JPS61114517A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To facilitate the forming process of large film while improving the productivity thereof by a method wherein an active material produced by decomposing a compound containing germanium and halogen as well as a nitride are separately supplied for a filming space to be irradiated with photo energy. CONSTITUTION:A polyethylenephthalate film substrate 103 is mounted on a holding base 102 while the air is exhausted from a deposit space 101. Next the deposit space 101 is supplied with N2 gas 150SCCM or the same gas mixed with PH3 gas or B2H6 gas 40SCCM using a gas supply 106. A decomposition space 102 (the holding base 102) is charged with solid Ge particles 114 and then heated by an electric furnace 113 to melt Ge while GeF4 is supplied through a leading-in tube 115 from a GeF4 cylinder to produce an active material of GeF2 which is further supplied for a filming space 101 (the deposit space 101) through another leading-in tube 116. Finally while sustaining the atmospheric pressure in filming space 101 at 0.1Torr, the substrate 103 is vertically irradiated with a 1kWXe lamp to form a nitrogen-containing amorphous deposited film.

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 plating, photo-CVD, etc. Generally, plasma CVD is the most popular method. Widely used and commercialized.

Deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity, including uniformity and reproducibility.
In terms of mass production, there is room to further improve the 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 the reaction mechanism is still 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, device-specific parameters must be selected for each device.
Therefore, the reality is that it is difficult to generalize the five 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 best to form it by plasma CVD. has been done.

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 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 quality uniform, while also being suitable for increasing the area of the film, improving film productivity, and facilitating mass production. The object of the present invention is to provide a method for forming a deposited film that can achieve the following.

The above purpose is to provide active species generated by decomposing compounds containing germanium and halogen and nitrogen compounds that chemically interact with the active species in the film formation space for forming a deposited film on the substrate. 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 separately introducing 1 and 1 and irradiating them with light energy to excite the nitrogen compound and cause it to react. be done.

[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, for example, abnormal discharge action.

Furthermore, 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. Therefore, the active species may contain constituent elements that constitute the deposited film to be formed, or may not contain such constituent elements. 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; The nitrogen compound may be a nitrogen compound that does not contain the constituent elements constituting the deposited film and can serve merely 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 (O), 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, for example, compounds containing N and H include NH3,
H2NNH2, primary to tertiary amines, halides of these amines, hydroxylamine, etc., compounds containing N, :X, NX3. N.

Compounds containing N and S such as X, N O2
Compounds containing N and 0, such as CN and its salts, HSCN and its salts, include N20. NO, No2゜N2O3,N
Compounds containing N and P, such as 2O4, N2O5, and No3, include P3N5, P2N3, and pNq, but the nitrogen compounds used in the present invention are not limited to these.

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 introduced into the film forming space from the decomposition 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. are selected and used as desired.

In the present invention, as the compound containing germanium and halogen introduced between one decomposition chamber, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic germanium hydride compound is replaced with a halogen atom is used. for,
For example, GeY2u+2. (u is an integer greater than or equal to 1, Y is F
, C.I.

Br or I. ) Chain germanium halide, Ge Y (v is an integer of 3 or more.

v 2v Y has the meaning given above. ) and the circular octave has the above-mentioned meaning. x+y=2u or 2u+2. ), and the like.

Specifically, for example, G e Fl, (GeF2)s, (G
eF2)b, (GeF2)*, ce2F6, Ge3
FB, G13HF3. GeH,,F2,GeC1,
(Gee 12 )5 , GeB r4゜(GeB r
2) 5, Ge2C16, Ge2C13F3, etc., which are in a gaseous state or can be easily gasified.

Furthermore, in the present invention, in addition to the active species generated by decomposing the compound containing germanium and halogen, active species generated by decomposing the compound containing silicon and halogen and/or carbon and halogen Active species generated by decomposing a compound containing can be used in combination.

