JPS58171040A - Photoconductive material - Google Patents

Abstract

PURPOSE:To obtain a photoconductive material superior in electrical, optical, photoconductive characteristics, and operation environment adaptability, by providing an amorphous material layer contg. Si and nonuniformly distributed Ge, and an amorphous material layer contg. Si on a substrate in this order. CONSTITUTION:A photoconductive material 100 is obtained by forming an amorphous material 102 on its substrate 101, and this layer 102 has a free surface 105 on the other side. The layer 102 has a layer structure of the first layer region (G)103 composed of a-Si(H, X) contg. Ge located on the side of the substrate 101, and the second photoconductive layer region (S)104 laminated on the region (G)103. The region (G)103 contains Ge in a distribution continuous in the layer thickness direction rich on the side of the substrate 101, and poor in the reverse direction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, R-rays, etc.). As a photoconductive material forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it has a high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)].
/dark current (Id)), has absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, has fast photoresistance, has a desired clear resistance value, and is resistant to the human body during use. Historically, solid-state imagers have been praised for their disadvantages, such as being pollution-free and being able to easily dispose of afterimages within a predetermined time. In the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in the above-mentioned method, the above-mentioned non-polluting property during use is important.

Amorphous silicon (hereinafter referred to as 1ia-84) is a photoconductive material that has recently been developed based on this point.
Publication No. 855718 describes an image forming member for electrophotography,
DE 2933411 A describes an application to a photoelectric conversion/reading device.

Uchisei et al., a photoconductive member composed of conventional A-84 and having a photoconductive layer has various electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. In terms of usage environment characteristics and stability over time, the reality is that there is a point where it is necessary to improve the combination of characteristics. When applied to photographic image-forming members, if an attempt is made to improve photosensitivity and increase ILb dark resistance at the same time, in Germany and the United States, there are many cases in which residual potential remains during use. If you continue to use this yuzu denrin material over and over again for a long time, fatigue will accumulate due to repeated use, and residue will appear where ghost dust appears, or iih continuous use. There are many cases where inconveniences such as a gradual decline in responsiveness occur when the a-8i is used repeatedly. The absorption coefficient in the longer wavelength range is relatively small than the wavelength range, and when matching with a semiconductor laser that is in practical use, it is difficult to use a long wavelength There is still room for improvement in that the side light is not used effectively.

In addition, if the irradiated light is sufficiently absorbed in the photoconductor and the amount of light reaching the support increases to T,
If the support itself has a high reflectance for light that passes through the photoconductive layer, interference due to multiple reflections will occur within the photoconductive layer, which is one of the causes of "blurring" in the image. In order to increase the resolution, the irradiation spora) k must be reduced to increase the thickness of the beam 9, and this is a big problem, especially when using a semiconductor laser as a light source.

Therefore, while efforts are being made to improve the characteristics of the 5di44 family itself, there is a need for gradual efforts to solve all of the nine problems mentioned above when designing photoconductive members. Since the A-8i was developed as
IQl! As a result of comprehensive and intensive research from the viewpoint of applicability and applicability as a photoconductive member used in an amorphous material containing at least FgrI11 Mizuki amorphous silicon;
It is composed of norogenated amorphous silicon or hydrogenated amorphous silicon containing hydrogen (hereinafter r a-84 (H, i quality gradually.

A photoconductive member designed and produced with the layer structure of the photoconductive member specified as described below does not exhibit superior properties in practical use, and is not as good as a conventional photoconductive member. Compared to φ41, it is more convenient in all respects, and is particularly excellent as a photoconductive member for electrophotography.
This invention is based on the discovery that the electrical, optical, and photoconductive properties are always stable. Therefore, it is an all-environment type that is hardly affected by the usage environment, has excellent photosensitivity characteristics on the long wavelength side, and is extremely resistant to light fatigue, does not cause deterioration even after repeated use, and has no residual potential. The main objective is to provide a photoconductive member that is not or hardly observed.

Another object of the present invention is to provide a photoconductive member TA which has photosensitivity in the entire visible light range, is particularly good in matching with an optical body laser, and has a fast photoresponse. Another feature of the present invention is that when applied as an image member for electrophotography, it can be used for electrostatic image formation so easily that ordinary electrophotography methods can be effectively applied. It is a further object of the present invention to provide a photoconductive member which has a sufficient charge retention ability without being subjected to charging treatment. It is an object of the present invention to provide a photoconductive member for electrophotography that can easily obtain high-quality images with high photosensitivity.
It is also to provide a photoconductive member kII having specific characteristics.

The photoconductive member of the present invention is composed of a support for the photoconductive member and a non-crystalline material containing a silylon atom and a germanium atom, an amorphous material containing a 1kloNIIiIiI region and a silicon adipose. According to the structural formula, a 20th layer region exhibiting photoconductivity is provided in the P piece from the support side, and has an amorphous layer having a nine-layer structure and R, and - the layer of the kite L - in the area V. It is assumed that the distribution of germanium atoms is non-uniform in the layer thickness direction.

