JPS63223656A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain a photosensitive body having high charge transfer characteristic, electrifiability, and sufficient surface potential even if the photosensitive body has a small film thickness of carbon film used therein by using carbon film contg. a specified amt. of H and modified with an element of the group IIIA or VA of the periodic table, and N atom or O atom, in a charge transfer layer. CONSTITUTION:In a function separating type photosensitive body constituted of a charge generating layer 3 and a charge transfer layer 2, carbon film contg. 0.1-67atom.% H basing on total atoms and modified with an element of the group IIIA or VA, and N atom or O atom, is used for the charge transfer layer 2. The specific resistance of a hydrocarbon type org. polymer film is reduced if an appropriate amt. of an element of the group IIIA or VA is added to the film as a chemical modifier. Moreover, exhibition of suitable charge transfer characteristic begins also by the addition. P-type charge transfer characteristic is exhibited by the addition of an element of the group IIIA, and N-type charge transfer characteristic is exhibited by the addition of an element of the group VA. In addition to the element of the group IIIA or VA, a trace amt. of N atom or O atom is added. Thus, the increase of dark attenuation with the lapse of time is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoreceptor having a carbon thin film as a charge transport layer.

BACKGROUND OF THE INVENTION Since the invention of the Carlson method, the application field of electrophotography has continued to make remarkable progress, and various materials have been developed and put into practical use for electrophotographic photoreceptors.

The main electrophotographic photoreceptor materials conventionally used include inorganic substances such as amorphous selenium, selenium arsenide, selenium tellurium, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine,
Cr such as disazo pigments, trisazo pigments, perylene pigments, triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, sudyryl compounds, pyrazoline compounds, oxazole compounds, oxadiazole compounds, etc.
Mechanical substances can be mentioned.

In addition, the structure includes a single layer structure in which these substances are used in the form of 91 bodies, a binder structure in which these substances are dispersed in a binder, and a charge generation layer and an electric charge transport layer are provided for each function. Laminated type (I is a structure, etc.)

However, the conventionally used electrophotographic photoreceptor materials each have drawbacks.

One of the problems is that they are harmful to the human body, but inorganic materials other than the amorphous silicon described above have unfavorable properties.

In addition, in order for an electrophotographic photoreceptor to be actually used in a copying machine, it must always maintain stable performance when exposed to harsh environmental conditions such as charging, exposure, development, transfer, neutralization, and cleaning. However, the above-mentioned A-type materials lacked durability and had many unstable factors in terms of performance.

In order to solve such problems, in recent years, photoreceptors, especially electrophotographic photoreceptors, have been manufactured using amorphous silicon (hereinafter referred to as a-S i Approximately four have been adopted.

The a-Si photoreceptor has various excellent properties. But a
-Si has a large relative dielectric constant ε of about 12, so in order to obtain a sufficient surface potential as a photoreceptor, essentially at least 25
There is a problem in that a film thickness of approximately μm is required. a-5
I photoreceptors require a long time to manufacture due to the slow deposition rate of the film in plasma CVD, and it is difficult to form a homogeneous film.
The longer the preparation time, the more difficult it becomes to obtain -3i.

As a result, the A-8i photoreceptor has drawbacks such as a high probability of image defects such as white spot noise occurring by about 1°, and high raw material costs.

Although various attempts have been made to improve the above drawbacks, it is essentially not desirable to make the film thinner than this.

On the other hand, the a-Si photoreceptor also has drawbacks such as poor adhesion between the substrate and a-9i, as well as poor corona resistance, environmental resistance, and chemical resistance.

In order to solve such problems, it has been proposed to provide an organic plasma polymerized film as an overcoat layer or undercoat layer of the A-8I photoreceptor. An example of the former is
For example, JP-A-59-214859, JP-A-51
-46130, JP-A-50-20728, etc. are known, and examples of rear units are, for example, JP-A-60
-63541, JP 59-136742, JP 59-38753, JP 59-281
61, Japanese Patent Laid-Open No. 56-60447, etc. are known.

The plasma polymerized film can be prepared from all kinds of organic compound gases such as ethylene gas, benzene, and aromatic compounds (for example, Ni, T, Bell (A, T, r3c)
ll), M, 5hen, et al., Journal of Applied Polymer Science (Jou
rnal orApplied Polymer 5c
17, pp. 885-892 (1973
However, organic plasma polymerized films prepared by conventional methods are used only for applications that require insulation. Therefore, these films were considered to be insulating films, or at least were used with the understanding that they were such films, with an electrical resistance on the order of 64-Ωcm, like ordinary polyethylene films. .

On the other hand, in recent years, thin films of diamond-like carbon have been proposed in the semiconductor field, but nothing is known about their charge transport properties.

The technique described in Japanese Patent Application Laid-Open No. 60-61761 discloses a photoreceptor coated with a diamond-like carbon insulating film having a thickness of 500 to 2 μm as a surface protective layer.

This carbon thin film is intended to improve the corona discharge resistance and mechanical strength of the a-Si photoreceptor. The polymer membrane is very thin, and charges move through the membrane through the tunnel effect, so the membrane itself does not require charge transport ability. In addition, there is no mention of the carrier transport properties of (f-machine plasma polymerized membrane),
- It does not solve the above-mentioned essential problems of Si.

JP-A-59-214859 discloses a technique in which an organic hydrocarbon monomer such as styrene or acetylene is coated as an overcoat layer with a thickness of about 5 μm by plasma polymerization. This improves peeling, durability, pinholes, and production efficiency of a-Si photoreceptors. There is no mention of the carrier transport properties of the a-machine plasma polymerized membrane, and there is no way to solve the above-mentioned essential problems of a-Si.

JP-A No. 51-46130 discloses that an organic hydrocarbon monomer such as styrene or Ediref is applied to a poly-N-onylcarbazole-based organic optical semiconductor to a thickness of 3 μm on the surface by a gas discharge. Discloses a photoreceptor on which a FR machine plasma polymerized film of 0.001 μm is formed. The purpose of this technology is to make it possible to use a poly-N-vinylcarbazole photoreceptor, which could only be used with positive charging, with bipolar charging.

This film is very thin at 0.001 to 3 μm and is used as a protective film like an overcoat. It is thought that the polymeric membrane is very thin and does not require charge transport ability. Also,
There is no description whatsoever regarding the carrier transportability of the polymer membrane, and it does not solve the above-mentioned essential problems of a-Si.

JP-A No. 50-20728 discloses a sensitizing layer on a substrate,
Has a technology been disclosed in which an organic photoconductive electrical insulator is sequentially laminated, and a glow discharge polymer film with a thickness of 0.1 to 1 μm is formed thereon? It has a protective purpose and is used as an overcoat.

'HQ composite gold film is always thin and does not require charge transport ability.

Unfortunately, there is no description whatsoever regarding the carrier transport properties of the polymer membrane, and it does not solve the above-mentioned essential problems of a-8i.

JP-A No. 60-635.11 discloses a photoreceptor using a diamond-like film of 200 to 2 μm in the undercoat layer of a-9i, but the pattern is similar to that of a substrate and a-Si. The purpose is to improve adhesion. The polymeric membrane can be very thin, and charges move through the membrane by tunneling.

Japanese Patent Application Laid-open No. 59-136742 discloses that about 5μ
A semiconductor device is disclosed in which an organic plasma polymerized film of m and a silicon pattern are sequentially formed. However, although the purpose of this organic plasma polymerized film is to prevent diffusion of aluminum, which is a substrate, into a-Si, there is no description of its manufacturing method, film quality, etc. Furthermore, there is no mention of the carrier transport properties of the TZ machine plasma polymerized membrane, and a
- It does not solve the above-mentioned essential problem of Si.

