Photosensitive member having an overcoat layer

A photosensitive member of the present invention comprises an electrically conductive substrate, a photoconductive layer and an overcoat layer. The photoconductive layer comprises selenium-arsenic alloy layer, or selenium layer and selenium-tellurium layer formed in this order. The overcoat layer comprises amorphous carbon containing hydrogen atoms, halogen atoms and at least one element selected from the group consisting of chalcogen, oxygen, nitrogen and elements in Group III and IV of the periodic table. The photosensitive member of this construction is harmless and excellent in electrophotographic characteristics inclusive of durability and surface hardness.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a photosensitive member comprising an 
overcoat layer on a monolayer construction of selenium-arsenic alloy or a 
laminate-layer construction of selenium-tellurium alloy. 
2. Description of the Prior Art 
Photosensitive members of amorphous selenium have been well known, and 
there have been many attempts to improve the disadvantages in heat 
resistance, spectral sensitivity, dark decay and the like of such members. 
For example, arsenic is doped into a selenium layer, or selenium-tellurium 
alloy layer is formed on a selenium layer to obtain a photosensitive 
member of laminated structure. 
It has conventionally been well known that photosensitive members composed 
of selenium-arsenic alloys (hereinafter referred to as Se-As) have the 
highest photosensitivity in spectral luminous efficiency of all the 
members and that members comprising a selenium layer having a 
selenium-tellurium layer (hereinafter referred to as Se-Te) laminated 
thereon has the highest sensitivity in long wavelength light which is 
required for a printer using semiconducting laser beams as a light source. 
However, conventional Se-As and Se-Te photosensitive members in common use 
have the following disadvantages. One disadvantage is that they are 
harmful to the human body. Although it is nearly impossible for the 
photosensitive member to come into direct contact with the human body, 
when such a photosensitive member is used in a copy machine, powder from 
said member adheres to the copy image due to surface friction caused by 
the member rubbing against the copy paper, cleaning materials, developer 
or other matter, and the powder is then discharged from the machine. 
Accordingly, when the copy is picked up by hand the person is directly 
contaminated by the selenium, arsenic and tellurium, the harmfulness of 
said substances being a matter for concern. Another disadvantage is poor 
durability. The surface hardness of Se-As and Se-Te photosensitive members 
barely meets the H level of the JIS standards for pencil lead hardness, 
consequently, the surface is readily damaged when friction is generated 
during use of the machine as described previously, or repeated harsh 
surface contact is made during paper jams and the resultant reversion to 
manual remedies. This damage markedly reduces the image quality due to 
so-called whiteouts on the copy image, and shortens the useful life span 
of the photosensitive material. 
In order to eliminate these disadvantages, the surface of the Se-As or 
Se-Te photosensitive member is covered with a protective layer. 
For example, Japanese Unexamined Patent Publications Nos. SHO 53-23636 and 
SHO 53-111734 disclose photosensitive members having a specific silicide 
applied on a selenium, selenium-tellurium alloy, and selenium-cadmium 
alloy photoconductive layers and hardened to form an insulating layer. 
Japanese Unexamined Patent Publication No. SHO 59-58437 discloses a 
photosensitive member having an amorphous Si:N or Si:O layer of 50 
angstroms to 2 microns in thickness formed on a selenium-arsenic alloy 
layer by the glow discharge process using silane gas and ammonia gas, or 
silane gas and nitrous oxide gas as starting materials. Japanese 
Unexamined Patent Publication No. SHO 60-61761 discloses a photosensitive 
member having an amorphous carbon or hard carbon layer formed on a 
photosensitive layer. Japanese Unexamined Patent Publication No. SHO 
62-9355 discloses a photosensitive member having an overcoat layer of 
amorphous carbon formed on the surface of a photo-exciting layer 
comprising hydrogenated/halogenated amorphous carbon or hydrogenated 
amorphous silicon. 
However, photosensitive members disclosed in Japanese Unexamined Patent 
Publications No. SHO 53-23636 and 53-111734 have a drawback that the 
surface of the members are readily damaged due to its poor surface 
hardness. Photosensitive members disclosed in Japanese Unexamined Patent 
Publications No. SHO 59-58437, 60-61761 and 62-9355 produce so-called 
image drift under conditions of high temperature and humidity. 
Particularly, Japanese Unexamined Patent Publication No. 60-61761 
discloses a photoconductive layer of amorphous silicon. Therefore, when 
this technique is applied to the members composed of selenium, there 
arises a problem of reduced chargeability. 
As apparent from the above, there is no disclosure in these publications of 
any means for resolving the basic disadvantages inherent in the 
aforementioned Se-As and Se-Te photosensitive members. 
SUMMARY OF THE INVENTION 
A main object of the present invention is to provide a non-injurious 
photosensitive member generally superior in electrophotographic 
characteristics and having high durability. 
Still another object of the invention is to provide a photosensitive member 
which does not produce so-called image drift. 
Still another object of the invention is to provide an overcoat layer of 
high hardness which has superior adhesion properties on the photosensitive 
member. 
A further object of the invention is to provide a photosensitive member 
having an overcoat layer which does not separate from said member when put 
into actual service in a copy machine. 
These and other objects of the present invention are achieved by providing 
a photosensitive member comprising a conductive substrate, a 
photosensitive layer formed by a selenium-arsenic alloy monolayer, or 
selenium and selenium-tellurium alloy layers formed in sequence, and an 
amorphous carbon overcoat layer provided over the photosensitive layer, 
said overcoat layer comprising halogen atoms and at least an atom selected 
from the group consisting of chalcogen atoms, oxygen atoms, nitrogen atoms 
and elements in Group III and IV of the periodic table.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
FIG. 1 shows an example of the construction of a photosensitive member of 
the present invention wherein a conductive substrate 3 has sequentially 
laminated thereon a photosensitive layer 2 and an overcoat layer 1 formed 
of an amorphous hydrocarbon layer. 
A photosensitive layer 2 is formed of a single layer composed of 
selenium-arsenic alloys (hereinafter referred to as Se-As member) on a 
conductive substrate 3, or formed of a selenium layer having a 
selenium-tellurium layer laminated thereon on a conductive substrate 3 
(hereinafter referred to as Se-Te member). 
The conductive substrate 3 may be at a minimum a material which is 
conductive on its outermost surface, and may be cylindrical, flexible 
belt, flat plate, or other arbitrary shape. 
The characteristics of the present invention is an overcoat layer 1 having 
halogen atoms and at least one element selected from the group consisting 
of chalcogen atoms, oxygen atoms, nitrogen atoms and elements in Group III 
and IV of the periodic table in an amorphous carbon layer (hereinafter 
referred to as an a-C layer). 