The photoconductive member of the present invention, which is designed to have the above-mentioned layer structure, can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, and photoconductive properties, and has excellent voltage resistance. In particular, when it is applied as an image forming member for electron transfer, there is no influence of residual potential on image formation and its electrical characteristics are stable. It has 9 high sensitivity and 8N ratio, has excellent light resistance and repeated use characteristics, is easy to adjust, produces clear tones, and has low resolution. It is possible to stably and repeatedly obtain high quality -gIIt.

Historically, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, particularly excellent mating with semiconductor lasers, and fast photoresponse.

Hereinafter, the light guide tim material of the present invention will be explained in detail.

111i! FIG. 9 is a schematic diagram showing the structure of the first embodiment of the present invention, shown in a sliding door for illustrating the layer 41111ft'ft of the photoconductive member.

A photoconductive member 100 shown in FIG. 1 has an amorphous layer 102k on a support 101 for the photoconductive member, and the amorphous layer 102 is formed on one end surface of a free hexagonal 105. The amorphous layer 102 is composed of iGe (i(,
(H,
G) The 20th layer region (8) 104, which is composed of 103 and a-84 (H, The germanium atoms enriched therein are continuous in the layer thickness direction of the tenth scissor layer region (G) 103 and are provided with the support 101.
Opposite @ (amorphous layer 1020 surface 105) o7
Kt in the first layer region ((j) 103 is present in the first layer region ((j) 103), which is distributed more toward the support 101 and is in good condition.

In the photoconductive member of the present invention, the 10th layer region (the distribution of the manicum glands abundant in q) has the above-mentioned distribution in the layer thickness direction, and the support It is desirable that the in-plane direction yc, which is half a line with the body's clothing l, has a uniform distribution.

In the present invention, in the second layer region (S) provided on the first layer region t (J), germanium atom-rich 6
By forming an amorphous layer r on such an amorphous layer, it is possible to absorb light in the entire range of wavelengths from a relatively wing wavelength to a relatively long wavelength range, including the pJ' viewing region. Therefore, a photoconductive member having excellent photosensitivity can be obtained.

In addition, the distribution of germanium atoms in the 20th layer region i is such that germanium atoms are continuously distributed in the entire layer region, and the distribution degree C of germanium atoms in the layer thickness direction is the second from the support side. Since the change decreases toward the layer region (81), the layer compatibility between the 10th layer region I and the 10th layer region 181 is excellent, and as will be described later, By making the germanium atom distribution O extremely large, the 20th layer region (8) can hardly contain long-wavelength light when used in semiconductor lasers, etc. In addition, in the photoconductive member of the present invention, it is possible to substantially completely absorb V& in the layer region 0 of the film and prevent drying due to reflection from the support. In this case, the J110 layer region, the 20 layer region (S), and the rag non-trading materials each have a common constituent capital of silicon atoms, so
Chemical stability is sufficiently ensured in the outward direction of lamination.

FIGS. 2 to 10 show typical examples of the distribution cliff in the layer thickness direction of germanium atoms contained in the first layer region 0 of the photoconductive member according to the present invention.

In Fig. 2 to Fig. 1θ, the horizontal axis shows the germanium atom distribution IfO, the vertical axis shows the layer thickness of the layer region of Hatake l, and tl shows the layer region of w41 on the support side (the end face of q). place t
l11, t7 is the layer region of 1 gl opposite to the support side (position in the direction of q). It will be done.

The second garden shows a first typical example of the distribution state of germanium atoms contained in the first pigeonhole in the layer thickness direction.

In the ψ angle shown in Fig. 2, the interface position tB where the surface of the layer xi containing germanium atoms (q) and the surface of the first layer dust region I fit together is shown. Up to the position Ct+, germanium atoms are contained in the first layer region - where germanium atoms are formed while the distribution concentration C of germanium atoms settles down to a certain pattern of 01. The interface position is gradually and continuously decreased until t7. At the interface position t7v, the distribution of germanium atoms at 11 degrees C is assumed to be C.

In the example δ shown in FIG. 3, a distribution state is formed such that the concentration is 01 at the position where it is contained.

One of the units in Figure 4 has position 1. From position t, in the trench, the distribution degree aFi of germanium atoms is assumed to be a constant value C6,
In the case of Figure 5, the distribution of germanium atoms #1 degree C is as follows from position t to position ty. Continuously gradually decreased from ill&Os to 11t
In the example shown in Figure 6, the germanium atom distribution 1
1[0 is position III and position 1. In between, the concentration is 0
．． To> with a constant value, and HII 1101@ at position 1. Between the position t and the position IT, the distribution is reduced in a degree CFi-order function until the position t, then the position tTK. In the example shown in FIG. 7, the distribution result fO is position t,
A constant value of *fOs* [take position, position t
4th to 9th place 11117 #i11 degrees 03. Yop concentration 0.
.