JP-A-59-28161 discloses a photoreceptor in which a T machine plasma polymerized film and a-St are sequentially formed on a substrate. It is a layer that functions as a blocking layer, an adhesive layer, or an anti-peel layer.The polymer film can be very thin, and the electrons move through the film due to the tunneling effect, and the film itself is capable of charge transport. In addition, there is no description of the carrier transport properties of organic plasma polymerized films, and there is no way to solve the above-mentioned essential problems of a-Si.

JP-A No. 59-38753 discloses that 10 to 100
Form a plasma-polymerized thin model of a human being, and a-3
A technique for forming an i-layer has been disclosed. The Tr machine plasma polymerized film is an undercoat layer that takes advantage of its insulating properties, and functions as a blocking layer or a peeling prevention layer. The polymer film is very thin, and charges move through the film due to the tunnel effect, and the film itself does not require charge transport ability.Also, there is no description of the carrier transport property of the fi machine plasma polymerization model. a −S i has 1
It does not solve the essential problem described in 1η.

] As mentioned above, conventionally, it has been proposed to use an insulating FT machine plasma layer or diamond-like film for the overcoat layer or undercoat layer, but the transfer of charge by them is fundamentally This is due to the tunnel effect and electrical breakdown phenomenon.

That is, the tunneling effect occurs when the thickness of the insulating layer is extremely small (generally on the order of angstroms), and electrons pass through the insulating layer.

On the other hand, electrical breakdown occurs when a small amount of charge carriers in a layer are accelerated by an electric field and acquire enough energy to ionize atoms of the insulator, and the ionization increases the number of carriers and the same process repeats. This is a phenomenon of increasing shear of carriers according to the mouse formula, which occurs in the case of extremely high electric fields (generally 100 V/μs or more).

For example, in the case of a photoreceptor structure in which an insulator and a semiconductor are laminated,
Charges generated in a semiconductor travel through the film due to the electric field, but cannot pass through the insulator at low electric fields. When the insulating layer is thin, this can be ignored as a surface level of 1111, or the influence on the so-called development characteristics in electrophotography is extremely small, so the deterioration of characteristics due to the presence of the insulating layer is not a problem. Next, consider the effects of repeated use. Charges accumulate in the insulating layer due to repeated use, but the high electric field (for example, 100V/μ1 or more) caused by the accumulated charges actually causes
F! ,,! Once the voltage is set, no further electric field will be applied due to electrical breakdown.

For example, when an insulating material that causes electrical dielectric breakdown at 100V/7zx is laminated to a thickness of 0.1 μm, the increase in so-called residual potential due to the insulating layer is only IOV even when repeated.

For the following reasons, when a general insulating material is used for the photoreceptor, the film thickness must be approximately 5 μm or less. Otherwise, the residual potential due to the insulating layer is −1,,′J
j! or more than 500V, causing fog in the copied image,
It becomes unusable.

Manoko JP-A-54-145540 discloses a technique for incorporating carbon as a chemical modifier into a silicon and/or germanium photoconductive layer, but the carbon content is between 0.1 and 30at0111iC. %(below,
atm, not written as %), and such a carbon film! 11 is in the direction of dark resistance, but it results in low sensitivity.

As mentioned above, conventionally used for photoreceptors (single-polymer films were used as undercoat layers or overcoat layers, but they require a carrier transport function. It is a 6-layer polymer film that does not have an insulating property, and is used based on the judgment that it is insulating.Therefore, its thickness is at most 5.
It is used only as an extremely thin film of the order of μ, and carriers pass through the film through the tunnel effect, or if the tunnel effect cannot occur, it is thin enough that it does not pose a problem as a practical residual potential. Used only in membranes.

While considering the application of the FF polymer film to an a-Si photoconductor, the inventors found that the 6-mer polymer film, which was originally thought to be insulating, had a certain hydrogen content and became electrically conductive. It was discovered that the resistance decreased and the material began to exhibit charge transport properties.

By utilizing this new knowledge, the present invention solves all the problems of the conventional A-8I photoreceptor, including problems with the A-Si film thickness, manufacturing time, manufacturing cost, etc. In addition, the present invention is applicable to photoreceptors using organic polymer films, especially organic plasma/R gold films, which have completely different properties and purpose of use than conventional photoreceptors. As a 1fA transport layer, it is possible to use a hydrogen-containing carbon film which has excellent charge transport ability, has a small residual potential even when the film IIl is 5 μm or more, and has excellent physical properties.

A further object of the present invention is to improve charge transport properties of 1:1 when this hydrogen-containing carbon film (1) is used as a charge transport layer.
The aim is to prevent the increase in attenuation over time and to improve its stability.

Means for Solving the Problems The present invention combines a charge generation layer (3) and a charge transport layer (2) in a functionally separated photoreceptor.
is a carbon film modified with an element of group 111A of the periodic table or an element of group VA, and a nitrogen atom or an oxygen atom, and containing hydrogen in an amount of 0'' to G7 atomic% based on the total atoms. Regarding the photoconductor 4-ro.

In order to be used as an electrophotographic photoreceptor, the laminated charge generation layer and charge transport layer must have a dark resistance of 108 Ωcm or more and a light-dark resistance ratio (i.e., gain) of 10" to 10.
’ degree is required.

The photoreceptor of the present invention is composed of at least a charge generation layer and a charge transport layer, and the charge transport layer includes at least one carbon layer containing hydrogen (hereinafter referred to as RA-C charge transport layer) The a-C charge transport layer is characterized by containing an element of group 111A or group VA of the periodic table, and a nitrogen atom or an oxygen atom, and adding 'tri' to the above characteristics. The hydrogen content in the a-C charge transport layer preferred for the present invention is O11 to 67aioIlic% (hereinafter referred to as atm,
(not written as %), preferably 1 to 60 atm, %, more preferably 30 to 60 atm.

%. If it is smaller than 0, l atm,%, it will not be possible to obtain a dark resistance suitable for electrophotography, leading to a decrease in charging ability, and (
If it is larger than i7 atm, %, the charge transport ability will be lowered, resulting in lower sensitivity and further deterioration in film formability.

The hydrogen-containing carbon film in the present invention has hydrogen content m ・1
It becomes amorphous or diamond-like depending on the shape and manufacturing method. In most cases, it takes an amorphous form, and the film itself is rich in three-dimensional crosslinks, hard, and has high resistance. On the other hand, when the manufacturing method and conditions obtained, for example, the plasma CVD method, the hydrogen content is reduced to about 4 oatm, % or less, it is possible to form a carbon film that is gradually close to a diamond shape, and such a film has a Vickers hardness. 2 (extremely hard, more than 100 -1-, and the electrical resistance is north of +0 BΩcm. However,
The carbon film also showed high charge transport properties.

The hydrogen content and structure in the a-C charge transport layer of the present invention can be determined by elemental analysis, infrared absorption spectrum, X-ray diffraction, 'II
- It can be determined by NMR or "C-NMrt".

The photoreceptor of the present invention further contains a Group 111 A element or a Group VA element oxygen or nitrogen atom as a chemical modifier in the electron transport layer.

The hydrocarbon-based hexagonal polymer film was originally thought to be insulating, but as a chemical modifier it
By adding a group element or a group VA element, the specific resistance decreases, and furthermore, it begins to show suitable charge transport properties, and the
By adding group 11A elements, type 1) charge transport properties can be improved to type V
Addition of group A elements shows N-type charge transport properties at 4°. The reason for this is not necessarily clear, but electrons with relatively unstable energy states trapped in the charge generation layer, such as π electrons, unpaired electrons, residual free radicals, etc.
The polarization caused by the incorporation of group A or group VA elements is likely due to changes in the steric structure, etc., which effectively improves charge transport properties.
It is presumed that it was for the purpose of doing so. Separately, the presence of Group IIIA or Group VA elements in the gas phase of the plasma reaction state changes the reaction state, for example, the active species (radicals, ions, etc.) generated by the decomposition of the source gas. It is also presumed that the density of electrons in a relatively unstable energy state in the produced film increased due to a change in the abundance ratio, a change in the dehydrogenation reaction due to group IIIA or group VA elements, or the like.