The amorphous carbon layer itself has a hardness rating of 4H, but becomes 
harder and damage resistant by means of the addition of halogen atoms, the 
addition of said atoms providing an overcoat layer 1 which has 
comparatively superior moisture resistance, assures suitable 
chargeability, and has superior transparency to light. 
The halogen atoms may be fulorine, chlorine, bromine, or iodine atoms. 
Fluorine atoms in particular provide exceptionally superior results from 
the standpoint of moisture resistance. 
The effective moisture resistance imparted by the addition of fluorine 
atoms is thought to be obtained from the introduction of strongly 
water-repellant fluorine atoms into the layer and the increased density of 
the layer due to a dehydration reaction induced by the fluorine atoms in 
the layer. 
The a-C layer of the present invention contains 0.01 to 50 atomic %, 
preferably 0.1 to 10 atomic %, and ideally 0.5 to 5 atomic % of halogen 
atoms based on the total amount of constituent atoms of the entire 
structure. 
The content of less than 0.01 atomic % of the halogen atoms is undesirable 
in view of moisture resistance. If the amount of halogen atoms exceeds 50 
atomic % based on all the constituent atoms of the a-C layer, the 
appropriate layer formation cannot necessarily be assured. 
Although the doping of halogen atoms results in improved moisture 
resistance, it does not afford sufficient characteristics in view of 
actual use of a photosensitive member. 
More specifically, the a-C layer containing halogen atoms possesses 
excellent moisture resistance at the time of starting the use of the 
member and sufficient intensity of film after repeated use under 
environmental conditions of room temperature and room humidity. However, 
moisture resistance after a long use is not sufficient. Our inventors have 
found that the image drift may be produced under environmental conditions 
of 35.degree. C. temperature and 80% of humidity after 10,000 copies were 
made. 
This may be caused from the fact that film resistance toward the direction 
of the surface is reduced because water is attached thereto by breaking 
weak bonds formed in the layer due to corona discharge. 
The present invention further adds at least one atom selected from the 
group consisting of chalcogen atoms, oxygen atoms, nitrogen atoms and 
elements in Group III and IV of the periodic table to the a-C layer in 
order to improve moisture resistance after repeated use. 
The chalcogen atoms may be sulfur, selenium or tellurium atoms. The Group 
III elements may be boron, aluminum, gallium, indium or thallium atoms. 
The Group IV elements may be silicon, germanium, tin or lead atoms. These 
atoms are believed to have their weak bonds forcibly broken and reformed 
during the reaction without bond dissociation induced by corona discharge 
and the like due to the formation of strong bonds between chalcogen/carbon 
atoms, oxygen/carbon atom, nitrogen/carbon atoms, Group III/carbon atoms 
and Group IV/carbon atoms, with the result that moisture adhesion is 
prevented. 
For this reason it is preferable that these atoms be used as separate 
material gases, to wit, it is desirable to conduct the reaction with the 
atoms in a temporarily dissociated state. 
The amounts of chalcogen atoms, oxygen atoms, nitrogen atoms and elements 
in Group III and IV of the periodic table to be present in the a-C layer 
of the present invention is preferably about 0.01 to 20 atomic %, more 
preferably about 0.1 to 10 atomic %, and most preferably about 0.5 to 5 
atomic based on all the constituent atoms of the a-C layer. 
The amount of elements in Group IV of the periodic table to be present in 
the a-C layer of the present invention is preferably about 0.01 to 40 
atomic %, more preferably about 0.1 to 15 atomic %, and most preferably 
about 0.5 to 5 atomic based on all the constituent atoms of the a-C layer. 
The content of less than 0.1 atomic % of these atoms is undesirable in view 
of moisture resistance after repeated use. If amounts of chalcogen atoms, 
oxygen atoms, nitrogen atoms and elements in Group III and IV of the 
periodic table exceeds 20 atomic % or the amount of IV atoms of the 
periodic table exceeds 40 atomic % based on all the constituent atoms of 
the a-C layer, the appropriate layer formation cannot necessarily be 
assured. In particular, a remarkable layer etching effect caused by the 
oxygen atoms during the layer formaiton process leads to an undesirable 
reduction in the speed of layer formation. 
Although there is no particular limitation on the amount of the 
above-mentioned atoms which may be contained in the a-C layer, the amount 
is necessarily restricted from the perspectives of the overcoat layer 
manufacturing and glow discharge processes. 
Although there is no particular limitation on the amount of the hydrogen 
atoms which may be contained in the a-C layer, the amount is necessarily 
restricted from the perspectives of the overcoat layer manufacturing and 
glow discharge processes, said amount being, in general, 5 to 50 atomic %. 
The contents of these atoms in the a-C layer can be determined by a usual 
method of elementary analysis, e.g. Auger electron spectroscopy or SIMS 
analysis. The a-C layer may contain chalcogen atoms, oxygen atoms, 
nitrogen atoms and elements in Group III and IV of the periodic table 
singly, and may contain two or more of the above types of atoms. 
The overcoat layer 1 of the present invention is formed at a thickness of 
0.01 to 5 microns, preferably 0.05 to 2 microns, and ideally 0.1 to 1 
microns. A layer with a thickness of less than 0.01 micron has reduced 
hardness and is readily damaged. Also a layer with the thickness exceeding 
5 microns has reduced transparency to light and causes reduced sensitivity 
of the photosensitive member because the exposed light cannot be 
effectively conducted to the selenium photosensitive layer. 
The aforesaid halogen, chalcogen, oxygen, nitrogen and elements in Group 
III and IV may be incorporated so as to be distributed uniformly 
throughout the width of said overcoat layer 1 or may be incorporated in 
uneven distribution. When distributed unevenly, the region having the 
majority of these atoms in the direction of the layer thickness shall have 
these atoms in such amounts that they are within the ranges heretofore 
described. 
High density distribution of halogen atoms in the vicinity of the surface 
of the layer in particular can be effected by post-layer formation plasma 
surface processing of the molecules containing the halogen atoms, in which 
case high density distributions of 40 to 50 atomic % is possible. 
The overcoat layer 1 of the photosensitive member of the present invention 
may be formed on an Se-As member or Se-Te member, thus achieving the 
objects of the present invention. 
The overcoat layer 1 is formed by means of a glow discharge process. The 
overcoat layer 1 is formed by discharging at reduced pressure 
gaseous-phase molecules containing at least carbon atoms and molecules 
containing hydrogen atoms together with molecules at least containing one 
element selected from the group consisting of chalcogen, oxygen,nitrogen 
and elements in Group III and IV, thereby diffusing on the substrate the 
activated neutral atoms and charged atoms in the plasma production region, 
and being induced by electrical or magnetic force or the like to form on 
the substrate in solid phase via a recombination reaction. The formation 
of the overcoat layer 1 can be regulated via the aforesaid plasma reaction 
(hereinafter referred to as a P-CVD reaction) to form an amorphous 
hydrocarbon layer incorporating at least chalcogen atoms, oxygen atoms, 
nitrogen atoms and III atoms and IV atoms of the periodic table. 