In the example shown in Figure 8, the distribution of germanium atoms IIIfC from position lft1I to position 1 is substantially reduced to fineness 01]. Stocks are decreasing linearly.

In FIG. 9, from position tB to position t1, the distribution concentration C of germanium atoms is #f from the concentration C,s.
It is linearly decreased to O+s, position 1, and position [t7
An example is shown in which * # Ots is a constant value between.

In the example shown in FIG. 1θ, the germanium atom distribution a1 degree C is at position 1. The firmness is "If," and the density is 01 until it reaches the position t. Initially, it is slow υ
Then, near the position t6, it is rapidly decreased to the position t, which becomes the result fO+a.

Between position t and position 1iit, the decrease is rapid at first, and then it is slowly and gradually decreased until position t.
, the concentration C1, and so on), between position t and position t, it decreases very slowly and steadily, and once it reaches C3, @ between position t and position 1T. In #, degree 0. It is reduced at one edge of the shape as shown in the figure so that it becomes more substantially zero.

As described above with reference to FIGS. 2 to 410, some typical examples of the distribution state of germanium atoms contained in the layer region I of 131 in the layer thickness direction, in the present invention, on the support side, The distribution of germanium atoms **0 has one part, and in the field FkJt, the distribution concentration oFi is quite low, and the distribution state of germanium atoms with nine parts is in the first layer. It is provided in area 0.

The first layer region 0 constituting the non-porous layer constituting the photoconductive member in the present invention is preferably a localized region containing germanium atoms at a relatively high concentration of 1ifi on the support side, as described above. (A) It is desirable to have k.

In the present invention, the localized region (A) Fi, Figures 2 to 1
In the present invention, the localized region (5) is preferably provided within 5μ from the interface position 11K, as explained using the symbols shown in FIG. In some cases, the total layer area (LT) is up to 5μ thick, and
It may also be part of the layer region (L, T).

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

The localized region (5) is defined as the distribution state of germanium atoms in the thickness direction of the germanium atoms contained therein.
The maximum value Omax of iilJf is for silicon atoms,
Usually U 1000 atomic ppm or more, preferably 5000 atomic ppm or more, optimally I
It is desirable that the layer be formed in such a manner that a distribution state of X 10' atomic ppm or more can be obtained.

That is, in the present invention, an amorphous layer containing germanium atoms has a layer thickness of 1 mm from the support side within 5 μm (1
It is preferable that the layer be formed so that the maximum value Omax of the degree of distribution exists in a layer region with a thickness of 5 μm from B.

In the present invention, wrinkles of hydrogen atoms (H) or lids of halogen atoms (X) or hydrogen atoms and halogen atoms contained in the second layer region <S> constituting the amorphous layer to be formed The sum of the amounts (i-i+x) is usually 1 to 40 at
omic %, preferably 5 to 60 atomic %, optimally 5 to 25 atomic %.

In the present invention, the cap of germanium atoms enriched in the first m region may be appropriately determined as desired to effectively achieve the object of the present invention, but usually U
l -9,5x 10' atomic ppm, preferably 100-3 x 10' atomic ppm
, optimally 500% 7 X 10' atomic
It is desirable to set it as ppm.

In the present invention, the lth layer region ((jl) and the second layer region (
The layer thickness μ of S) is one of the positive factors for effectively achieving the purpose of this book. Great care must be taken when designing conductive members.

In the present invention, the layer thickness Ill of the first layer region ((it).

μ, usually 30A to 50μ, preferably 40A to
The layer thickness T of the second layer region (81 is usually 0.40μ, optimally tli50A~30μ).
5-90μ, preferably 1-80μ, #'i per jl
It is desirable that the thickness be 2 to 50μ.

The layer thickness 'rl of the layer region 0 of jIl and the 20th layer region (S) 0
The sum of the layer thicknesses T (T, +T) is Kl!
Recognizing the organic relationship between the desired properties and the percent properties desired in the entire amorphous layer, we decided to increase the number of Kotoden s1N units (D
Depending on the patient's wishes, the doctor's prescription δ will be adjusted accordingly.

In the photoconductive member of the present invention, the above 0 (T).

+T) number Vi yoke is usually 1 to 100μ
, preferably 1 to 80 μ, most preferably 2 to 50 seconds.

In a more preferred embodiment of the present invention, the above-mentioned layer thickness Ill and layer thickness T are set as appropriate for each when normally satisfying the relationship rB/T≦1. It is desirable to select a value that is ・Layer thickness T in the above case,
In selecting the value of layer thickness T, more preferably '
M゛, /T≦0.9, optimally T, /Ill≦0.8
The layer thickness TB and the layer thickness 'rowL are adjusted so that the following relationship is satisfied.
It is preferable that
In the above case, it is desirable that the layer thickness of the layer region I of 1p11 be as thin as possible by a9, and preferably Fia
oμ or less, more preferably 25μ or less, optimal l/CF1
It is desirable that the thickness be 20μ or less. In the present invention, if necessary, the first layer constituting the amorphous layer
Specific examples of the halogen atom (3) contained in the layer region 0 and the second layer region (8) include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as something.

