JPS6125152A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To obtain a photoreceptive member which has high sensitivity and high SN ratio and can utilize efficiently incident light by forming a photoreceptive member consisting of an amorphous layer contg. Si and Ge, amorphous photoconductive layer contg. Si and surface layer having an antireflection function on a base and providing many non-parallel boundary faces in the direction perpendicular to the thickness direction. CONSTITUTION:The amorphous layer 1002 contg. Ge and Si and contg. at least either of hydrogen and hologen atoms according to need is formed on the base 1001 and the photoconductive layer 1003 contg. Si and contg. at least eigher of the hydrogen and halogen ions according to need is formed thereon. The surface layer 1005 having antireflection function is formed thereon, by which the photoreceptive member 1004 contg. the photoreceptive layer 1000 is obtd. The layer 1000 is so formed as to contain the many non-parallel faces in the plane perpendicular to the thickness direction thereof. The interference by the reflection from the boundary faces is thus decreased and the high SN ratio is obtd. Since the layer 1005 is provided, the reflected light decreases and the efficient use of the incident light is made possible.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the use of light (here, light in a broad sense, such as ultraviolet rays, visible light,
It relates to a light-receiving member that is sensitive to electromagnetic waves such as infrared rays, X-rays, gamma rays, etc. More specifically, the present invention relates to a light receiving member suitable for using coherent light such as laser light.

[Conventional technology]

As a method of recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light-receiving member with a laser beam modulated according to the digital image information.
A well-known method is to then develop the latent image and, if necessary, perform processes such as transfer and fixing to record an image.

Among these, in image forming methods using electrophotography, image recording is generally performed using a small and inexpensive He--Ne laser or semiconductor laser (usually having 650 to 650 b).

In particular, as a light-receiving member for electrophotography that is suitable when using a semiconductor laser, it has a much better consistency in the photosensitivity region than other types of light-receiving members, and also has a Vickers hardness. For example, JP-A No. 54-86341 and JP-A-Sho 56-
A light-receiving member made of an amorphous material containing silicon atoms (hereinafter abbreviated as "RA-3i") disclosed in Japanese Patent No. 83746 is attracting attention.

Of course, if the photoreceptive layer is a single-layer a-5i layer, in order to maintain its high photosensitivity and ensure a dark resistance of 1012 Ωcm or more required for electrophotography, hydrogen atoms and halogen atoms are required. In addition to these, it is necessary to structurally contain poron atoms in a specific amount range in a controlled manner in the layer, so layer formation must be strictly controlled. There are considerable limitations on the tolerances in component design.

For example, Japanese Patent Laid-Open No. 54-121743 is an example of a system that can expand this design tolerance and make effective use of high light sensitivity even if the dark resistance is low to some extent.
No. 1, JP-A-57-4053, JP-A-57-4
As described in Japanese Patent Publication No. 172, the photoreceptive layer may have a layer structure of two or more layers having different conductivity characteristics, and a depletion layer may be formed inside the photoreceptive layer.
No. 178, No. 52179, No. 52180, No. 581
A barrier layer was provided between the support and the photoreceptive layer, and/or on the upper surface of the photoreceptive layer, as described in Japanese Patent No. 59, No. 58160, and No. 5816.1. A light-receiving member has been proposed that has a multilayer structure and has an apparently increased dark resistance.

Through such proposals, a-Si light-receiving members have made dramatic progress in terms of commercialization design tolerances, ease of manufacturing management, and productivity, and are moving toward commercialization. The speed of development is accelerating.

When laser recording is performed using a light-receiving member with such a multilayered light-receiving layer, the thickness of each layer is uneven, and the laser light is coherent monochromatic light, so the light-receiving layer is Reflected from the free surface of the laser beam irradiation side, each layer constituting the light-receiving layer, and the layer interface between the support and the light-receiving layer (hereinafter, both the free surface and the layer interface are collectively referred to as the "interface"). There is a possibility that each of the reflected lights may cause interference.

This interference phenomenon causes the so-called,
This appears as an interference fringe pattern and causes image defects. Particularly when forming a half-tone image with high gradation, the image becomes noticeably unsightly.

Furthermore, as the wavelength region of the semiconductor laser light used becomes longer, the absorption of a portion of the laser beam in the photoreceptive layer decreases, so that the above-mentioned interference phenomenon becomes remarkable.

This point will be explained with reference to the drawings.

Figure 1 shows light IO incident on a certain layer constituting the light-receiving layer of a light-receiving member and reflected light R reflected at the upper boundary 1fi102.
1 shows reflected light R2 reflected at the lower interface 101.

If the average layer thickness of the layer is d, the refractive index is n, and the wavelength of the light is uneven due to the difference in thickness, then the reflected lights R,, R2 are 2nd; m (m is an integer, and the reflected lights strengthen each other). Depending on which of the 2nd conditions is met, the amount of absorbed light and the amount of transmitted light of a certain layer change.

In a multilayered light-receiving member, the interference effect shown in FIG. 1 occurs in each layer, and as shown in FIG. 2, a synergistic adverse effect occurs due to each interference. Therefore, interference fringes corresponding to the interference fringe pattern appear in the visible image transferred and fixed onto the transfer member, causing a defective image.