These hydrocarbons need not always be in a gaseous phase at room 
temperature at atmospheric pressure but can be in a liquid or solid phase 
insofar as they can be vaporized on melting, evaporation or sublimation, 
for example, by heating or in a vacuum. Examples of useful hydrocarbons 
are saturated hydrocarbons, unsaturated hydrocarbons, alicyclic 
hydrocarbons, aromatic hydrocarbons and the like. Such hydrocarbons are 
usable in combination. 
A wide variety of hydrocarbons are usable. Examples of useful saturated 
hydrocarbons are normal paraffins such as methane, ethane, propane, 
butane, pentane, hexane, heptane, octane, nonane, decane, undecane, 
dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, 
octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, 
tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, 
triacontane, dotriacontane, pentatriacontane, etc.; isoparaffins such as 
isobutane, isopentane, neopentane, isohexane, neohexane, 
2,3-dimethylbutane, 2-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 
2,4-dimethylpentane, 3,3-dimethylpentane, tributane, 2-methylheptane, 
3-methylheptane, 2,2-dimethylhexane, 2,2,5-dimethylhexane, 
2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 2,3,3trimethylpentane, 
2,3,4-trimethylpentane, isononane, etc.; and the like. 
Examples of useful unsaturated hydrocarbons are olefins such as ethylene, 
propylene, isobutylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 
2-methyl-1-butene, 3-methyl-1-butene, 2- methyl-2-butene, 1-hexene, 
tetramethylethylene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like; 
diolefins such as allene, methyl-allene, butadiene, pentadiene, hexadiene, 
cyclopentadiene and the like; triolefins such as ocimene, alloocimene, 
myrcene, hexatriene and the like; acetylene, methylacetylene, 1-butyne, 
2-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, 1-decyne, 
butadyine and the like. 
Examples of useful alicyclic hydrocarbons are cycloparaffins such as 
cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 
cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, 
cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane and 
the like; cycloolefins such as cyclopropene, cyclobutene, cyclopentene, 
cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene and the 
like; terpenes such as limonene, terpinolene, phellandrene, sylvestrene, 
thujene, carene, pinene, bornylene, camphene, fenchene, cyclofenchene, 
tricyclene, bisabolene, zingiberene, curcumene, humulene, 
cadinenesesquibenihene, selinene, caryophyllene, santalene, cedrene, 
camphorene, phyllocladene, podocarprene, mirene and the like; steroids; 
etc. 
Examples of useful aromatic hydrocarbons are benzene, toluene, xylene, 
hemimellitene, pseudocumene, mesitylene, prehnitene, isodurene, durene, 
pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, 
cumene, styrene, biphenyl, terphenyl, diphenylmethane, triphenylmethane, 
dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, 
phenanthrene and the like. 
Considering the formation of a layer of good quality, unsaturated 
hydrocarbons are desirable because they are reactive. Especially, the most 
desirable compounds are butadiene and propylene in view of film-forming 
ability, ease of gas handling and cost. 
The hydrogen content of the a-C layer of the invention is variable in 
accordance with the film forming apparatus and film forming conditions. 
The hydrogen content can be decreased, for example, by elevating the 
substrate temperature, lowering the pressure, reducing the degree of 
dilution of the starting materials, applying a greater power, decreasing 
the frequency of the alternating electric field to be set up, increasing 
the intensity of a d.c. electric field superposed on the alternating 
electric field or desired combination of such procedures. 
The halogen compounds to be used need not always be in a gaseous phase at 
room temperature at atmospheric pressure but can be in a liquid or solid 
phase insofar as they can be vaporized on melting, evaporation or 
sublimation, for example, by heating or in a vacuum. While halogens such 
as fluorine, chlorine, bromine and iodine are usable in this invention, 
examples of useful halogen compounds are inorganic compounds such as 
hydrogen fluoride, chlorine fluoride, bromine fluoride, iodine fluoride, 
hydrogen chloride, bromine chloride, iodine chloride, hydrogen bromide, 
iodine bromide and hydrogen iodide; and organic compounds such as alkyl 
halides, aryl halides, styrene halides, polymethylene halides, haloforms, 
halogen substituted hydrocarbons and the like. Examples of such alkyl 
halides are methyl fluoride, methyl chloride, methyl bromide, methyl 
iodide, ethyl fluoride, ethyl chloride, ethyl bromide, ethyl iodide, 
propyl fluoride propyl chloride, propyl bromide, propyl iodide, butyl 
fluoride, butyl chloride, butyl bromide, butyl iodide, amyl fluoride, amyl 
chloride, amyl bromide, amyl iodide, hexyl fluoride, hexyl chloride, hexyl 
bromide, hexyl iodide, heptyl fluoride, heptyl chloride, heptyl bromide, 
heptyl iodide, octyl fluoride, octyl chloride, octyl bromide, octyl 
iodide, nonyl fluoride, nonyl chloride, nonyl bromide, nonyl iodide, decyl 
fluoride, decyl chloride, decyl bromide, decyl iodide and the like. 
Examples of useful aryl halides are fluorobenzene, chlorobenzene, 
bromobenzene, iodobenzene, chlorotoluene, bromotoluene, chloronaphthalene, 
bromonaphthalene and the like. Examples of useful styrene halides are 
chlorostyrene, bromostyrene, iodostyrene, fluorostyrene and the like. 
Examples of useful polymethylene halides are methylene chloride, methylene 
bromide, methylene iodide, ethylene chloride, ethylene bromide, ethylene 
iodide, trimethylene chloride, trimethylene bromide, trimethylene iodide, 
dibutane chloride, dibutane bromide, dibutane iodide, dipentane chloride, 
dipentane bromide, dipentane iodide, dihexane chloride, dihexane bromide, 
dihexane iodide, diheptane chloride, diheptane bromide, diheptane iodide, 
dioctane chloride, dioctane bromide, dioctane iodide, dinonane chloride, 
dinonane bromide, didecane chloride, didecane iodide and the like. 
Examples of useful haloforms are fluoroform, chloroform, bromoform, 
iodoform and the like. 
Useful examples of halogen substituted hydrocarbons are carbon 
tetrafluoride, vinylidene fluoride, perfluoroethylene, perfluoropropane, 
perfluoropropylene, difluoropropane, and the like. 
From the perspectives of film-forming ability, ease of gas handling and 
cost, the most desirable compounds are carbon tetrafluoride, 
perfluoroethylene, perfluoropropylene and the like. 
