JPS6126050A - Light receiving member - Google Patents

Abstract

PURPOSE:To prevent light interference and to form a good image by laminating on a substrate the first layer contg. Si and Ge and the second layer contg. Si and a surface layer in succession and increasing Ge concn. in the first layer on the side of the support. CONSTITUTION:The first amorphous layer 1002 contg. Si and Ge and the second amorphous layer 1003 contg. Si and further a surface layer 1005 are laminated on the substrate 1001 to form a light receiving layer 1000. The interfaces 1006, 1007 of each layer are formed not parallel to each other, and each is minutely roughened to prevent the interference of the lights reflected from the interfaces. The Ge concn. in the first layer is increased on the side of the substrate 1001 to enhance efficiency of absorption of the longer wavelength semiconductor laser beams by Ge. The surface layer 1005 is made of an amorphous material of Si and C to prevent light reflection with its surface and to enhance humidity resistance, successive repeating use characteristics, and dielectric breakdown strength, thus permitting the light receiving member to be adapted to image formation by using a monochromatic coherent light.

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,
The present invention relates to a light-receiving member 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 for 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, and then the latent image is developed and A well-known method is to record an image by performing processes such as transfer and fixing accordingly. 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 an emission wavelength of 650 to 820 nm).

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-SiJ) disclosed in Japanese Patent No. 83746 is attracting attention.

Of course, if the photoreceptive layer is a single-layer a-Si layer, in order to maintain its high photosensitivity and ensure the dark resistance of 1Q12Ωcm 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 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
59, No. 58160, and No. 58161, a multilayer structure in which a barrier layer is provided between the support and the photoreceptive layer or/and on the upper surface of the photoreceptive layer is used. , a light-receiving member with apparently increased dark resistance has been proposed.

Through such proposals, the A-3J type light-receiving material has made dramatic progress in its commercialization design tolerances, ease of manufacturing management, and productivity, and is expected to be commercialized. The speed of development towards this goal 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 monochromatic light with re-interference. 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 the laser light in the photoreceptive layer decreases, so the above-mentioned interference phenomenon is remarkable.

This point will be explained with reference to the drawings.

In FIG. 1, light (2) incident on a certain layer constituting the light-receiving layer of a light-receiving member is shown. and the reflected light R3 reflected at the upper interface 102,
It shows reflected light R2 reflected from the lower interface 101''-r.

If the average layer thickness of a layer is d, the refractive index is n, and the wavelength of light is λ, then the layer thickness of a certain layer is uneven in one or more layers. -m
λ (m is an integer 1 reflected light strengthens each other) and 2nd = (m + ↓
) input (m is an integer, reflected light weakens each other), 2 The amount of absorbed light and the amount of transmitted light of a certain layer change depending on which of the following conditions is met.

In a light-receiving member having a multilayer structure, the interference effect shown in FIG. 1 occurs in each layer, and as shown in FIG. 2.

A synergistic negative effect of each interference occurs. 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 to overcome this inconvenience is to diamond-cut the surface of the support and provide unevenness of ±500 to ±1000 OA 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 images.

In other words, in the first method, the surface of the support is simply provided with a large number of irregularities of a specific size, so although it does prevent the appearance of interference fringes due to the light scattering effect, it does not affect the light scattering. Since the specularly reflected light component still remains, in addition to the remaining interference fringe pattern due to the specularly reflected light, the irradiation spot spreads due to the light scattering effect on the support surface, resulting in a substantial This was a cause of a decrease 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. 5t
There are disadvantages such as damage caused by plasma during layer formation, which reduces the original absorption function, and also adversely affects the subsequent formation of the a-Si 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, for example, the incident light weight. A part of the light is reflected on the surface of the light-receiving layer 302 and becomes reflected light R, and the rest enters the inside of the light-receiving layer 302 and becomes transmitted light I.

A portion of the transmitted light amount 1 is scattered on the surface of the support 302 and becomes diffused light, 2, 3, etc., and the rest is specularly reflected and becomes reflected light R2, A part of it becomes the emitted light R3 and goes outside. Therefore, the emitted light R3, which is a component that interferes with the reflected light R1, remains, so the interference fringe pattern still 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 light-receiving member having a multilayer structure, even if the surface of the support 401 is irregularly roughened, as shown in FIG. Light R
Each of the specularly reflected lights R3 on the 1+ support 401 surface interferes, and an interference fringe pattern is generated according to the thickness of each layer of the light receiving member. Therefore, in a light-receiving member having a multilayer structure, the support 4
It was impossible to completely prevent interference fringes by irregularly roughening the 01 surface.

In addition, when the surface of the support is irregularly roughened by a method such as sandblasting, the degree of roughness varies widely between lofts, and even in the same lot, the degree of roughness is uneven. There was a problem with manufacturing management. 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, the incident light at that part is 2. ndl=mλ or 2ndl=(m+station) input is established, resulting in a bright area or a dark area, respectively. In addition, for the entire photoreceptive layer, the layer thickness dl of the photoreceptive layer is
-, d2. d3. d, the maximum difference in the thickness of each layer is one or more, and because there is one layer, 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 imaging using coherent monochromatic light and that is easy to manufacture and manage.

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 which, in addition to the above-mentioned excellent properties, is further excellent in durability, continuous repeatability, electrical pressure resistance, use environment properties, mechanical durability, and light-receiving properties. It is about providing.

[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 second layer, and a surface layer made of an amorphous material containing silicon atoms and carbon atoms, the photoreceptive layer having a multilayer structure provided in this order from the support side; has one or more pairs of non-parallel interfaces within the layer, a large number of the non-parallel interfaces are arranged in at least one direction within a plane perpendicular to the layer thickness direction, and the non-parallel interfaces are each smoothly connected in the arrangement direction. In the light-receiving member, the first light-receiving member
The distribution of germanium atoms in the layer is non-uniform in the layer thickness 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 multilayered light-receiving layer is provided on a support (not shown) having irregularities that are finer and smoother than the required resolution of the device, and along the slopes 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, the coherent light incident on this minute portion (short range) causes interference in the minute portion, producing a minute interference fringe pattern.

Furthermore, if the interface 703 between the first layer 701 and the second layer 702 and the free surface 704 of the second layer 702 are non-parallel as shown in FIG. amount of light. Since the traveling directions of the reflected light R1 and the emitted light R3 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. be as small as possible. As a result, the amount of light incident on the minute portions is averaged.