As this 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, SiY2u+2 (u is 1 or more). an integer of Y
is F, C1, Br or engineering. ) Chained silicon halide represented by St Y (v is an integer of 3 or more, v 2v Y has the above-mentioned meaning), Cyclic silicon halide represented by Si HY (u and Yuxy have the above-mentioned meaning) Has x+y=2u or 2u+2
It is. ), and the like.

Specifically, for example, SiF4, (SiFz)s.

(S iF2 )6, (SiF2)4. Si2 F6,
Si3Fq, SiHF3. SiH2F2
．． 5iC1a (SiC12)5, SiBr4
, (S i Br2)s, 5i2C16,S
Examples include those in a gaseous state or easily gasifiable, such as C13F3.

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

Further, as the compound containing carbon and halogen, 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, CY u 2u+2 (U is an integer of 1 or more, Y is F, CI, Br or I), CY (v
is an integer of 3 or more, and Y has the above-mentioned meaning v 2v . ) Cyclic silicon halide, CH
Examples include chain or cyclic compounds represented by Y (u and Y have the above-mentioned meanings, x+y=2u or 2u+2).

Specifically, for example, CF4, (CF2)S, (CF2)6
・(CF2)4・C2F6・C3F8・CHF3,
CH2F2, CC14(CC12)5, CBra, (
CB F2) 5, C2C16, C2C13F3
Examples include those in a gaseous state or those that can be easily gasified.

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

In order to generate active species, for example, when generating active species of a compound containing germanium and a halogen, in addition to this compound, a germanium compound such as simple germanium, hydrogen, or a halogen compound ( For example, F2 gas, C12 gas, gasified Br2.I2, etc.) can be used in combination.

In the present invention, as a method for generating active species in the decomposition space, the discharge energy,
Excitation energies such as thermal energy, light energy, etc. are used.

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

In the present invention, the ratio of the amount of nitrogen compounds in the membrane 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, halogen compounds (for example, F2 gas, C
12 gas, gasified Br2. I2, etc.), inert gas such as argon, neon, etc., silicon compounds, carbon compounds, germanium compounds as raw materials for forming a deposited film, and oxygen compounds as raw materials for forming a deposited film and/or film forming materials in the film forming space. It can also be used by introducing it into When using multiple of these raw material gases, they can be mixed in advance and introduced into the film forming space, or these raw material gases can be supplied individually from independent sources and then introduced into the film forming space. It can also be introduced.

Silanes, siloxanes, and the like in which hydrogen, halogen, or hydrocarbon groups 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 some or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with halogen atoms.

Specifically, 1 For example, SiH, Si2 H6, Si
3 HB, Sia H+. , S i, H+ 7
.

SiH such as S i6 Hl (p is 1 or more p 2p
+2 Preferably it is an integer of 1 to 15, more preferably 1 to 10. ) A linear silane compound represented by

SiH35iH(SiH3)SiH3,5iH3SiH
(SiH3)Si3H7, Si7 H5SiH(Si
H3) A chain silane compound having a branch represented by Si Hp 2p+2 (p has the above-mentioned meaning) such as Si2 H5, and some of the hydrogen atoms of these linear or branched chain silane compounds. or a compound completely substituted with halogen atoms, 5i3H6,Si4H8,5i
sH+. , 5i6H1□ etc. (Q is 3 or more,
A cyclic silane compound preferably represented by 3 to q2 (an integer of 1 to 6), 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. Compound,
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
, 5iH3C1, SiH3Br, SiH3I, etc.
S X (X is a halogen atom, r is 1 or more, preferably 1
~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.

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 one or more constituent atoms such as silicon, halogen, sulfur, etc.
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 (C2H6), propy(C3HB), n
-Butane (n-C4H1゜), Pentane (Cs H+
z)-Ethylene hydrocarbons include ethylene (C2
H4), propylene CC3Hb), butene-1 (C
Examples of acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4), butyne (C4H6), and the like.