The amount of halogen atoms incorporated in the amorphous carbon layer can 
be regulated at least by means of increasing or decreasing the amount of 
molecules containing halogen atoms used in the P-CVD reaction. 
Examples of molecules containing at least chalcogen atoms are H.sub.2 S, 
CH.sub.3 (CH.sub.2).sub.4 S(CH.sub.2).sub.4 CH.sub.3, CH.sub.2 
.dbd.CHCH.sub.2 SCH.sub.2 CH.dbd.CH.sub.2, C.sub.2 H.sub.5 SC.sub.2 
H.sub.5, C.sub.2 H.sub.5 SCH.sub.3, thiophene, H.sub.2 Se, (C.sub.2 
H.sub.5).sub.2 Se, H.sub.2 Te and the like. 
From the perspectives of film-forming ability, ease of gas handling and 
cost, the most desirable compounds are H.sub.2 S, H.sub.2 Se and the like. 
While oxygen and ozone are usable for this purpose, examples of useful 
oxygen compounds are inorganic compounds such as water (water vapor), 
hydrogen peroxide, carbon monoxide, carbon dioxide, carbon suboxide; 
organic compounds having a functional group or linkage such as hydroxyl 
group (--OH), aldehyde group (--COH), acyl group (RCO-- or --CRO), ketone 
group (&gt;CO), ether linkage (--O--), ester linkage (--COO--), 
oxygen-containing heterocyclic ring or the like. Examples of useful 
organic compounds having a hydroxyl group include alcohols such as 
methanol, ethanol, propanol, butanol, allyl alcohol, fluoroethanol, 
fluorobutanol, phenol, cyclohexanol, benzyl alcohol and furfuryl alcohol. 
Examples of useful organic compounds having an aldehyde group are 
formaldehyde, acetaldehyde, propioaldehyde, butyraldehyde, glyoxal, 
acrolein, benzaldehyde, furfural and the like. Examples of useful organic 
compounds having an acyl group are formic acid, acetic acid, propionic 
acid, butyric acid, valeric acid, palmitic acid, stearic acid, oleic acid, 
oxalic acid, malonic acid, succinic acid, benzoic acid, toluic acid, 
salicylic acid, cinnamic acid, naphthoic acid, phthalic acid, furoic acid 
and the like. Examples of suitable organic compounds having a ketone group 
are acetone, ethyl methyl ketone, methyl propyl ketone, butyl methyl 
ketone, pinacolone, diethyl ketone, methyl vinyl ketone, mesityl oxide, 
methylheptenone, cyclobutanone, cyclopentanone, cyclohexanone, 
acetophenone, propiophenone, butyrophenone, valerophenone, dibenzyl 
ketone, acetonaphthone, acetothienone, acetofuron and the like. Examples 
of useful organic compounds having an ether linkage are methyl ether, 
ethyl ether, propyl ether, butyl ether, amyl ether, ethyl methyl ether, 
methyl propyl ether, methyl butyl ether, methyl amyl ether, ethyl propyl 
ether, ethyl butyl ether, ethyl amyl ether, vinyl ether, allyl ether, 
methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl 
ether, anisole, phenetole, phenyl ether, benzyl ether, phenyl benzyl 
ether, naphthyl ether, ethylene oxide, propylene oxide, trimethylene 
oxide, tetrahydrofuran, tetrahydropyran, dioxane and the like. Examples of 
useful organic compounds having an ester linkage are methyl formate, ethyl 
formate, propyl formate, butyl formate, amyl formate, methyl acetate, 
ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl 
propionate, ethyl propionate, propyl propionate, butyl propionate, amyl 
propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl 
butyrate, amyl butyrate, methyl valerate, ethyl valerate, propyl valerate, 
butyl valerate, amyl valerate, methyl benzoate, ethyl benzoate, methyl 
cinnamate, ethyl cinnamate, propyl cinnamate, methyl salicylate, ethyl 
salicylate, propyl salicylate, butyl salicylate, amyl salicylate, methyl 
anthranilate, ethyl anthranilate, butyl anthranilate, amyl anthranilate, 
methyl phthalate, ethyl phthalate, butyl phthalate and the like. Examples 
of useful heterocyclic compounds are furan, oxazole, furazane, pyran, 
oxazine, morpholine, benzofuran, benzoxazole, chromene, chroman, 
dibenzofuran, xanthene, phenoxazine, oxirane, dioxirane, oxathiorane, 
oxadiazine, benzoisooxazole and the like. 
From the perspectives of film-forming ability, ease of gas handling and 
cost, the most desirable compounds are carbon dioxide, oxygen and the 
like. 
While nitrogen per se is usable, examples of useful nitrogen compounds 
include inorganic compounds such as ammonia, and organic compounds having 
a functional group or linkage such as amino group (NH.sub.2), cyano group 
(--CN), nitrogen-containing hetero-cyclic ring or the like. Examples of 
useful organic compounds having an amino group are methylamine, 
ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine, 
octylamine, nonylamine, decylamine, undecylamine, dodecylamine, 
tridecylamine, tetradecylamine, pentadecylamine, cetylamine, 
dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, 
trimethylamine, triethylamine, tripropylamine, tributylamine, 
triamylamine, allylamine, diallylamine, triallylamine, cyclopropylamine, 
cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, 
methylaniline, dimethylaniline, ethylaniline, diethylaniline, toluidine, 
benzylamine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, 
naphthylamine, ethylenediamine, trimethylenediamine, 
tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 
diaminoheptane, diaminooctane, diaminononane, diaminodecane, 
phenylenediamine and the like. Examples of useful organic compounds having 
a cyano group are acetonitrile, propionitrile, butyronitrile, 
valeronitrile, capronitrile, enanthonitrile, caprylonitrile, 
pelargonnitrile, caprinitrile, lauronitrile, palmitonitrile, 
stearonitrile, crotononitrile, malonitrile, succinonitrile, 
glutaronitrile, adiponitrile, bezonitrile, tolunitrile, cyanobenzylic 
cinnamonitrile, naphthonitrile, cyanopyridine and the like. Examples of 
useful heterocyclic compounds are pyrrole, pyrroline, pyrrolidine, 
oxazole, thiazole, imidazole, imidazoline, imidazolidine, pyrazole, 
pyrazoline, pyrazolidine, triazole, tetrazole, pyridine, piperidine, 
oxazine, morpholine, thiazine, pyridazine, pyrimidine, pyrazine, 
piperazine, triazine, indole, indoline, benzoxazole, indazole, 
benzimidazole, quinoline, cinnoline, phthalazine, phthalocyanine, 
quinazoline, quinoxaline, carbazole, acridine, phenanthridine, phenazine, 
phenoxazine, indolizine, quinolizine, quinuclidine, naphthyridine, purine, 
pteridine, aziridine, azepine, oxadiazine, dithiazine, benzoquinoline, 
imidazothiazole and the like. 