Furthermore, in the state where no nlA group or VA group elements are added, the polymerization model tends to cause a decrease in transport properties as time passes after film formation, but when nlA group or VA group elements are added as chemical modifiers, By doing so, the electric charge f of the charge transport layer: η
It has been found that transportability is stably ensured without deterioration over time. Furthermore, the addition of Group IIIA or Group VA elements guarantees suitable potential attenuation in the bright attenuation characteristics in the low electric field region of the photoreceptor, and lowers the so-called L I) C base to low (
However, we have found that there is an effect that can suppress the generation of residual potential. Furthermore, it has been found that the addition of an IuA group or VA group element improves the film formation rate, which is essential in creating a charge transport layer that requires a certain level of film thickness.

On the other hand, when only group IIIA or VA elements were added, the dark decay increased over time in addition to the above-mentioned characteristics. It has been found that by adding a minute amount of nitrogen or oxygen atoms in addition to group elements, it is possible to prevent the increase in dark decay over time without impairing the above characteristics.

Contained as a chemical modifier in the present invention
The spear of Group A or Group VA elements is 5 for all constituent atoms.
0000 atm, ppm or less, preferably 1000~
50000 atm, ppm, more preferably 5000~
200 (l Oatm, ppm).

[9 of Group 11A or Group VA elements is 50,000 atm
, pp+n, the impurity level increases, leading to a decrease in electrical performance. On the other hand, [[A group color is V
If the layer does not contain any Group A elements, for example, if the Group ■Δ elements or Group VA elements are so small that they cannot be detected by Auger analysis, the charge transport properties of the charge transport layer are insufficiently improved.

In the present invention, Group 111A elements and Group VA elements should not be added at the same time; if the charge transport layer is desired to be used as a film having P-type transport characteristics, a Group 111A element should be added and N-type elements added. If you want to use the transport properties as a kerosene membrane, you should add 4'' of Group VA base.

In the present invention, the amount of oxygen atoms contained as a chemical modifier is 7 arm, % or more, and optimally 4,7 atm, % or less based on the total constituent atoms. 7 oxygen atoms
aun,%, the charge transport property cannot be sufficiently improved. On the other hand, if it does not contain any oxygen atoms, for example, it is oxygen-free to the extent that oxygen is not detected by Auger analysis. In this case, it is not possible to improve the dark decay characteristic, which increases over time, by adding an element of the NlA group or the VA group.

Nitrogen atoms are 5 atm,% of all nitrogen atoms.
Below F, preferably 3°9 ATM, including RF of 3.9% or less.

Even if the amount of nitrogen atoms is more than 5 atm.%, or if the amount of nitrogen atoms is so small that it cannot be detected by Auger analysis, the same problem as with oxygen atoms will occur.

The nitrogen source r and the oxygen atoms may be added at the same time, and in that case, both atoms may be added in such a way that the amount of each atom added does not exceed the above-mentioned range.

Here, carbon atoms, hydrogen atoms in the a-C layer according to the present invention,
The il of nitrogen atoms and oxygen atoms, Group IIIA or Group VA elements can be determined by conventional methods of elemental analysis, for example (by using f@ elemental analysis, Auger analysis, etc.). Although the charge transport layer does not have clear photoconductivity for visible light or light near the emission wavelength of a semiconductor laser, it stably provides suitable charge transport properties, and also has good charging ability and durability. It has excellent photoreceptor performance such as weather resistance and environmental pollution resistance, and it also has excellent light transmittance, so it provides an extremely high degree of freedom especially when forming a laminated structure as a functionally separated photoreceptor. It is a thing.

The a-C charge transport layer of the present invention preferably has an optical energy gear Egopt of 1.5 to 3. It is preferable that the OeV, 19 and relative permittivity ε be in the range of 2.0 to 6.0.

It is considered that a film with a small 1>gopL (<1.5 eV) forms many degrees near the band edge, that is, at the lower end of the conduction band or the upper end of the filling band. Therefore, such a-C
Since the charge transport layer has a low carrier mobility and a short carrier life, it may not necessarily be sufficient as a charge transport layer for a photoreceptor. A model with a large EgOpt (>3.0 eV) has a large EgOpt value (>3.0 eV), which is easy to form a barrier with the charge generating material and transport material used in electrophotography. Injection of carriers from the material and the transport material into the a-C charge transport layer with large ■εgopt may not be successful, and as a result, good photoreceptor properties may not be obtained.

On the other hand, if the relative dielectric constant is greater than 6.0, the charging ability will deteriorate and the sensitivity will also deteriorate. Of course, in order to improve this, it may be possible to increase the thickness of the a-C charge transport layer.
Undesirable. The reason why ε is set to 2° or more is because if it is less than that, the physical properties become polyester-like and the charge transport ability decreases.

Iεgopt and ε have a relatively good correlation with the hydrogen content fl in the aC charge transport layer when the hydrogen content fl is low. On the other hand, when the hydrogen content is high, there is a change in the correlation compared to when it is low. This is considered to be because 'I gopt and ε, especially ε, are greatly influenced by the structural characteristics of the aC charge transport layer.

The charge generating layer used in the photoreceptor according to the present invention is not particularly limited and includes, for example, amorphous selenium, selenium arsenide, selenium telluride, cadmium sulfide, zinc oxide, and optionally different elements (such as hydrogen, boron, etc.) to change the properties. carbon, nitrogen,
Inorganic substances such as amorphous silicon containing (oxygen, fluorine, phosphorus, sulfur, chlorine, bromine, germanium, etc.), polyvinyl carbazole, cyanine compounds, phthalonanine compounds, azo compounds, perylene compounds, triaryl Methane compounds, triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, oxanone compounds, oxadiazole compounds, thiazine compounds, xanthene compounds,
Organic substances such as pyrylium compounds, quinacridone compounds, indigo compounds, polycyclic quinone compounds, disbenzimidazole compounds, induthrone compounds, and squarylium compounds can be used.

Other materials can be used as long as they absorb light and generate charge carriers with extremely high efficiency.

As will be described later, the charge generation layer may be provided at any position on the photoreceptor, for example, it may be provided at any of the top layer, bottom layer, and intermediate layer. The layer thickness depends on the type of material, especially its spectral absorption characteristics, exposure light source, purpose, etc., but is generally set so that it absorbs 90% or more of light of 555 nm. For example, in the case of a-9i:)I, it is about 0.1 to 1 μm.

In the a-C charge transport layer of the present invention (7), some of the hydrogen present may be replaced with halogen, such as fluorine, chlorine, bromine, etc. Such a film has improved water repellency and abrasion resistance. Ru.

For normal electrophotography, the η thickness of the a-C charge transport layer is 5 to 5.
The thickness may be 0 μm, especially 7 to 20 μm, but if it is thinner than 5 μm, the charging ability will be low and sufficient density of the copied image cannot be obtained. If it is thicker than 50 μm, it is not preferable in terms of productivity.

This a-C charge transport layer has light transmittance, high dark resistance, and rich ITi charge transport properties, and has a film thickness of 5 μm as described above.
Therefore, carriers can be transported without causing charge traps.

The charge transport layer a-C of the present invention is formed by a method of forming via an ionic part such as ionization vapor deposition or ion beam vapor deposition, a method of forming via a plasma state such as a direct current, high frequency, low frequency, or microwave plasma method, or a low pressure CVD method. , a vacuum evaporation method, a -sputtering method, a method of forming from neutral particles such as a photo-CVD method, or a combination thereof. However, for example, when the charge generation layer is formed by high-frequency plasma or CVD, it is preferable to form the a-C charge transport layer by the same method, as this leads to savings in manufacturing equipment cost and process labor.