In the present invention, in order to form the first layer region composed of a-8i (g) () (, A-8iGe(H,X) is produced by glow discharge method.
In order to form a layer region (04) composed of w, 1, basically, a raw material gas for supplying Si, which supplies silicon atoms (8i), and a raw material gas for supplying Si, and germanium atoms ((je)k, which are supplied) are used. ] Supply O raw material gas and hydrogen atoms 04 as necessary
JI, which can be made to have a reduced pressure inside the MA family gas t1 for injecting raw materials Fi/and NOROGUN atoms 9Q, into the side chamber at the desired gas pressure to generate a glow discharge in the deposition chamber. , while the distribution of germanium atoms enriched on the surface of a predetermined support, which has been set in advance at a predetermined position, is controlled according to a desired desaturation rate curvature.
What is necessary is to form a layer consisting of X). In addition, in the case of forming by sputtering method, for example, an inert gas such as Ar, He, etc. or a gas mixture thereof is used as a gas atmosphere, and the target is made of 81 and 9 targets. When sputtering using two targets or using a mixed nine target of Si and 1*,
Gas for introducing hydrogen atoms (c) or halogen atoms (deposition chamber for sputtering) if necessary. The substances obtained include 8tk44, 8x)1. , dtransportation H1゜Si4 river 0, etc. Gaseous or gasified water-volcanized silicon (silane #A) is considered to be effective for VC use, especially ease of handling during layer creation work and di supply efficiency. Si, di, and H are preferable in terms of quality and performance. -2- The raw material gas for supplying 9 and the substances that accompany the cell 9 are (jcH, -11
H@*ue, H,, ()e,)110, Ge
5 HHL, (jesHH, GC?H1@+Ge,
Germanium hydride in a gaseous state or capable of being gasified, such as H, , ue, rig, etc., can be effectively used.
In terms of supply efficiency, etc., (jet, Ge, t-1
,.

ue, )i, are listed as preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, -.interhalogen compounds, -.logan-substituted silane derivatives, etc. Preferred examples include halogenated adducts that are in a gaseous state or can be gasified.Also, in history, silicon atoms, halogen atoms, and metal structures Ift, JI! In the present invention, hydrogenation of a halogen atom ti' in an elementary gas state or which can be gasified is effective, and examples of halogen compounds preferably used in the present invention include elementary compounds. , specifically, halogen atoms such as fluorine, chlorine, bromine, and iodine, HrF, Olk", 0111g.

Brk'@, BrF, , IF, , IP,
, IOj, IBr, and other halogen-related compounds.

Specifically, examples of silicon compounds containing halogen atoms, silane self-conductors substituted with halogen atoms, etc.
diF, , 8i, F, , 81014, 8j
Silicon halides such as Br, etc. can be mentioned as preferred.

In the case of forming the characteristic photoconductive member of the present invention by the glow discharge method using such a silicon compound containing halogen atoms, water as a raw material gas to be supplied along with the raw material gas for supply is used. Chemical gas [Even if you don't use it,
A layer region ((Jt) consisting of a-8i(je) containing halogen atoms can be formed on a desired support.

A lifting platform that uses glow discharge VC to create a layer containing halogen atoms, basically Si
A halogenated compound that will be a raw material gas for supply, a germanium hydride that will be a raw material gas for supply, and Ar, H,, He.
Gases such as tI5r are introduced into a deposition chamber forming a first torture zone Iτ with a constant mixing ratio of tI5r, and a glow discharge is generated to form a plasma atmosphere of these scum.1. , the first layer area lt on the desired support.
-Although it is superior in form, it is possible to control the introduction ratio of hydrogen atoms-
In order to make the measurement easier, a layer of hydrogen scum or a silicon compound gas containing 1 g of water atoms may be mixed with 15 to form a layer on these scum. O is not used alone, but can be used in combination of multiple types at a certain mixing ratio. For example, in the case of a sputtering method, a target made of Si and a target made of (Je) are formed, or a target made of di and ue is formed in the first layer region ((J).
Using this, sputtering is performed in a desired gas plasma, and in the case of ion blating, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are evaporated and kneaded. The evaporated material is placed in a vapor deposition boat and heated and evaporated using this lk-me resistance heating method, or electrons and one-shot ff1 (kABI&), etc., and the flying evaporated material is passed through the desired gas plasma through the air. I can do it.