From the perspectives of film-forming ability, ease of gas handling and 
cost, the most desirable compounds are nitrogen, ammonia and the like. 
Examples of molecules containing at least III element of the periodic table 
are B.sub.2 H.sub.6, BCl.sub.3, BBr.sub.3, BF.sub.3, B(OC.sub.2 
H.sub.5).sub.3, AlCl.sub.3, Al(Oi-C.sub.3 H.sub.7).sub.3, (CH.sub.3).sub.3 
Al, (C.sub.2 H.sub.5).sub.3 Ga, (C.sub.2 H.sub.5).sub.3 In and the like. 
From the perspectives of film-forming ability, ease of gas handling and 
cost, the most desirable compounds are diborane, trimethylaluminum and the 
like. 
Examples of molecules containing at least IV element of the periodic table 
are SiH.sub.4, Si.sub.2 H.sub.6, Si.sub.2 F.sub.2 H.sub.4, 
Si(OCH.sub.3).sub.4, Si(OCH.sub.3).sub.4, GeH.sub.4, GeF.sub.4, Ge.sub.2 
H.sub.6, (OC.sub.2 H.sub.5).sub.4 Sn, Sn(OCH.sub.3).sub.4 and the like. 
From the perspectives of film-forming ability, ease of gas handling and 
cost, the most desirable compounds are silane, germane and the like. 
The amount of these atoms, i.e., chalcogen atoms, oxygen atoms, nitrogen 
atoms and III and IV atoms of the periodic table, incorporated in the a-C 
layer can be regulated at least by means of increasing or decreasing the 
amount of molecules containing these atoms in the P-CVD reaction. 
FIGS. 2 and 3 show single examples of a glow discharge decomposition 
apparatus for forming the overcoat layer of the present invention. FIG. 2 
shows a plane-parallel plate P-CVD apparatus and FIG. 3 shows a 
cylindrical P-CVD apparatus. 
First, an explanation of the apparatus shown in FIG. 2 follows hereinafter. 
FIG. 2 shows an apparatus for preparing the photosensitive member of the 
invention. First to sixth tanks 701 to 706 have enclosed therein starting 
material compounds which are in gas phase at room temperature and a 
carrier gas and are connected respectively to first to sixth regulator 
valves 707 to 712 and first to sixth flow controllers 713 to 718. Useful 
carrier gases are hydrogen gas, argon gas and helium gas. First to third 
containers 719 to 721 contain starting material compounds which are liquid 
or solid at room temperature, can be preheated by first to third heaters 
722 to 724 for vaporizing the compounds, and are connected to seventh to 
ninth regulator valves 725 to 727 and seventh to ninth flow controllers 
728 to 730, respectively. The gases to be used as selected from among 
these gases are mixed together by a mixer 731 and fed to a reactor 733 via 
a main pipe 732. The interconnecting piping can be heated by a pipe heater 
734 which is suitably disposed so that the material compound, in a liquid 
or solid phase at room temperature and vaporized by preheating, will not 
condense during transport. A grounded electrode 735 and a power 
application electrode 736 are arranged as opposed to each other within the 
reactor 733. Each of these electrodes can be heated by an electrode heater 
737. The power application electrode 736 is connected to a high-frequency 
power source 739 via a high-frequency power matching device 738, to a 
low-frequency power source 741 via a low-frequency power matching device 
740 and to a d.c. power source 743 via a low-pass filter 742. Power of one 
of the different frequencies, for example, a low frequency of 10 KHz to 
1,000 KHz, or a high frequency of 13.56 MHz and the like, is applicable to 
the electrode 736 by way of a connection selecting switch 744. Direct 
electrical power may also be additionally applied. The internal pressure 
of the reactor 733 is adjustable by a pressure control valve 745. The 
reactor 733 is evacuated by a diffusion pump 747 and an oil rotary pump 
748 via an exhaust system selecting valve 746, or by a cooling-removing 
device 749, a mechanical booster pump 750 and an oil rotary pump 748 via 
another exhaust system selecting value 746. The exhaust gas is further 
made harmless by a suitable removal device 753 and then released to the 
atmosphere. The evacuation piping system can also be heated by a suitably 
disposed pipe heater 734 so that the material compound which is liquid or 
solid at room temperature and vaporized by preheating will not condense 
during transport. For the same reason, the reactor 733 can also be heated 
by a reactor heater 751. An electrically conductive substrate 752 is 
placed on the electrode 735 in the reactor. 
Heaters may be selected according to the characteristics of the starting 
material gases to be used, but they are often unnecessary, particularly 
when the vaporization point of the starting material gases under normal 
pressure is -50.degree. C. to +15.degree. C., thus allowing the 
simplification of the manufacturing apparatus. 
In general, the provision of the aforesaid heater types is preferred in 
order to prevent production of a fine powder polymer within the reactor 
733 when the vaporization point of the strating material gases is lower 
than -50.degree. C., and to prevent coalescence within the various piping 
when the vaporization point of the strating material gases is higher than 
+15.degree. C. 
Although FIG. 2 shows that the substrate 752 is fixed to the grounded 
electrode 735, the substrate may be attached to the power application 
electrode 736, or to both the electrodes. 
FIG. 3 shows another type of apparatus for preparing the photosensitive 
member of the invention. This apparatus has the same construction as the 
apparatus of FIG. 2 with the exception of the interior arrangement of the 
reactor 833. The numerals shown by 700 order in FIG. 2 are replaced by the 
numerals at 800 order in FIG. 8. With reference to FIG. 3, the reactor 833 
is internally provided with a hollow cylindrical electrically conductive 
substrate 852 serving also as the grounded electrode 735 of FIG. 2 and 
with an electrode heater 837 inside thereof. A power application electrode 
836, similarly in the form of a hollow cylinder, is provided around the 
substrate 852 and surrounded by an electrode heater 837. The conductive 
substrate 852 is rotatable about its own axis by motor from outside. 
The reactors shown in FIGS. 2 and 3 for preparing the photosensitive member 
are first evacuated by the diffusion pump to a vacuum of about 10.sup.-4 
to about 10.sup.-6 torr, whereby the adsorbed gas inside the reactor is 
removed. The reactor is also checked for the degree of vacuum. At the same 
time, the electrodes and the substrate fixedly placed on the electrode are 
heated to a predetermined temperature. A photosensitive member comprising 
a conductive substrate and a single photosensitive layer formed thereon 
and composed of selenium-arsenic alloys or a photosensitive layer composed 
of selenium layer having a selenium-tellurium layer laminated thereon may 
be used. 
