JPH01133060A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain a photosensitive body using an organic polymer film, especially, an organic plasma polymerized film by using as an electric charge transfer layer a hydrocarbon plasma polymerized film specified in infrared absorption spectra. CONSTITUTION:The electrophotographic sensitive body to be used is a functionally separated type having a charge generating layer 3 and the charge transfer layer 2 of the hydrocarbon plasma polymerized film having a peak absorption coefficient alpha1 near 890cm<-1> of the terminal olefin infrared absorption spectra (>C=CH2) and a peak absorption coefficient alpha2 of an intramolecular methylene group (-CH2-) near 2,925cm<-1>, and an alpha1/alpha2 ratio of 0.2-2, thus permitting the obtained photosensitive body to be superior in characteristics, such as electrostatic chargeability, charge transfer performance, and residual potential, and sufficient in surface potential even when the film thickness is small, accordingly, reduced in manufacturing cost and time, and a good image to be obtained.

Description

[Detailed description of the invention] Ru.

Prior art Invention of the Carlson method (1938, USP 222176)
) Since then, the application field of electrophotography has continued to develop significantly, and various materials have been developed and put into practical use for photoreceptors.The main photoreceptor materials that have been used in the past include amorphous selenium, Inorganic substances such as arsenic, selenite, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine, disazo pigment, trisazo pigment, perylene pigment, triphenylmethane compound, triphenylamine compound, hydrazone compound, styryl compound, pyrazoline compound , oxazole compound,
Examples include organic substances such as oxadiazole compounds.

In addition, the configurations include a single-layer structure in which these substances are used alone, and a bang-like structure in which these substances are dispersed in a binder.
Examples include a laminated tank acid in which a charge generation layer and a charge transport layer are provided for each mold structure and function.

However, each of the conventionally used photoreceptor materials has drawbacks.

One of them is their toxicity to the human body, but for inorganic substances other than the amorphous silicon mentioned above,
All of them had undesirable properties.

In addition, in order for the photoreceptor to actually be used in a copying machine,
It is necessary to maintain stable performance at all times even when exposed to harsh environmental conditions such as charging, exposure, development, transfer, static elimination, and cleaning.
All of them lacked durability and had many unstable factors in terms of performance.

In order to solve these problems, in recent years, amorphous silicon (hereinafter abbreviated as a-Si) produced by a plasma chemical vapor deposition method (hereinafter referred to as plasma CVD method) has been used for photoreceptors.

The a-Si photoreceptor has various excellent properties. But a
-S i has a large dielectric constant ε of about 12, so there is a problem that a film thickness of at least about 25 μI11 is essentially required in order to obtain a sufficient surface potential as a photoreceptor. In the plasma CVD method, the a-Si photoreceptor requires a long time to produce because the film deposition rate is slow, and the longer the production time becomes, the more difficult it becomes to obtain a homogeneous a-8t film. As a result, the a-Si photoreceptor has drawbacks such as a high probability of image defects such as white spot noise 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 has poor adhesion between the substrate and the a-Si.

Furthermore, there are also drawbacks such 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 an undercoat layer for A-8I photosensitive materials. An example of the former is
For example, JP-A-60-61761, JP-A-59-2
14859, JP-A-51-46130, JP-A-50-20728, etc. are known.
Examples of the latter include, for example, JP-A-60-63541, JP-A-59-136742, and JP-A-59-3.
8753, JP-A-59-28161, JP-A-56-6-0447, etc. are known.

Organic plasma polymerized films can be prepared from all kinds of organic compound gases such as ethylene gas, benzene, and aromatic silanes (e.g., Ni, T, Be1l).
), M Shen et al., Journal of Applied Polymer Science (Jo
Urnal or Applied Polymer
5science), Volume 17, pp. 885-89'2 (
(1973), etc.), but organic plasma polymerized films prepared by conventional methods are used only for applications requiring insulation. Therefore, these films were considered to be insulating films having an electrical resistance of about <10'' ΩCR like ordinary polyethylene films, or at least were used with the understanding that they were such films. 1986-
The technique described in Japanese Patent No. 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.

Further, there is no description whatsoever regarding the carrier transport properties of organic plasma polymerized films, and the above-mentioned essential problems of a-Si are not solved.

Japanese Unexamined Patent Publication No. 59-214859 discloses a technique of coating an organic transparent film with a thickness of about 5 μm as an overcoat layer by plasma polymerization of organic hydrocarbon monomers such as ethylene and acetylene. It improves peeling, durability, pinholes, and production efficiency of a-8i. There is no description whatsoever regarding the carrier transport properties of organic plasma polymerized films, and it does not solve the above-mentioned essential problems of a-Si.

JP-A No. 51-46130 discloses that N-vinylcarbazole is coated on the surface with a thickness of 3 μm to 0.0 μm by glow discharge.
A photoreceptor on which an organic plasma polymerized film of 0.01 μm is formed is disclosed. 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 0.001
It is very thin at ~3 μm and is used as an overcoat. It is thought that the polymerized film is very thin and does not require charge transport ability. Furthermore, there is no description whatsoever regarding the carrier transport properties of the polymeric 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,
An organic photoconductive electrical insulator is sequentially laminated, and a layer of 0.00 mm thick is further layered on top of the organic photoconductive electrical insulator. A technique for forming a glow discharge polymerized film of +=μm has been disclosed, but this film is intended to protect the surface so as to withstand wet development and is used as an overcoat. Polymerized membranes are very thin and do not require charge transport capabilities.