At this time, in order to remove halogen atoms in the layer formed even when the sputtering method or ion grating method collapses, a gas of the above-mentioned halogen compound or the above-mentioned silicon compound containing halogen atoms C is introduced into the side chamber. It is a good idea to introduce 1 g of the gas into the surrounding air and mix it with cedar.Also, when using a water wheel, add raw material waste for introducing water into the water, for example, H2, Alternatively, it is better to create a plasma atmosphere of the gases such as silanes and/or water-enhanced germanium in a deposition chamber for sputtering.

In the present invention, the above-mentioned halogen compound resources or silicon compounds enriched with roken are effectively used as the raw material gas for the halogen compound + Rumor Rokujyuji Atomic Hironjin, but other materials are also available. , Hi', Hol-state r
, halogenated materials such as Hl, 5tH2k"2, 5i
) I, i, , 41012 to 81, 8iHL3/
, , 5t)ilBrl.

Halogen [silicon hydride, such as 5IFiBr3, and ue
Multiply ゛1゜GeHl by 'l, Get4Bk', (
je rule/, , UeH204, cmti, ol.

lje listening rl, GeHIHr, , (je)i,
Br, (jeHI, , GeH,■, , (j
Hydrogen atoms such as aH, I → hydrogenated germanium halogenide, etc. are one of the constituent costs]・halogenide, Uei1
'4. Ge014. CJeer, GeI4.
GeF, , Ge01□(jeBr, .

(jeI, % germanium halide, etc., gaseous or gasifiable substances are also effective 10th layer stacking (L
The hydrogen atoms in these substances can be cited as substances for J-shaped structures.
In the present invention, a suitable I-halogen atom is introduced into the VlA of the layer formation, which is extremely effective for improving electrical or photoelectric properties at the same time as halogen atom. It is used as a raw material for fattening.

Add atoms to water 3 structurally in the first layer region 0
cr rt, above tD and other K d,, relativei F'18ik4
4.8111 (@.

Germanium or germanium compounds for supplying water voluminized silicon such as Si, H, , 81, H1@, etc., and their relatives are Gti-i, Nail hH@, GeBH@,
(le4u, , (je, H6, (je,)i, .

ue, Hl, , ()e, H, , (je, H@, etc.) are made to coexist in the deposition chamber with silicon or a silicon compound for supplying ram and Si k to generate a discharge. Bamboo ◆ can also be produced by ◎ In a preferred example of the present invention, the amorphous layer formed [constituting the first layer region (1 g of water contained in Is the amount of rogene slaves or the sum of the amounts of hydrogen atoms and halogen atoms ()1+X) normally 0.01?
40 atomic%, preferably 0.05-05-
30ato*s optimally U O, 1-25atomi
c- and Sarel's are preferred.

In the first layer region I, there are δ (to water bulk atoms) or/and kt ffi 1till-to r( in halogen atoms).
- control, for example, the support temperature and/or the water volume), the amount of starting material used to form the halogen atomic compound into the deposition system, the discharge boost, etc. is good.

In the present invention, the second
The VC forming the layer region (8) is the layer region (8) of the above-mentioned chart 1 (<the starting material from the starting material from Deenoshijiyama for J4 formation, excluding the starting material that will become the raw material gas for Ge supply gas). [The starting material for forming the 20th layer region (81) (IIJt-) can be used to form the first (D layer region ((Jlτ), using the same method and conditions as Vc, i.e., In the present invention, the second layer region (Sl
For example, the formation of k is performed by a true total Jth product method that utilizes a discharge phenomenon τ such as a glow discharge method, a sputtering method, or an ion blating method. For example, by glow discharge method, a second
The layer of - castle tsl ffi forms vc rx, the basic 1c is 1st generation and 9 silicon glands (8i) k can supply 8i
Along with the raw material gas for supply, depending on the cost, a person is placed in a deposition chamber where the pressure inside the gas deposition chamber can be reduced to reduce the pressure for water bulk atomic H for 4 people or/and halogen atomic prisoners. A discharge event is generated, and a layer consisting of a-8i (H, , for example, in an atmosphere of Ar, t'Fe% inert gas, or a mixed gas such as a β-st base.
When sputtering a target made up of 100% water and/or halogen atoms, it is sufficient to introduce the gas into the deposition chamber for sputtering.

Book @ light of light 4 (in the parts, j of germanium atom
The 20th layer is eclipsed and is not enriched with germanium atoms. The conduction characteristics of (8) can be adjusted as desired.

As such a substance, impurities used in the semiconductor field can be removed, and in this paper, the second layer region (8) to be formed.
,

Specifically, P-type impurities include atoms belonging to the back of the periodic table (group atoms), such as B (#jl) and Ar.
(aluminum), Ga (gallium), In (
Among them, H and Ga are particularly preferably used.

As n-type impurities, ego, periodic clothes * atoms belonging to group V (
Group V atoms), for example, P (@ ), As (Arsenic 1g
), sb (antimony), Hi (bismuth), etc., and P is particularly preferably used.

It is As.