The organic compound for forming the a-C layer does not necessarily have to be in a gas phase (1. If it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure, it can be in a liquid phase or a solid state. Can be used in tandem.

As the hydrocarbon, for example, methane series hydrocarbons, ethylene series hydrocarbons, acetylene series hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc. may be used.

Methane group hydrocarbons include, for example, methane, -thane, propane, butane, pentane, hexane, heptane,
Octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, tocosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octadecane, nonacosane, triacosane, dotriacosane, pentatria Normal paraffins such as contane, isobutane, isopentane, neopentane, isohexane, neohexane, 2,3-dimethylbutane, 2
-Methylhexane, 3-ethylpenkune, 2,2-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpenkune, tributane, 2-methylhebutane, 3
-Methylhebutane, 2.2-dimethylhexane, 2.2
．． 5-methylhexane, 2,2.3-trimederpentane, 2,2.4-)dimethylbentane, 2,3.3-
- Isoparaffins such as trimedelpentane, 2,3,4-trimethylpentane, isonanone, etc. may be used.

Examples of ethylene series hydrocarbons include ethylene, bu[
! Pyrene, isobutylene, 1-butene, 2-butene,!
-Pentene, 2-pentene, 2-methyl-1-butene,
3-methyl-1-butene, 2-medy-2-butene, l
-hexene, tetramethylethylene, l~heptene, l
- Reffins such as octene, l-nonene, l-decene, and diolefins such as allene, methylalene, butadiene, pentadiene, hexadiene, cyclopentadiene, [2] and ocimene, allocimene, myrcene, hexatriene, etc. Triolefin, etc. are used.

Examples of acetylenic hydrocarbons include acetylene,
Methylacetylene, l-butene, 2-butyne, l-bendine,! -Hexyne, 1-heptine, l-octene, 1
~nonine, l-decyne, etc. are used.

Examples of ring hydrocarbons include cyclopropane, cyclobutane, cyclopencune, cyclohexane, cyclohebutane, cyclooctane, Schiff [J nonane, cyclodecane, cycloundecane, Schiff [1 dodecane, cyclotrideca, cyclotetradecane, cyclopentadecane,
Cycloparaffins such as cycloundecane, cycloolefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, tsuku[1-decene], limonene, terbirun, phelandrene, silvestrene, thuene, karene, and pinene. , Bornilev, Canhuen,
Terpenes such as fuenchen, cyclofenchen, tricyclene, pizzaborev, zingiberev, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, kanholev, phya-klaten, bodocarbrene, milev, and steroids are used. reactor.

Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene,
Propylbenzene, cumene, styrene, biphenyl, terphenyl, diphenylmethane, triphenylmethane,
Dibenzyl, methylben, isothene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

As carrier gas, IL, Ar, Ne 11ie
etc. are appropriate.

Forming a-C charge transport layer using plasma method etc.'4°
During filtration, hydrogen-containing rTfft was 40atl11. % or less, it is preferable to use a raw material prepared by relaxing a saturated hydrocarbon with hydrogen. Particularly preferred saturated hydrocarbons are methane, ethane, propane, butane and the like. The pressure inside the reactor is low and the process is performed at high voltage. The conditions for forming a diamond-like carbon film by a plasma method or an ion beam method are described in, for example, the Journal of Applied Physics (J, Δpp1. Phys.) 1 point (10) Oct.! 981゜No. 6151-61
It is described on page 57. The method for producing LaLaron diamond-like carbon is not limited to this, and may be formed by a sputtering method or the like.

Since diamond-like carbon has excellent wear resistance and moisture resistance, a charge transport layer containing diamond-like carbon may be disposed on the surface side.

Further, when provided on the substrate side, charge injection is suppressed. Also, when forming a charge generation layer on this using high frequency plasma,
It has advantages such as preventing plasma damage.

As mentioned above, the a-C charge transport layer may be made of amorphous carbon, in which case the hydrogen content is 40 to 67 aLm,%.
It is. Such an amorphous carbon layer can be formed by diluting an unsaturated hydrocarbon such as edgeleaf, butadiene, acetylene, propylene, etc. with hydrogen and using a plasma discharge or ion beam method.

The internal pressure of the reactor during plasma discharge is higher than in the case of diamond-like carbon membranes, and the voltage is lower.

When amorphous carbon is used as a charge transport layer in combination with an a-Si charge generation layer, a photoreceptor with better charging ability and sensitivity than a single a-8g layer can be obtained. By arranging it, it acts as a charge injection prevention layer.It also improves surface hardness, printing durability, moisture resistance, corona resistance, and adhesion.

In the present invention, a compound of an element of Group IIA of the Periodic Table is used to add an element of Group ■Δ of the Periodic Table to the a-C film. Here, elements of group 1 [IA of the periodic table] refer to boron atoms (3), aluminum (AQ) atoms, gallium (Ga) atoms, and indium atoms (In).

The phase state of these Group 1IIA element compounds of the periodic table is not necessarily a gas phase at room temperature and normal pressure;
In addition, since there are only a few compounds in the gas phase, if the compound can be vaporized by melting, evaporating, raising 71%, etc. by heating or reducing pressure, it can be used in the same phase as the liquid phase.

Compounds containing Natsu 3 that can be used in the present invention include 1 ((
OCtll s)3, o211s, [3Ci23, nn
n,,13F.

etc. are exemplified.

Compounds containing A12 include A12 (Oj C311
t)*, (C113)-ΔQ, (C,ll 5)3A
(!, (+ Cal1g)3AQ, A I2CQ 3
etc. are exemplified.

As a compound containing Ga, Ga(Oi-C311?)3
, (C113)3ea, (Czlls)+Ga, c
Examples include acI2ff and Ga1lr3.

[Compounds containing n include I n (Oi 03H7)
3, (Czlls)3E n, etc. are exemplified.

In the present invention, it is contained as a chemical modifier.
The amount of Group 1A elements is mainly determined by the plasma reaction -) Introduction of the Group 111A element compounds described above into the reaction chamber! It can be controlled by increasing or decreasing n.

By increasing the amount of the Group 1IIA element introduced, it is possible to increase the amount of the Group 1TIA element added to the a-C film by 3. 1) By reducing the amount of the Group 1A element compound introduced, it is possible to lower the amount of the Group 1IIA element added to the a-C film according to the present invention.

In the present invention, in order to add elements from groups V7 to V7 of the periodic table into the a-C film, a compound containing elements from group VA of the periodic table is used. The element refers to a phosphorus atom (P), an arsenic (As) atom, an antimony (Sb) atom, and a bismuth atom (ni).

The phase state of these Group VA element compounds of the periodic table does not necessarily have to be a gas phase at room temperature and normal pressure, and rather there are few compounds in a gas phase, so they can be melted, evaporated, or evaporated by heating or reduced pressure. If it can be vaporized through sublimation or the like, it can be used in a solid phase rather than in a liquid phase.

Examples of Group VA elements of the periodic table that can be used in the present invention include the following.

I] as compounds containing P O(OCH3)3, (
C,11,)3P,13113,POCl23,PF3
, PF5.1) Cff, r”, I'CILF3, PC1
23, PI3r3, etc.; As a compound containing As
[13, A s CQ 3, Δsnr,, A s F3
, Ashs, ASC(!3, etc.: Sb (OCyll 5) 3.5bCC3, Sb t as a compound containing Sb
[3, SbF3.5bCIL etc. are exemplified.

In the present invention, the amount of the VA group element contained as a chemical modifier can be adjusted as in the case of the nlA group element.