A method for solving this problem is to diamond-cut the surface of the support and provide unevenness of ±500A to ±10000A to form a light-scattering surface (for example,
162975), a method of providing a light absorption layer by subjecting the surface of an aluminum support to black alumite treatment, or dispersing carbon, colored pigments, or dyes in a resin (for example, JP-A-57-165845); A method of providing a light-scattering and anti-reflection layer on the surface of an aluminum support by subjecting the surface of the support to a satin-like alumite treatment or by sandblasting to provide fine grain-like irregularities (e.g., Japanese Patent Laid-Open No. 16554/1983) ) etc. have been proposed.

Unfortunately, these conventional methods have not been able to completely eliminate the interference fringe pattern that appears on the image. In other words, the first method involves forming a large number of concavities of a specific size on the surface of the support. However, since the specularly reflected light component still remains as light scattering, the interference fringes due to the specularly reflected light are In addition to the remaining pattern, the irradiation spot spread due to the light scattering effect on the surface of the support, causing a substantial reduction in resolution.

In the second method, complete absorption is impossible with the black alumite treatment, and the reflected light on the surface of the support remains. In addition, when a colored pigment dispersed resin layer is provided, when forming the a-5i layer, a degassing phenomenon occurs from the resin layer, and the layer quality of the formed light-receiving layer is significantly deteriorated. 5i
There are disadvantages such as being damaged by plasma during layer formation, reducing the original absorption function, and adversely affecting the subsequent formation of the a-St layer due to deterioration of the surface condition.

In the case of the third method of irregularly roughening the support surface, the third method
As shown in the figure, 1, for example, the incident light I0 is transmitted to the photoreceptive layer
A part of the light is reflected on the surface of the light receiving layer 302 and becomes reflected light R1, and the rest enters the inside of the light-receiving layer 302 and becomes transmitted light 11. A part of the transmitted light 11 is scattered on the surface of the support 302 and becomes diffused light K I + K2 + K
3... It becomes a fist, the rest is specularly reflected and becomes reflected light R2, and a part of it becomes emitted light R3 and goes outside.

Therefore, since the emitted light R3, which is a component that interferes with the reflected light R1, remains, the interference fringe pattern cannot be completely erased.

Furthermore, if the diffusivity of the surface of the support 301 is increased in order to prevent interference and multiple reflections inside the light-receiving layer, the resolution decreases because light is diffused within the light-receiving layer and causes halation. There was also the drawback of doing so.

In particular, in a multilayered light-receiving member, even if the surface of the support 401 is irregularly roughened, as shown in FIG.
Reflected light R2 on the surface of layer 402 + reflected light R1 on the second layer
+ Each of the specularly reflected lights R3 on the surface of the support 401 interferes,
An interference fringe pattern occurs depending on the thickness of each layer of the light-receiving member.

Therefore, in a light-receiving member having a multilayer structure, the support 40
1. It has been impossible to completely prevent interference fringes by irregularly roughening the surface.

In addition, when the surface of the support is irregularly roughened by methods such as sandblasting, the degree of roughness varies greatly between lofts, and even in the same lot, the degree of roughness is uneven, making it difficult to manufacture. Management was not good. In addition, relatively large protrusions are frequently formed randomly, and such large protrusions cause local breakdown of the photoreceptive layer.

In addition, if the support surface 501 is simply roughened regularly, the fifth
As shown in the figure, the light-receiving layer 502 is usually deposited along the uneven shape of the surface of the support 501.
The sloped surface of the unevenness of the light-receiving layer 502 becomes parallel to the sloped surface of the unevenness of the light-receiving layer 502.

Therefore, in that part, the incident light satisfies 2ndl=m or 2nd+=(m10)λ, which becomes a bright part or a dark part, respectively. In addition, for the entire photoreceptive layer, the layer thickness dI of the photoreceptive layer is
Since there is one layer with no restriction on the layer thickness such that the maximum of the differences between T d21 d3 + d4 is one or more, a bright and dark striped pattern appears.

Therefore, just by regularly roughening the surface of the support 501,
It is not possible to completely prevent the occurrence of interference fringes.

Furthermore, even when a multi-layered light-receiving layer is deposited on a support whose surface is regularly roughened, the specularly reflected light on the surface of the support as explained for the single-layered light-receiving member in FIG. In addition to the interference with the reflected light on the surface of the light-receiving layer, interference due to the reflected light at the interface between each layer is added, so that the degree of interference fringe pattern development becomes more complicated than that of a light-receiving member with a single-layer structure.

[Purpose of the invention]

It is an object of the present invention to provide a new light-sensitive light-receiving member which eliminates the above-mentioned drawbacks.

Another object of the present invention is to provide a light-receiving member that is suitable for image formation using coherent monochromatic light and that is easy to control in manufacturing.

Still another object of the present invention is to provide a light-receiving member that can simultaneously and completely eliminate the interference fringe pattern that appears during image formation and the appearance of spots during reversal development.

Another object of the present invention is to provide a light-receiving member that allows digital image recording using electrophotography, especially digital image recording with halftone information to be performed clearly, with high resolution, and with high quality.

Yet another object of the present invention is to provide a light-receiving member having high photosensitivity, high signal-to-noise ratio characteristics, and good electrical contact with the support.

Another object of the present invention is to provide a light receiving member that can reduce light reflection on the surface of the light receiving member and efficiently utilize incident light.