In the present invention, the final charge of the material having the conductive characteristic τ which is present in the second layer region (S) is determined by the conduction time required in the layer region 181 or by the conduction time required in the layer region 181. The characteristics of other layer regions provided in direct contact with the layer region, the characteristics of the edge contact interface with the other layer regions, etc. can be selected as appropriate in terms of organic chest connection.・ In the present invention, the amount of the proboscis that controls the 4% body content contained in the 20th layer region (8) is usually as follows:
0.001-1000 atomic ppm, preferably 0.05-500 atomic ppm, optimal K FiO, 1-200 atomic ppm.

In order to structurally introduce a conductive substance, for example, an atom of the I1'th group or a group A, into the 20th layer region (8), it is necessary to introduce a substance of the Oboro group during layer formation. The starting material for use or the starting material for adding Group V atoms is placed in a layer stacking chamber in the form of scraps,
It is good to use it together with other starting materials to form the 20th layer region.The starting materials for this unpleasant group adenoid formation are gaseous or It is preferable to use a material that can be easily converted into yc gas at least under stratified acid conditions. As such I@弘 and atomic 4 necessary departure W*, specifically as Ipponkuzijin necessary, B@
M@, H6Hs@, 81M, , n, n,,
.

B, it, BIHl1, B@"14 hydrogenation-cable, Bk"a*BO2*13Br,% halogenation d
Honka mentions @Others, ktol@, UaUI
B, Ua (OHH)H, InL]j3, 'tolB, etc. can also be mentioned.

Although effective VC is used in the present invention as a necessary source material for mV & atoms, Pit is used for introducing phosphorus atoms.
, , Hydrogenated phosphorus such as P@k14, P-I, Pi',.

PF, , PCl3, Pot, , PHr,
, Pk3r, , Pl, S collar D phosphorus oxide is ◆killed. In addition, Ash, l ASF M, Ash/
@, AlBr1 +Ask'@, sbH,,8
bFB, 8bfI'g, 5bOj B, 5
b(J4, BIHl eBiOjs, B1Br,
etc. can also be cited as effective starting materials for introducing Group V atoms.

The supporting body used in the present invention is either electrically conductive or electrically insulating. As a conductive support, for example, N1 (Jr., stainless steel) is used.

A/, tJr, Mo, Au, Nb,
'f'a, V, 'i'i, Pt, P
d% of metals or alloys thereof. As the electrically insulating support, polyester.

Polyenalene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Synthetic films or sheets of polyvinylidene chloride, polystyrene, polyamide, and glass.

1 piece of paper etc. is normally used.・These are O electric li
! The triangular support preferably has at least one Table I
fot - The electric charge was processed, the cough was removed and the following table 11o11
It is desirable that another layer be provided on the il ◎ For example, if it is glass, the surface is Ni0r.

Mu1. Or, Mo, Au, Ir, Nb, 'i"a
, V, Ti, Pt, Pd.

In, 0. ,8nO,,ITO(hlo,+8nO,
) etc., or if it is a synthetic film of polyester film, N1Ur, kl, mug, Pb,
Zn, Ni, MuU.

A thin layer of metal such as Or, Mo, Ir, Nb, Ta, V, Ti, Pi, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted in the tR direction.

The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape may be determined depending on the needs. Since it is used as a member, in the case of continuous mail 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 a photoconductive member of the desired thickness is formed. However, the 1 mft VL, which requires good burning resistance as a photoconductive member, is made as thin as possible in order to fully exhibit its function as a support. In this case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is usually set to be 10μ or more.Next, an example of the method for forming the photoconductive member of the present invention I will explain the outline of this.

! Figure 11 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in Figure 0 are filled with raw material gases for forming the photoconductive member of the present invention. The analogy is 1102) diluted with 1e 8
iH, gas (purity 'j9.999%, hereinafter referred to as di/He
It is abbreviated as ) cylinder, 1ioa diluted with) Ie [99,
9991, hereafter) btF4/ ) (abbreviated as e @ ) cylinder, 1105t 9999911) cylinder.

In order to flow these gases into the reaction chamber 1101, gas cylinders 1102 to 11060, valves 1122 to 1126,
Leak pulp 1135 is closed't4IT
Also, inflow pulps 1112-1116, outflow pulps 1117-1121, auxiliary pulps 1132, 1
After confirming that 133 is open, first open the main pulp 1134 to exhaust the reaction m 1101 and each gas pipe.

Next, the appearance of the vacuum needle 1136 is approximately 5 x 10' tor.
r rc & -) Auxiliary pulp 1132.11 at nine points
33, close the outflow pulps 1117-1121.