Furthermore, there is no mention of the carrier transport properties of the polymer film, nor does it solve the above-mentioned essential problems of a-Si.

JP-A-60-63541 discloses a photoreceptor using a diamond-like organic plasma polymerized film of 200 to 2 μm as an a-Si undercoat layer.
The purpose of the organic plasma polymerized film is to improve the adhesion between the substrate and the a-Si.

Polymerized membranes can be very thin, charges move through the membrane by tunneling, and the membrane itself does not require charge transport capabilities. Furthermore, there is no description whatsoever regarding the carrier transport properties of the A-machine plasma polymerized membrane, and it does not solve the above-mentioned essential problems of A-8i.

JP-A-59-28161 discloses a photoreceptor in which an a-machine plasma polymerized film and an a-Si are sequentially formed on a substrate. The organic plasma polymerized film is an undercoat layer that takes advantage of its insulating properties, and functions as a blocking layer, HFj contact layer, or peel prevention layer. The polymeric membrane can be very thin, charges move through the membrane by tunneling, and the membrane itself does not require 11-carrying capacity. Further, there is no description whatsoever regarding the carrier transport properties of organic plasma polymerized films, and the above-mentioned essential problems of a-Si are not solved.

JP-A No. 59-38753 discloses that 10 to 100
Form an organic plasma polymerized thin film on top of the a-9i
Techniques for depositing layers are disclosed. The organic plasma polymerized film is an undercoat layer that takes advantage of its insulating properties and functions as a blocking layer or anti-peeling layer.The polymeric film can be very thin, and charges move through the film due to the tunnel effect. However, the film itself does not require charge transport ability.Furthermore, there is no description of the carrier transport property of the organic plasma polymerized film, and it does not solve the above-mentioned essential problems of a-Si.

Japanese Patent Application Laid-open No. 59-136742 discloses that about 5μ
A semiconductor device is disclosed in which an organic plasma polymerized film and a silicon film of m 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 description whatsoever regarding the carrier transport properties of organic plasma polymerized films, and a-
It does not solve the above-mentioned essential problem of S i.

JP-A-56-60447 discloses a method for forming an organic photoconductive film by plasma polymerization, but there is no mention of the possibility of application in electrophotography, and furthermore, there is no mention of the possibility of application in electrophotography. Alternatively, it is disclosed as a photoconductive layer, which is different from the present invention. Moreover, it does not solve the above-mentioned essential problems of a-Si.

Problems to be Solved by the Invention As mentioned above, the permeable polymerization layer conventionally used in photoreceptors has been used as an undercoat layer or an overcoat layer, but these require a carrier transport function. This film is used based on the judgment that the organic polymer film is insulating. Therefore, its thickness is at most 5
It is used only as an extremely thin film of about μ2, and carriers pass through the film by tunnel effect, or if tunnel effect cannot be expected, the film is thin enough that it does not pose a problem as a practical residual potential. It is only used in

While considering the application of organic polymer films to photoreceptors, the present inventors found that organic polymer films, which were originally thought to be insulating, contained terminal olefins (〉C=C+■t). It has been found that by increasing the amount, the electrical resistance decreases and the charge transport property begins to be exhibited.

By utilizing this new knowledge, the present invention solves all the problems of the conventional a'' Si photoreceptor, such as problems in the film thickness, manufacturing time, manufacturing cost, etc. of the a-3i, and also It is an object of the present invention to provide a photoreceptor using an organic polymer film, particularly an organic plasma polymer film, which has completely different purposes and characteristics from conventional ones, and a method for manufacturing the same.

Means for solving the problem, that is, the present invention provides a charge generation layer (3) and a charge transport layer (2).
) in a functionally separated photoreceptor having a charge transport layer (
As 2), a hydrocarbon plasma polymerized film is provided, and the infrared absorption spectrum of the polymerized film has a terminal olefin (> C=C
H2) peak absorption coefficient α1 near 890 cm-'
The present invention relates to a photoconductor characterized in that the ratio αI/α between the peak absorption coefficient α of the present invention and the peak absorption coefficient α near 2925ca+-′ due to methylene (CHt-) groups is 0.2 to 2.0.

The photoreceptor of the present invention is composed of at least a charge generation layer and a charge transport layer.

The photoreceptor of the present invention is characterized by having a hydrocarbon polymer film as a charge transport layer, and the infrared absorption spectrum of the polymer film has a peak absorption coefficient α1 near 890 cm-' due to terminal olefins (>C=CH*) and methylene 2925cx- by group
The ratio α1/α of the peak absorption coefficient α near ' is 0.2
(Hereinafter, the polymer film of the present invention will be referred to as an a-C film).

The absorption coefficient of the infrared absorption spectrum in the present invention is calculated from the transmittance and the film thickness using the following formula [■]; [In the formula, α represents the absorption coefficient, d represents the film thickness, and T/To represents the transmittance. It is represented by ko.