In the present invention, an oxygen compound is used to add oxygen atoms into the a-C film. The phase state of the oxygen compound does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. be. Examples of oxygen compounds include oxygen, ozone, water (steam), hydrogen peroxide, -carbon oxide, carbon dioxide, carbon suboxide, -nitrogen oxide, nitrogen dioxide, dinitrogen trioxide, dinitrogen trioxide, and trioxide. Inorganic compounds such as nitrogen, hydroxide (
-0If), aldehyde group (-COH), acyl J, l
; (It CO-, -C110), ketone group (> CO
), 21.(73,%(-N Ot), nitroso group (-
No), sulfone group (-8O311), ether bond (
-0-), ester bond (-COO), peptide bond (
-COH2-), a compound with a functional group or bond (f) such as an oxygen-containing heterocycle, and metal alkoxides are used.As organic compounds having a hydroxyl group,
For example, methanol, ethanol, propatool, butanol, allyl alcohol, fluoro(l ethanol, fluorobutanol, phenol, cyclohexanol,
Benzyl alcohol, furfuryl alcohol, etc. are used. Examples of organic compounds for filtering aldehyde groups include formaldehyde, acetaldehyde, propionaldehyde, ditylaldehyde, glyoxal,
Acrolein, benzaldehyde, furfural, etc. are used. Examples of organic compounds from which anlu group can be obtained include 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, and cinnamon. Acid, naphthoic acid, phthalic acid, furanic acid, etc. are used. Examples of organic compounds having a ketone group include acetone, ethyl methyl ketone, methyl propyl ketone,
Butyl methyl ketone, binacolon, diethyl ketone, methyl vinyl ketone, mesityl oxide, methylhebutenone, cyclobutanone, cyclopentanone, cyclohexanone, acetophenone, propiophenone, butyrophenone, valerophenone, dibenzyl ketone, acetonaphtone, acetophenone, acetofuron, etc. be used. Examples of the organic compound having a nitro group include nitrobenzene, nitrotoluene, nitroxylene, and nitronaphthalene. Examples of the organic compound having a nitroso group include nitrosobenzene, nitrosotoluene, nitrosonaphthalene, and nitrosocresol. As the organic compound having a sulfone group, for example, methanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, etc. are used. Examples of organic compounds that form ether bonds include 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, and ethyl. amyl ether, vinyl ether, allyl ether, methyl vinyl ether, methyl allyl ether,
Ethyl vinyl ether, ethyl allyl ether, anisole, phenetol, phenyl ether, benzyl ether, phenylbenzyl ether, naphthyl ether,
Ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane, etc. are used. Examples of organic compounds having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate,
Propyl acetate, butyl acetate, amyl acetate, methyl nobionate, ethyl propionate, propyl propionate, butyl propionate, amyl butyrate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, butyric acid amyl, methyl valerate, ethyl valerate, propyl acid, 71 Acid propyl, methyl salicylate, →J ethyl lylylate, propyl salicylate, butyl salicylate, amyl salicylate, methyl anthranilate, ethyl anthranilate, butyl anthranilate, amyl anthranilate, methyl phthalate, ethyl phthalate, butyl phthalate etc. are used.

As the organic compound having a pebudide bond, for example, glyceroglopebudide, glyceroid pebudide, etc. are used. Examples of the heterocyclic compound include furan, oxazole, furasan, pyran, oxazine, morpholine,
Benzofuran, benzoxazole, chromene, chromane, dibenzofuran, xanthine, phenoxazine, oxolane, dioxolane, oxathiolane, oxadiazine, t\nzisoxazole, etc. are used. Examples of metal alkoxides include lithium isopropylate, lithium tertiary butyrate, sodium isopropylate, potassium isopropylate, magnesium edylate, calcium etylate, strondium edylate, barium edylate, barium isopropylate, and poric acid. Methyl ester, boric acid ethyl ester, boric acid butyl ester, aluminum edileate,
Aluminum isopropylate, aluminum butyrate, gallium isopropylate, methyl silicate, ethyl silicate, isopropyl silicate, germanium methylate, germanium propylate, germanium methylate, methyl phosphate, antimony ester, anhydrous Dimonbutylate, Indium isopropylate, Zinc dilate, Yttrium isopropylate, Lanthanum isopropylate, Titanium isopropylate, Ditanium butyrate, Zirconium ethylate, Zirconium isopropylate, Hafniu J1 isopropylate, Vanadium methylate, Vanadium methylate Vanadium methylate, vanadyl ethylate, vanadyl tanyarybutyrate, niobium ethylate, tankle ethylate, iron isopropylate, tin methylate, tin ethylate, tin isopropylate, tin butyrate, and the like are used.

In the present invention, a nitrogen compound is used to add nitrogen atoms into the a-C film. The phase state of the nitrogen compound does not necessarily have to be a gas phase at room temperature and normal pressure; it can be a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It can also be used in phases. Examples of nitrogen compounds include inorganic compounds such as nitrogen, ammonia, -nitrogen oxide, nitrogen dioxide, dinitrogen trioxide, dinitrogen pentoxide, and nitrogen trioxide, and amino groups (-NH
y), cyano method (-CN), nitro group (-N Ot),
Nito [! So I (-No), isocyanate ester bond (-NGO), isothiocyanate ester bond (-Nc
S), an azothioether bond (-N=NS-), a peptide bond (-coN+t-), a nitrogen-containing heterocycle, or other functional group or bond? T machine compound should be used. Examples of organic compounds having an amino group include methylamine, ethylamine, propylamine, butylamine,
amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodenylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, dimethylamine, diethylamine, dipropylamine, dibdelamine, cyamylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, allylamine, diallylamine,
Triallylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, methylaniline, dimethylaniline, ethylamine, NoJ, thylaniline, toluidine, benzylamine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, Naphthylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, noaminohebutane, diaminooctane,
Diaminononane, diaminodecane, phenylenediamine, etc. are used. Examples of organic compounds having a cyano group include acetonitrile, propionitrile, butillonitrile, valeronitrile, capronitrile, enantonitrile, caprylonitrile, ferargonitrile,
cabrinitrile, lauronitrile, palmitonitrile,
Stearonitrile, di[notonenitrile, malonitrile, stearonitrile, daltarnitrile, adiponitrile, benzonitrile, tolnitrile, cyanobenzylcinnamate nitrile, naphthonitrile, cyanoviridine, etc. are used. Examples of organic compounds having a nitro group include nitrobenzene, nitrotoluene, nido[
1-xylene, nitronaphthalene, etc. are used. Examples of the organic compound having a nitroso group include nitrosobenzene, nitrosotoluene, nitrosonaphthalene, and nitrosocresol. has an isocyanate ester bond (T compounds include, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, phenyl isocyanate,
Ethyl isocyanate and the like are used. Examples of the organic compound having an isothiocyanate bond include methyl isothiocyanate, amyl isothiocyanate, propyl isothiocyanate, butyl isothiocyanate, amyl isothiocyanate, amyl isothiocyanate, phenyl isothiocyanate, benzyl isothiocyanate, and the like. Examples of organic compounds having an azothioether bond include benzenediazothiophenyl ether, thalolbenzenediazothiophenyl ether, brobenzenediazothiophenylneiko II/-nitrobenzenediazothiophenyl ether, phenyldiazomercaptonaphthalene, methoxyphenyldiazo Mercaptonaphthalene, benzenediazothioglycolic acid, brobenzenediazothioglycolic acid, nitrobenzenediazothioglycolic acid, etc. are used. As the organic compound having a peptide bond, for example, glycerol peptide, glyceroid peptide, etc. are used. As the heterocyclic compound, pyrrole, pyrroline, pyrrolidine, oxazole, thiazole, imidazole, imidacilline,
Imidaridine, pyrazole, pyrazoline, pyrazolidine, triazole, tetrazole, pyridine, piperidine, oxazine, morpholine, thiazine, pyridazine, pyrimidine, pyranone, piperazine, triazine, indole, indoline, benzoxazole, indazole, benzimidazole, quinoline, cinnoline, phthalazine, Phthalocyanine, quinazoline, quinxaline, carbazole, acridine, phenanthridine, phenazine, phenoxazine, indolizine, quinolidine, quinuclidine, naphthynone, purine, pteridine, aziridine, azepine, oxacyanone, dithiazine, benzoquinoline, imidazothiazole, etc. are used.

