 0 solid particles 204 are packed in one decomposition chamber space 202, heated in an electric furnace 203 to melt C, and CF4 is blown therein from a cylinder to generate active species of 0 F2. After that, it is introduced into the film forming space 201.

On the other hand, from the introduction pipe 217, 5izH and F2 are introduced into the film forming space 2.
01 will be introduced. The atmospheric pressure in the film forming space 201 is set to 1.0T.
I K W X e lamp 218. while keeping it at orr.
218...- irradiate light perpendicularly to the circumferential surface of the AI cylinder 211.

The AI cylinder 211 is heated and maintained at 280°C by the heater 2O8 and rotated, and the exhaust gas is passed through the exhaust valve 21.
Exhaust through 2. In this way, the photosensitive layer 13 is formed.

Further, the intermediate layer 12 is supplied with Si 2 Hb, N2, F2, and B2H from the introduction pipe 217 prior to the photosensitive layer.

(B2H6 is 0.2% by volume %) mixed gas is introduced,
The film was formed with a film thickness of 2000.

Comparative Example 1 A 13.56 MHz high frequency device was installed in the film forming space 201 in FIG. A drum-shaped electrophotographic imaging member having the following configuration was formed.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 9 and Comparative Example 1.

〔Effect of the invention〕

According to the method for forming a deposited film of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the film to be formed are improved, and high-speed film formation is possible at a low substrate temperature. Also,
It improves reproducibility in film formation, makes it possible to improve film quality and make the film uniform, and is advantageous for increasing the area of the film.
Improved membrane productivity and mass production can be easily achieved. Furthermore, since light energy is used as excitation energy, the film can be formed even on a substrate with poor heat resistance, and the process can be shortened by low-temperature treatment.

[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. FIGS. 2 and 3 are schematic diagrams for explaining the configuration of an apparatus for carrying out the method of the present invention used in Examples, respectively. DESCRIPTION OF SYMBOLS 10... Image forming member for electrophotography, 11-Φ・Substrate, 12... Intermediate layer, 13... Photosensitive layer, 101.201... Film formation space, 111.202... Salary decomposition space, 106.107,108,109゜213.214,215,216゜...Gas supply #1ff, 103, 21 1.
17.218 Fist: Light energy generator.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, active species generated by decomposing a compound containing carbon and halogen and a nitrogen compound that chemically interacts with the active species are separated. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing a nitrogen compound into the substrate and irradiating the nitrogen compound with light energy to excite the nitrogen compound and cause it to react.