JPS61193432A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To attain enlargement, improvement of productivity and mass production of the title films by a method wherein an active compound containing silicon and halogen as well as another active compound produced from an oxygen contained filming compound are separately fed to a filming space to form the title films on a substrate by means of irradiating them with photoenergy. CONSTITUTION:An active compound A produced by decomposing a silicon and halogen contained compound as well as another active compound B produced from an oxygen filming compound chemically reacting to the former are separately fed to a filming space to form the title films on a substrate by means of irradiating them with photoenergy. The life of applicable active compound A is recommended to exceed 10 seconds in terms of productivity and easy handling while., e.g, SiF4 or the like may be recommended for the applicable silicon and halogen contained compound. Likewise a compound comprising single substance of oxygen such as O2, O3 etc. as well as another compound comprising oxygen and one or exceeding two kinds of atoms other than oxygen may be recommended for the oxygen contained compound. Finally the preferable weight ratio of active compounds B and A may be 8:2-4:6.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention is suitable for forming a deposited film containing oxygen, particularly a functional film, particularly a deposited film having a photosensitive layer for semiconductor devices and electrophotography. Concerning methods.

[Prior art]

For example, vacuum evaporation, plasma CVD, cV'D, reactive sputtering, ion blasting, photo-CVD, and other methods have been tried to form amorphous silicon films. The CVD method is widely used and commercialized.

Deposited films composed of amorphous silicon for 100 years have been improved in terms of electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity and mass production including uniformity and reproducibility. There is still room for further improvement of the overall characteristics.

The reaction process in forming an amorphous silicon deposited film using the conventionally popular plasma CVD method is much 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,
Because it depends on the combination of many parameters such as the flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure, structure of reaction vessel, pumping speed and plasma generation method, etc. becomes unstable and often has a significant adverse effect on the deposited film formed.

Moreover, parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions. On the other hand, in order to develop an amorphous silicon film that fully satisfies and exhibits excellent electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. There is.

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 capital investment in mass production equipment, and the management items for mass production also become complex, with narrow control tolerances and equipment adjustments. Because it is subtle,
These have been pointed out as problems that should be improved in the future. On the other hand, with the conventional technology using the normal CVD method,
This method requires high temperatures, and a deposited film with practically usable properties has not been obtained.

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 arsenic oxide films.

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

[Objective and Summary of the Invention] The object of the present invention is to improve the properties, film formation speed, and reproducibility of the film formed, and to make the film quality uniform, while also making it suitable for large-area films and improving film production. An object of the present invention is to provide a method for forming a deposited film that can easily achieve improved performance and mass production.

The above purpose is to prevent active species (A) generated by decomposing a compound containing silicon and nitrogen into a film forming space for forming a deposited film on a substrate. By introducing active species (Bl) generated from an oxygen-containing compound for film formation, which chemically interacts with each other, and causing a chemical reaction by irradiating them with light energy, This is achieved by the deposited film forming method of the present invention, which is characterized by forming a deposited film.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film forming space for forming a deposited film, the active species generated by decomposing a compound containing silicon and halogen and an oxygen-containing compound for film forming are used. By applying light energy to these active species (B) in the coexistence with the activated species (B), the chemical interaction caused by these is caused, promoted, and amplified, so that the deposited film that is formed is , etching effects, or other adverse effects such as abnormal discharge effects.

Further, according to the present invention, a more stable CVD method can be achieved by arbitrarily controlling the atmospheric temperature in the film forming space and the substrate temperature as desired.

Furthermore, excitation energy is applied uniformly or selectively to each active species that reaches the vicinity of the substrate for film formation;
Using light energy, it is possible to irradiate the entire substrate using an appropriate optical system to form a deposited film, or to selectively control and irradiate only desired areas to form a deposited film. It is advantageously used because it has the convenience of being able to form a deposited film by irradiating only a predetermined graphical portion using a resist or the like.