The a-C film of the present invention has an infrared absorption spectrum in which the ratio of the peak absorption coefficient α near 890cx-' due to the terminal olefin to the peak absorption coefficient α near 2925cx-' due to the methylene group is 0.2 or less. 2.0, more preferably 0
, 3 to 1,5, especially 0.4 to 1.3; if it is smaller than 0.2, suitable transport properties cannot be obtained and it cannot be used as a photoreceptor; if it is larger than 2.0, it is suitable. This causes a decrease in charging ability, deterioration of film quality, and a decrease in film formability.

Generally, the peak absorption coefficient derived from the terminal olefin group and methylene group follows the formula [r] and is αl/α.

When the value of is greater than 0.2, the specific resistance becomes 01Ω.
It will be below C1 level, carrier mobility will be 0-7cx per month.
"V 1 sec or more ◇In the a-C film of the present invention,
There are various groups derived from carbon atoms, such as methyl, methylene, or methine groups, or carbon atoms with various bonding styles, such as single, double, or triple bonds, but α1 according to formula [1] /α2 value is 0.2 to 2
．． It is important in the present invention that the value be 0.

The thickness of the a-C layer is suitably 5 to 50 .mu.m, particularly 7 to 2'0 .mu.m; if it is thinner than 5 .mu.m, the surface potential is 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 layer has excellent light transmittance, relatively high dark resistance, and rich charge transport properties.
Even if the film thickness is set to 5 μm or more as described above, carriers are transported without causing charge traps.

Hydrocarbons are used as the organic gas for forming the a-C layer.

The phase state of the hydrocarbon does not necessarily have to be a gas phase at room temperature and normal pressure, but it can be melted by heating or reduced pressure, etc.
As long as it can be vaporized through evaporation, sublimation, etc., it can be used in either a liquid phase or a solid phase.

Examples of the hydrocarbons used include methane series hydrocarbons, ethylene series hydrocarbons, acetylene series hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

Examples of methane series hydrocarbons include methane, ethane,
Propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, heptadecane,
Normal paraffins such as heptadecane, octadecane, nonadecane, eicosane, heneicosane, tocosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octadecane, nonacosane, tri-acontane, todoriaconcune, pentatriaconcune, isobutane, isopentane, neobentane, isohexane, Neohexane, 2゜3-dimethylbutane,
2-methylhexane, 3-ethylpenkune, 2,2-dimethylpentane, 2゜4-dimethylpentane, 3,3-
Dimethylbencune, tributane, 2-methylhebutane,
3-methylhebutane, 2,2-dimethylhexane, 2,
2゜5-dimethylhexane, 2,2.3-trimethylpentane, 2,2.4-trimethylpentane, 2.3゜3
Isoparaffins such as -trimethylpentane, 2,3.4-trimethylpentane, and isonanone are used.

Examples of ethylene series hydrocarbons include ethylene, propylene, isobutylene, 1-butene, 2-butene,
Pentene, 2-pentene, 2-methyl-1-butene, 3
-Methyl-1-butene, 2-methyl-2-butene, 1-
Hexene, tetramethylethylene, l-heptene,! −
Olefins such as octene, ■-nonene, and 1-decene, diolefins such as allene, methylalene, butadiene, pentadiene, hexadiene, and cyclopentadiene, and triolefins such as ocimene, alloonemene, myrcene, and hexatriene are used. .

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

Examples of ring hydrocarbons include cyclopropane, cyclobutane, cyclopencune, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cycloundecane, cyclohexadecane, and the like. Paraffin and cycloolefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexane, cycloheptene, cyclooctene, cyclononene, cyclodecene, limonene, terbirun, phelandrene, silvestrene, tsene,
Carene, pinene, bornylene, camphuene, fenchen, cycloundecane, tricyclene, pisabolene, zingiberene, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarprene,
Terpenes such as mylene, steroids, etc. are used.

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, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

Suitable carrier gases include H2, Ar, Ne, He, and the like.

In the present invention, it is most preferable to form the a-C organic polymer film through a plasma state such as a direct current, high frequency, or microwave plasma method, but it may also be formed through an ion state such as ionization vapor deposition or ion beam vapor deposition. Alternatively, it may be formed from neutral particles using a vacuum evaporation method, a sputtering method, or a combination thereof.

What is important in this case is the infrared absorption peak ratio α based on the terminal olefin groups and methylene groups in the organic polymer film.

/α is formed to be 0.2 to 2.0 as described above. For this purpose, it is preferable to form the a-C film by an alternating current (low frequency, high frequency, microwave) plasma method, in which case the substrate is placed on an electrode to which plasma generation power is applied. is preferred. Further, it is preferable that the charge generation layer is formed by the same method as the a-C film, as this leads to reductions in manufacturing equipment costs and process labor.

The charge generation layer of the photoreceptor of the present invention is not particularly limited, and may be an amorphous silicon (a-Si) film (including various different elements such as I(, C, OSS) to improve the characteristics).

N, P, I3. may contain halogen, Ge, etc., and may have a multilayer structure), Se film, 5e-A
S film, 5e-Te film, CdS film, copper phthalocyanine, inorganic substances such as zinc oxide and/or bisazo pigments, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthine dyes, cyanine dyes, styryl Organic pigments such as biryllium dyes, azo pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, induthrone pigments, squarylium pigments, and phthalocyanine pigments. Examples include resin films containing substances.