[Summary of the invention]

The light-receiving member of the present invention includes a support; a first layer made of an amorphous material containing silicon atoms and germanium atoms; and a first layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity. a light-receiving layer having a multilayer structure in which a second layer and a surface layer having an antireflection function are provided in order from the support side; It has an interface, a large number of non-parallel interfaces are arranged in at least one direction in a plane perpendicular to the layer thickness direction, and each of the non-parallel interfaces is smoothly connected in the arrangement direction.

Hereinafter, the present invention will be specifically explained with reference to the drawings.

FIG. 6 is an explanatory diagram for explaining the basic principle of the present invention.

In the present invention, a support (not shown) having irregularities smaller and smoother than the required resolution of the apparatus has a multilayered light-receiving layer along the slope of the irregularities. The photoreceptive layer has a second layer as shown in FIG. 6(A).
Since the layer thickness of the layer 602 changes continuously from d5 to d6, the interface 603 and the interface 604 have a tendency toward each other.

Therefore, this minute part (short range)! The coherent light incident on l causes interference in the minute portion, producing a minute interference fringe pattern.

Furthermore, if the interface 703 between the second layer 602 and the second layer 702 and the free surface 704 of the second layer 702 are non-parallel as shown in FIG. Since the traveling directions of the reflected light R and the emitted light R3 for a light amount of 0 are different from each other, when the interfaces 703 and 704 are parallel (r
(B) The degree of interference is reduced compared to J).

Therefore, as shown in Figure 7 (C), when the pair of interfaces are non-parallel (A) than when they are parallel (B), even if there is interference, the difference in brightness of the interference fringe pattern is ignored. And the more you get, the smaller it gets. As a result, the amount of light incident on the minute portions is averaged.

As shown in FIG. 6, this is true even if the thickness of the second layer 602 is macroscopically non-uniform (dy≠ds), so the amount of incident light is uniform over the entire layer area. (r in Figure 6)
(D) See J).

In addition, to describe the effect of the present invention in the case where the light-receiving layer has a multilayer structure and coherent light is transmitted from the irradiation side to the second layer, as shown in FIG. There are reflected lights R,, R2, R3, R4, and R5 for the light Io. Therefore, in each layer, what was explained above with reference to FIG. 7 occurs.

Therefore, when considering the entire photoreceptive layer, interference is a synergistic effect in each layer, so according to the present invention, as the number of layers constituting the photoreceptive layer increases, the interference effect can be further prevented. I can do it.

Further, interference fringes generated within a minute portion do not appear in one image because the size of the minute portion is smaller than the irradiation light spot diameter, that is, smaller than the resolution limit. Moreover, even if it appears in the image, it will not cause any substantial trouble because it is below the resolution of the eye.

In the present invention, it is preferable that the uneven inclined surface has a mirror finish in order to reliably align the reflected light in one direction.

The size of the minute part is suitable for the present invention! If the spot diameter of the irradiated light is L, then
It is.

By designing in this way, the diffraction effect can be actively utilized, and the appearance of interference fringes can be further suppressed.

In addition, in order to more effectively achieve the purpose of the present invention, the difference in layer thickness (d5 db) in a minute portion should be determined as follows, where the wavelength of the irradiation light is input, d, , -d6≧2n( n' (the refractive index of the second layer 602).

In the present invention, at least any two layer interfaces are in a nonparallel relationship within the layer thickness of a minute portion of a multilayered photoreceptive layer (hereinafter referred to as a "microcolumn"). The layer thickness of each layer is controlled within the microcolumn when forming each layer, but any two layer interfaces may be in a parallel relationship within the microcolumn as long as this condition is satisfied.

However, the layers forming parallel layer interfaces must have a uniform layer thickness over the entire region so that the difference in layer thickness at any two positions is λ 2n (refractive index of the n' layer) or less. preferably formed.

In order to more effectively and easily achieve the object of the present invention, the first layer containing silicon atoms and germanium atoms and the second layer containing silicon atoms constituting the photoreceptive layer are formed by:
The plasma vapor phase method (PCVD method), photo-CVD method, and thermal CVD method are employed because the layer thickness can be accurately controlled at an optical level.

The smooth irregularities provided on the surface of the support can be used to fix a cutting tool with an arc-shaped cutting edge in a predetermined position on a cutting machine such as a milling machine or lathe, and rotate the cylindrical support according to a program designed in advance according to the desired results. By regularly moving in a predetermined direction while rotating, the surface of the support is accurately cut, and a desired smooth uneven shape, pitch, and depth are formed. The sinusoidal linear protrusion created by the unevenness formed by such a cutting method has a helical structure centered on the central axis of the 5-cylindrical support. An example of such a structure is shown in FIG. 9, where L is the length of the support, r is the diameter of the support,
P is the helical pitch and D is the groove depth.

The helical structure of the sinusoidal protrusion may be a double or triple helical structure, or a crossed helical structure.

Alternatively, a linear structure along the central axis may be introduced in addition to the fs spiral structure.

In the present invention, each dimension of the smooth irregularities provided on the surface of the support in a controlled manner is set so as to effectively achieve the purpose of the present invention, taking into consideration the following points. .

That is, firstly, the a-3T layer constituting the photoreceptive layer is structurally sensitive to the condition of the surface on which the layer is formed, and the layer quality changes greatly depending on the surface condition.

Therefore, it is necessary to set the dimension of the smooth irregularities provided on the surface of the support so as not to cause a deterioration in the layer quality of the a-5t layer.