One of the differences between the method of the present invention and the conventional CVD method is that it uses active species activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and also to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

In the present invention, the active species (A) refers to active species generated from the oxygen-containing metal compound (which chemically interacts with Bl to impart energy or cause a chemical reaction, etc.). , which has the effect of promoting the formation of a deposited film.Therefore, the active species (A) may include constituent elements constituting the deposited film to be formed, or may contain various constituent elements thereof. Correspondingly, the oxygen-containing compound used in the present invention may serve as a raw material for forming the deposited film by containing constituent elements constituting the deposited film to be formed. The oxygen-containing compound may be an oxygen-containing compound that can be obtained, or it may be an oxygen-containing compound that does not contain the constituent elements constituting the deposited film to be formed and can simply serve as a raw material for film formation.

Alternatively, an oxygen-containing compound that can be used as a raw material for forming these deposited films and an oxygen-containing compound that can be used as a raw material for film formation may be used together.

The oxygen-containing compound used in the present invention is activated space (B)
Preferably, it is already in a gaseous state before being introduced into the gas, or it 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 activation space (B).

Oxygen-containing compounds include oxygen (α), ozone (0,)
Compounds of oxygen as a simple component such as, and compounds having oxygen and one or more types of atoms other than oxygen as constituent atoms can be mentioned. The atoms other than oxygen include hydrogen (H), halogen (X=F, CI, Br or ■), sulfur (S),
Carbon (C), silicon (S'), germanium (Ge),
In addition, most atoms of elements belonging to each group of the periodic table that can be combined with oxygen and that constitute a compound that can achieve the purpose of the present invention can be used. can do.

Incidentally, for example, compounds containing O and H include H,0,
Compounds containing H, 0, etc., 0 and S include Sα, SO
Oxides such as 1, compounds containing 0 and C include NoC
Compounds containing 0 and Si, such as oxides such as olCol, include disiloxane <HI S ios iHs>,
Siloxanes such as trisiloxane (HIS tos tHt), (CH-) *S i (OCOCH,)
, , CH,S i (OCOCH,) , organoacetoxysilane, (CH,) , 810CH,
, (CH,), S i (OCHm) l , CHI
Alkylalkoxysilanes such as S r (OCHI)1, (CH,), S t 0H1 (CI(l)t (
C6HI) SiOH, (CtHJt8 i (OH
) Compounds containing 0 and Qe, such as organosilanols in 1, and Ge oxides, hydroxides, and gels in 1.
Niacids, T-LGeOGeH, H, Ge0GeH
, 0-GeH, and other organic germanium compounds.

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

In the present invention, the activated species (A) from the activation space (A) introduced into the film forming space have a lifetime of 0.1 seconds or more, more preferably 1 second, from the viewpoint of productivity and ease of handling. A length of at least 1 second, preferably at least 10 seconds, is selected and used as desired.

In the present invention, as the compound containing silicon and halogen introduced into the activation space (A), for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used. For example, 5
luY2u+2 (u integer greater than or equal to 1, YiJF, CI,
At least one of the following is selected from Br and ■. ) Chain silicon halide, SiY (
v is an integer greater than or equal to 3v 2 v, and Y has the above-mentioned meaning. ), cyclic silicon halide, sI I(Y (u'xy and Y have the above meanings, x+y=2u or 2u+
It is 2. ), and the like.

Specifically, for example, sip,,(s;p,),,(sip
, ), , (SiFt)4. Si! F's, S is F
s, 81) (Fm, S IH* Fm 1SIC1
g(SiC11)l, SiBr4, (SIB'r*)v
, Si, C1s, Slx Brs, 5IHC"i,
S +HBr5, S +I(Is, S tm C
Examples include those in a gaseous state or those that can be easily gasified, such as 1s Fm.

In order to generate active species, in addition to the above-mentioned compound containing silicon and halogen, other silicon compounds such as simple silicon, hydrogen, and halogen compounds (for example, F,
Gas, CI, gas, gasified Brt, It, etc.) can be used in combination.

In the present invention, methods for generating active species (A) and (Bl) in activation spaces (A) and (B), respectively, include microwave, RF, low frequency,
Activation energy such as electric energy such as DC, thermal energy such as heater heating or infrared heating, and light energy is used.

By adding activation energy such as heat, light, or discharge in the activation spaces (A) and (Bl) to the above, active species (A) and (Bl) are generated, respectively.