In addition, any material that absorbs light and generates charge carriers with extremely high efficiency can be used.

The charge generation layer may be provided at any position on the photoreceptor, for example, the top layer, the bottom layer, or the middle layer. The film thickness depends on the type of material, especially its spectral absorption characteristics, exposure light source, purpose, etc., but generally it is 90% for 550 nm light.
The setting is made so that the above amount of absorption can be obtained. In the case of a-Si, it is 0.1 to 3 μm.

In the present invention, a heteroatom other than carbon or hydrogen may be mixed in order to adjust the charging characteristics of the a-C charge transport layer. For example, in order to further improve the hole transport properties, atoms of Group I of the periodic table or halogen atoms may be mixed. In order to further improve the electron transport properties, atoms of group V of the periodic table or alkali metal atoms may be mixed. In order to further improve the transport properties of both positive and negative carriers, 5iSGe, alkaline earth metals, and chalcogen atoms may be mixed. A plurality of these atoms may be used, or they may be mixed only at specific positions in the charge transport layer depending on the purpose, or they may have a concentration distribution, etc., but in any case, the important thing is that , the ratio αl of the infrared absorption peak based on the terminal olefin and methylene group in the polymer film
/α is 0.2 to 2.0 as described above.

1 to 12 are schematic cross-sectional views showing one embodiment of the photoreceptor of the present invention. In the figure, (1) indicates a substrate, (2) an a-C charge transport layer as a charge transport layer, and (3) a charge generation layer. In the photoreceptor of the embodiment shown in FIG. 1, when the photoreceptor is charged, for example, ten times and then imaged, charge 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 a-cTri charge transport layer (2). In the present invention, during this charging, the a-C charge transport layer may contain an element of Group 1IIA of the periodic table to be adjusted to P type. In this case, 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 N-type Norano for the charge generation layer (3). For example, a-Si is suitable because it is itself a weak N-type. However, elements of group VA of the periodic table may also be included.

This is effective in preventing surface charge injection and electron movement.

Group IIIA elements used for P-type adjustment include B.
, AQSGa, In, etc., and B is particularly preferred. By mixing a VA group element, for example, phosphorus, in the a-Si charge generation layer, the surface layer may be made into a relatively stronger N type. In this case as well, the polarity of the a-C charge transport layer is adjusted to P type. When the photoreceptor shown in FIG. 1 is used with one charge, contrary to the above, the a-C charge transport layer (2) may contain phosphorus to adjust it to N type, and the charge generation layer (3) may be used as the a-C charge transport layer (3). When using 9i, it may contain B.

The photoreceptor shown in Figure 2 is an example in which the a-C charge transport layer (2) is used as the uppermost layer. Charge generation layer (3
), it may be relatively N-type to facilitate the movement of electrons. - When used for charging, B or the like may be contained and adjusted in the opposite manner.

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 a charge generation layer (3)
It is preferable that the lower a-C charge transport layer (2) is adjusted to be P-type, while making it easier to move electrons by making it more N-type.

The photoreceptors shown in FIGS. 4 to 6 are examples of the photoreceptors 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 history (4).
Charge generation layer (3) or a-C charge transport layer (2)
This is intended to protect the surface and improve the initial surface potential. For the surface protective layer, a known substance may be used, and the aC charge transport layer of the present invention may be used. This protective layer (4) may also contain a layer [[A] if necessary.

It may also be doped with a Group VA element.

The photoreceptors shown in FIGS. 7 to 9 are examples in which an a-C charge transport layer used as a charge transport layer is used as an undercoat layer (5) on a substrate (1) as a barrier layer or an adhesive layer. Of course, other known materials may be used for the undercoat layer. The barrier layer has a rectifying function of effectively blocking charge injection from the substrate (1) and transporting the charges generated in the charge generation layer (3) to the substrate side. In this sense, when the barrier layer is charged, the mA group element,
- It is desirable to contain a Group VA element during charging.

Further, the thickness of the barrier layer is preferably 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. 10 to 12).

In order to incorporate the 1st nA group element into the a-C charge transport layer,
A film may be formed by using an appropriate gaseous compound containing these elements together with a hydrocarbon gas in an ionized state or a plasma state. Also, formed a C? The Ii transport layer may be doped by exposing it to a compound gas containing an IrfA group element.

B-containing compounds that can be used in the present invention include B (O
C2H5)3, B t HelB C(!3, BBr3
, B.F.

etc. are exemplified.

Compounds containing Af2 include A12 (Oi C1H7
)i, (Ctr 3)3 A 12, (CtH6), A
(+CJte)iAI21AI2C (13, etc.) are exemplified.

As a compound containing Ga, Ga(Oi 03H7)*
, (CHo)*Ga, (CtHs)+C;a, Ga
There are C12z, GaB r3, etc.

In-containing compounds include In(Oi C5H7)
*(CJrs)3 r n etc.

The introduction m of the IIIA group element is 20000 atm, PPm or less, relative to the sum of its introduced atomic weight and carbon atomic weight,
atomic is abbreviated as atom), more preferably 3 to
lO00atm, ppm.