In order to prevent heat conversion of the selenium photosensitive layer at 
this time, it is desirable that the substrate temperature be set at 
180.degree. C. or less for a single layer composed of selenium-arsenic 
alloys, and 100.degree. C. or less (room temperature to 100.degree. C.) 
for a layer composed of selenium layer having a selenium-tellurium layer 
laminated thereon. 
Subsequently, material gases are fed into the reactor from the first to 
sixth tanks and the first to third containers (i.e. from those concerned), 
each at a specified flow rate, using the flow controllers concerned, i.e. 
first to ninth flow controllers and the interior of the reactor is 
maintained in a predetermined vacuum of about 0.05 to 5.0 torr by the 
pressure control valve. After the combined flow of gases has become 
stabilized, the high-frequency power source, for example, is selected by 
the connection selecting switch to apply a low-frequency power to the 
power application electrode. This initiates discharge across the two 
electrodes, forming a solid layer on the substrate with time. The layer 
deposition rate is 10 angstroms/min to 3 microns/ min, with a range of 100 
angstroms/min to 1 micron/min being preferable, and a range of 500 
angstroms/min to 5000 angstroms/min being ideal. A layer deposition rate 
of less than 10 angstroms/min is undesirable from a production standpoint, 
while a rate greater than 3 microns/min is undesirable because it gives 
rise to layer unevenness. The discharge is discontinued upon the thickness 
reaching the desired value. Consequently, the a-C layer of the invention 
is obtained which serves as a overcoat layer. 
A photosensitive member overcoating layer of the present invention 
manufactured by the aforesaid process is clearly non-crystalline as 
determined by the peak x-ray diffraction, contains carbon as well as 
hydrogen as structural atoms as determined by the peak infrared absorption 
based on the absorption spectrum of the carbon and hydrogen bonds, said 
layer is thus understood to be an amorphous hydrocarbon layer. 
Furthermore, the peak absorption for a photosensitive member overcoating 
layer of the present invention manufactured by the aforesaid process may 
also be measured based on the content of halogen, chalcogen, oxygen, 
nitrogen or III or IV element, and carbon bonds as determined via the 
infrared absorption spectrum. 
It is preferred that a photosensitive member overcoating layer of the 
present invention has a dielectric constant of about 2.0 to 6.0, with an 
optical band gap of about 1.5 to 3.0 [eV]. 
The present invention will be described with reference to the following 
examples. 
EXAMPLES 1 and 2 
Using a glow discharge decomposition apparatus shown in FIG. 3, an overcoat 
layer of the present invention for a photosensitive member was prepared. 
First, the interior of the reactor 733 was evacuated to a high vacuum of 
about 10.sup.-6 torr, and the first, second, third and fourth regulator 
valves 707, 708, 709 and 710 were thereafter opened to introduce hydrogen 
gas from the first tank 701, butadiene gas from the second tank 702, 
carbon tetrafluoride gas from the third tank 703 and hydrogen sulfide gas 
from the fourth tank 704 into the first flow controller 713, the second 
flow controller 714, the third flow controller 715 and the fourth flow 
controller 716 respectively at an output pressure of 1.0 kg/cm.sup.2. 
The dials on the flow controllers were adjusted to supply the hydrogen gas 
at a flow rate of 300 sccm, the butadiene gas at 30 sccm, the carbon 
tetrafluoride gas at 90 sccm and the hydrogen sulfide gas at 3 sccm to the 
reactor 733 through the main pipe 732 via the intermediate mixer 731. 
Further, in the member of Example 2, phosphine gas for adjusting 
chargeability was simultaneously introduced into the reactor 733 at a flow 
rate of 3 sccm. 
After the flows of the gases were stabilized, the internal pressure of the 
reactor 733 was adjusted to 0.5 torr by the pressure control valve 745. 
On the other hand, the substrate 752 was used, said substrate being a 
cylindrical aluminum substrate measuring 80 mm in diameter and 330 mm in 
length and having an Se-As photosensitive layer (Example 1) and an Se-Te 
photosensitive layer (Example 2) previously formed thereon to a film 
thickness of approximately 50 microns in accordance with conventional 
methods and using a separate vacuum evaporation device. 
The temperature of substrate 752 was raised from room temperature to 
120.degree. C. (Example 1) or 50.degree. C. (Example 2) about a 20 minute 
period prior to the introduction of the gases. 
With the gas flow rates and the pressure in stabilized state, 160-watt 
power with a frequency of 70 KHz was applied to the power application 
electrode 736 from the low-frequency power source 741 preconnected thereto 
by the selecting switch 744 to conduct plasma polymerization for 2 
minutes, forming an a-C layer, 0.2 microns in thickness, as an overcoat 
layer. 
After completion of the film formation, the power supply was discontinued, 
the regulator valves except for the one for hydrogen gas were all closed. 
Then, only the hydrogen gas was introduced into the reactor 733 at a flow 
rate of 200 sccm with a pressure of 20 Torr to decrease the temperature of 
the substrate to 30.degree. C. for about 15 minutes. Thereafter, the 
regulator valves for hydrogen gas was closed, whereupon the vacuum was 
broken and the photosensitive member of the present invention was removed. 
When subjected to organic quantitative analysis and Auger electron 
spectroscopy, the a-C layer thus obtained was found to contain 45 atomic % 
of hydrogen atoms, 3.7 atomic % of halogen atoms, i.e., fluorine atoms and 
1.2 atomic % of chalcogen atoms, i.e., sulfur atoms based on all the 
constituent atoms contained therein. Further, the layer was found to 
contain 0.9 atomic % of phosphorus atoms in Example 2. 
Characteristics 
The overcoat layers obtained in Examples 1 and 2 had a surface hardness of 
about 6 H based on measurements for pencil lead hardness as provided in 
Japanese Industrial Standards JIS K-5400, and it is understood that the 
high degree of surface hardness was a marked improvement. 
Further, the member has photosensitive characteristics which is unchanged 
compared with the member without overcoat layer, indicating that the 
overcoat layer of the photosensitive member of the present invention does 
not impair the inherent sensitivity of the Se-Te photosensitive member. 
In addition, the photosensitive members obtained in Examples 1 and 2 were 
exposed to atmospheric conditions of low temperature-low humidity 
(10.degree. C. and 30% humidity) and high temperature-high humidity 
(50.degree. C. and 90% humidity) which were alternated every 30 minutes 
each over a 6 hour period, and cracking or separation of the overcoat 
layer was not observed, from which results it is understood that the 
photosensitive member having the overcoat layer of the present invention 
has superior adhesive properties regarding its adhesion to the Se-As and 
Se-Te photosensitive layers 
When the photosensitive members obtained in Examples 1 and 2 were installed 
in a Minolta Model EP 650Z copy machine and copies made using a normal 
optical system for Example 1 and an optical system modified to a 
conventional semiconductor laser exposure system comprising a 
semiconductor laser, polygon mirror scanner, drive system and the like for 
Example 2, clear images were obtained. In addition, so-called image drift 
was not observed when copies were made under environmental conditions of 
35.degree. C. temperature and 80% humidity. Neither was any separation of 
the overcoat layer noted when said layer came into contact with the 
developer, copy paper, and cleaning components within the copy machine. 