In the present invention, activation space CB) in the film forming space
The ratio of the amount of active species (B) generated from the oxygen-containing compound to the active species (A) from the activation space (A) in
In the present invention, in addition to oxygen-containing compounds, hydrogen gas, nitrogen compounds (e.g., F, gas, C11
gas, gasified Br, etc.), inert gas such as helium, argon, neon, etc., 1'f? : Silicon-containing compounds, carbon-containing compounds, as chemical substances for forming deposited films.
A germanium-containing compound or the like can also be introduced into the activation space (B). When using a plurality of these chemicals, they can be mixed in advance and introduced into the activation space (B), or they can be individually supplied from independent sources. , activation space (8
They can be introduced into one area, or they can be introduced into individual activation spaces and activated.

As the silicon-containing compound for forming the deposited film, silanes, siloxanes, etc. in which silicon is bonded with hydrogen,... rogene, or a hydrocarbon group, etc. can be used. Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms of the chain and cyclic silane compounds are substituted with chloride atoms.

Specifically, for example, s int, s i, HA, S
+s Hs, 8 i, ) (to, S I,
S i such as Hu, S+aT4a, H2p+2 (+)
is 1 or more, preferably 1 to 15, preferably 1 to 10
is an integer. ), a linear silane compound represented by 8i
)(18iH(s iH,)S *H,,s *H,s
1H(sIH,)s Ix HW, S i, HW
S z ] (S iHs ) SitI (Si of a etc. ■1
゜, +2(1) has the above meaning. ) Chain silane compounds having branches represented by S il ) Ta
, s i, Ha , 8'sH+o, S l 6 HI
Si such as t, T(2, (q is 3 or more, preferably 3 to
It is an integer of 6. ), a compound in which some or all of the hydrogen atoms of the cyclic silane compound are substituted with other cyclic silanyl groups and/or chain silanyl groups,
Examples of compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are replaced with norogen atoms include s+u,
p, s iHi C, 1, s iHs Br, s iH
a Si, H, 'X ((XH) sogen atom,
r is 1 or more, preferably 1 to 10, more preferably 3 to
An integer of 7, s + t = 2 r + 2 or td2
It is r. ) halogen mono-substituted chain or cyclic 7
These include oran compounds. These compounds may be used alone or in combination of two or more.

In addition, carbon-containing compounds for forming a deposited film include chain-like or cyclic saturated or unsaturated hydrocarbon compounds, carbon and hydrogen as the main constituent atoms, and one or two types of silica, halogen, sulfur, etc. Among M-organic compounds having the above-mentioned constituent atoms, M-organic silicon compounds having hydrocarbon groups as constituents, those in a gaseous state or those that can be easily vaporized are preferably used. Among these, examples of hydrocarbon compounds include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetin hydrocarbons having 2 to 4 carbon atoms, etc. Hydrocarbons include methane (C1(,), ethane (C,H,), propane (C.

H,), n-buty (n'' Ci T(to)-pentane (C, I-T',, ), ethylene hydrocarbons include ethylene (C, H,), propylene (C, H,) ,
Butene-1 (C, H,), Silane-2 (C, H,),
Isobutylene (C,H,), pentene (C,H,.),
Acetylene (C, H,) is an acetylene hydrocarbon.
, methylacetylene (C,T(,), butyne (C,T-
T, ), etc.

As the halogen-substituted hydrocarbon compound, at least one of the hydrogens that are the opening components of the above-mentioned hydrocarbon compound is F
, CI, B r , I, and compounds in which hydrogen is substituted with F', CI are particularly effective. Replace hydrogen...
One or more rogens can be used in one compound.
It may be Hi.

Examples of the M silicon compound used in the present invention include organosilane and organohalogensilane. As organosilane, organosilane, general formula; R, n5i
H+-n, RmSiX4-m (R: alkyl group,
Aryl group; X:F.

CI, Br, I; n=1.2, 3, 4. m =
1.2,3. ), and representative examples include alkylsilanes, arylsilanes, alkylsilanes, and tori-lunosilanes.

in particular, As organochlorosilane, Trichloromethylsilane CH, 5iCI.

Dichlorodimethylsilane (C1,>, sIc+.