As shown in FIG. 6, the same can be said even if the thickness of the second layer 602 is macroscopically non-uniform (d7), so the amount of incident light becomes uniform over the entire layer area ( (See r(D)J in Figure 6).

In addition, to describe the effect of the present invention when coherent light is transmitted from the irradiation side to the second layer when the light-receiving layer has a multilayer structure, as shown in FIG. ◇For 7, there are reflected lights R,,R2°R3,R,,R5. 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 the minute portion do not appear in the 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 is below the resolution of the eye, so it does not actually cause any trouble.

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 portion (one period of the uneven shape) suitable for the present invention is ≦L, where L is the spot diameter of the irradiation light.

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 in the microscopic area Cds d et al.) is expressed as d 5−− d 6 〉(n : refractive index of the second layer 602)n.

In the present invention, at least two of the layer interfaces are in a non-parallel relationship within the layer thickness of a microscopic portion of a multilayered photoreceptive layer (hereinafter referred to as a "microcolumn"). The layer thickness of each layer is controlled within the microcolumn during the formation of each layer, but if this condition is satisfied, any two layer interfaces will be in a parallel relationship within the microcolumn. It's okay.

However, the layers forming parallel layer interfaces are uniform layers over the entire area so that the difference in layer thickness at any two positions is 1, A - (refractive index of layer) n or less. It is desirable that it be formed thickly.

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:
Plasma vapor phase method (PCVD method), optical CVD method, and thermal CVD method are employed because the layer thickness can be accurately controlled at an optical level.

The smooth unevenness provided on the surface of the support allows a cutting tool having an arc-shaped cutting edge to be fixed at a predetermined position in a cutting machine such as a milling machine or lathe. By regularly moving in a predetermined direction while rotating, the surface of the support is accurately cut to form a desired smooth uneven shape, pitch, and depth. The sinusoidal shadow linear protrusion created by the unevenness formed by such a cutting method has a helical structure centered on the central axis of the cylindrical support. An example of such a structure is shown in Figure 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 depth of the groove. be.

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 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-5f 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 deterioration in the layer quality of the a-St layer.

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

In addition, when cleaning the blade, we investigated the problem of layer build-up mentioned above, which causes premature damage to the blade, the intermediate points in the process of electrophotography, and the conditions for preventing interference fringes. , the pitch of the recesses on the surface of the support is preferably 500yLm to 0.3ILm,
More preferably 200pm-1pm, optimally 50pm
~5JLm is desirable.

Further, the maximum depth of the recess is preferably 0.1 g, m to 5 m.
p, m, more preferably 0, 31Lm to 3-gm,
The optimum range is preferably 0.6 gm to 2 gm.

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 adjacent recesses and projections is preferably 1 degree to 20 degrees. Every time,
More preferably, the angle is 3 degrees to 15 degrees, most preferably 4 degrees to 10 degrees.

Further, the maximum difference in layer thickness due to non-uniformity of the layer thickness of each layer deposited on such a support is preferably 0 within the same pitch.
, 17zm to 2pm, more preferably 0.1gm
-1.5 pm, optimally O.2 gm - lpm.

The photoreceptive layer of the photoreceptive member of the present invention includes a first layer made of an amorphous material containing silicon atoms and germanium atoms, and a photoconductive layer made of an amorphous material containing silicon atoms. Because it has a multilayer structure in which the second layer showing the show.

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. It has excellent light fatigue resistance and repeated use characteristics, and can stably produce high-quality images with high density, clear halftones, and high resolution! Wear.

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.

The light receiving member of the present invention will be described in detail below with reference to one drawing.

FIG. 1θ 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 No. 109 has a light-receiving layer 1000 on a support toot for the light-receiving member.

The photoreceptive layer 1000 is made of an amorphous material (hereinafter referred to as ra-sice (H, X)", !: Abbreviation Suru) Te411! Narisareta 11th floor) layer (G) 1'002
and a-5i (hereinafter ra-3t(H,X)) containing at least one of a hydrogen atom and a halogen atom (X) as necessary.
A second layer (abbreviated as J) and having photoconductivity (
S) 1003 and surface layer 1005 are laminated in order*
Has **.

The germanium atoms contained in the first layer (G) 1002 are continuous in the layer thickness direction of the first M(G) 1002 and are different from the side on which the support 1001 is provided. It is contained in the first fi(G) 1002 so that it is distributed more on the support 1001 side than on the opposite side (the surface layer 1005 side of the photoreceptive layer 1000).

In the light-receiving member of the present invention, the distribution state of germanium atoms contained in the first layer (G)′ is as shown in fi in the layer thickness direction, and It is desirable that the distribution be uniform in the parallel in-plane direction.

In the present invention, the second layer (S) provided on the first # (G) does not contain germanium atoms, and a photoreceptive layer is formed in such a layer structure. As a result, a light-receiving member having excellent photosensitivity to light of all wavelengths from relatively short wavelengths to relatively short wavelengths including the visible light region can be obtained.

In addition, the distribution state of germanium atoms in the first layer CG) is such that germanium atoms are continuously distributed in the entire layer region,
Since the distribution concentration C of germanium atoms in the layer thickness direction is given a change that decreases from the support side toward the second layer (S), the first layer (G) and the second layer (S) By making the distribution concentration C of germanium atoms extremely large at the edge of the support, as will be described later, the second layer (S) can be used when a semiconductor laser or the like is used. The first layer (G) can substantially completely absorb light on the long wavelength side, which is almost completely absorbed, and can prevent interference due to reflection from the support surface.

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 #i component of silicon atoms. As a result, chemical stability is sufficiently ensured at the laminated interface.

11 to 19 show typical examples of the distribution state of germanium atoms contained in the first layer (G) of the pre-receiving member in the present invention in the layer thickness direction.

In addition, in each figure, the layer thickness and concentration are shown in an extreme form because if the values are shown as they are, the differences between each figure will not be clear, and these figures should be understood as schematic. In order to achieve the object of the present invention, the actual distribution is as follows: t
, (1≦i≦8) or C0 (1≦i≦20), or the entire distribution curve should be multiplied by an appropriate coefficient.

11 to 19, the horizontal axis shows the distribution concentration C of the manium atoms, the vertical axis shows the layer thickness of the first layer (G), and tB shows the thickness of the first layer (G) on the support side. The position of the end face of
tT indicates the position of the end surface of the layer (G) on the opposite side to the support side. That is, the first layer containing germanium atoms (G
), layers are formed from the tB side toward the tT side.