In addition, as organosilicon compounds, (CH3)a Si, CH3S ic 13, (CH
3) 25iC12, (CH3) 35iC1, C2H2S
Organochlorosilane such as iCl2, CH3SiF2
C1, CH35iFC12, (CH3) 2 S t
FC1, C2Hc, S 1F2C1, C2) (5Si
FC17, C3H75fF2C1, (:3H7SiFC
Organochlorofluorosilane such as 12, [(CH3)
Organodisilazane such as 3silz, [(C3H7)3Si12, etc. 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, etc. are bonded to germanium can be used, such as GeH (a is an integer of 1 or more). , b = 2a + 2b or 2a), a polymer of this germanium hydride, a part or all of the hydrogen atoms of the germanium hydride are replaced with halogen atoms. Compounds, 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, other germanium sulfides, imides, etc. can be mentioned.

Specifically, for example, GeH4, Ge2H6゜Ge3H8
, n-Ge4H1. , tert-Ge4Hl. ,
Ge3 H6, Ges H,o, GeH3F, GeH
3C1, GeH2F2, H6Ge6 F et al.
, Ge (CH3) 4 , Ge
(C2H3)a , Ge (C6H5)a .

Ge (CH3)2 F2 , GeF2 , Ge F4
, GeS, etc. These germanium compounds may be used alone or in combination of two or more.

Furthermore, as oxygen compounds, oxygen (O2), ozone (
03), etc., as well as oxygen and atoms other than oxygen
Compounds having a species or two or more species as constituent atoms can be mentioned. The atoms other than oxygen include hydrogen (H), halogen 7
(X=F, C1, Br or I), sulfur (S), carbon (C), silicon (Si), germanium (Ge), phosphorus CP), boron (B), alkali metal, alkaline earth metal, transition In addition to metals, atoms of elements belonging to each group of the periodic table that can be combined with oxygen can be used.

Incidentally, examples of compounds containing O and H include F20.
Compounds containing 0 and X, such as H2O2, include HXOlH
Oxygen acids such as X Oa, oxides such as x20, x2o7, and compounds containing 0 and S are H2SO4, H2
Acids such as SO4 and oxides such as SO2 and SO3, 0 and C
Compounds containing acids such as H2CO3 and CO, C
Compounds containing O and St, such as oxides such as O2, include siloxanes such as disiloxane (H3S its iH3) and trisiloxane (H3S its iH20S iH3); compounds containing O and Ge include oxidation of Ge; substances, hydroxides, germanic acids, H3Ge0Ge
Organic germanium compounds such as H3, H3Ge0GeH20-GeH3, compounds containing 0 and P, and shite are H3P
03, acids such as H3P Oa and P2O3, P2o5
Examples of oxides such as H2BO and compounds containing O and B include
Oxygen compounds used in the present invention are not limited to these, but examples include acids such as No. 3 and oxides such as B2O2.

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 element used is p-type impurity, periodic table part 1II.
Group A elements such as B, At.

Suitable examples include Ga, In, T1, etc., and examples of n-type impurities include elements of Group V and A of the periodic table, such as N.
, P, As, Sb, Bi, etc. are mentioned as preferable ones, and 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 and optical 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
3, AsH3, AsF3, AsF5. AsC13,S
bH3, S bF5 , S iH3, BF3.

BCl3, BBr3, B2H6, B4H1°, B5H9
・BsH+ 1. B6HIO・B6H,2,AIC13
etc. can be mentioned. Compounds containing impurity elements are
One type may be used or two or more types may be used in combination.

In order to introduce a compound containing an impurity element as a component into the film forming space, it can be mixed with the nitrogen compound etc. in advance, or it can be introduced individually from multiple independent gas supply sources. be able to.

Next, the present invention will be explained with reference to a typical example of an electrophotographic imaging member formed by an uninvented method.

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

A photoconductive member 10 shown in FIG. 1 can be applied as an electrophotographic image forming member, and an intermediate member is provided on a support 11 for use as a photoconductive member, if necessary. 1
2. and a photosensitive layer 13.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, Steer 1/S, A1. Cr, Mo, Au, Ir, Nb, T
Examples include metals such as a, V, Ti, PL, 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 may be NiCr, A1. C
r, Mo, Au, I r, Nb, Ta, V, Ti, Pt
, Pd, In203.5n02.