Under normal room conditions, 250,000 copies were made and clear images 
were obtained to the last. Additionally, the surface was subjected to 
component analysis after making the 250,000 copies using Auger analysis 
and neither selenium, tellurium, or the like were detected. From these 
results, it can be understood that the overcoat layer of the present 
invention improved the harmful aspects and increased durability while it 
did not impair image quality. 
Evaluations after 10,000 copies, 50,000 copies, 100,000 copies or 250,000 
copies, each test being conducted at 35.degree. C. and 80% relative 
humidity, revealed no evidence of image drift, confirming the superior 
temperature resistance after printing. The results of these evaluations 
are shown in Table 2. In the table, the [O] mark indicates evidence of 
image drift detected under conditions of 35.degree. C. and 80% relative 
humidity; the [.DELTA.] mark indicates partial image drift under identical 
conditions; the [x] mark indicates image drift throughout the entire copy 
under identical conditions. 
It can be understood from the aforesaid data that the photosensitive member 
having an overcoat layer of the present invention achieves durability 
without loss of image quality, and that it particularly provides superior 
performance in regard to moisture resistance after printing. 
EXAMPLES 3 to 20 
Photosensitive members were prepared as similarly as with Example 1, each 
member comprising a photosensitive layer and an overcoat layer provided in 
this order as shown in FIG. 1. 
Table 1 shows the various condition values for forming an overcoat layer. 
Table 1 shows the conditions different from Example 1 for forming an 
overcoat layer and classified into 21 items (1) to (21). These items are 
described at the top column of the Table. Some condition values shown at 
each item are common to each example, while others are varying in each 
example. 
Table 1 shows the items (1) to (21) as follows: 
(1) flow rate of hydrogen gas from the first tank (701) (sccm) 
(2) flow rate of material gas from the second tank (702) (sccm) 
(3) flow rate of dopant gas from the third tank (703) (sccm) 
(4) flow rate of dopant gas from the fourth tank (704) (sccm) 
(5) flow rate of dopant gas from the fifth tank (705) (sccm) 
(6) flow rate of dopant gas from the first container (719) (sccm) 
(7) temperature of the first heater (722) (.degree.C.) 
(8) pressure (Torr) 
(9) temperature of the substrate (.degree.C.) 
(10) time for heating the substrate (minute) 
(11) dimension of the substrate (diameter.times.length) (unit: mm) 
(12) power (watt) 
(13) time for plasma polymerization (minute) 
(14) thickness of the layer (micron) 
(15) frequency from the power source (KHz) 
(16) hydrogen content (atomic %) 
(17) to (19) content of dopant contained in the overcoat layer (atomic %) 
(20) photosensitive layer on which the overcoat layer is formed. In this, A 
represents Se-As layer and B represents Se-Te layer 
(21) thickness of the photosensitive layer Molecular formulas shown in 
Table 1 represent following compounds: 
C.sub.3 H.sub.6 : propylene 
C.sub.3 F.sub.6 : perfluoropropylene 
H.sub.2 Se: hydrogenated selenium 
C.sub.4 H.sub.6 : butadiene 
CF.sub.4 : carbon tetrafluoride 
B.sub.2 H.sub.6 : diborane 
PH.sub.3 : phosphine 
(CH.sub.3).sub.3 Al: trimethylaluminum 
CO.sub.2 : carbon dioxide 
NH.sub.3 : ammonia 
SiH.sub.4 : monosilane 
GeH.sub.4 : germane 
In Examples 3 to 20, after completion of the film formation, the power 
supply was discontinued, the regulator valve except for the one for 
hydrogen gas were all closed. Then, only the hydrogen gas was introduced 
into the reactor 733 at a flow rate of 200 sccm with a pressure of 20 Torr 
to decrease the temperature of the substrate to 30.degree. C. for about 15 
minutes. 
Characteristics 
The photosensitive members obtained in Examples 3 to 20 have almost the 
same characteristics as that in Example 1. From these results, it can be 
understood that the photosensitive member having an overcoat layer of the 
present invention achieves durability without loss of image quality, and 
that it particularly provides superior performance in regard to moisture 
resistance after printing. The results of evaluations for each Example are 
shown in Table 1. 
COMATIVE EXAMPLES 1 AND 2 
Overcoat layers were formed on an Se-As photosensitive member (Comparative 
Example 1) and an Se-Te photosensitive member (Comparative Example 2) as 
per Examples 1 and 2 except for omitting the inflow of hydrogen sulfide 
gas. 
The overcoat layers obtained in Comparative Examples 1 and 2 exhibited poor 
moisture resistance after printing as shown in Table 1 due to the absence 
of chalcogen atoms, thus confirming their impracticality. 
COMATIVE EXAMPLES 3 AND 4 
Overcoat layers were formed on an Se-As photosensitive member (Comparative 
Example 3) and an Se-Te photosensitive member (Comparative Example 4) as 
per Examples 3 and 4 except for omitting the inflow of perfluoropropylene 
gas. 
The overcoat layers obtained in Comparative Examples 3 and 4 exhibited poor 
moisture resistance after printing as shown in Table 1 due to the absence 
of halogen atoms, thus confirming their impracticality. 
COMATIVE EXAMPLES 5 AND 6 
Overcoat layers were formed on an Se-As photosensitive member (Comparative 
Example 5) and an Se-Te photosensitive member (Comparative Example 6) as 
per Examples 1 and 2 except for omitting the inflow of carbon 
tetrafluoride gas and hydrogen sulfide gas. 
The overcoat layers obtained in Comparative Examples 5 and 6 exhibited poor 
moisture resistance after printing as shown in Table 1 and produced image 
drift under high temperature conditions prior to use in resistance tests 
due to the absence of chalcogen atoms and halogen atoms, thus confirming 
their impracticality. 
TABLE 1 
__________________________________________________________________________ 
Ex 
(1) 
(2) (3) (4) (5) (6) (7) 
(8) 
(9) 
(10) 
No 
sccm 
sccm sccm sccm sccm sccm .degree.C. 