FIG. 11 shows a first typical example of the distribution state of germanium atoms contained in the first layer (G) in the layer thickness direction.

In the example shown in FIG. 11, the surface on which the first layer (G) containing germanium atoms is formed and the first layer (G)
) The first layer C in which germanium atoms are formed while the distribution concentration C of germanium atoms takes a constant value of 01 from the interface position tB in contact with the surface of
G) and is contained in position 1. Therefore, from the concentration C2 to the interface position tr, the distribution concentration C of germanium atoms is
is assumed to be C3.

In the example shown in FIG. 12, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from the position tB to the position tT, and reaches the concentration C5 at the position meter 〇. forming a state.

In the case shown in Fig. 13, from position tB to position t2,
The distribution concentration C of germanium atoms is kept constant at the concentration C6, and gradually and continuously decreases between the position t2 and the position t□, and at the position tT, the distribution concentration C is substantially zero. (Here, substantially zero means that the amount is less than the detection limit).

In the case shown in FIG. 14, the distribution concentration C of germanium atoms gradually decreases continuously from the concentration C8 from position t to position tr, and becomes substantially zero at position tT.

In the example shown in FIG. 15, the distribution concentration C of germanium atoms is C9 between the position tB and the position t3.
is a constant value, and the concentration is CIO at position tr. Between position 3 and position tT, the distribution density C is linearly decreased from position t3 to position tT.

In the example shown in FIG. 16, the distribution concentration C is at the position t
From position B to position t4, the concentration C1l takes a constant value, and from position t4 to position tT, the distribution state is such that the concentration decreases in a linear function from concentration CI2 to concentration CI3.

In the example shown in FIG. 17, from position tB to position tT, the distribution concentration C of germanium atoms is the concentration CI4.
It decreases in a linear function so as to substantially reach zero.

In FIG. 18, from position tB to position t5, the distribution concentration C of germanium atoms decreases linearly from concentration CI5 to concentration C1G, and from position t to position t.
Between □ and □, an example is shown in which the concentration CI6 is set to a constant value.

In the example shown in FIG. 19, the distribution concentration C of germanium atoms is a concentration C1,7 at the position tB, and is slowly decreased from this concentration CI7 until reaching the position t6, and near the position t6. , is rapidly decreased to a concentration CI8 at position t6.

Between the position t and the position t7'', the decrease is rapid at first, and then slowly and gradually decreased to the position t.
7, the concentration becomes CI9, and between the positions Mt7 and t8, it is gradually decreased very slowly to reach the concentration C2° at the position meter 8.

Between position 0 and position tT, the concentration is reduced from C2° to substantially zero according to a curve shaped as shown in the figure.

Above, - from FIGS. 11 to 19, the first layer (G
), as described above, in the present invention, the support side has a portion with a high distribution concentration C of germanium atoms, and the interface On the tT side, the distribution concentration C is. A distribution of germanium atoms is provided in the first layer CG), which has a portion that is considerably lower than on the support side.

The first layer CG) constituting the light receiving layer constituting the receiving member in the present invention preferably has a localized region (A) containing germanium atoms at a relatively high concentration on the support side as described above. It is desirable to have

In the present invention, the localized region (A) is
Explaining using the symbols shown in FIG. 9, it is desirable to provide within 5IL from the interface position t.

In the present invention, the localized region (A) is located at the interface position t.
The total layer area (LT) up to 5 final thickness.

In some cases, it may be a part of the layer region (LT).

Whether the localized region (A) is a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed.

The localized region ('A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of germanium atoms with respect to silicon atoms is
It is desirable that the layer be formed in such a manner that it can have a distribution state of preferably 1000 atomic cppm or more, more preferably 5000 atomic cPPm or more, and optimally IXIO4 atomic ppm or more.

That is, in the present invention, the first layer containing germanium atoms is formed such that the maximum value Cmax of the distribution concentration exists within 5p (layer region of 5μ thick from tB) in the layer thickness from the support side. It is preferable that it be formed.

In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the amounts of hydrogen atoms and halogen atoms contained in the second layer (S) constituting the photoreceptive layer to be formed The sum (H+X) is preferably 1 to 40 atomic%,
More preferably 5 to 30 atomic%, optimally 5
It is desirable that the content be ~25 atomic%.

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 to 8 x 10510
5ato ppm, optimally 500-7X105at
It is desirable that the amount be omic ppm.

In the present invention, the layer thickness of the first layer (G) and the second layer (S) 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 layer (G) is preferably 30A to 50L, more preferably 40A to 40K,
Optimally, it is desirable to set it to 50A to 30tL.

Further, the layer thickness T of the second layer (S) is preferably 0.5 to 9
0g, more preferably 1-80g, optimally 2-50g. It is desirable that this is done.

The sum of the layer thickness TB of the first layer (G) and the layer thickness T of the second layer (S) (TB + T) is determined by the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. It is determined as desired when designing the layers of the light-receiving member based on the organic relationship between the two.

In the light receiving member of the present invention, the numerical range of (TB+T) is preferably 1 to 100 L, more preferably 1 to 808 L, and most preferably 2 to 50 L. .

In a more preferred embodiment of the present invention, the above-mentioned layer thickness TB and layer thickness T are appropriately selected to satisfy the relationship TB/T≦1. It is desirable that

In the selection of the values of layer thickness TB and layer thickness T in the above case, it is more preferable that TB/T≦0.9. Optimally, it is desirable that the values of layer thickness TB and layer thickness T be determined so that the relationship T B/T'≦0.8 is satisfied.

In the present invention, the content of germanium atoms contained in the first layer (G) is LX 10 Satomic
In the case of ppm or more, the layer thickness TB of the first layer (G)
It is desirable that the thickness be fairly thin, preferably 30. or less, more preferably 25 pL or less, optimally 2
It is desirable that it be 0p 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 a thing.

According to the present invention, in order to form the first layer (G) composed of a-3iGe (H', It is made by a vacuum deposition method.