If it is conductive treated by providing a thin film such as ITO (In2o3+5n02), or if it is a synthetic resin film such as polyester film, Nfcr, At,
Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir,
The surface is treated with a metal such as Nb, 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 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.
It effectively prevents carriers from flowing into the photosensitive layer 13 and is generated in the photosensitive layer 13 by irradiation with electromagnetic waves.

It has a function of easily allowing the photocarrier moving toward the support 11 to pass from the photosensitive fi 13 side to the support 11 side.

This intermediate layer 12 is made of, for example, amorphous silicon (hereinafter referred to as a-S t (
It has a layer structure (denoted as H,

In the present invention, the content of substances controlling conductivity such as B and P contained in the intermediate layer 12 is as follows.

Preferably 0.001-5X104 atomic ppm
, more preferably 0.5 to IXIO4atomic
ppm, optimally 1-5x103 atomic pp
It is desirable to set it to m.

When forming the intermediate layer 12, it can be performed continuously up to the formation of the photosensitive layer 13. In that case, as raw materials for forming the intermediate layer, active species generated between the decomposed cloths, a nitrogen compound in a gaseous state, 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. Compound.

A gas of a compound containing an oxygen compound and an impurity element as a component is separately introduced into the film forming space where the support 11 is installed, and by using light energy, the support 11. ): The intermediate layer 12 may be formed.

The compound containing germanium and halogen that is introduced into the decomposition space to generate active species when forming the intermediate layer 12 is
Active species such as G e F 2' are easily generated at high temperatures.

The layer thickness of the intermediate layer 12 is preferably 30'A to 10JL.
, more preferably 40λ to 8JL, most preferably 50λ to 5JL.

The photosensitive layer 13 has, for example, an a-5i (H,

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

The photosensitive layer 13 is made of non-doped a-5i (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 substance that governs the conduction characteristics of the same polarity is added to the intermediate layer 1.
If the actual amount contained in 2 is large, it may be contained in a smaller amount than the actual amount.

In the formation of the photosensitive layer 13, as in the case of the intermediate layer 12, a compound containing germanium and halogen is introduced into one decomposition chamber, and active species are generated by decomposing these at high temperature.
Introduced into the film forming space. In addition, in addition to this, gaseous silicon compounds and, if necessary, nitrogen compounds, hydrogen,
By introducing a gas of a compound containing a halogen compound, an inert gas, a carbon compound, a germanium compound, an oxygen compound, an impurity element as a component into the film forming space where the support 11 is installed, and using light energy, A photosensitive layer 12 may be formed on the intermediate layer 12.

In addition to this example, the method of the present invention can also be used to form Si3N4 insulator films by CVD, partially nitrided Si films, etc. that constitute 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, the nitrogen concentration can be distributed in the layer thickness direction.
iIII can be formed. Alternatively, by appropriately combining hydrogen, halogen, silicon compounds, germanium compounds, carbon compounds, oxygen compounds, etc. in addition to nitrogen compounds, N and these HlX, St, 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 Figure 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 liquid raw material compounds, an appropriate vaporization device is provided. In the figure, the gas supply sources 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. The ones marked with "e" are valves 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 6
In the figure, 112 is a decomposition space, 113 is an electric furnace, 114 is solid Ge particles, and 115 is an introduction pipe for a compound containing gaseous germanium and halogen, which is a raw material for active species. The seeds are introduced into the film forming space 101 via the introduction pipe 116.

Reference numeral 117 denotes a light energy generating device, 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
is placed on the support table 102, and the inside of the deposition space 101 is evacuated using an exhaust device, and the inside of the deposition space 101 is evacuated.

The pressure was reduced to rr. At the substrate temperature shown in Table 1, NN2150SCC or a mixture of NN2150SCC and 405CCM of PH3 gas or BzH6 gas (both diluted with 11000 pp hydrogen gas) was introduced into the deposition space using the gas supply source 108.