Secondly, if the free surface of the photoreceptive layer is extremely uneven, it becomes impossible to perform cleaning completely after image formation.

Further, when cleaning the blade, there is a problem that the blade becomes damaged quickly.

After considering the above-mentioned problems in layer deposition, process problems in electrophotography, and conditions for preventing interference fringes, we found that:
The pitch of the four parts of the support surface is preferably 500 Bm-
0.3#Lm, more preferably 200#Lm Nl#L
m, preferably 50#Lm to 5gm.

Further, the maximum depth of the recess is preferably 0. IILm~5
ILm, more preferably 0.3 #Lm ~ 3 ILm,
The optimum value is 0.6 pm to 2 pm. When the pitch and maximum depth of the recesses on the surface of the support are within the above range, the slope of the slope connecting the minimum and maximum points of each of the adjacent recesses and projections is preferably 1 degree to 20 degrees. degree, more preferably 3 degrees to 15 degrees, most preferably 4 degrees to 10 degrees.

Further, the maximum difference in layer thickness due to the non-uniformity of the layer thickness of each layer deposited on such a support is preferably 0.
1 pm to 2 ILm, more preferably 0, lILm-1,
5Bm, optimally 0.2#Lm~Igm.

The light-receiving layer in the light-receiving member of the present invention is a first layer made of an amorphous material containing silicon atoms and germanium atoms.
layer, a second layer that is made of an amorphous material containing silicon atoms and exhibits photoconductivity, and a surface layer that has an antireflection function are provided in order from the support side, making it extremely Shows excellent electrical, optical, photoconductive properties, electrical voltage resistance, and use environment characteristics.

In particular, when applied as a light-receiving member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high signal-to-noise ratio. Therefore, it has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

Furthermore, the light-receiving member of the present invention has high photosensitivity in the entire visible light region, and is particularly excellent in photosensitivity characteristics on the long wavelength side, so it is particularly excellent in matching with semiconductor lasers,
Moreover, the light response is fast.

Hereinafter, one light receiving member of the present invention will be explained in detail with reference to the drawings.

FIG. 1O is a schematic structural diagram schematically shown to explain the layer structure of a light receiving member according to an embodiment of the present invention.

A light-receiving member 1004 shown in FIG. 10 has a light-receiving layer 1000 on a support 1001 for the light-receiving member.

The light-receiving layer 1000 is made of an amorphous material (hereinafter referred to as ra-SiGe (H, ) abbreviated as J)
A first layer (G) 1002 composed of a-St (hereinafter abbreviated as ra-5i(H,X)J) containing at least one of hydrogen atoms and halogen atoms (X) as necessary. It has a layer structure in which a second layer (S) 1003 having photoconductivity and a surface layer 1005 having an antireflection function are laminated in this order.

The germanium atoms contained in the first layer (G) 1002 are continuous and uniform in the layer thickness direction of the first layer (G) 1002 and in the in-plane direction parallel to the surface of the support. It is contained in the first layer (G) 1002 so as to be distributed.

In the present invention, the second layer (G) provided on the first layer (G)
The layer (S) does not contain germanium atoms, and by forming a light-receiving layer in such a layer structure, it can absorb all wavelengths from relatively short wavelengths to relatively short wavelengths, including the visible light region. The present invention provides a light-receiving member having excellent photosensitivity to light having wavelengths in the range.

In addition, the distribution state of germanium atoms in the first layer (G) is such that germanium atoms are continuously distributed over the entire layer region, so when a semiconductor laser or the like is used, the second layer (S ) can substantially completely absorb light on the long wavelength side, which is almost completely absorbed in the first layer (G).
Interference due to reflection from the support surface can be prevented.

Further, in the light-receiving member of the present invention, each of the amorphous materials constituting the first layer (G) and the second layer (S) has a common constituent element of silicon atoms. Therefore, the laminated interface is sufficiently acidified to ensure chemical stability.

In the present invention, the content of germanium atoms contained in the first layer is determined as desired so as to effectively achieve the object of the present invention, but is preferably 1.
~9.5X105 at.

micppm, more preferably 100-8X105at
omic ppm, optimally 500-1.7X105
It is preferable that the amount is at omf c ppm.

In the present invention, the layer thickness of the first layer (G) and the second layer (3) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the light receiving member to ensure that the desired properties are fully imparted to the light receiving member.

In the present invention, the layer thickness TB of the first calendar (G) is preferably 30A to 50g, more preferably 40A to 40g.
, optimally, it is desirable to set it to 50A to 3o#L.

Further, the layer thickness T of the second 71 (S) is preferably 0.
5 to 90 IL, more preferably 1 to 80 IL, optimally 2
It is desirable that it be between 50 and 50.

The sum (TB+T) of the layer thickness TB of the first layer (G) and the layer thickness T of the second layer (S, ) is based on the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. Based on the organic relationship between the
To be determined accordingly.

In the light receiving member of the present invention, the numerical range of (TB+T) is preferably 1 to 10G, more preferably 1 to 8oIL, and most preferably 2 to 5.01L. desirable.

In a more preferred embodiment of the present invention.

The above layer thickness TB and layer thickness T are preferably TB/
It is desirable that appropriate numerical values be selected for each so as to satisfy the relationship T≦1.

In selecting the numerical values of layer thickness TB and layer thickness T in the above case, it is more preferable that T/T≦0.9. It is preferable that the values of layer thickness TB and layer thickness T are optimally determined such that the relationship TB/T≦0.8 is satisfied.