For example, a-3iGe (H,
In order to form the first layer CG) consisting of X), basically, a raw material gas for Si supply that can supply silicon atoms (Si) and a source gas for supplying germanium atoms (Ge) can be supplied. Raw material gas for Ge supply and hydrogen atoms (H
) A raw material gas for introduction and/or a raw material gas for introducing halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. It is sufficient to form a layer consisting of a-3iGe(H, In addition, in the case of forming by sputtering method, S is formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases.
When sputtering is performed using two targets: a target composed of i and a target composed of Ge, or a mixed target of Si and Ge, hydrogen atoms (H) are added as necessary. Or/and a gas for introducing halogen atoms (X)' may be introduced into the deposition chamber for sputtering.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4, Si2H6, Si3
Silicon hydride (silanes) in a gaseous state or capable of being gasified, such as HB, S 14 Hlo, etc., can be used effectively, and in particular, ease of handling during layer creation work, S
ii S f Ha , S i in terms of good feeding efficiency, etc.
2H6 is preferred.

As a material that can be a source gas for supplying Ge, GeH
4,Ge2)(6,Ge3He,Ge4H+ o
-Ge5H12, Ge6 Hl4, Ge7H+ b
- Germanium hydride in a gaseous state or that can be gasified, such as G ee Hs e and Geg H2o, is cited as one that can be effectively used, especially for ease of handling during layer creation work, good Ge supply efficiency, etc. In terms of GeH,,G
Preferable examples include e2 H6 and Ge3 HB.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into

Furthermore, silicon hydride compounds containing 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, CJljF, ClIF5, BrF5
．． Examples include interhalogen compounds such as BrF3, IF3, IF, ICJI, and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF4. Si2 F6. Si0 sentence. , SiBr4, and other silicon halides are preferred.

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 Si together with a raw material gas for supplying Ge. a-3iGe containing halogen atoms on a desired support without using silicon oxide gas
It is possible to form a first layer (G) consisting of:

When creating the first layer (G) containing halogen atoms according to the glow discharge method, basically, for example, silicon halide is used as a raw material gas for supplying St, and hydrogenation is used as a raw material gas for supplying Ge. First, germanium and gases such as Ar, I(2, He, etc.) are mixed at a predetermined mixing ratio and gas flow rate.
A first layer (G) can be formed on the desired support by introducing the first layer (G) into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to make it easier to control the ratio of hydrogen atoms introduced, these gases are further mixed with a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms to form a layer. Also good.

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

In order to form the first layer (G) made of a-3iGe (H, In the case of the ion blating method, sputtering is performed in a desired gas plasma atmosphere using two targets made of Si and Ge, or a target made of Si and Ge.
Polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are respectively accommodated as evaporation sources in the evaporation port, and the evaporation sources are heated and evaporated by a resistance heating method, an electron beam method (HB method), etc. to form flying evaporators. This can be done by passing 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 is sufficient to introduce the gas to form 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, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, halogenated gases such as HF, HCI, HBr, and HI can be used. Hydrogen, SiH2F2, SiH2I2, SiH2C,...
, 5iHC sentence 3, S 1H2B r2 , S 1HBr
Halogen-substituted silicon hydrides such as GeHF3. G
eF2 F2, GeB3 F, GeHBr3
, GeB2 CJ! 2, GeB3 C1, Ge
HBr3 , GeB2 B r2 , GeB3
Br, GeHI3, GeB212,
Halides containing a hydrogen source such as hydrogenated germanium halide such as GeH3I as one of the constituent elements, GeF4
．． GeCl, , GeBr, , Ge I4. GeF2. G
Gaseous or gasifiable substances such as germanium halides such as eCu2, GeBr2, GeI2, etc. may also be mentioned as useful starting materials for the formation of the first layer CG).

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 hydrogen atoms into the first layer (G),
In addition to the above, H2, or SiH4, Si2 H6,5i
3HB, 5i4H1゜, etc., with germanium or germanium compound for supplying Ge, or
GeH4, Ge2H6, Ge3 HB, Gea H
s o , Ge5H12, Ge6H14, Ge7H1
This can also be achieved by causing germanium hydride such as 6, GeBHlB, Ge9H20, and silicon or a silicon compound for supplying Si4 to coexist in a 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
tomic%, optimally o, i ~ 25 at om
It is desirable to set it as ic%.

To control the amount of hydrogen atoms (H) and/or halogen atoms (x) contained in the first layer (G), for example, the support temperature or/and hydrogen atoms (H) or halogen atoms The amount of the starting material used to contain (X) introduced into the deposition system, the discharge force, etc. may be controlled.

In the present invention, in order to form the second layer (S) composed of a-3i (H,
The starting material (starting material (II) for forming the second layer (S)) excluding the starting material that becomes the raw material gas for supplying Ge from the starting material (I) for forming the second layer (S) is used to form the second layer (S). 1st layer (G)
It can be carried out according to the same method and conditions as in the case of forming .

That is, in the present invention, to form the second layer (S) composed of a-3i(H,X), for example, a glow discharge method,
This is accomplished by a vacuum deposition method using a discharge phenomenon such as a sputtering method or an ion blating method. For example, in order to form the second layer (S) composed of a-5f (H, Along with the raw material gas, a raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as needed is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. may be caused to occur, and a layer consisting of a-3i (H,

In addition, when forming by sputtering method, for example, Ar
, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) when sputtering a target composed of St in an atmosphere of an inert gas such as He or a mixed gas based on these gases. may be introduced into the deposition chamber for sputtering.

In the light-receiving member 1004 shown in FIG. In order to achieve the object of the present invention in terms of properties, mechanical durability, and light receiving properties, one piece is provided.

The surface layer 1005 in the present invention is composed of silicon atoms (Si
), a carbon atom (C), and optionally a hydrogen atom (H) or/and a halogen atom (X) (hereinafter referred to as ra-(SiC1)x -xy (H,X) I J It is written as .However, O<x, y≦
y 1).

a-(St C1) (H,X)+ tx-
The surface layer 1005 having an xy-y structure is formed by a plasma vapor deposition method (PCVD method) such as a glow discharge method, a photo CVD method, a thermal CVD method, a sputtering method, an electron beam method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. The glow discharge method is preferred because of its advantages, such as relatively easy control of manufacturing conditions for manufacturing the receptor member, and easy introduction of carbon atoms and halogen atoms together with silicon atoms into the surface layer 1005 to be manufactured. Alternatively, a sputtering method is preferably employed. Furthermore, in the present invention, the surface layer 1005 may be formed using a glow discharge method and a sputtering method in the same apparatus system.

To form the surface layer 1005 by the glow discharge method, a-(St Cr) (H, x) +.