Chlortrimethylsilane ('CH5) -5iC
1 trichloroethylsilane CtI (fisic1
1 dichlorodiethylsilane (CI'ua)t
As the S i-CL organochlorofluorosilane, chlordifluoromethylsilane CT-k S i
F-CI dichlorofluoromethylsilane CI(l
s r Fc r sChlorfluorodimethylsilane (CH,), s t Fcl Chlorethyldifluorosilane (C,Hs) SiF, CI dichloroethylfluorosilane Cr 'H* St F C
l tChlordifluoropropylsilane C'S Ht
S i F's C'I 'Dichlorofluoropropylsilane C+LSiFC1tAs organosilane, Tetramethylsilane (C1,) 4S
I ethyltrimethylsilane (CH, >1
s;c, II.

Triethylmethylsilane (CT'T,),
S iC, ) f triethylmethylsilane CH
M Si (C1) (l) a Tetraethylsilane (cm H,), Si organohydrogenosilane includes: Methylsilane CHI s r tL l Dimethylsilane (CtI,) *8'
Ht trimethylsilane (cH,), stH diethylsilane (Ct ■Tx )* StHm triethylsilane (CI Hl) s s i
H tripropylsilane (C, H,) self-si
H'/ 7 x Nilsif 7 (Co
Hg ) t S ' Hz As the organofluorosilane, □ trifluoromethylsilane CH, S i F.

Difluorodimethylsilane (CH,), S t
p.

Fluoro-trimethylsilane (CH,), SiF ethyltrifluorosilane Cm Hl SiFs diethyldifluorosilane (Ct Hl)s s
ipt triethylfluorosilane (Cm Hl)
m S IF trifluoropropylsilane (Cm
i('y) 81Fm organobromosilane is bromotrimethylsilane (CHs) a 8iBr
"Dibromdimethylsilane (CHI') t
81Brt, etc. In addition, organoborins such as hexamethyldisilane [((IT, ),
Si').

As organadisilane, hexamethyldisilane C(CI'(m)s
'S 1"L hex" sapropyl disilane [(C
, IT, ) s's i').

etc. can also be used.

One type of 'fK compound may be used for these carbons, or two or more types may be used in combination.

In addition, germanium-containing compounds for forming deposited films include:
Inorganic or organic germanium compounds in which hydrogen, halogen, or hydrocarbon groups are bonded to germanium can be used, such as 1dGe'aHb' (a is l or more).
is an integer of b-'2a+2 or 2a. ) Chained or cyclic germanium hydride, polymers of this germanium hydrogen, good compounds by replacing the front part with halogen atoms, □ hydrogenation 1. Part or all of the hydrogen atoms of germanium hydride. Examples include organic germanium compounds such as compounds in which part or all of the hydrogen atoms of germanium are replaced with M radicals such as alkyl groups and aryl groups, and optionally halogen atoms, and other germanium compounds.

Specifically, for example, G e Ha , G e r )
I6, Oeh 1-1a, n-Ge4 HIO,t
ert-Ge4H,o,Qe, 1-16,
Ges HIO, Ge IJm F, Ge HICl.

GeHI F! , He Gem F6 , Ge (C
H-)a,Qe (C,H,),,Ge (C6H,)
4, Ge(CHI)l FM, GeF't 5G
Examples include eF4 and GeS. These germanium compounds may be used alone or in combination of two or more.

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. As the impurity element to be used, as an n-type impurity, an element of Group 1 II A of the periodic table, such as B, AI, Q
Preferred examples include a, In, T1, etc., and n
Type impurities include elements in group A of the periodic table, such as P.
, As, Sb.

Preferred examples include Bi, and B in particular.

Oa, P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical characteristics.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under active species formation conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to select Such compounds include PH,, P, H,, PF
, ,PF,,PCII,A,5T(l,A,SFI,
ASFw, ASCl, 5bE(l, 5bFI%5iH
1,BlL11,BC's,BBr,,B,H6,B,
H,,,B, H,,B,H,,,B,I(,,,B,
Examples include H, , Al cI, and the like. The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity-introducing substance may be introduced and activated together with a valley substance that generates activation spaces (Al and/or activation spaces (l, active species (A) and active species), respectively, or , may be activated in a third activation space (0) that is different from the activation space (A) and the activation space (13).