The thickness of the a-C charge transport layer is preferably thicker from the viewpoint of charge retention ability, but thinner from the viewpoint of productivity and charge transportability.

When used in ordinary electrophotography, the amount is preferably 5 to 50 μl, preferably 7 to 20 μl. This a-C layer has light transmittance, high dark resistance, and is rich in charge transport properties, and when the film thickness is set to 5 μm or more as described above, it transports carriers without causing charge traps.

In the present invention, the charging characteristics of the a-C charge transport layer are set to 51
In order to shift by one node, an element from Group NlA or Group VA of the periodic table is mixed.

When the photoreceptor is used with ten charges, the substrate side is relatively P type and the front side is N type, and when it is used with negative charges, the substrate side is relatively N type and the front side is relatively ■ type. By doing so, a reverse bias effect is produced.

This achieves effects such as improved charging ability, reduced dark decay, and improved sensitivity. That is, in a photoreceptor formed by laminating an a-C charge transport layer and a charge generation layer, no matter which layer is on the surface side or the substrate side, when positively charged, the surface side is relatively N type, and the substrate side is relatively 1 type. ) group VA and mA groups are contained in the charge transport layer and, if necessary, in the charge generation layer.

This prevents the injection of surface charges, interlocks the movement of electrons to the surface and the movement of holes toward the substrate, and prevents the injection of electrons from the substrate. - When charged, it acts in the opposite way to the above.

Such polarity adjustment may be achieved by gradually increasing the content of uIA or VA elements in a single layer toward the substrate or surface, or by adding a uniform concentration of
Contains He group or VA group elements.

A single a-C charge transport layer may be provided on the substrate side or the surface side. In addition, if necessary, a-
The C charge transport layer may be provided so that a depletion layer is formed in the junction region.

1 to 12 are schematic cross-sectional views showing one embodiment of the photoreceptor of the present invention. In the figure, (1) is the substrate, (2) is a-C
The charge transport layer (3) indicates the charge generation layer. In the photoreceptor of the embodiment shown in FIG. 1, for example, when the photoreceptor is charged ten times and then imaged, carriers are generated in the charge generation layer (3) and electrons neutralize the surface charges. On the other hand, holes are transported to the substrate (1) side, guaranteed by the excellent charge transport properties of the aC charge transport layer (2).

In the present invention, during charging, the a-C charge transport layer contains an element of Group IA of the periodic table and is adjusted to P type.

In this way, holes can more easily move toward the substrate, improving sensitivity, and injection of electrons from the substrate can be reliably prevented. It is preferable to use an N-type charge generation layer (3), and for example, a-8L is suitable because it is itself a weak N-type. Group II elements of the periodic table may be included. This is effective in preventing surface charge injection and electron movement.

A VA group element, such as phosphorus, may be mixed into the a-S+ charge generation layer to make the surface layer a relatively stronger N type. In this case as well, the polarity of the a-C charge transport layer may be adjusted to the [) type. When the photoreceptor shown in FIG. 1 is used with one charge, contrary to the above, a-C charge transport Eta! /Q 't+-&N l
#-jll>el fkl punishment 1-ryu MJ-k +7
When a-St is used as the c/6ii generation layer (3), B may be contained.

The photoreceptor shown in Fig. 2 is an example in which the a-CTi charge transport layer (2) is used as the uppermost layer. A charge generation layer (
In contrast to 3), it is relatively N-type to facilitate the movement of electrons. - When used for charging, B etc. may be included and adjusted in reverse.

The photoreceptor shown in FIG. 3 is an example in which the a-C charge transport layer (2) is used above and below the charge generation layer (3). When used with ten charges, the upper a-C charge transport layer ( 2) is made more N-type with respect to the electron generation layer (3) to facilitate the movement of electrons, and the lower a-C electron transport layer (2)
) is preferably adjusted to P type.

The photoreceptor not shown in FIGS. 4 to 6 is an example of the photoreceptor shown in FIGS. 1 to 3 in which a surface protective layer with a thickness of 0.01 to 5 μm is further provided as an overcoat layer (4).
Charge generation layer (3) or a-C charge +6f transport layer (2)
This is intended to protect the surface and improve the initial surface potential. Any known material may be used for the surface protective layer, and in the present invention, it is preferable from the viewpoint of the manufacturing process that it be provided by f'' machine plasma polymerization.

A transport layer of the present invention may be used. This protective layer (4) may be doped with Group 11A and Group VA elements, if necessary.

The photoreceptor shown in FIGS. 7 to 9 is attached to the substrate (+) at a-0
This is an example in which the layer is used as an undercoat layer (5) as a barrier layer or as an adhesive layer. Otsuchirun and other known materials are used as the undercoat layer. In this case, it is preferable to provide 11 by organic plasma polymerization. The barrier layer effectively blocks the charge injection from the substrate (1) and also prevents the charge generated in the charge generation layer (3).
rT has a rectifying function that transports the water to the substrate side. In this color, it is desirable that the barrier layer contains a group 111A element when charged with an I charge, and a group VA element when charged with a negative charge. Moreover, it is preferable that the thickness of one barrier layer is 0.01 to 5 μm.

Furthermore, the photoreceptor shown in FIGS. 7 to 9 may be provided with an overcoat layer (4) shown in FIGS. 4 to 6 on the substrate (FIGS. 1O to 12).

Contained in the charge transport layer (2)? Examples of different elements that may be added include Si, Gc, and/or Sn in an amount equal to or less than toatm relative to the sum of their addition fit and carbon atomic weight, thereby forming a charge generation layer. It becomes easier to inject charge from the
Effects such as increase in memory and memory reduction can be obtained. Furthermore, the adhesion to the AC substrate, the charge generation layer, etc. is improved.

In order to introduce these elements, a method similar to that described in the introduction of group IIIA elements may be employed.

For Si introduction, 5LI-1s, (CtHa)sSiHlS
iF,, S 1lltcQ*, S ICI24, S
i(OCIl+) 5i(OCtII,), 5(
OC3117), etc., and G e H4NG for Ge introduction.
e C124, G e (OCt H4) 4% G e
(Ct tl S)4 etc., and for Sn introduction, (C1
13)+5n1(Cstls)4srl.

5nCQh etc. may be used.

It is also possible to adjust the band gap by adding St or Ge to the charge transport layer to reduce the interface barrier with the charge generation layer. In Figure 1, a large amount (> 10 atm, %) of G
By avoiding the uneven distribution of the e-doped portion on the substrate side, the reflection of excess light is prevented and interference fringes are formed.

It is also possible to prevent the occurrence of blur. Also, 5i1G (
! By adding , a hard film with wear resistance and water repellency can be formed.

Further, other elements may be introduced into the charge generation layer of the photoreceptor of the present invention to adjust its characteristics.

The charge transport layer may be colored (e.g., yellow, blue, brown) depending on its manufacturing conditions (bonding state) and impurities.
In the configurations shown in FIGS. 2 to 4, 5, 6, and 8 to 12, this can be used to provide the effect of cutting harmful light to the electron 6:j generation layer. can.

The a-C charge transport layer of the photoreceptor of the present invention may further contain sulfur and/or various metals, or a portion of hydrogen may be replaced with halogen or alkali metal.