In the present invention, the content of germanium atoms contained in the first layer (G) is lXl05at.

mic ppm or more, it is desirable that the layer thickness TB of the first layer (G) be considerably thinner, preferably 30. Hereinafter, it is more preferably 25 #L or less, most preferably 20 #L or less.

In the present invention, if necessary, the first
Specific examples of the halogen atoms (X) contained in the layer (G) and the second layer (S) include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as something.

In the wood invention and invention, in order to form the first layer (G) composed of a-3iGe (H, X), for example, a glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon such as a sputtering method or an ion blating method. For example, by glow discharge method, a-5iGe (H,X)
Basically, to form the first layer (G) composed of
Introduce the raw material gas for supply and, if necessary, the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (x) into the deposition chamber in which the internal pressure can be reduced at a desired gas pressure state. A glow discharge is generated in the deposition chamber, and a-
It is sufficient to form a layer consisting of 3iGe (H,
A target composed of Si and a Ge
Using two targets made up of or SL,
! When performing sputtering using a mixed target of =Ge, a gas for introducing hydrogen atoms (H) and/or norogen atoms (X) may be introduced into the sputtering deposition chamber as necessary.

Substances that can be used as raw material gas for supplying Si used in the present invention include 5iHa, Si2H6, Si3H
B, Si4Hl. Silicon hydride (silanes) in a gaseous state or which can be gasified such as SiH4, etc. can be effectively used. In particular, SiH4, Si2H6 is preferred.

As a material that can be a source gas for supplying Ge, GeH
4, Ge, , H6, Ge3 HB , GeaHlo, G
e5H+2 , Ge6H1a, Ge7) (+ b ,
Germanium hydride in a gaseous state or that can be gasified, such as G eB HI B , G, and es H2o, can be effectively used, especially because of its ease of handling during layer creation work, good Ge supply efficiency, etc. In terms of GeH4, Ge
2 H6, 'Ge3 HB are preferred.

There are many 7-halogen compounds that are effective as the raw material gas for introducing the halogen atoms used in the present invention, such as halogen gas, halogen compounds, halogen compounds, and halogen-substituted 7-halogen compounds. Preferred examples include gaseous or gasifiable l\rogen compounds such as silane derivatives.

Further, silicon hydride compounds containing I\halogen atoms, which are in a gaseous state or can be gasified and which have silicon atoms and halogen atoms as constituent elements, can also be mentioned as effective in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, C1F, ClF3. BrF5. BrF
Interhalogen compounds such as 3, IF3, IF, ICIL, and IBr can be mentioned. Specific examples of silicon compounds containing halogen gas, so-called silane derivatives substituted with l\halogen atoms, include 5iFa, Si2F6. Si0 sentence.

Preferred examples include silicon halides such as S i Bra.

When forming the characteristic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying St together with a raw material gas for supplying Ge. a-5iGe containing halogen atoms on a desired support without using silicon oxide gas
It is possible to form a first layer (G) consisting of:

According to the glow discharge method, the first layer containing halogen atoms (
G), basically, for example, silicon halide is used as a raw material gas for supplying Si, germanium hydride is used as a raw material gas for supplying Ge, Ar, F2. A gas such as He is introduced into a deposition chamber for forming the first layer (CG) at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. The first layer (G) can be formed on the desired support by using these gases, but in order to more easily control the ratio of hydrogen atoms introduced, hydrogen gas or A layer may also be formed by mixing a desired amount of silicon compound gas containing hydrogen atoms.

Moreover, each gas may be used not only as a single species but also as a mixture of a plurality of them at a predetermined mixing ratio.

A first layer CG made of a-SiGe(H,X) is formed by reactive sputtering or ion blating.
), for example, in the case of a sputtering method, two targets, one made of Si and one made of Ge, or a target made of Si and Ge, are used and sputtered in a desired gas plasma atmosphere. death.

In the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are respectively accommodated as evaporation sources in the evaporation port, and these evaporation sources are heated using the resistance heating method or the electron beam method ( A vehicle can be produced by heating and evaporating the flying evaporates using the EB method or the like and passing them through a desired gas plasma atmosphere.

At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It would be a good idea to introduce the gas and create a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as F2, or the above-mentioned silanes or/
Gases such as germanium hydride and the like may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gases.

In the present invention, a halogen compound or a silicon compound containing a halogen is effectively used as a raw material gas for introducing a halogen atom.
In addition, silicon halides such as HF, HCI, HBr, HI, 5iH2F2SiH2I2.5iH2C Emperor 2,5
iHC: 3.5iH2Br2.5iHBr3, etc., halogen-substituted silicon hydride, and GeHF3, GeB2F
2, GeHa F, GeHBr3. GeB2 CJ12
, G e Hs Cl, GeHBr3 , GeH2B
r2, GeB3 Br, GeHI3,
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as GeB2 12 and GeH3I, GeF, GeC, GeBra, Ge
I4. GeF2. GeC1,, GeB r2, Ge
Gaseous or gasifiable substances such as germanium halides such as I2 can also be mentioned as useful starting materials for forming the first layer (G).

Among these substances, halides containing hydrogen atoms introduce halogen atoms into the layer when forming the first layer (G), and at the same time introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen.