In order to activate the impurity-introducing substance, the above-mentioned activation energy listed in "Generating Active Species (A) and Active Species (B)" can be appropriately selected and employed. The active species (PN) generated by activating the impurity introduction substance are mixed with the active species (A) and/or the active species O'3) in advance, or are introduced independently into the film forming space.

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

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

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

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13 can be created by the method of the present invention. In history, the photoconductive member 10 is a protective layer provided to chemically and materially protect the surface of the photosensitive layer 13, or a t-part barrier layer and/or an upper barrier provided for the purpose of improving electrical withstand pressure. If layers are present, they can also be created by the method of the present invention.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NtCr, Steer L/S, A, 1. Cr, MO, Au.

Examples include metals such as Ir, Nb, Ta, ■, 'pi, pi, 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, polyvinylchloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is preferably provided on the conductive treated surface side.

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

AI, CrsMo, AusI'%Nb,
T a, ■, T 1 s P' s P ds I
n! Os , S n O * , ITO (I n, O
NjCr, AI% Ag1 if it is conductive treated by thin flifit &'j such as s+SnO, ) or synthetic resin film such as polyester film.
Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb,
The surface is conductively treated by treating with metals such as Ta, V, 'l''i, pt, etc. by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating with the above metals.The shape of the support is as follows: It can be of any shape, such as cylindrical, belt-like, plate-like, etc., and the shape is determined depending on the desire.
For example, if the photoconductive member 10 of FIG. 1 is to be used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder for continuous high-speed copying.

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

This intermediate layer 12 has, for example, silicon atoms as its base material,
Amorphous silicon containing hydrogen (H) and/or halogen (X) and oxygen (0) as constituent atoms as required is hereinafter referred to as a-s r (H,X).

0). ) and is electrically conductive.

In the present invention, B is contained in the intermediate layer 12.

The content of the substance controlling conductivity such as P is preferably 0.001 to 5 x 10'atomic pp
m.

More preferably 0.5 to I x 10' atomic
ppm.

The optimum range is 1 to 5 x 10'' atomic ppm.

When the intermediate layer 12 has similar or the same constituent components as the photosensitive layer 13, the formation of the intermediate layer 12 must be carried out continuously from the formation of the intermediate layer 12 to the formation of the photosensitive layer 13. I can do it. In that case, the active species (Al generated in the activation space (A) and the chemical substance for film formation introduced into the activation space [F]) serve as raw materials for forming the intermediate layer. The active species (B) and the active species (T3
) and are introduced into the film forming space where the support 11 is installed, either separately or mixed as appropriate, and by applying light energy to the coexistence atmosphere of each introduced active species, The intermediate layer 12 may be formed on the support 11.

When forming the intermediate layer 12, the compound containing silicon and the active species (A) that is introduced into the activation space (A) and generates the active species (A) easily generates active species such as, for example, arp, *. More preferably, the compound is selected from those listed above.

The layer thickness of the intermediate layer 12 is preferably 3oA-t.

μ, more preferably 40A to 8μ, optimally 50A to 5μ
It is desirable that this is done.

The photosensitive layer 13 is composed of, for example, a-3i(H,X),
It has both a charge generation function of generating photocarriers by laser light irradiation and a charge transport function of transporting the charges.

The thickness of the photosensitive layer 130 is 1~'1
00μ, more preferably 1 to 80μ, optimally 2′ to
It is desirable that the thickness be 50μ.

The photosensitive layer 13 is a non-doped a-8i (H, (For example, n-type) may contain a substance that dominates the conduction characteristics, or if the actual amount contained in the intermediate layer 12 is large, a substance that has the same polarity conduction characteristics may be contained. , it may be contained in an amount much smaller than the loading amount.

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

FIG. 2 is a schematic diagram showing an example of a PIN type diode device type using an a-8i deposited film doped with an impurity element, which is manufactured by carrying out 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 one p-type semiconductor layer 26. 28 is a conductive wire connected to an external electric circuit device.