As the VA group element used for polarity adjustment, PlAsS
Although Sb is included, P is particularly preferred. This group VA element can also be introduced into the a-C charge transport layer in the same manner as the group I[IA element.

Compounds containing Group V and A elements that can be used in the present invention include:
There are the following:

Examples of compounds containing P include PO(OCHJ3, (CyH
s) 3P, PHz, POCl25, etc.: Compounds containing AS such as A S Hs, ASC (!3, AsBr5, etc.)
As a compound containing b, S b (OCt H6) 3.5b
Examples include Cffs and SbH3.

The amount of the VA group element introduced is about 20000 atm, l) pm or less, more preferably about 1 to 1000 atm, ppm, based on the sum of the introduced atomic weight and the carbon atomic weight.

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

Examples of different elements that may be contained in the charge transport layer (2) include Si, Ge, and/or Sn in an m amount of 10 atoms or more based on the sum of the amount added and the amount of carbon atoms. By mixing , charge injection from the charge generation layer becomes easy, and effects such as a reduction in residual 71st position, an increase in sensitivity, and a reduction in memory can be obtained. Furthermore, the adhesion to the AI2 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, SiH+, 5itHa, (C2H5)3S
+F(.

Sin,, 5iHzCfJt, 5icmJ4,
S i(OCH3)4,s ;(o Ctl-1
s)+, Si(OC*H7)4, etc., and G for Ge introduction.
e H4, GeCL, G eco C2H4) 4, G
e(Ctl(s)) 4 etc., and for Sn introduction (cm
-1z)4Sn, (Ctr+5)asnSSnCL, etc. may be used.

It is also possible to adjust the band gap by adding Si or Ge to the charge transport layer to reduce the interface barrier with the charge generation layer. In Figure 1, polyfi (>10'atom,
%) is unevenly distributed on the substrate side, it is possible to prevent the reflection of excess light and prevent the occurrence of interference fringes and blurring. Furthermore, by adding 5iSGe, a hard film with wear resistance and water repellency can be formed.

Nitrogen, oxygen, sulfur and/or various metals may be further mixed into the a-C\r1 transport layer of the photoreceptor of the present invention, or a portion of hydrogen may be replaced with halogen or alkali metal. good.

Generally, nitrogen sources include N2, NH,, N t 01NO
,No,, Ct Hs N Ht, HCN,
(CH3) ffN.

CHiNHz or the like is used, and by mixing it, the interface barrier with the charge generation layer can be reduced.

As an oxygen source, Ol, 03, N, 01NO1CO1C
Examples include O,, CH, COcm-r, and CH3CHO, and by mixing these, the charging ability is improved. Furthermore, in the case of plasma CVD, introducing oxygen (0) has the secondary effect of increasing the film formation speed.

Examples of sulfur sources include CSt, (CtHa)ts, and Has.

Examples include SF8 and SO7. Mixing sulfur is effective in absorbing light and preventing interference. Additionally, the introduction of sulfur (S) has the secondary 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 mixed and used: Ba: Ba (O
CJIs)s, Ca: Ca(OCt Hs)3, Fe
:Fe(Oi-CsH7)3, (C,H,), Fe
S Fe(Co)6,l-1r:1(f(Oi C
3H□)+, ni:K(Oi C3H7), L i:
Li(Oi-CJI 7), La:La(O
i-C3H? )4, vt g : M g (oc
2 ■-r 5 ) 2, (CpHs)tMg, Na
:Na(Olc:l 7), Nb:Nb(O
CJfs)s, Sr:5r(QC)1. ),,T
i: Ti(Oi CtH7)n, Ti(OC4H8
)4, T i CLq T e: Fl t
T es (CH3)tT e, S e2Ht S esTa: Ta (OC2H3)! ,V:V
O(OCtHs)+, Y;Y(Oi C3H?)3,
Z n: Z n (OC!H5)2, (cm-r,),
Zn, (CtHs)tZnSZr:Zr(Oi-CsH
t)t,Cd:(CHJtCd,Co:Cot(Co)
e, Or: Cr(CO)6, Mn+Mn(CO)+o,
Mo+Mo(CO)e, MoF6, MoCf! eSW:
W(Co)e, WF,,WCa,.

Also, by replacing some of the hydrogen in the a-C charge transport layer with halogen or alkali metal, water repellency, abrasion resistance, and light transmittance are improved, especially for fluorine such as 10 F, CF! , -cF
* etc. are formed, and the refractive index n becomes smaller (1, 39)
, 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 -CF and - become CF.

As a carbon and halogen source, c 2 H5CQ-C
z) (sBr, cHffcc, CH3Br, C0Cat
SCCQ2Ft, CHCi2Ft, CF,,03F,,
HC&.

Examples include C122 and F2.

Examples of 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. When using, for example, an a-Si layer formed using a glow discharge decomposition device as the charge generation layer, it is possible to perform plasma polymerization using the same vacuum device, so that the a-C charge transport layer and the surface It is particularly preferable to form the protective layer, barrier layer, etc. by plasma polymerization.