In addition, the decomposition space 10.2 is filled with solid Ge particles 114,
Ge is heated in an electric furnace 113 to melt it, and GeF4 is injected into it from a cylinder through a GeF introduction pipe 115 to generate active species of GeF2', which are then passed through an introduction pipe 116 into the film forming space 101. Introduce.

While maintaining the atmospheric pressure in the film forming space 101 at 0.1 Torr, the substrate was irradiated perpendicularly from a 1KWXe lamp to form a non-doped or doped nitrogen-containing amorphous deposited film (film thickness 700λ). Film formation speed is 35
It was A/sec.

Next, each of the obtained non-doped or P-type samples was placed in a vapor deposition tank and heated in a comb-shaped A at a vacuum degree of 10'''' Torr.
After forming an l-gap electrode (length 250 p, width 5 ts), dark current was measured with an applied voltage of 10 V, dark conductivity σ was determined, and each sample was evaluated.

The results are shown in Table 1.

Examples 2 to 4 Along with N2, S i2 H6, G・e2 H6 or C2
A nitrogen-containing amorphous deposited film was formed in the same manner as in Example 1 except that H& was introduced into the film forming space. 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 5-8 Instead of N2 (7), NH3, NOF, NO2 or N20
The same nitrogen-containing amorphous deposited film as in Example 1 was formed except that .

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 a solid Ge grain, 205 is an active species raw material introduction tube, 206 is an active species introduction tube, 207 is a motor, and 208 is an active species introduction tube. Heating heater, 209 is a blowout pipe, 210 is a blowout pipe, 211 is an AI cylinder, 21
2 indicates an exhaust valve. Also, 213 to 216
1 is a raw material gas supply source similar to 106 to 109 in FIG. 1, and 217 is a gas introduction pipe.

An At cylinder 211 is suspended in the film forming space 201, and a heater 208 is provided inside the cylinder so that it can be rotated by a motor 207. Reference numerals 218, 218, .

In addition, solid Ge grains 204 are packed in one decomposition chamber space 202, heated in an electric furnace 203 to melt the Ge, and GeF is injected into it from a cylinder to generate active species of GeF2. After that, it is introduced into the film forming space 201.

On the other hand, Si2H6 and H2 are introduced into the film forming space 2 through the introduction pipe 217.
01 will be introduced. The atmospheric pressure in the film forming space 201 is set to 1 and 0.
While keeping Tor r r, l K W X e lamp 2
18.218...11@- to At cylinder 211
Light is irradiated perpendicularly to the circumferential surface of the

The Al cylinder 211 is heated and maintained at 280°C by the heater 2O8 and rotated, and the exhaust gas is discharged 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 Si2H6, N2, H2 and B2H6 (B2 in volume %) from the introduction pipe 217 prior to the photosensitive layer.
A mixed gas containing H6 (0.2%) was introduced, and the film thickness was 2000A.
The film was formed using

Comparative Example 1 GeF4 and Si
A drum-shaped electrophotographic image forming member having a similar layer structure was formed from 2 H6, N2, H2, BzH, etc. by equipping the film forming space 201 of FIG. 4 with a 13.56 MHz high frequency device.

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

〔Effect of the invention〕

According to the deposition 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 low substrate temperature. Also,
It improves the reproducibility of r& membranes, makes it possible to improve membrane quality and make the membrane uniform. It is also advantageous for increasing the area of membranes, and it is possible to improve membrane productivity and easily achieve mass production. can. 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. No. 10/Φ Image forming member for electrophotography, 11...
Substrate, 12 -... Intermediate layer, 13...11 Photosensitive layer, 101.201... Film formation space, 111.202... Fist decomposition space, 106.107, 108, 109° 213.214, 215, 216 . ... gas supply source, 103.211... substrate. 117.218--Light energy generator.

Claims (1)

[Scope of Claims] Active species generated by decomposing a compound containing germanium and halogen are present in a film forming space for forming a deposited film on a substrate, and chemically interacts with the active species. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by separately introducing nitrogen compounds and irradiating them with light energy to excite the nitrogen compounds and cause them to react.