These semiconductor layers are a-8i (I(,X), a-8i
(0,H,X), a-8iGe (0,I(,X
) etc., and the method of the present invention can be applied to the production of any layer, but in particular, by producing the semiconductor layer 26 by the method of the present invention, the conversion efficiency can be increased. I can do it.

As the group 1\-21, a conductive, semiconductive, or electrically insulating group is used. If the base body 21 is conductive, the thin film electrode 22 may be omitted. Examples of semiconductive substrates include Sl, Oe, OaAS, and ZnO.
, ZNS, and other semiconductors. Thin film electrode 22.27
For example, NiCr, AI, Cr, Mo, An,
Ir, Nb.

Ta1V, Ti, P t, pct, I n 20
a, 5nOI, ITO(1,n,O,+S
A thin film such as nQ, ) is vacuum deposited,
It can be obtained by providing it on the substrate 21 through a process such as beam evaporation or sputtering.

The layer thickness of the electrode 22.27 is preferably 30 to 5
X 10"A, more preferably 100~5x10sA
It is desirable that this is done.

In order to make the film constituting the semiconductor layer of the previous hpi n-type or p-type as necessary, n of the impurity elements is added during layer formation.
It is formed by doping a type impurity, a p-type impurity, or both impurities into the layer to be formed while controlling the amount thereof.

When forming 11-type, i-type, and p-type semiconductor layers by the method of the present invention, any one layer or all of the layers can be formed by the method of the present invention, and the film formation is performed using activated space confinement. Compounds containing silicon and halogen are introduced into the system, and by exciting them under the action of activation energy and decomposing them into zero,
For example, active species (N) such as S r eF** are generated, and the active species (a) are introduced into the film forming space. ,
A germanium-containing compound and a gas of a compound containing an inert gas and an impurity element if necessary are excited and decomposed by activation energy to generate each active species (BJ), and each is separately or Formation may be carried out by appropriately mixing 1 and using light energy introduced into the film formation space where the support 11 is installed.The active species introduced into the film formation space undergoes chemical interaction. , accelerated or amplified to form a deposited film on the support 11. The thickness of the semiconductor layer is preferably 100 to 1
．． A range of 0'A, more preferably 300 to 200OA is desirable.

The thickness of the i-type semiconductor layer is preferably 50
0-10'i more preferably 1000-10000A
A range of is desirable.

In addition to this example, the method of the present invention can also be used to form slo, insulator film, partially oxidized S' film, etc. by CVD method that constitute semiconductor devices such as ICs, transistors, diodes, and photoelectric conversion elements. It is suitable for, for example, active species (B
) By controlling the introduction timing, amount, etc., it is possible to form an S1 film having an oxygen concentration distribution in the layer thickness direction.

Alternatively, in addition to oxygen-containing compounds, silicon-containing compounds,
By appropriately combining germanium-containing compounds, carbon-containing compounds, etc., O and these Si, Oe, C
It is also possible to form a film body with desired characteristics by using a combination of such as a structural unit.

Specific examples of the present invention are shown below.

Example 1 I-type, p-type, and n-type oxygen-containing amorphous deposited films were formed using the apparatus shown in Figure 1 through the following operations.

In the second figure, 101 is a film forming house, and a desired substrate 1 is placed on the substrate support stand 102 inside.
03 is placed.

Reference numeral 104 denotes a heater for heating the substrate, and is supplied with power through conductive wires 105 through 1 to generate heat. The heater 104 is used when heating the substrate 104 before the film forming process, or when performing an annealing process to further improve the properties of the formed film after forming the film. It is powered and generates heat. The heater 104 is not driven during film formation.

106 to 109 are gas supply systems, which contain oxygen-containing compounds, and optionally hydrogen, halogen compounds, inert gases, carbon-containing compounds, carbon-containing compounds, germanium compounds, and compounds containing impurity elements. etc., depending on the number of items.

If these gases are liquid in standard conditions, an appropriate vaporizer is provided.