As a sulfur source, CS t, (CJIs)*S, HtS
.

Examples include SF6, SO, etc. Mixing sulfur is effective in absorbing light and preventing interference. Also introduced sulfur (S) 4°
This also has the side effect of increasing the film formation speed.

Examples of metals that can be mixed include the following (the following are examples of gases that can be used for mixing).

1) a:13a(OCtlls)3; Ca: Ca
(OCtHs)s:Fe: Fe(Of-Csl[7)
s, (Ct)Is)*Pe-Fe(GO)s; Il
r; If(Of-CsHt): to: KOi-Csl
lt; Li: Li0l-C3H7:La:La(
Of-C, summer 1t) 4; Mg: Mg(O
G)Is)t, (Cdls)tMg; Na:
Na0i-C3H7; 'Nb: Nb(OCtHs
)s; Sr: 5r(OCHs)t;i' i:
'I' i (Of-C311?) I T t (OC4H9
)I1'icl! *; Ta: 'l”a(OCtH
s)s;V: VO(OCyl[s)+, VO(Ot
C4He)s;Y: Y(Oi-Csll,)s
; Zn+ Zn(OCyl5)z, (C113)!
Zn, (cwt-ts)tzn;Zr: Zr(Oi
-C3117)+; Cd: (CH3)tcd:C
o: Cot(Co)a; Cr: Cr(Co)s;
Mn: Mr+t(CO)+o; Mo: Mo(G
O)1, MOFII, MoCQe: W: W(CO
)s, W F s, W C+2s; 1'c: II
tTe; Se: IItSeo Also, by replacing some of the hydrogen in the a-C charge transport layer with halogen, water repellency, abrasion resistance, and light transmission properties are improved.
, CF*, CF3, etc. are formed, the refractive index n becomes small (1, 39), and an antireflection effect appears.

Furthermore, when the a-C charge transport layer obtained according to the present invention is post-treated with argon and then brought into contact with the atmosphere, carbonyl groups are introduced and the surface is activated, and -CI" and - become C1".

As a carbon and halogen source, Ctl-1aCQ.

C2113C12, C113C(!1C1(s13r,
C0CQ*, CcQ2Ft, CI-ICQPt, CF
4.1lcI2. Ch, F! etc. are exemplified.

Carbon and alkali metal sources include lithium tert-butyralate, potassium acrylate, and the like.

The photoreceptor of the present invention has a charge generation layer and a charge transport layer. Therefore, at least two steps are required to manufacture it. The charge generation layer in the photoreceptor of the present invention is not limited in its manufacturing method; for example, it may be produced by the same manufacturing method as the charge transport layer (a-C film) in the present invention, or by electrodeposition in a liquid phase. It may be formed by a coating method such as a coating method, spraying, or dipping. Among these, it is preferable to form the film by the same manufacturing method as that for the charge transport layer in the present invention, as this leads to reductions in manufacturing equipment costs and process labor.

FIGS. 13 and 14 show a capacitively coupled plasma CVD apparatus which is a photoreceptor manufacturing apparatus according to the present invention. FIG. 13 shows a parallel plate plasma CVD apparatus, and FIG. 14 shows a cylindrical plasma CVD apparatus. In both devices, the electrode plates (22), (25) and the substrate (24) are of a flat type in FIG. 13, and the electrode plate (30) and the substrate (31) are of a cylindrical type in FIG. They are different in that they exist. In addition, in the present invention, inductively coupled plasma CV
It can be produced using D equipment.

The method for manufacturing the photoreceptor of the present invention will be explained using a parallel plate type plasma CVl (CVI) apparatus (FIG. 13) as an example. (6) to (1) in the figure
0) are the first to fifth tanks in which hydrocarbon gas, carrier gas, or doping gas are sealed, respectively;
Each tank is connected to first to fifth regulating valves (11) to (15) and mass flow controllers (16) to (20). These gases are sent into the reaction chamber (23) via the main pipe (21).

A high frequency power source (2) is connected to the reaction chamber (23) via a capacitor.
6) is connected to the flat electrode plate (22) and electrically grounded.
) on which are placed flat ground electrode plates (25) are provided facing each other. Further, the flat electrode plate (22) is connected to a DC voltage source (28) via a coil (27), and in addition to the power applied from the high frequency or low frequency power source (26), a DC bias voltage is additionally applied. It has become so. Further, the conductive substrate (24) placed on the electrode plate (25) is heated to, for example, room temperature to 350° C. by a heating means (not shown).

In the above configuration, for example, when manufacturing the photoreceptor shown in FIG. 1, the reaction chamber (23) is brought into a constant vacuum state, and then hydrocarbon gas is supplied from the first tank (6) via the main pipe (21). For example, butadiene gas, second tank (7)
From the fourth tank (9), for example, as a carrier gas, 0. Gas, B and I16 gases are supplied from the fifth tank. On the other hand, 30 watts to Ikw was applied to the flat electrode plate (22) from the high frequency power source (26).

A plasma discharge is generated between both electrode plates by applying a power of
atm, % or less oxygen atoms, 50000 atm.

Form an a-C charge transport layer (2) containing ppm of boron atoms. The charge transport layer (2) contains hydrogen from 0.1 to 67 at.
m.

%, but this hydrogen content depends on the type of starting material gas,
It depends on the manufacturing conditions such as raw material gas and diluent gas (II 1, inert gas) ratio, discharge power, pressure collar substrate temperature, DC bias voltage, annealing temperature, discharge frequency, etc., but from DC voltage source (28) 50V to IKV. It can also be controlled by applying a bias voltage of .

By increasing the bias voltage, the hydrogen content can be reduced and the hardness of the a-C charge transport layer itself can be increased to <4. The a-C charge transport layer thus formed has excellent light transmittance and dark resistance, and is extremely excellent in the transportability of Chorno carriers. Incidentally, the present invention includes 13,1111 in this layer.
Gas is introduced and controlled to P type to further enhance the electron transportability. If PII3 gas is used instead of B, It gas, it is possible to control it to N type.

Next, the charge generation layer (3) includes second and third tanks (7),
From (8), 111.5i) I is formed as a layer having a -Si as a matrix by introducing a gas.

1'; gopL depends on the type of starting material gas, the ratio of material gas to diluent gas (LL, inert gas), discharge power, pressure collar substrate temperature, DC bias voltage, annealing temperature, discharge frequency, etc. Among these, discharge power, substrate temperature,
Annealing temperature is a factor that can significantly change E gopt.

r; gopt according to the present invention can be calculated from the absorption edge plotted by Fi1 -hv (where α represents the absorption coefficient and hv represents the optical energy).

The dielectric constant of the a-C charge transport layer depends particularly on the starting material gas, discharge power, DC bias generated by discharge (or externally applied), etc., and by changing these factors, films with different dielectric constants can be formed. can get.

The capacitively coupled plasma CVD apparatus shown in FIG. 15 uses a monomer such as Ca1ls as the a-C charge transport layer source, and the monomer (33) is heated in a constant temperature bath (32). , the tube (34) connected to the reaction chamber is also heated, and the monomer is turned into a vapor to be sent to the reaction chamber (2).
3). The other configurations are the same as in FIG. 13.

In the following examples, when forming a plate-like photoreceptor, the first
3 will be explained using FIG. 14 when forming a cylindrical photoreceptor. However, when using raw materials that are gaseous at room temperature, Figures 13 and 14 are directly applied, but when raw materials are not gaseous, that is, solid or liquid, as shown in Figure 15, It is necessary to separately provide vaporizing means (32), (33), and (34) for vaporizing the solid or liquid. Although not shown, the same applies to a cylindrical photoreceptor manufacturing apparatus. In order to avoid complexity, all of the following embodiments will be explained with reference to FIGS. 13 and 14.