The charge transport layer of the photoreceptor according to the present invention, for example, decomposes molecules in a gas phase by discharge under reduced pressure, and diffuses active neutral species or charged 7vL species contained in the generated plasma atmosphere onto the substrate, and Alternatively, it is preferable that the polymer be generated by a so-called plasma polymerization reaction, which is induced by magnetic force or the like and deposited as a solid phase by a recombination reaction on a substrate.

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.

First, explanation will be given using FIG. 13.

In FIG. 13, (7,01) to (706) are the first to sixth tanks in which the raw material compound and carrier gas, which are in a gaseous state at room temperature, are sealed, and each tank is connected to the first to sixth control valves ( 707) to (712) and the first to sixth fluid insect controllers (713) to (718).

In the figure, (719) to (721) are first to third containers filled with raw material compounds that are in a liquid or solid phase at room temperature, and each container is connected to a first to third heater (721) for vaporization.
22) to (724), and each container is further connected to seventh to ninth control valves (725) to (727) and seventh to ninth flow rate controllers (728) to (730). has been done.

These gases are mixed in a mixer (731) and then sent into a reaction chamber (733) via a main pipe (732).

The pipes along the way can be heated by appropriately placed pipe heaters (734) so that the gas, which is the vaporized raw material compound that is in a liquid or solid state at room temperature, does not condense on the way. .

A pair of electrodes (735) and (736) are installed facing each other in the reaction chamber, and electrode selection switches (754) and (755) are installed facing each other.
), each electrode can be used both as a ground electrode and as a power application electrode. Further, each electrode can be heated by an electrode heater (737).

A high frequency power source (739) and a low frequency power matching device (74) are connected to the power applying electrode via a high frequency power matching device (738).
A low frequency power source (741) is connected to the low frequency power source (741) through a low-pass filter (742), and a DC power source (743) is connected through a low-pass filter (742), and power with different frequencies can be applied by a frequency selection switch (744).

The pressure inside the reaction chamber can be adjusted by a pressure control valve (745), and the pressure inside the reaction chamber can be reduced by using a diffusion pump (747) and an oil rotary pump (748) via an exhaust system selection valve (746).
), or by a cooling exclusion device (749), mechanical booster pump (750), or oil rotary pump.

The exhaust gas is further rendered safe and harmless by an appropriate exclusion device (753) before being exhausted into the atmosphere. These exhaust system piping can also be heated by appropriately placed piping heaters so that the gas, which is the vaporized raw material compound that is in a liquid or solid phase at room temperature, does not condense on the way.

For the same reason, the reaction chamber can also be heated by a reaction chamber heater (751), and a conductive substrate (
752) is installed.

The apparatus shown in FIG. 14 is basically the same as the apparatus shown in FIG. 13, and the shape of the inside of the reaction chamber (733) is
52) is changed in accordance with the fact that it is cylindrical. The substrate also serves as an electrode (735) and an electrode (736).
) and the electrode heater (737) both have a cylindrical shape.

In the above printing process, the reaction chamber is equipped with a diffusion pump (747)
The pressure is reduced to about lo-4 to lo-8 in advance, and the degree of vacuum is checked and the gas adsorbed inside the device is desorbed.

At the same time, the electrode heater (737) heats the electrode (736) and the conductive substrate (752) fixedly disposed on the electrode to a predetermined temperature.

Next, the raw material gas is transferred from the first to sixth tanks (701) to (706) and the first to third containers (719) to (721) to the first to ninth flow rate controllers (713) to (718),
(728) to (730) are introduced into the reaction chamber (733) while converting them into constant flow ffi, and the pressure regulating valve is used to introduce the reaction chamber (733) into the reaction chamber (733).
733) maintain a constant reduced pressure inside.

After the gas flow rate has stabilized, turn the frequency selection switch (744
), for example, selects the low frequency power source (741), and by switching the electrode selection switches (754) and (755), the electrode (736) is grounded and low frequency power is applied to the electrode (735).

A discharge starts between both electrodes, and as time passes, the substrate (752
) a solid-phase a-C film is formed on the top.

This charge transport layer is composed of αl/α of moe produced according to the present invention.
, the ratio is 0.2 to 2.0. This α
The I/α ratio can be controlled by manufacturing conditions such as electric power, power frequency, electrode spacing, pressure, substrate temperature, source gas, gas concentration, gas flow rate, etc. Similar control can be achieved by narrowing the electrode spacing, increasing the substrate temperature, increasing the pressure, decreasing the molecular weight of the source gas, increasing the gas flow rate, etc. Also, from the DC power supply (743), 50
Similar control is possible even if bias voltages of V to IKV are applied in a superimposed manner. Of course, the opposite effect can be obtained by reversing the direction of control. These control methods are based on the charge transport layer,
For the purpose of imparting additional properties such as hardness and translucency, or for the purpose of ensuring manufacturing stability, a plurality of methods may be employed as appropriate.

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

Example I (1)' (Formation of a-C layer) In the glow discharge decomposition apparatus shown in FIG. 04 from the first tank (70I) by opening the first and second regulating valves (707) and (708).
Ha gas, H from the second tank (702).