The raw material gas for x - xy formation is mixed with a dilution gas at a predetermined mixing ratio if necessary, and introduced into a vacuum deposition chamber where a support is installed, and the introduced gas is subjected to glow discharge. A'-'(S i Cr' ) (H,X)
t.

x −xy All you have to do is deposit it.

In the present invention, the raw material gas for forming a-(SiCr)x-xy(H,X)I includes silicon atoms (Si), carbon atoms (C), hydrogen atoms (
Most of gaseous substances or gasified substances containing at least one of H) and halogen atoms (X) as a constituent atom can be used.

When using a raw material gas having Si as a constituent atom as one of Si, C, H, and X, for example, a raw material gas having Sl as a constituent atom, a raw material gas having C as a constituent atom,
If necessary, a raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing Si as a constituent atom,
Raw material gas containing C and H as constituent atoms or/and C and X
Also, a raw material gas containing Si as constituent atoms is mixed at a desired mixing ratio, or a raw material gas containing Si as constituent atoms and a raw material gas containing Si, C, and H as constituent atoms. Alternatively, a mixture of a raw material gas containing Si, C, and X as constituent atoms can be used.

Separately, C is added to the raw material waste whose constituent atoms are Si and H.
A raw material gas containing St and X as constituent atoms may be mixed and used, or a raw material gas containing C as constituent atoms may be mixed and used with a raw material gas containing St and X as constituent atoms.

In the present invention, F is preferable as the halogen atom (X) contained in the surface layer 1005.

CJI, Br, and I, with F and CM being particularly desirable.

In the present invention, raw material gases that can be effectively used to form the surface layer 1005 include gaseous materials or substances that can be easily gasified at room temperature and pressure. .

In the present invention, SiH4, Si2H6, 5i3HB, 5i4H1 (,
Silicon hydride gas such as silanes (Stane), C
and H as constituent atoms, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylenic hydrocarbons having 2 to 3 carbon atoms, \\rogen alone, \\
Hydrogen halides, interhalogen compounds, silicon halides,
/X rogane-substituted silicon hydride, silicon hydride, etc. can be mentioned. Specifically, methane (C
Ha ), ethane (02H6), propane (C3H8
)-1n-butane (nC4Hlo), pentane (CsHl2), and ethylene hydrocarbons,
Ethylene (C2H4), propylene (C3H6), butene-1 (C4I(e)), butene-2 (C4He)
, Isobutylene (C4H8), Pentene (Cs
Hlo), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4),
Butyne (C4H6), '\Halogen gases include fluorine, chlorine, bromine, and iodine; hydrogen halides include FH, Hl, HCu, and HBr; and interhalogen compounds include BrF, CIF, ClF5, and CJL.
F5, BrF5, BrF3, IF7, IF5.
1cfL, IBr, as silicon halide, Si
F4. S 1zF6. 5iCu3Br, 5iCJ1
2Br2. 5iCfLBr3, 5iC13I, SiB
r4, as the halogen-substituted silicon hydride, SiH2F
2.5iH2C statement 2. 5iHCu3, SiH30, 5iH3Br, 5iH3Br, 5iH2Br2. 5
tHB r3, as silicon hydride, SiH4゜Si
2 H & 1sj3H81si4HI. Silane (S
iiiane), etc.

In addition to these, CF4.00M4, SB r4, C
HF3, CH2F2, CH3F, CH2O, C
Halogen-substituted paraffinic hydrocarbons such as H3B r , CH3I, C2H5CI, fluorinated sulfur moxibustion compounds such as SF4 and SF6, Si (CH3)4.5i (C2
Alkyl silicides such as H9)4 and 5iC1(CH3)3
, S iC statement 2 (CH3) 2 1 S rC1
Silane derivatives such as halogen-containing alkyl silicides such as 3CH3 can also be mentioned as effective.

These surface layer 1005 forming substances are the surface layer 1 to be formed.
When forming the surface layer 1005, silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms are selected and used as desired so that silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms are contained in the 005 in a predetermined composition ratio.

For example, 5i can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and can form a layer with desired characteristics.
(CH3)n and 5iHC statement 3 containing halogen atoms. 5iH2C sentence 2, SiC sentence.

Alternatively, a (Si CH'
)(CM+X −x H) 1 can be formed.

To form the surface layer 1005 by the sputtering method, target a single-crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C, and process these as necessary. Sputtering may be performed in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements.

For example, if a Si wafer is used as a target, raw material gases for introducing C, H or/and X are diluted as necessary and introduced into a sputtering deposition chamber, and these gases The Si wafer may be sputtered by forming plasma.

Alternatively, Si and C may be used as separate targets, or by using a single mixed target of Si and C, if necessary, in a gas atmosphere containing hydrogen atoms and/or halogen atoms. , by sputtering. As the material gas for introducing C, H, and X, the material for forming the surface layer 1005 shown in the glow discharge example described above can also be used as an effective material in the sputtering method.

In the present invention, so-called rare gases such as He, Ne, Ar, etc. are preferably mentioned as the diluting gas used when forming the surface layer 1005 by a glow discharge method or a sputtering method. I can do it.

The surface layer 1005 in the present invention is carefully formed to provide the desired properties.

In other words, a substance whose constituent atoms are Si, C, and H or/and
Since it exhibits properties ranging from conductivity to semiconductivity to insulating properties, and from photoconductive properties to non-photoconductive properties, in the present invention, a that has desired properties depending on the purpose is used. −(
The conditions for creating -X y are strictly selected according to the desired conditions so that S ixCl ) (H,X)+y' is formed. For example, in order to provide the surface layer 1005 with the main purpose of improving electrical voltage resistance, a (SiC□) (H+X) lyx
-xy is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, when the surface layer 1005 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the degree of electrical insulation described above is relaxed to some extent, and the surface layer 1005 is made of a non-woven material having a certain degree of sensitivity to the irradiated light. a-(SiCI)(H,X)+ as a crystalline material.

x −xy is created.

on the second layer surface a-(Si C1) (H, yX)+.

When forming the surface layer 1005 consisting of a-(S'i CI ) (H,X) 1x with the property
It is desirable that the temperature of the support during layer formation be strictly controlled so that -xy -y can be formed as desired.