In the figure, the gas supply systems 106 to 109 are marked with a for branch pipes, b for flow meters, and C for pressure gauges that measure the pressure on the cylinder pressure side of each flow rate. Those marked with d or e are pulps for adjusting the flow rate of each gas. 1
23 is the activation chamber CB) for generating activated species (B).
11) A microwave zolazma generator 122 that generates active energy for generating active species (B) is provided around the activation chamber 123. Gas introduction pipe 110
The raw material gas for generating active species (B) supplied from the activation chamber (B) is activated and the generated active species (B
) is introduced into the film forming chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge. In the figure, 112 is an activation chamber (
A), 113 is an electric furnace, 114 is 81 solid particles, 115 is an introduction pipe for a compound containing silicon in a gaseous state and No.
The active species (A) generated in step 2 is introduced into the film forming chamber 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 to the raw material gas flowing in the direction of the arrow 119 to excite the film forming raw material gas and cause a reaction, thereby forming an oxygen-containing amocephus deposited film on the entire substrate 103 or on a desired portion. Further, in the figure, 120 is an exhaust valve, and i21 is an exhaust pipe.

First step, base 1 made of polyethylene terephthalate film
03 was placed on the support table 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device, and the pressure was reduced to i or"T Orr. Using the gas supply source 106,
o1%)' 1-Ei OS CCM.

Alternatively, a mixture of this and P Ha gas or B, H6 gas (all diluted with ioooppm hydrogen gas) 408C'CM is introduced into the activation chamber (B) through the gas introduction pipe 1-10.
It was introduced in 123. Activation*(B) O, gas, etc. introduced into the 123 are activated by the microwave plasma generator 122 and converted into active oxygen, etc., and the active oxygen etc. are introduced into the film forming chamber 101 through the introduction pipe 124. Ta.

In addition, 81 solid particles 114 were packed in the activation chamber (A) 102, heated in an electric furnace 113, kept at 1100°C,
The active species (
5tFs* as A) was generated, and the S+Ft* was introduced into the film-forming cable 101 through the introduction tube 116.

While maintaining the atmospheric pressure in the film forming chamber 101 at 9.4'porr, the substrate is irradiated vertically from an IKWXe lamp to form an undoped, doped, or amorphous deposited film (thickness: 700 A) containing acid oxides. Ta.

The film formation rate was 2OA/S'ec.

Next, each of the obtained non-doped or p-type samples was placed in a vapor deposition tank, and a comb-shaped AI was placed at a vacuum level of 10'porr.
After forming a gap electrode (gap length 250μ, width 5mm), the dark current was measured with an applied voltage of 10V, and the dark conductivity σ
The film characteristics of each sample were evaluated by determining d.

The results are shown in Table 1. “Examples 2 to 4 0. (diluted to 10vol 1% with He) and 812F's,
GetHa and C, H, 117) were introduced into the activation chamber fil at a ratio of 1:9, and activated species (B)
Example 1 except that a was generated and introduced into the film forming chamber 101.
An oxygen-containing amorphous deposited film was formed in the same manner as described above.

The dark conductivity was measured and the results are shown in Table 1. According to the present invention, an oxygen-containing amorphous deposited film with excellent electrical properties and sufficient doping can be obtained.

Examples 5 to 8 Instead of 0, H,Sits iH,,H,Ge0G
An oxygen-containing amorphous deposited film was formed in the same manner as in Example 1 except that eH, CO, or OF was used.

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

Example Hair Using the device shown in Figure 3, the first
A drum-shaped electrophotographic image forming member having a layer structure as shown in the figure was prepared.

In FIG. 3, 201 is a film forming chamber, 202 is an activation chamber (
A), 203 is an electric furnace, and 204 is solid Si@.

205 is an active species (At raw material introduction tube, 206 is an active species (A) introduction tube, 207 is a motor, 208 is a heating heater used in the same manner as 104 in FIG. 3, 209.21
0 is a blowout pipe, 211 is an AI cylinder, and 212 is an exhaust valve. Also, immigration.

An AI 71J substrate 211 is suspended in the film forming chamber 201, and a heater 208 is provided inside the substrate 211 so that it can be rotated by a motor 207.