Gas was allowed to flow into the mass flow controllers (713) and (714) under an output pressure gauge of IKg/cm'. Then, adjust the scale of each mass flow controller to set the C4He flow rate to 60 sec and Hz to 300 s.
ecm and flowed into the reaction chamber (733). After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 2 Tor4.

On the other hand, the conductive substrate (752) is 40X40XI
++un aluminum plate is preheated to 160°C, and when the flow rate of each gas is stable and the internal pressure is stable, the connection selection switch (744) is used to turn on the low frequency power supply (744).
41) and press the electrode selection switch (754), (75
5), the electrode (736) is grounded and the electrode (736) is grounded.
735) to I 50 volt power (frequency,.

Several 200 KHz) was applied to perform plasma polymerization for about 70 minutes to form a charge transport layer with a thickness of about 20 μm on the conductive substrate (752).

FIG. 17 shows a spectrum chart obtained by measuring the a-C film obtained as described above using a Fourier transform infrared absorption spectrometer (manufactured by Perkin-Nilmer). In Figure 17, a is 8
90CJ! -', b is the transmittance peak at 2925CM-'. From formula [1], the infrared absorption peak ratio α of the a-C film
, (890)/α, (2925) was 0157.

(n) (Formation of 7ri charge generation layer) The application of power from the low frequency power source (741) was temporarily stopped, and the inside of the reaction chamber was evacuated.

2nd regulating valve (708), 4th fA regulating valve (710), 5th
The regulating valve (711) and the sixth regulating valve (712) are opened, and H and gas are supplied from the second tank (702), SiH4 gas is supplied from the fourth tank (704), and PH3 is supplied from the fifth tank.
Gas (PH, mixed gas of Hl, PH3/H.

= 449 ppm), NtO gas is supplied from the 6th tank to the mass flow controller (
714), (716), (717), and (718). Adjust the scale of each mass flow controller to set the flow rate of H7 to 210 sccm and the flow rate of SSiH+ to 90 sccm.
The flow rate of secmSPH3 is I, 2secm, Nt
The flow rate of O was set at 0.9 and was allowed to flow into the reaction chamber.

After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 5 Torr.

When the gas flow rate is stable and the internal pressure is stable, select the high frequency power source (739) with the connection selection switch (744),
By switching the electrode selection switches (754) and (755), the electrode (735) is grounded and 35W is applied to the electrode (736).
electric power (frequency: 13.56 MHz) was applied to generate glow discharge. This glow discharge was performed for 5 minutes to form an a-Si:H mouse deposit with a thickness of about 0.5 μm.

The obtained photoreceptor had an initial surface potential (Vo) = -595v
Half exposure ff1E1/2 at olt is 1,61J
ux ・see , residual potential Vr (output 801ux-s
EC's snout was irradiated for 1 second) at -9 volts. Furthermore, when an image was formed and transferred onto this photoreceptor, a clear image was obtained.

Also, V in positive charging characteristics. = E1/2 when 467 volt is 1.9 Qux-8eCSvr is 10 vo
lt, and a clear image was obtained even when the image was formed and transferred with positive charging.

Table 1 shows the film forming conditions and the characteristics of the photoreceptor obtained. V in the table. is the initial surface potential, E1/2 is the half-reduced exposure amount, Vr is the residual potential, and DDRs is the ratio of dark decay in 5 seconds from the initial charging potential.

In addition, in the evaluation of repeated stability, ◎ means that the initial electrostatic properties hardly changed after 10,000 times of charging and exposure, and in the evaluation of humidity resistance, ◎ means that the temperature was 35℃ and relative humidity was 8
This shows that clear images were obtained under a 5% environment.

Examples 2 to 7 According to Example I, photoreceptors having the configuration shown in FIG. 1 were obtained under the conditions shown in Tables 2 to 12. The infrared absorption peak ratio α1/α of the obtained a-C film and the characteristics of the photoreceptor are also shown in Tables 2 to 12.
It was shown to.

Table 2 (Example 2) Table 3 (Example 3) Harm 4 (%14): B F, r Jewelry Ml 5) Table 8 (Example 8) Table 9 (Example 9) Comparative Examples 1, 2 A photoreceptor having the structure shown in FIG. 1 was obtained in the same manner as in Example 3.4, except that the substrate was fixed to the ground electrode side when forming the a-C charge transport layer. Table 13 shows the infrared absorption peak ratio α1/α2 of the obtained a-C model and the characteristics of the photoreceptor.

In the table, rxJ means that a clear image could not be obtained, and "-" means that evaluation could not be performed because the quality of the image was poor.

Further, an infrared absorption spectrum diagram of the a-C film obtained in Comparative Example 2 is shown in FIG. In Figure 18, a is 890
cx', b is the transmittance peak of 2925cx'.

The peak ratio αl/α is 0. It was I4.

The resulting photoreceptor had a low initial surface potential and a high residual potential, and the copied image had low density and fog in non-image areas, making it impossible to form a good image.

Comparative Example 3 According to Example I, a photoreceptor having the structure shown in FIG. 1 was obtained under the conditions shown in Table 14. The infrared absorption peak ratio α1/α of the obtained a-C film was 2.4.

The film quality of the obtained a-C film was very poor, with cracks and peeling occurring partially.

In addition, regarding the characteristics of the photoreceptor, the charging ability was small and it was not possible to form an image that could be evaluated.