In the present invention, the formation of the surface layer 1005 is carried out by appropriately selecting the optimum range in accordance with the method of forming the surface layer 1005 in order to effectively achieve the desired purpose. 400°C, more preferably 50/-350°C,
The optimal temperature is preferably 100 to 300°C. Compared to other methods, the formation of the surface layer 1005 requires delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness.
Because it is relatively easy, glow discharge method and Suba・
Although it is advantageous to adopt the interning method, when forming the surface layer 100'5 by these layer forming methods, the discharge power during layer formation is created in the same manner as the support temperature described above. (St C,) (H,X)1.

x −xy It is one of the important factors that influences the characteristics of

a (S iC+ ) (H+
The discharge power conditions for effectively creating yx −xy with good productivity are preferably 10 to 100 OW, more preferably 2
It is desirable that the power is 0 to 750W, most preferably 50 to 650W.

The gas pressure in the deposition chamber is preferably 0.0 l-IT.

rr, more preferably about 0.1 to 0.5 Torr.

In the present invention, the values in the above-mentioned ranges are mentioned as the preferable numerical ranges of the support temperature and discharge power for creating the surface layer 1005, but these layer creation factors can be determined independently and separately. 2) a−(Si C+′ ) (H,′X)+ with desired properties rather than those desired.

It is desirable that the optimum value of each layer forming factor be determined based on mutual organic relationship so that the surface layer 1005 consisting of x - xy is formed.

The amount of carbon atoms contained in the surface layer 1005 in the light-receiving member of the present invention is the same as the conditions for forming the surface layer 1005.
Surface layer 1 that provides desired properties to achieve the object of the present invention
This is an important factor in the formation of 005.

The amount of carbon atoms contained in the surface layer 10 (15) in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the surface layer 1005.

That is, the amorphous material represented by the general formula a-(SiCI) x -xy (H, ra-3~1-CI J and written a
-a. However, 0<a<1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as ra -(S
i C1) Written as Hl J.

b - bc - c 0<b, c<1)', an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms (hereinafter 'a (SidC+))
It is written as (H,X) + ko. However, 0-d e
−6 <d, e<1).

In the present invention, the surface layer 1005 is a-3taC, -a
When the surface layer 1005 is composed of
%, more preferably 1-80 atomic%, optimally 1
A desirable range is 0 to 75 atomic%. In other words, if you display a in the previous a-3iC1, a
-a a is preferably 0.1 to 0.99999, more preferably 0.2 to 0.99, and optimally 0.25 to 0.9.

In the present invention, the surface layer 1005 is a' (S ib
C+)Hl, the surface layer b
The amount of carbon atoms contained in c - c 1005 is preferably lX
10-3 to 90 atomic%, more preferably 1 to 90 atomic%, optimally 10 to 80a
It is desirable to set it to tomic%. The content of hydrogen atoms is preferably 1 to 40 atomic
%, more preferably 2 to 35 atomic %, most preferably 5 to 30 atomic %, and the light-receiving member formed when the hydrogen content is in these ranges is excellent in practical terms. It can be fully applied as such.

That is, the previous a-(S i , c, -b). Hl-8
b is preferably 0.1 to 0°999
99, more preferred niha, 0.1-0.99, optimally 0
．． 15-0.9, C is preferably 0.6-0.99,
More preferably 0.65 to 0°98, optimally 0.7 to 0
．． 95 is desirable.

The surface layer 1005 is a (S ia C1-d),
e(H,X), -8, the surface layer 10
The content of carbon atoms contained in 05 is preferably 1X10-3 to 90 atomic%, more preferably 1 to 90 atomic%, most preferably 10 to 8
It is desirable to set it to 0 atomic%. The content of halogen atoms is preferably 1 to 20a
It is preferable that the halogen atom content be within this range, so that light-receiving members prepared with a halogen atom content within this range can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably 1
9 atomic% or less, more preferably 13 atomic%
It is desirable that it be less than m i c%.

That is, the previous a (S idC1a) e(H・X)+
If expressed as d and e, e d is preferably 0.1 to 0.99999, more preferably 0.1 to 0.99, optimally 0.15 to 0.9, e
is preferably 0.8 to 0.99, more preferably 0.8
2-0.99. The optimum range is 0.85 to 0.98.

The number range of the layer thickness of the surface layer 1005 in the present invention is one of the important factors for effectively achieving the object of the present invention.

In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose.

In addition, the layer thickness of the surface layer 1005 is determined based on the relationship between the amount of carbon atoms contained in the layer and the layer thicknesses of the first layer and the second layer, as required for each layer region. It needs to be appropriately determined as desired based on organic relationships depending on the characteristics.

In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production.

The layer thickness of the surface layer 1005 in the present invention is preferably 0.003 to 30 JL, preferably 0.004 to 20 JL.
The preferred range is 0.005 to 10 l.

The surface layer 1005 can serve primarily as a protective layer for mechanical durability and as an antireflection layer optically.

The surface layer 1005 is suitable to function as an antireflection layer when the following conditions are met.

That is, assuming that the refractive index of the surface layer 1005 is n2, the layer thickness is d, and the wavelength of the incident light is λ.

When d=-□n or an odd multiple thereof, the surface layer is suitable as an antireflection layer. Further, when the refractive index of the second layer is n, when the refractive index n of the surface layer satisfies n=(n) and the layer thickness of the surface layer is d or an odd multiple thereof, the surface layer is most suitable as an antireflection layer. When a-3i:H is used as the second layer, since the refractive index of a-3t:H is about 3.3, a material with a refractive index of 1.82 is suitable for the surface layer. a-
By adjusting the amount of C, SiC:H can have a refractive index of such a value, and can also sufficiently satisfy mechanical durability, interlayer adhesion, and electrical properties. It is the most suitable material for the surface layer.

In addition, when placing emphasis on the role of the surface layer 1005 as an antireflection layer, the layer thickness of the surface layer is 0.05 to 2 μm.
More preferably, it is m.

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

-Metals such as Pt and Pd, or 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. . 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, NiCr, Af
L, Cr, Mo, Au, Ir, Nb.

Ta, V, Ti, Pt, Pd, In2O3.

5n02, ITO (In203+5n02), etc., or a synthetic resin film such as polyester film, NiCr, A9. , Ag, Pb.

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

A thin film of metal such as T/a, V, Ti, P, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, and the surface is made conductive. Granted.

The i-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 appropriately determined so as to form a desired light-receiving member, but if flexibility is required as a light-receiving member, the support can sufficiently function as a support. It is made as thin as possible within this range. Men and others 1. In such cases, support manufacturing J:, 7! From the viewpoints of handling, mechanical strength, etc., it is preferably 1 OJL or more.