The present invention will be explained below with reference to Examples.

Example 1 (1) (Formation of a-C charge transport layer) In the glow discharge decomposition apparatus shown in FIG. 1, second, fourth and fifth regulating valves (11),
(12), (14) and (15) are opened, and 1,3-butadiene (CdI2) gas is extracted from the first tank (6).
IL gas from the second tank (7), oxygen (0,) gas from the fourth tank (9), and 11. de1
+(, iL gas diluted to 0%, output gauge 1kg/c
mass flow controllers (16), (
17), (19) and (20). Then, adjust the scale of each mass flow control (J-ra) to set the flow rate of C4116 to 60 scn+ and lft to 30 scn+.
0 secmS13 tlla/ II t 5 sc
cm.

0, so that it becomes l sccm, and the reaction chamber (2
3) It flowed into the interior. After each flow rate became stable, p and q were adjusted so that the internal pressure of the reaction chamber (23) was 1.5 Torr.

On the other hand, as the conductive substrate (24), 50
Preheat to 150°C using an aluminum temporary X50ix, and when the gas flow rate and internal pressure are stable, turn on the low frequency power supply (26) and apply l
Plasma polymerization was performed for 23 minutes by applying an electric current of 20 watts (60KIIz), and the conductivity J, (
Temporarily (24
An a-C71i cargo transport layer (2) having a thickness of approximately 15 μm and containing rm, % boron atoms and 3 arm, % oxygen atoms was formed. The manufacturing conditions are summarized in Table 1 along with other Examples.

(u) 7[! Formation of charge generation layer (Se-As charge generation layer) After forming the charge transport layer, a charge generation layer of 5e3As having a thickness of 0.5 .mu.m was formed as a charge generation layer by a conventional method of vacuum evaporation.

(fi+) Evaluation of photoconductor characteristics The obtained photoconductor was subjected to a commonly used Carlson process, and the initial surface potential (Vo) when positively charged was 17.
The exposure amount required to reach the potential of 2 (+, > 1/2 (
12ux -5ec)), decay rate of potential after being left in the dark for 5 seconds after charging (DDR5 (%)), residual potential (VR
) was measured.

Furthermore, the change over time refers to the change in the photoconductor characteristics after being left indoors for 10 months, and the rate of change in V, El/2, v1≧ is 150 to +100%, which is extremely good. [(ζ month, V,, El/2, rate of change of VR -50
~+200% and those that can be used as photoreceptors are indicated by "○".

The results of the above-L are summarized in Table 2.

Example 2-t.

A photoreceptor was produced in the same manner as in Example 1, except that the flow rate of oxygen and the flow of BJIa/IL gas having different concentrations were changed.

The manufacturing conditions are summarized in Table 1, and the photoreceptor characteristics are summarized in Table 2. Example 1
A photoreceptor with the same configuration was fabricated.

However, the chemically modified atoms contained in the electron 6:j transport layer are
Oxygen (GO, used), Phosphorus (pH, ). Production was carried out in the same manner as in Example 1, and the conditions at that time are summarized in Table 3.

As the charge generation layer, an a-3i heavy charge generation layer was used. That is, after the charge transport layer was formed, the application of power from the low frequency power source (26) was stopped, the mass flow controller was set to O, and the inside of the reaction chamber (23) was sufficiently degassed. After that, 100% 5il-1 gas was supplied from the third tank (8) for 90 sec, and H and gas were supplied from the second tank (7) at 2
10 sec+n, NtO gas was allowed to flow into the reaction chamber for 1 sec from a tank (not shown), and the internal pressure was set to 1.0 T.
After adjusting the substrate temperature to 230° C., a high frequency power source (not shown) was turned on and a power of 2 watts was applied. Discharge was continued for 8 minutes to form an a-Si layer (3) with a thickness of about 0.4 μR.

The obtained photoreceptor was evaluated in the same manner as in Example 1.

The results are shown in Table 4.

Table 4 A photoreceptor (configuration shown in FIG. 2) was prepared in which a charge generation layer and a charge transport layer were sequentially laminated on a conductive base.

As the charge generation layer, a photoreceptor was used in which monochloroaluminum monochlorophthalate [1 cyanine (AeCQPC (C12)) was formed to a thickness of 500 nm by a conventional vacuum deposition method.

The charge transport layer was prepared using the glow discharge decomposition apparatus shown in FIG. It was formed using the same procedure as .

Electron 6:j The transport layer contains nitrogen (N11) as a chemically modified atom.
3 gases are used) and aluminum ((CHs)*A (! gases are used).

Table 5 shows the manufacturing conditions of the charge transport layer. The characteristics of the obtained photoreceptor were evaluated in the same manner as in Example 1, and the results are shown in Table 6.

Table 6 A photoreceptor (configuration shown in FIG. 2) was prepared in which a charge generation layer and a charge transport layer were sequentially laminated on a conductive plate.

As a charge generation layer, an a-S+ photosensitive layer was formed.

The a-9i layer has an r32118/5il14 ratio of 2pp.
It was formed in the same manner as in Example 11, except that [3, II@ gas was introduced so as to be I11.

The charge transport layer was formed in the same manner as in Example I using a discharge decomposition apparatus (not shown in FIG. 13).

Chemically modified atoms include nitrogen (IICN gas) and arsenic (Δ
5110/Ilt gas).

Table 7 shows the manufacturing conditions for the charge transport layer. The characteristics of the obtained photoreceptor were evaluated in the same manner as in Example 1, and the results are shown in Table 8.

Table 8 Effect of perforation The photoreceptor having the carbon film according to the present invention as a charge transport layer has excellent charge transport properties and charging ability, and even though the film thickness is thin, a sufficient surface potential can be obtained, and a good image can be obtained. be able to. According to the present invention, when using a-5i in the charge generation layer, it is possible to obtain a thin film photoreceptor that could not be achieved with a conventional a-9i photoreceptor.

Furthermore, by introducing nitrogen atoms or oxygen atoms and WiA group elements or VA group elements, the charge transport properties and stability over time of the charge transport layer are improved. The stability of properties over time is improved.

In the photoreceptor of the present invention, the raw materials thereof are inexpensive, each necessary layer can be formed in the same tank, and the layers may be vaguely thick or thin, so that the manufacturing cost is low and the manufacturing time is short.

Even when the carbon film according to the present invention is formed into a thin film, pins and one-neel do not easily occur and can be formed homogeneously, so that it is easy to make the film thin. Furthermore, since it has excellent corona resistance, acid resistance, moisture resistance, heat resistance, and rigidity, it improves the durability of the photoreceptor when used as a surface protective layer.

[Brief explanation of the drawing]

1 to 12 show schematic cross-sectional views of the photoreceptor of the present invention. FIGS. 13 to 15 are diagrams showing an example of an apparatus for manufacturing a photoreceptor according to the present invention. The symbols in the figure are as follows. (1)...Substrate (2)...A-C charge transport layer (3)...Charge generation layer (4)...Overcoat layer (5) Undercoat layer (6) - (lO)・・・
Tanks (11) to (15)...: J, 'a valve (16)
) ~ (20)...Mass flow controller (21)
... Main pipe (22) ... Flat electrode plate (2
3)...Reaction chamber (24)...Flat type substrate (
25)... Flat earth electrode plate (26)... High frequency or low frequency power supply (27)... Coil

Claims (1)

[Claims] 1. In a functionally separated photoconductor having a charge generation layer (3) and a charge transport layer (2), the charge transport layer (2) contains a group IIIA element or a group VA element of the periodic table, and a nitrogen atom or oxygen. Atom-modified hydrogen with 0 to total atoms
．． A photoreceptor characterized by being a carbon film containing 1 to 67 atomic%.