To structurally introduce a hydrogen atom into the first calendar (G),
In addition to the above, F2. Or SiH4, Si2 H6,5i
Silicon hydride such as 3HB, 5iaHso, etc. with germanium or a germanium compound for supplying Ge, or
GeH,, Ge2H&, Ge3He,
Gea Hlot Ge.

HI2, Ge6H14, Ge7H16, Gee)
(,B,Ge9H2゜etc.) and St.
This can also be carried out by coexisting silicon or a silicon compound in the deposition chamber to generate a discharge.

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the first layer (G) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts (H+X) is preferably 0.01 to 4
0 atomic%, more preferably 0.05-30a
atomic%, optimally O11-25atomic
It is desirable that it be expressed as %.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (x) contained in the width of the first layer (G), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (
What is necessary is to control the amount of the starting material used to contain X) introduced into the deposition system, the discharge force, etc.

In the present invention, the second
To form the layer (S), starting materials [second It can be carried out using the starting material (■) for forming the layer (S) and according to the same method and conditions as in the case of forming the tsl calendar (G).

That is, in the present invention, to form the second layer (S) composed of a-Si(H,X), for example, a glow discharge method,
The second layer (S) composed of a-3i (H, In order to form this, basically, together with the raw material gas for supplying Si that can supply the silicon atoms (Si) described above, as necessary, the introduction of hydrogen atoms (H) and/or halogen atoms (X) is required. A raw material gas for use is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber, and a -3i (H, ) to form a calendar consisting of

In addition, when forming by sputtering method, for example, jfA
When sputtering a target composed of Si in an atmosphere of an inert gas such as r, He, or a mixed gas based on these gases, it is necessary to introduce hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into the deposition chamber for sputtering.

In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the amounts of hydrogen atoms and halogen atoms contained in the second calendar C5'' constituting the photoreceptive layer to be formed The sum (HIX) is preferably 1 to 40 atomic%,
More preferably, it is 5 to 30 atomic %, and optimally 5 to 25 atomic %.

The thickness of the surface layer 1005 having an antireflection function is as follows.

It is determined as follows.

The thickness d of the surface layer having an antireflection function is preferably as follows, where n is the refractive index of the material of the first surface layer and the wavelength of the irradiated light is .

Further, as the material for the surface layer 1005, it is optimal to use a material having a refractive index of n=(n), where na is the refractive index of the second layer on which one surface layer is deposited.

Considering such optical conditions, the thickness of the antireflection layer 1 is preferably 0.05 to 2 pm, assuming that the wavelength of the exposure light is in the wavelength range from near infrared to visible light. be.

In the present invention, materials that can be effectively used for the surface layer 1005 having an antireflection function include, for example, M
g F 2 + A 120 s + Z r O2
1Ti02, ZnS, CeO2, CeF2.530
2, SiO, Ta205 *AiF3, Na
F.

Inorganic fluorides such as Si3N4, inorganic oxides and inorganic nitrides,
Alternatively, organic compounds such as polyvinyl chloride, polyamide resin, polyimide resin, vinyl fluoride, melamine resin, epoxy resin, phenol resin, and cellulose acetate may be used.

In order to achieve the object of the present invention more effectively and easily, these materials can be used by vapor deposition, sputtering, plasma vapor deposition (PCVD), Optical CVD method, thermal CVD method, and coating method are adopted.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the electrically conductive support include NiCr, stainless steel, Al, Cr, Mo, Au,
Nb, Ta, V, Ti.

Examples include metals such as Pt and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. be done. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, NiC'r, A
IL, Cr, Mo, Au, Ir.

Nb, Ta, V, Ti, Pf, Pd, In2O3゜5
Conductivity is imparted by providing a thin film made of n02, ITO (In203 +5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, All, Ag, Pb.

Zn, Ni, Au, Cr, Mo, Ir, Nb.

Conductivity is imparted to the surface by providing a thin film of metal such as Ta, V, Ti, Pt, etc. on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal.

The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined depending on the needs.1 For example, the light receiving member 1004 in FIG. If used as a member for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape.
The thickness of the support is determined as appropriate so that the desired partial receiving member can be formed, but if flexibility is required as a light receiving member, the thickness of the support may be sufficiently determined to function as a support. is,
It is made as thin as possible within the range. However, in such a case, from the viewpoints of manufacturing and handling of the support, mechanical strength, etc., it is preferably 10% or more.

Next, an outline of an example of a method for manufacturing a light-receiving member according to the present invention will be explained.

FIG. 11 shows an example of a light-receiving member manufacturing apparatus.

In the figure, raw material gas for forming the light receiving member of the present invention is sealed in gas cylinders 1102 to 1106. As an example, 1102 is Si, H4 gas (purity 99.999%, hereinafter 5tH4 (abbreviated as) cylinder, 11
03 is GeH4 gas (purity 99.999%, hereinafter referred to as Ge
1104 is a S i F4 gas (purity 99.99%, hereinafter abbreviated as S i F4) cylinder, 1
105 is a He gas (99.999% purity) cylinder, 11
06 is a H2 gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1101, valves 1122 to 1126 of gas cylinders 1102 to 1106,
Make sure the leak valve 1135 is closed,
In addition, inflow valves 1112 to 1116 and outflow valve 111
7-1121, confirm that the auxiliary valves 1132 and 1133 are open, and first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, the vacuum gauge 1136 reads approximately 5X10. -'T.