Next, an outline of an example of the method for manufacturing the light receiving member of the present invention will be described.

FIG. 20 shows an example of a light-receiving member manufacturing apparatus.

In the figure, gas cylinders 2002 to 2006 and 2045 are sealed with raw material gas for forming the light receiving member of the present invention, and as an example, 2002 is 5iH
a gas (purity 99.999%, hereinafter abbreviated as SiH4)
Cylinder, 2003 is GeH4 gas (purity 99.999%
, hereinafter abbreviated as GeH4) cylinder, 2004 is SiF
4 gas (purity 99.99%, hereinafter abbreviated as SiF4)
Cylinder, 2005 is He gas (purity 99, 999
%) cylinder, 2006 is H2 gas (purity 99°999%)
) cylinder, 2045 is CH4 gas (purity 99.999%
) It is a cylinder.

In order to flow these gases into the reaction chamber 2001, the valves 2022 to 2022 of the gas cylinders 2002 to 2006 and 2045 are used.
2026.2044, make sure the leak valve 2035 is closed and also the inlet valves 2012-201
6.2043, outflow valve 2017-2021.204
1. Confirm that the auxiliary valves 2032 and 2033 are open, and then open the main valve 20'34 to exhaust the reaction chamber 2001 and each gas pipe. Next, when the reading of the vacuum gauge 2036 becomes approximately 5X10-6 Torr, the auxiliary valve 2032.2033 and the outflow valve 201
7-2021. Close 2041.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 2037, Kasu cylinder 2002 Yo'J
S i H4 gas, gas boiler 2003Jl:S Ge
H4 gas, H2 gas valve 2022.2 from 2006
Open 023.2026 and check the outlet pressure gauge 2027.20
28.Adjust the pressure of 2031 to 1Kg/'cm2, gradually open the inflow valve 2012.2013.2016,
Flow into the mass flow controllers 2007, 2008, and 2011, respectively. Subsequently, the outflow valve 2017, 2
018.2021. The auxiliary valves 2032.2o33 are gradually opened to allow each gas to flow into the reaction chamber 2001. SiH4 gas flow rate at this time, GeH.

Adjust the outflow valves 2017, 2018, and 2021 so that the ratio of gas flow rate and H2 gas flow rate becomes the desired value, and adjust the vacuum gauge 20.20 so that the pressure inside the reaction chamber 2001 becomes the desired value. ．． Main impulse 203 while looking at the reading of 36
Adjust the aperture number 4. After confirming that the temperature of the base 2037 is set to a temperature in the range of 50 to 400'O by the heating heater 2038,
40 to a desired power to generate a glow discharge in the reaction chamber 2001, and at the same time, the flow rate of GeH4 gas is adjusted manually or by a method such as an external drive motor to gradually open the pulp 2018 according to a pre-designed gas change rate curve. The distribution concentration of germanium atoms contained in the formed layer is controlled by performing a changing operation.

The glow discharge is maintained for a desired time in the manner described above, and the first layer (G) is formed on the base 2037 to a desired layer thickness. At the stage where the first layer (G) has been formed to the desired layer thickness, glow discharge is maintained for the desired time according to the same conditions and procedures, except for completely closing the outflow valve 2018 and changing the discharge conditions as necessary. By doing so, a second layer (S) containing substantially no germanium atoms is formed on the first layer (G).
) can be formed.

゛After forming the second layer (S), the second layer is formed by maintaining glow discharge for a desired time under the same conditions and procedures except for setting the mass flow controllers 2007 and 2042 to a predetermined flow rate ratio. A surface layer mainly composed of silicon atoms and carbon atoms can be formed to a desired thickness on the layer (S).

During layer formation, it is desirable that the base 2037 be rotated at a constant speed by a motor 2039 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 The shape shown in Fig. 9 (length L) is 35.7 mm, the diameter (
r) 80 mm, pitch (P) 25 μm, depth D) 0.
An Al support with a spiral groove surface shape of 8 pm was prepared.

Next, using the deposition apparatus shown in FIG. 20 and following various operating procedures under the conditions shown in Table 7, an a-5t photoreceptive layer was deposited on the aforementioned Al support (sample No. 1-1). ).

Note that the first layer c7) a-(St:Ge):H layer is.

The mass flow controllers 2007 and 2008 of GeH4 and SiH4 are controlled by computer (HP98) so that the flow rates of GeH4 and SiH4 are as shown in Fig.
45B).

Incidentally, the surface layer was deposited as follows.

After the second layer is deposited, as shown in Table 7, the CH4 gas flow rate is 5tH4/CH to the Si H4 gas flow rate.
Set the mass flow controller corresponding to each gas so that it is 4-1/30, and use 150W of high frequency power to reach 0.54m.
A thick a-3iC(H) was deposited.

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. 21(A), the surface of the surface layer 2105 was parallel to the surface of the support 2101. In this case, the difference in the total layer thickness between the center and both ends of the Al support is I
gm (Sample No. 1-2).

In addition, in the case of the sample No. 1-1, FIG. 21(B)
As shown in the figure, the surface of the surface layer 2105 and the surface of the support 21ot were non-parallel. In this case, the difference in average layer thickness between the center and both ends of the Al support was 2 uLm.

Regarding the above two types of electrophotographic light receiving members, wavelength 7
Image exposure was carried out using a device shown in FIG. 26 using a semiconductor laser of 80 nm with a spot diameter of 80 ILm, and the image was developed and transferred to obtain an image. An interference fringe pattern was observed in the superficial light-receiving member shown in FIG. 21(A).

On the other hand, in the light-receiving member having the surface properties shown in FIG. 21(B), no interference fringe pattern was observed and electrophotographic properties sufficient for practical use were obtained.

Example 2 After depositing up to the second layer in the same manner as in the case of samples No. 1-1 of Example 1, the hydrogen (H2) gas cylinder was replaced with argon (
Ar) Replace the gas cylinder with a gas cylinder, clean the deposition device, and place a sputtering target made of St and a sputtering target made of graphite on the cathode electrode so that the area ratio is as shown in Table 1 Sample No. 10L. Stretch. 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.
．． The surface layer of sample No. 101 in Table 1 was deposited on the support by sputtering the surface material by introducing a glow discharge at a high frequency power of 150 W to 0.015 Torr.