Torr 
.degree.C. 
min 
__________________________________________________________________________ 
3 
300 
C.sub.3 H.sub.6 
30 
C.sub.3 F.sub.6 
90 
H.sub.2 Se 
4 
-- -- 
-- -- 
-- 
0.5 
50 20 
4 
300 
C.sub.3 H.sub.6 
30 
C.sub.3 F.sub.6 
90 
H.sub.2 Se 
4 
PH.sub.3 
2 -- -- 
-- 
0.5 
50 20 
5 
300 
C.sub.4 H.sub.6 
30 
CF.sub.4 
90 
B.sub.2 H.sub.6 
3 
-- -- 
-- -- 
-- 
0.5 
120 
20 
6 
300 
C.sub.4 H.sub.6 
30 
CF.sub.4 
90 
B.sub.2 H.sub.6 
3 
PH.sub.3 
2 -- -- 
-- 
0.5 
50 20 
7 
300 
C.sub.3 H.sub.6 
30 
C.sub. 3 F.sub.6 
90 
-- -- 
-- -- 
(CH.sub.3).sub.3 
4 65 
0.5 
50 20 
Al 
8 
300 
C.sub.3 H.sub.6 
30 
C.sub.3 F.sub.6 
90 
-- -- 
PH.sub.3 
2 (CH.sub.3).sub.3 
4 65 
0.5 
50 20 
Al 
9 
300 
C.sub.4 H.sub.6 
30 
CF.sub.4 
90 
CO.sub.2 
20 
-- -- 
-- -- 
-- 
0.5 
120 
20 
10 
300 
C.sub.4 H.sub.6 
30 
CF.sub.4 
90 
CO.sub.2 
20 
PH.sub.3 
2 -- -- 
-- 
0.5 
50 20 
11 
300 
C.sub.3 H.sub.6 
30 
C.sub.3 F.sub.6 
90 
O.sub.2 
10 
-- -- 
-- -- 
-- 
0.5 
50 20 
12 
300 
C.sub.3 H.sub.6 
30 
C.sub.3 F.sub.6 
90 
O.sub.2 
10 
PH.sub.3 
2 -- -- 
-- 
0.5 
50 20 
13 
300 
C.sub.4 H.sub.6 
30 
CF.sub.4 
90 
N.sub.2 
20 
-- -- 
-- -- 
-- 
0.5 
120 
20 
14 
300 
C.sub.4 H.sub.6 
30 
CF.sub.4 
90 
N.sub.2 
20 
PH.sub.3 
3 -- -- 
-- 
0.5 
50 20 
15 
300 
C.sub.3 H.sub.6 
30 
C.sub.3 F.sub.6 
90 
NH.sub.3 
10 
-- -- 
-- -- 
-- 
0.5 
50 20 
16 
300 
C.sub.3 H.sub.6 
30 
C.sub.3 F.sub.6 
90 
NH.sub.3 
10 
PH.sub.3 
2 -- -- 
-- 
0.5 
50 20 
17 
300 
C.sub.4 H.sub.6 
30 
CF.sub.4 
90 
SiH.sub.4 
3 
-- -- 
-- -- 
-- 
0.5 
120 
20 
18 
300 
C.sub.4 H.sub.6 
30 
CF.sub.4 
90 
SiH.sub.4 
3 
PH.sub.3 
3 -- -- 
-- 
0.5 
50 20 
19 
300 
C.sub.3 H.sub.6 
30 
C.sub.3 F.sub.6 
90 
GeH.sub.4 
4 
-- -- 
-- -- 
-- 
0.5 
50 20 
20 
300 
C.sub.3 H.sub.6 
30 
C.sub.3 F.sub.6 
90 
GeH.sub.4 
4 
PH.sub.3 
2 -- -- 
-- 
0.5 
50 20 
__________________________________________________________________________ 
Ex (11) 
(12) 
(13) 
(14) 
(15) 
(16) 
(17) 
(18) 
(19) (21) 
No mm watt 
min 
.mu.m 
KHz 
at. % 
at. % 
at. % 
at. % 
(20) 
.mu.m 
__________________________________________________________________________ 
3 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
Se 
1.9 
-- 
-- 
A 50 
330 
4 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
Se 
1.9 
P 0.5 
B 50 
330 
5 80 .times. 
160 
2 0.2 
70 
45 F 3.7 
B 0.8 
-- 
-- 
A 50 
330 
6 80 .times. 
160 
2 0.2 
70 
45 F 3.7 
B 0.8 
P 0.6 
B 50 
330 
7 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
Al 
2.5 
-- 
-- 
A 50 
330 
8 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
Al 
2.5 
P 0.5 
B 50 
330 
9 80 .times. 
160 
2 0.2 
70 
45 F 3.7 
O 1.4 
-- 
-- 
A 50 
330 
10 80 .times. 
160 
2 0.2 
70 
45 F 3.7 
O 1.4 
P 0.9 
B 50 
330 
11 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
O 0.8 
-- 
-- 
A 50 
330 
12 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
O 0.8 
P 0.5 
B 50 
330 
13 80 .times. 
160 
2 0.2 
70 
45 F 3.7 
N 1.2 
-- 
-- 
A 50 
330 
14 80 .times. 
160 
2 0.2 
70 
45 F 3.7 
N 1.2 
P 0.9 
B 50 
330 
15 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
N 1.0 
-- 
-- 
A 50 
330 
16 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
N 1.0 
P 0.5 
B 50 
330 
17 80 .times. 
160 
2 0.2 
70 
45 F 3.7 
Si 
3.7 
-- 
-- 
A 50 
330 
18 80 .times. 
160 
2 0.2 
70 
45 F 3.7 
Si 
3.7 
P 0.8 
B 50 
330 
19 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
Ge 
4.6 
-- 
-- 
A 50 
330 
20 80 .times. 
200 
2 0.25 
125 
45 F 2.7 
Ge 
4.6 
P 0.5 
B 50 
330 
__________________________________________________________________________ 
TABLE 2 
______________________________________ 
No. Copies 
No. Copies 
No. Copies 
No. Copies 
Example 10,000 50,000 100,000 250,000 
______________________________________ 
Ex. 1 O O O O 
Ex. 2 O O O O 
Ex. 3 O O O O 
Ex. 4 O O O O 
Ex. 5 O O O O 
Ex. 6 O O O O 
Ex. 7 O O O O 
Ex. 8 O O O O 
Ex. 9 O O O O 
Ex. 10 O O O O 
Ex. 11 O O O O 
Ex. 12 O O O O 
Ex. 13 O O O O 
Ex. 14 O O O O 
Ex. 15 O O O O 
Ex. 16 O O O O 
Ex. 17 O O O O 
Ex. 18 O O O O 
Ex. 19 O O O O 
Ex. 20 O O O O 
Com. Ex. 1 
O .DELTA. X X 
Com. Ex. 2 
O .DELTA. X X 
Com. Ex. 3 
.DELTA. X X X 
Com. Ex. 4 
X X X X 
______________________________________