When the temperature reaches rr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, Si
H4 gas, GeH4 gas from the gas cylinder 1103, open the valves 1122.1123 and check the outlet pressure gauge 1127.
Adjust the pressure of 1128 to 1Kg70m2, and open the inflow valve 1.
112 and 1113 are gradually opened to allow flow into mass flow controllers 1107 and 1108, respectively. Subsequently, the outflow valves 1117.1118. The auxiliary valve 1132 is gradually opened to allow each gas to flow into the reaction chamber 1ioi.

At this time, the outflow valve 1117.11 is adjusted so that the ratio between the S i H4 gas flow rate and the GeH4 gas flow rate becomes the desired value.
18 and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure within one reaction chamber 1toi becomes the desired value. And the base 113
7 temperature is 50-400℃ by heating heater 1138
After confirming that the temperature is set within the range, the power source 1140 is set to a desired power to generate a glow discharge in the reaction chamber 1101, thereby containing germanium atoms in the formed layer.

The glow discharge is maintained for a desired time in the manner described above to form the first layer (G) on the base 1137 to a desired layer thickness. At the stage when the first layer (G) has been formed to a desired layer thickness, glow discharge is performed for a desired time according to the same conditions and procedures, except for completely closing the outflow valve 1118 and changing the discharge conditions as necessary. By maintaining the second layer (S) substantially free of germanium atoms on the first layer (G),
) can be formed.

Next, in order to deposit a surface layer on the second layer (S), a hydrogen (H2) gas cylinder of, for example, 1106 is heated to an argon (A
r) Replace with a gas cylinder, clean the deposition device, and spread the surface layer material all over the cathode electrode. After that, the layer formed up to the second layer (S) is placed in the device, and after the pressure is reduced, argon gas is introduced to generate a glow discharge, and the surface layer material is sputtered to form the surface layer to the desired thickness. do.

During layer formation, it is desirable that the substrate 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 The shape shown in FIG. 9 (length L) is 357 mm, the diameter (r
) 80mm, pitch (P) 25pm, depth D) 0.8
An Al support with a spiral groove surface shape of 1 Lm was prepared.

Next, using the deposition apparatus shown in FIG. 11, the conditions No.
An a-Si photoreceptive layer was deposited on the aforementioned A1 support (Sample No. 1-1) according to various operating procedures under the conditions shown in Table 4.

The second surface layer was deposited as follows.

After depositing the second layer, replace the hydrogen (H2) gas cylinder with argon (
Ar) The gas cylinder is replaced with a gas cylinder, the deposition apparatus is cleaned, and a surface layer material shown in Table 1 Condition No. 101 is applied all over the cathode electrode. The light-receiving member is installed, and the pressure inside the deposition apparatus is sufficiently reduced using a diffusion pump. Then turn off the argon gas to 0.
．． 015T.

rr, a glow discharge was generated with a high frequency power of 150 W, and the surface material was sputtered to deposit a surface layer of Condition No. 101 in Table 1 on the support.

Separately, a photoreceptive layer was formed on a cylindrical Al support with the same surface properties in the same manner as above except that the discharge power during formation of the first and second layers was 50 W.
As shown in FIG. 12, the surface of the surface layer 1205 is
It was parallel to the surface of 01. In this case, A
The difference in the total layer thickness between the center and both ends of the support was Igm (Sample No. 1-2).

Further, in the case of the sample No. 1-1, the surface of the surface layer 1305 and the surface of the support 1301 were non-parallel as shown in FIG. In this case, the difference in average layer thickness between the center and both ends of the Al support was 2 m.

A light-receiving member was produced in the same manner as above except that the surface layer was formed as shown in Table 1 Condition No. 102 to 122.

Regarding the above light receiving member for electrophotography, the wavelength is 780n.
Image exposure was carried out using a semiconductor laser having a diameter of 80 .mu.m with a spot diameter of 7 using the apparatus shown in FIG. 14, and the image was developed and transferred to obtain an image. In the superficial light-receiving member shown in FIG. 12, an interference fringe pattern was observed.

On the other hand, in the light-receiving member having the surface properties shown in FIG. 13, interference fringes i-like were not observed, and a member showing electrophotographic characteristics sufficient for practical use was obtained.

Example 2 The surface of a cylindrical Ai support was machined using a lathe as shown in Table 2. These (Cylinder No., 101-108)
Sample No. 1- of Example 1 was placed on a cylindrical Al support of
Electrophotographic light-receiving members were produced under the same conditions as in Example 1 (Sample No. 111-118). At this time, the difference in average layer thickness between the center and both ends of the Al support of the electrophotographic light-receiving member was 2.2 lm.

When the cross-sections of these electrophotographic light-receiving members were observed with an electron microscope and differences in the pitch of the light-receiving layers were measured, the results shown in Table 3 were obtained. These light-receiving members were subjected to image exposure with a spot diameter of 80 gm using the apparatus shown in FIG. 14 using a semiconductor laser with a wavelength of 780 nm in the same manner as in Example 1, and the results shown in Table 3 were obtained.

Example 3 An electrophotographic light-receiving member was formed in the same manner as Sample No. 1-1 of Example 1 under the conditions shown in Table 5.

These electrophotographic light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and then developed, transferred, and fixed to obtain a visible image on plain paper.

No interference fringes were observed in the image obtained in this case, and the image had sufficient characteristics for practical use.