In the same way, by changing the area ratio of Si and graphite targets, the surface layer was
A light-receiving member was produced in the same manner as above except that it was formed as shown in No. 7. 'Each of the electrophotographic light-receiving members thus obtained was subjected to image exposure with a laser in the same manner as in Example 1, and the process up to transfer was repeated approximately 50,000 times.
When the image was evaluated, the results shown in Table 1 were obtained.

Example 3 Sample No. 1-1 of Example 1 except that when forming the surface layer, the flow rate ratio of SiH4 gas and CH4 gas was changed to change the content ratio of silicon atoms and carbon atoms in the surface layer. Each of the electrophotographic light-receiving members was produced in exactly the same manner as described above.

For each of the electrophotographic light-receiving members thus obtained,
As in Example 1, image exposure was performed with a laser, and the process up to transfer was repeated approximately 50,000 times, and then one image evaluation was performed.
The results shown in Table 2 were obtained.

Example 4 When forming the surface layer, SiH4 gas, SiF4 gas, CH4
An electrophotographic light-receiving member was prepared in exactly the same manner as in the case of Sample No. 1-1 in Example 1, except that the content ratio of silicon atoms and carbon atoms in the surface layer was changed by changing the gas flow rate ratio. We created each.

For each of the electrophotographic light-receiving members thus obtained,
After image exposure with a laser as in Example 1 and repeating the process up to transfer approximately 50,000 times, image evaluation was performed.
The results shown in Table 3 were obtained.

Example 5 Sample No. 1- of Example 1 except for changing the layer thickness of the surface layer.
Each of the electrophotographic light-receiving members was produced by the same method as in Example 1.

For each of the electrophotographic light-receiving members thus obtained,
As in Example 1, the steps of image formation, development, and cleaning were repeated, and the results shown in Table 4 were obtained.

Example 6 An electrophotographic light-receiving member was prepared in the same manner as in Example 1 for sample No. 1-1, except that the discharge power during the preparation of the surface layer was 300 W and the average layer thickness was 2 gm. did.

The average layer thickness difference between the surface layer of the electrophotographic light-receiving member thus obtained was 0.5 gm between the center and both ends. Also,
The layer thickness difference in the minute portion was O.lpm.

No interference fringes were observed in such an electrophotographic light-receiving member, and the steps of image formation, development, and cleaning were repeated using the same apparatus as in Example 1, and the result was sufficient for practical use.

Example 7 The surface of a cylindrical An support was machined using a lathe as shown in Table 5. 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 Nos. 111 to 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 l.

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 6 were obtained. These light-receiving members were subjected to image exposure with a spot diameter of 807 zm using the apparatus shown in FIG. 26 using a semiconductor laser having a wavelength of 780 nm in the same manner as in Example 1, and the results shown in Table 6 were obtained.

Example 8 An electrophotographic light-receiving member was formed in the same manner as in the case of Sample No. 1-1 of Example 1 under the conditions shown in Table 7.

Note that the first layer a-(Si:Ge):H layer is Ge
The GeH4 and SiH4 flow controllers 2007 and 2008 were connected to a computer (HP984
5B).

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. Such an image forming process was continuously repeated 100,000 times.

No interference fringes were observed in any of the images obtained in this case, and the characteristics were sufficient for practical use. Further, there was no difference between the initial image and the 100,000th image, and the images were of high quality.

Example 9 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 8.

Note that the first layer a-(St:Ge):H layer is Ge
The mass flow controllers 2007 and 2008 for GeH4 and SiH4 are controlled by computer (HP9) so that the flow rates of H4 and SiH4 are as shown in Fig.
845B).

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. 2 Such an image forming process was continuously repeated 100,000 times.

No interference fringes were observed in any of the images obtained in this case, and the characteristics were sufficient for practical use. Further, there was no difference between the initial image and the 100,000th image, and the images were of high quality.

Example 1O 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 8.

In addition, for the first layer (S i : Ge): H layer, the mass flow controllers 2007 and 2008 of GeH4 and SiH4 are controlled by a computer (HP) so that the flow rates of GeH4 and SiH4 become as shown in FIG.
9845B).

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. Such an image forming process was continuously repeated 100,000 times.

No interference fringes were observed in any of the images obtained in this case, and the characteristics were sufficient for practical use. Further, there was no difference between the initial image and the 100,000th image, and the images were of high quality.

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-3t 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 profilometer (SE-3C) from Koita Research Institute before forming the photoreceptive layer, and the average surface roughness was found to be 1.8 pm. did.

When this comparative electrophotographic light-receiving member was attached to the apparatus shown in FIG. 26 used in Example 1 and the same measurements were performed, clear interference fringes were formed in the entire black image.

Table 5 Table 6 According to the present invention, it is suitable for image formation using coherent monochromatic light, easy to manufacture and manage, and simultaneously and completely eliminates the interference fringe pattern that appears during image formation and the appearance of spots during reversal development. can be resolved,
Furthermore, it is possible to provide a light-receiving member that has excellent mechanical durability, particularly abrasion resistance, and light-receiving properties.

[Brief explanation of drawings]

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 in which the interfaces of each layer of the light-receiving member are 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. FIGS. 11 to 19 are explanatory diagrams for explaining the distribution state of germanium atoms in the first layer. FIG. 20 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 21 is a structural diagram of a light receiving member produced in an example. FIG. 22 to FIG. 25 are explanatory diagrams showing changes in gas flow rate in the example. FIG. 26 shows an image exposure apparatus used in the example. 1000......Photoreceptive layer 1001...AM support 1002...
...First layer 1003... Second layer 1004... Light receiving member 1005...
......Surface layer 2601......Light receiving member for electrophotography 26
02... Semiconductor laser 2603...
...Fθ lens 2604...Polygon mirror 2605...Plan view of exposure device 2606...Side view of exposure device . Fig. 3 IN4 Fig. 5 Cause Fig. 7 (A) (B) Fig. 10 Fig. 11 Fig.' @ 72 Fig. 13 Fig. 1K 14 Fig. 1K 14 Fig. 76 Fig. 17 Cta tg diagram 72 Figure 21 Figure II 22 rI! J fM 23 Figures (all) 1N24 Figure m 25 Figure N 1%"l (minute) Figure 26

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 photoreceptive layer having a multilayer structure in which a surface layer made of an amorphous material containing silicon atoms and carbon atoms is provided in order from the support side;
A photoreceptor having a pair or more of non-parallel interfaces, 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. A light-receiving member, characterized in that the distribution state of germanium atoms in the first layer is non-uniform in the layer thickness 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.