In addition, the activation chamber (A) 202 is filled with solid S1 grains 204, heated in an electric furnace 203, kept at 1100°C, and S
The activated species (
1) as sIp, *B generation while inlet pipe 217-1
From 5itHe, 01 and H3's S l!
Ho, 0. H, gas is in the activation chamber (B) 220,
The activated oxygen and hydrogen were subjected to activation processing such as plasma generation by the microwave plasma generator wt221, and were introduced into the film forming chamber 201 through the introduction pipe 217-2. At this time, impurity gases such as PH, B, H, etc. are also activated from the IKWXe pipe 218 to the AI cylinder 2.
Light is irradiated perpendicularly to the curved surface in 11.

The AI cylinder base 211 was rotated, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust valve 212. In this way, the photosensitive layer 13 was formed.

Further, the intermediate layer 12 is inserted into the introduction tube 217--before the photosensitive layer.
' from S I * Fs , Os (S I m Fs
:0*=1 : 10")', ■1. and B,
H, (B with capacity Chi.

A mixed gas containing 0.2% H is introduced, and the layer thickness is 200OA.
The film was formed using

Comparative example l SiF4 and SimFa, Ot, He and BIH.

A drum-shaped film forming chamber with the layer structure shown in FIG. An electrophotographic imaging member was formed.

In Example 9 and Comparison Row 1, the manufacturing conditions and performance of the drum-shaped electrophotographic formation member (A%) are shown in Table 2. A P ]' N-type diode shown in Figure 2 was fabricated.

First, a polyethylene naphthalate film 21 on which a 100OA ITO film 22 was vapor-deposited was placed on a support stand, and a 10-
After reducing the pressure to '1''orr, active species 8'F''t* generated in the same manner as in Example 1 were introduced into the film forming chamber 101. In addition, S1mHa gas, PH gas, and gas (diluted with 1000 ppm hydrogen gas) were introduced into the activation chamber (BJ 123) and activated.Then, the activated gases were introduced into the inlet pipe 116.
into the film forming chamber 1°1 through the film forming chamber, and the pressure f in the film forming chamber is
P-doped nma-8i Ge was irradiated with an IKWXe lamp while maintained at 0.3 Torr.
A (H,X) film 24 (thickness: 700 A) was formed.

Next, P T-1, a non-doped a S I G e (T-(+
) Film 25 (thickness: 5000A) was formed.

Next, p-type oxygen-containing 'f'Va doped with 5liT (O gas together with a gas, B!H6 gas (tooppm water line gas dilution), and B under the same conditions as n-type except for
-8i (HIX) film 26 (thickness: 700 A) was formed. Furthermore, a film thickness of 1 was formed on this p-type film by vacuum evaporation.
A PIN type diode was obtained by forming an Al electrode 27 of 000A.

The IV characteristics of the thus obtained diode element (area: 1 or/l) 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,
At light irradiation intensity AMI (approximately 100 mWl-), conversion efficiency is 8.4 inches or more, open circuit voltage is 089■, short circuit current is 10.1
．． mA-/crl was obtained.

Example Example//ruβ Instead of O2 as an oxygen compound, HISiO8iH3,
A PIN type diode was manufactured. The rectification characteristics and photovoltaic effect of this sample were evaluated, and the results are shown in Table 3.
According to the present invention, a-sl (H) has better optical and electrical characteristics than conventional ones.

It was found that X, 0) can be obtained.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible without maintaining the substrate at a high temperature. becomes. 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 facilitating mass production. can be achieved. Furthermore, excitation energy is generated in the film forming space.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an image forming member for Kameko photography 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...F-image forming member for electrophotography, 11...
...Base, 12...Intermediate layer, 13...Photosensitive layer, 21...Base, 22.27...Thin film electrode, 24... ... n-type semiconductor layer, 25 ... i-type semiconductor layer, 26 ... n-type semiconductor layer, 101 , 2 +) 1 ... film-forming chamber, 11 flea ,
202...Activation room (A), 123.220.
...Activation room (B), 106, 107, 108,
109,213°214.215,216.・・・・・・
- Gas supply system, 103.211...Base, 117.218...Light energy generator.

Claims (1)

[Claims] Chemically interacts with active species (A) generated by decomposing a compound containing silicon and halogen in a film forming space for forming a deposited film on a substrate. , active species generated from oxygen-containing compounds for film formation (
A deposited film forming method characterized in that a deposited film is formed on the substrate by separately introducing B) and irradiating them with light energy to cause a chemical reaction.