Next, to give an example of forming an amorphous layer on the cylindrical substrate 1137, the gas cylinder 1102 (j) 5
ti(4/He gas, gas cylinder 1103J)Ge
搗/1-1e gas xl pulp 1122, 1123t - Open and adjust the pressure of outlet pressure gauge 1127. (Destiny flows into J7, 110g. Pull 11, followed by outflow pulp 1117.
111M, axially moving pulp 1132 gradually opens to allow each gas to flow into the reaction chamber 1101. At this time: d 1
f(4/ )ie gas amount and Ge)1. /) 1e Outflow pulp 1117. so that the ratio with the gas flow rate becomes the desired ratio.
1118 k Adjust the pressure in the reaction chamber 1ioi to /
*The reading of the vacuum gauge 1136 is tj so that the value of ji11 is obtained.
While the main pulp 1134 is in the open warehouse #II. After confirming that the temperature of the substrate 1137 is within the range of 50 to 400"0 by the heating heater 1138, the electric power 1140 is set to F9rgJ1 and the inside of the reaction chamber 1101 is heated. to cause a glow discharge,
At the same time, the pulp 1118 is tightened and the flow rate of He gas is adjusted manually or by using an externally driven motor to gradually change the opening of the pulp 1118 according to the nine change rate curves, thereby forming a layer containing the helium. Distribution of germanium atoms −f? i-Control ◇ As above, maintain the glow discharge for the desired time to form the first layer region 1 (Jf) on the substrate 1137 to the desired layer thickness.□ Apply the first layer to the desired layer thickness. The glow discharge is maintained for the desired time according to the same conditions and conditions, except for completely closing the outflow pulp 1118k and changing the discharge conditions according to necessity. By doing so, it is possible to form a layer region (S) of J12 which is not substantially enriched with germanium atoms on the layer region 0 of the kite 1.

$20 In order to contain the substance t-gold that controls conductivity in the layer region tS+, the second layer 1iij* (for example, B during formation)1. , P)l, etc., into the deposition chamber 110.
All you have to do is add it to the gas introduced into 1.

During layer formation, it is preferable that the base body 1137t'i be rotated at a constant speed by a motor 1139 in order to equalize the layer formation.

About the examples below i11! I will clarify.

Example 1 ll! shown in FIG. 11! The gas flow rate of GaH,/MeHe gas 1H4/H@1 gas is applied on the cylindrical ^1 substrate according to the change rate M line of the gas flow rate ratio shown in FIG. 12 under the conditions shown in 1st@. A 1-formation was carried out by changing the ratio over an hour of layer formation to obtain an image-forming member for photographic use.

The photoimage-forming member thus obtained was placed in a charging device and subjected to a corona test of 0.5-80114 at θs and OTV, and the light image immediately irradiated with light* was created using a tungsten Lang light source at 21ux- The seC Koshun was irradiated with a d1 trans-type test chart t4L.

Immediately after the sacrifice, by cascading a charged developer (including toner and carrier) onto the image forming member, 1 dl of toner is drawn onto the surface of the material.
I got mine. Toner ml'ii! on the imaging member! fr,
When the image was transferred onto transfer paper using es and atV corona charging, a +71 image of clear, higher density with good resolution and gradation reproduction was obtained.

Example 2 G.H4/Me gas and a LH,/H.gas were produced using the gas production apparatus shown in FIG. The gas flow rate ratio was changed with the elapsed layer formation time, and the other conditions were the same as in Example 1 to form the layers to obtain a four-electron one-image forming member.

The material for forming the friend layer thus obtained was 4# similar to that in Example 1! An image was formed on the transfer paper using sweat and a procedure, and a clear image quality was obtained after swiping at nine points.

Example 5 The gases of GeH4/Me gas and 81M4/H gas were prepared using the gas production apparatus shown in FIG. 11 and according to the rate of change curve of the gas fit filter ratio shown in FIG. Layer creation of flow rate ratio - time 1 & I! The other strips were the same as in Example 1, and the number of layers was changed to form an electrophotographic imaging member of 47't.

) Using the thus obtained image forming material, KdlJ111 was formed on a transfer paper using the same curling procedure as in Example 1, and a very clear image quality was obtained.

Example 4 By the sea bream Jfi Seiro shown in FIG. , under the conditions shown in Table 4, and according to the change weight of the gas flow ratio shown in Figure 15, Gek14/l (gas flow completion ratio tm of e gas and s t[4/e gas) with elapsed time. An electrophotographic image forming member was obtained by carrying out all the forming operations under the same conditions as in Example 1.

When 11 holes were formed on the transfer paper using the thus obtained star-forming member under the same conditions as in Example 1 and in the f-order, a clear shadow was obtained in the 1st stage.

Example 5 ・Manufacturing S shown in FIG. 11! ? , -, the gas flow ratio of G@m4/He gas and 81H4/H@ gas is set to /l1li mu according to the rate of change curve of gas flow ratio shown in FIG. d change with time 14,
Layer formation was carried out under the same conditions as in Example 1 to obtain an electrophotographic image forming member.

Regarding the image forming member thus obtained, Example 1 and +g
When a 1-image was formed on transfer paper using J.T.'s sweat dye and hand dye, an extremely bright 11# fiber was obtained.