Comparative Example 4 According to Example 1, a photoreceptor having the structure shown in FIG. 1 was obtained under the conditions shown in Table 15. The infrared absorption peak ratio α1/α2 of the obtained a-C film was 2.2. Although the film forming properties were good, the charging ability of the obtained photoreceptor was so small that no evaluationable images could be formed.

The superiority of the charge transport layer of the present invention was recognized.

Comparative Examples 5 to 9 Photoreceptors having the structure shown in FIG. 1 were obtained in the same manner as Examples 8 to 12, except that the substrate was fixed to the ground electrode during formation of the aC charge transport layer. Table 16 shows the film thickness and characteristics of the photoreceptor obtained. In the table, "△" indicates that the image density is slightly low, "x" indicates that the image density is low and capri is seen in the non-image area, and "r-J" indicates that the image quality was poor and evaluation could not be performed. means.

All of the obtained photoreceptors had a thin film thickness, did not show sufficient charging ability, and had a large residual potential compared to the initial surface potential.
A good image could not be formed. The superiority of the photoreceptor manufacturing method of the present invention was recognized.

Further, FIG. 15 shows αl/α of the half-decreased exposure amount (corresponding to the reciprocal of the sensitivity of the photoreceptor) for the examples and comparative examples.

Figure 16 shows the α1/α2 dependence of the residual potential per unit film thickness of the photoreceptor.

As shown in FIGS. 15 and 16, in order to obtain a photoreceptor with high sensitivity and low residual potential, a-C
It was recognized that it is important that αl/αd of the charge transport layer is 0.2 to 2.0.

Table 13 Table 15 (Comparative Example 4) Effects of the Invention The rT photoconductor using the organic plasma polymerized film of the present invention as a charge transport layer has excellent characteristics such as charging ability, charge transport property, sensitivity, and residual potential, and has a thin film thickness. Even when the surface is heated, a sufficient surface potential can be obtained and a good image can be obtained. According to the present invention, when using a-8i in the charge generation layer, the conventional a-8i
- It is possible to obtain a thin-film photoreceptor that could not be achieved with an Si photoreceptor.

The raw materials for the photoreceptor of the present invention are inexpensive, the necessary six layers can be formed in the same tank, and the film thickness can be thin, so the manufacturing cost is low and the manufacturing time is short.

The organic plasma polymerized film according to the present invention does not easily generate bin poles even when formed into a thin film, and can be formed homogeneously, so that it can be easily made into a thin film. Furthermore, it has excellent corona resistance, acid resistance, moisture resistance, heat resistance, and rigidity, so when used as a surface protective layer, the durability of the photoreceptor is improved.

[Brief explanation of the drawing]

1 to 12 show schematic cross-sectional views of the photoreceptor of the present invention. FIG. 13 and FIG. 14 are diagrams showing an example of an apparatus for manufacturing a photoreceptor. FIG. 15 is a diagram showing the value dependence of the half-decreased exposure amount of the photoreceptor, αI/α. FIG. 16 is a diagram showing the dependence of the residual potential of the photoreceptor on the α1/α2 value. FIGS. 17 and 18 are diagrams showing infrared absorption spectra of the a-C film. The symbols in the figure are as follows. (1)...Substrate (2)...Charge transport layer (a
-C layer) (3)...charge generation layer (4)...overcoat layer (5)...undercoat layer (701) to (706)...tank (707) to (712) and ( 725) ~ (727)・
・・Control valves (713) to (718) and (728) to (730)・
・・Flow control device (mass flow controller) (
719) ~ (721)... Container (722) ~ (724)... Heater (731)... Mixer (732)... Main pipe (
733)...Reaction chamber (734)...Pipe heater (735)...Ground electrode (736)...Power application electrode (737)...Power heater (738)...High frequency power Matching box (739)...High frequency power supply (740)...Low frequency power matching box (III)...Low frequency power supply (742)...Low pass filter (743)...DC power supply (744)... ... Frequency selection switch (745) ... Pressure control valve (746) ... Exhaust system selection valve (7f7) ... Diffusion pump (748) ... Oil rotary pump (749) ... Cooling exclusion device (750 )...Mechanical booster pump (751)
... Reaction heater (752) ... Conductive substrate (75
3)...Exclusion device (754), (755)...Electrode selection switch Patent applicant Minolta Camera Co., Ltd. Representative Patent attorney Maeda Haji and 2 others Figure 1
Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 15
Figure 0 0.5 1.0d%+ +88
4) /dz (2920) Fig. 16 00.51.0 cl+ (884) 10 (2 (2920) Fig. 17 Ripple per tcm

Claims (1)

[Claims] 1. In a functionally separated photoreceptor having a charge generation layer (3) and a charge transport layer (2), a hydrocarbon plasma polymerized film is provided as the charge transport layer (2), and the infrared absorption spectrum of the polymerized film is 89 due to terminal olefin (>C=CH_2)
The ratio α_1/α_2 between the peak absorption coefficient α_1 near 0 cm^-^1 and the peak absorption coefficient α_2 near 2925 cm^-^1 due to the methylene (-CH_2-) group is 0.2 to 2.0. photoreceptor.