Example 4 An electrophotographic light-receiving member was formed in the same manner as in Sample No. 1-1 of Example 1 under the conditions shown in Table 6.

These electrophotographic light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and then developed, transferred, and fixed to obtain a visible image on plain paper.

No interference fringes were observed in the image obtained in this case, and the image had sufficient characteristics for practical use.

Example 5 An electrophotographic light-receiving member was formed in the same manner as Sample No. 1-1 of Example 1 under the conditions shown in Table 7.

These electrophotographic light-receiving members were subjected to one-image exposure using the same image exposure apparatus as in Example 1, and then developed, transferred, and fixed to obtain a visible image on plain paper.

No interference fringes were observed in the image obtained in this case, and the image had sufficient characteristics for practical use.

Comparative Example As a comparative experiment, instead of the Al support used when producing the electrophotographic light-receiving member of Example 1, an Al support whose surface was roughened by sandblasting was used. An a-3i electrophotographic light-receiving member was prepared in exactly the same manner as in the case of sample No. 1-1 of Example 1 described above.

A whose surface was roughened by sandblasting at this time
・The surface condition of the support was measured using a universal surface profile measuring instrument (SE-3C) of Koita Research Institute before forming the photoreceptive layer, and the average surface roughness was 1.8 g, m. It has been found.

When this comparative electrophotographic light-receiving member was attached to the apparatus shown in FIG. 14 used in Example 1 and the same measurements were performed, clear interference fringes were formed in the entire black image.

[Effects of the Invention] As described above in detail, the present invention is suitable for image formation using coherent monochromatic light, is easy to manage in production, and is compatible with the interference fringe pattern that appears during image formation. The appearance of spots during reversal development can be simultaneously and completely eliminated.
Furthermore, it has high light sensitivity.

To provide a light-receiving member that has high signal-to-noise ratio characteristics and good electrical contact with a support, is suitable for digital image recording, and can reduce light reflection on the surface and efficiently utilize incident light. be able to.

[Brief explanation of the drawing]

FIG. 1 is a general explanatory diagram of interference fringes. FIG. 2 is an explanatory diagram of interference fringes in the case of a multilayer light receiving member. FIG. 3 is an explanatory diagram of interference fringes due to scattered light. FIG. 4 is an explanatory diagram of interference fringes due to scattered light in the case of a multilayer light receiving member. FIG. 5 is an explanatory diagram of interference fringes when the interfaces of each layer of the light receiving member are parallel. FIG. 6 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer of the light-receiving member are non-parallel. FIG. 7 is an explanatory diagram of a comparison of reflected light intensity when the interfaces of each layer of the light-receiving member are parallel and non-parallel. FIG. 8 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer are non-parallel. FIG. 9 is an explanatory diagram of the surface condition of the support. FIG. 10 is an explanatory diagram of the layer structure of the light receiving member. FIG. 11 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 12 and FIG. 13 are structural diagrams of the light-receiving member produced in the example. FIG. 14 is an explanatory diagram of the image exposure apparatus used in the example. 1000...Photoreceptive layer 1001...A support 1002...
...First layer 1003... Second layer 1004... Light receiving member 1401...
......Light receiving member for electrophotography 1402...
...Semiconductor laser 1403...f
θ lens 1404...Polygon mirror 1
405... Plan view of exposure apparatus 1406.
......Side view of the exposure device. Figure 3 Figure 4 Figure 45 Figure 7! 1 (A) (B) i Figure 10 Figure 11 Figure 1. S QQ Figure 12 → S4

Claims (14)

[Claims] (1) Support; a first layer made of an amorphous material containing silicon atoms and germanium atoms; a second layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity; , a light-receiving layer having a multilayer structure in which a surface layer having an anti-reflection function is provided in order from the support side; the light-receiving layer has one or more pairs of non-parallel interfaces within a short range;
A light-receiving member characterized in that a large number of the non-parallel interfaces are arranged in at least one direction in a plane perpendicular to the layer thickness direction, and each of the non-parallel interfaces is smoothly connected in the arrangement direction. (2) The light receiving member according to claim 1, wherein the arrangement is regular. (3) The light receiving member according to claim 1, wherein the arrangement is periodic. (4) The light receiving member according to claim 1, wherein the short range is 0.3 to 500 μm. (5) The light-receiving member according to claim 1, wherein the non-parallel interface is formed based on regularly arranged smooth irregularities provided on the surface of the support. (6) The light receiving member according to claim 5, wherein the smooth irregularities are formed by sinusoidal linear protrusions. (7) The light-receiving member according to claim 1, wherein the support body is cylindrical. (8) The light-receiving member according to claim 7, wherein the sinusoidal linear protrusion has a helical structure within the plane of the support. (9) The light receiving member according to claim 8, wherein the helical structure is a multiple helical structure. (10) The light-receiving member according to claim 6, wherein the sinusoidal linear protrusion is divided in the direction of its ridgeline. (11) The light receiving member according to claim 7, wherein the ridgeline direction of the sinusoidal linear projection is along the central axis of the cylindrical support. (12) The light receiving member according to claim 5, wherein the smooth unevenness has an inclined surface. (13) The light-receiving member according to claim 12, wherein the inclined surface is mirror-finished. (14) The light according to claim 5, wherein the free surface of the light-receiving layer has smooth irregularities arranged at the same pitch as the smooth irregularities provided on the support surface. Receptive member.