Actual WAN 6 Using the Satoshi manufactured by Tomo as shown in Fig. 11, according to the rate of change curve of the gas flow rate ratio shown in Fig. #117 under the conditions shown in Table 6,
The gas flow rate ratio of G@Ha//11@ gas and 81Ha/H・4 gas was varied with the layer formation time, and the other conditions were the same as in Example 1. Obtain the forming member.

The image forming member thus obtained was printed on transfer paper under the same conditions and procedures as in Example 1, and an extremely clear image quality was obtained.

Example 7 As shown in FIG. 11, Ge
Gas flow ratio of 5IH4/H gas and 5IH4/H gas. Layer formation: layer formation was carried out using the same conditions as in Example 1, except for the formation of a layer for Ichiko photography. Obtained nine pieces of cedar palm wood.

Examples 1 and 14 of the thus obtained running image Liaocheng Zheng material
When a IIIi image was formed on transfer paper using the same conditions and curling procedure, a clear image quality was obtained for the first time.

Example 8 In Example 1, 8t% was used instead of 8tH4/Ha gas.
The same method as in Example 1 was used except that a/Hsn was used and the conditions shown in Table 8 were used. An electrophotographic imaging member was obtained using T.

The thus obtained nine-point forming member was formed on a transfer paper using the same curling procedure as in Example 1, and an extremely clear image was obtained. I got the truth, my friend.

Example 9 In Example 1, 5 was used instead of 1e gas in s LH4/
Using ty4/n gas and under the conditions shown in No. 9, a layer forming member for photographic use was obtained in the same manner as in Example 1, except for the coating.

When an image was formed on a transfer paper using the thus obtained image forming member under the same conditions and manually as in Example 1, an extremely clear image quality was obtained.

Example 10 Fire in Example 1, but instead of 131H4/kle gas (S L Ha /H11) S i F4 /M e
) An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that gas L was used and the -r conditions shown in Table 10 were used.

When an image was formed on the thus obtained image-forming thin material on a transfer paper under the same conditions as in Example 1, an extremely clear image quality was obtained.

Example 11 In Examples 1 to 10, each of the square-forming members for one-child photographs was made in the same manner as in the conditions shown in each example, except that the conditions for creating the second drop were changed to the conditions shown in Table 11. Created.

The image forming member thus obtained was subjected to Ithi-coating on a transfer paper under the same conditions and under the same conditions as in Example 1, and the results shown in Table 11 were obtained.

C. Example 12 In Examples 1 to 1.0, the conditions for creating the second layer were
Each of the electrophotographic image forming members was produced under the same conditions as those shown in the Tani Examples except that the conditions shown in the table were used.

When the image forming member thus obtained was subjected to actual forming, the results shown in Table 12 were obtained.

Example 15 In Example 1, except that a 8101 GaAA conductor laser (10, nw) was used instead of the tungsten lamp to form the cylindrical ring. Toner transfer for a self-forming member for single-child photography prepared under the same conditions as in Example 1 using the same toner as in Example 1.
In terms of image quality evaluation, I was able to obtain a clear, high-quality image with excellent reproducibility.

Common layer forming conditions in the above embodiments of the present invention are shown below.

Substrate temperature: Germanium atom (Ge) containing layer - 1111 approximately 200°C Germanium atom (Ge) non-containing layer - m
Approximately 250°C Discharge frequency: 13.58 MHz Reaction chamber pressure during reaction: 0.3 Torr

[Brief explanation of drawings]

FIG. 1 is a personal layer structure diagram for explaining the layer structure of the light guiding wL member of the present invention, and FIGS. 2 to 10 are for explaining the distribution state of germanium atoms in the amorphous layer, respectively. FIG. 11 is a schematic explanatory diagram of the device used in the present invention, and FIGS. 12 to 18 respectively show the change rate of gas flow ratio in this embodiment. FIG. 100...Optoelectronic member 101...Support 102...Amorphous layer Applicant Canon Inc. "t:+!l!? Ars comrade! Hi No. 16M Male 771Y

Claims (1)

[Scope of Claims] (1) A first oMS region made of an amorphous material containing silicon atoms and germanium atoms and a non-crystalline material containing silicon atoms on a support for a photoconductive member and a cough support. a second layer region made of a crystalline material and exhibiting conductive conductivity;
The distribution state of germanium atoms in the tenth layer region is non-uniform in the layer thickness direction. The photoconductive member 0 (3) 10th layer region and the 2nd layer region according to claim 1, wherein one of the photoconductive members contains water bulk atoms.
The photoconductive member according to the second product 0 in which at least one of the layer regions contains rogen rhinoceros %1FF111 (4) Distribution of germanium atoms in the first layer region The photoconductive member according to claim 1, wherein the photoconductive member has a distribution state in which the state is distributed more toward the support.