JPS58219560A - Recording body - Google Patents

Abstract

PURPOSE:To obtain a recording body having a low dark attenuation rate and high sensitivity, by coating a substrate with three amorphous silicon carbide-hydride layers doped with impurities and a photosensitive layer of amorphous silicon hydride doped with an impurity. CONSTITUTION:A substrate 1 is coated with the 3rd amorphous silicon carbide- hydride and/or -fluoride layr 5 (expressed as a-SiC:H layer hereunder) provided with P type electric condutivity by adding a IIIA group element in the periodic table, and the layer 5 is coated with the 2nd a-SiC:H layer 2. The layer 2 is coated with a photoconductive layer 3 of amorphous silicon hydride and/or fluoride provided with >=10<10>OMEGA-cm dark resistivity by adding a IIIA group element, and the layer 3 is further coated with the 1st a-SiC:H layer 4 of 50-2,000Angstrom thickness provided with >=10<13>OMEGA-cm dark resistivity by adding a IIIA group element to obtain the desired recording body.

Description

[Detailed description of the invention]

The present invention relates to a recording medium, such as an electrostatic recording medium such as a photoelectric element or an electrophotographic photoreceptor. Conventionally, as an electrophotographic photoreceptor, Se, or Se and As,
Photoreceptor doped with Te, Sb, etc., ZnO or CdS
Photoreceptors, etc., in which the compound is dispersed in a resin binder are known. However, these photoreceptors have problems in terms of environmental pollution, thermal stability, and mechanical strength. On the other hand, electrophotographic photoreceptors using amorphous silicon (hereinafter referred to as a-8i) as a matrix have been proposed in recent years. a-8t has a so-called dangling bond in which the bond of 5i-8i is broken, and many local focusing points exist within the energy gap due to this defect. For this reason, hopping conduction of thermally excited carriers occurs, resulting in a low dark resistance, and photoexcited carriers are trapped in units of stations, resulting in poor photoconductivity. Therefore, the dangling bonds are filled by compensating the defects with hydrogen atoms () and bonding 5iKH. Such amorphous hydrogenated silicone (hereinafter referred to as a-S
It is called i:■t. ) resistivity in the dark it 10',
~10'Ω-cm, which is about 1/10,000 times lower than that of amorphous Se. Therefore, a photoreceptor consisting of a single layer of a-8i:)i has a large dark decay □ rate of surface potential,
The problem is that the initial charging potential is low. However, on the other hand, when irradiated with light in the visible and infrared regions, the resistivity is greatly reduced, so it has extremely excellent properties as a photosensitive layer of a photoreceptor. In addition, a photoreceptor with a surface of a-8i: Until now, sufficient studies have not been conducted regarding the properties of silicon carbide.For example, it has been found that if the product is left for more than a month, it will be affected by moisture and its acceptance potential will drop significantly.On the other hand, amorphous silicon carbide (hereinafter referred to as a-5iC:H.)
The manufacturing method and existence of -Ph11. Mag,
Vol. 35'' (1978), etc., and its characteristics include high heat resistance and surface hardness, and a-8i
:High dark resistivity compared to H (x012~10'3Ω
It is known that the optical energy gap changes over a range of 1.6 to 2.8 eV from carbon t<. An electrophotographic photoreceptor mineral combining such a-8iC:H and a-8i:H has been proposed, for example, in JP-A-57-17952. According to this K, the a-8i:n layer is a photosensitive (photoconductive) layer, and a first a-stc layer is formed on this light-receiving surface.
: Form n layer, back side - H (support electrode side) K No. 20a
-8iC: An n-layer is formed to form a photoreceptor with a three-layer structure. The inventor of the present invention has investigated the photoreceptor having such a three-layer structure, and found that the carrier from the support (substrate) side,
In particular, when positively charged, electrons are easily injected, and as a result, the positive charge on the surface is neutralized, resulting in poor retention of surface potential. I understand that. At the same time, we also discovered that it is important to limit the thickness of the uppermost a-8tc:n layer to a specific range, and have arrived at the present invention. That is, the characteristic structure of the recording medium according to the present invention is the third amorphous hydrogenated and/or fluorinated carbonized film! J:ry
(Example) f a-8iC:H) layer and a second amorphous hydrogenated and/or fluorinated silicon carbide (e.g. a
a photoconductive layer consisting of an amorphous hydrogenated and/or fluorinated silicon (e.g. a-8i:)i); a first amorphous hydrogenated and/or fluorinated silicon carbide (e.g. a-8i:)i) layer; The third amorphous hydrogenated and/or fluorinated silicon carbide layer is made into a P-type by containing an OTA group 1 element in the periodic table. The photoconductive layer contains an element of group mA of the periodic table, and/or the fluorinated silicon carbide layer contains an element of group mA of the periodic table.
By having a film thickness of 0^ and containing an element of group mA of the periodic table, the above-mentioned features of the three-layer structure can be utilized, and in particular, the amorphous hydrogenated and/or fluorinated silicon carbide layer of the third layer can be utilized. exists on the substrate side, it can effectively prevent the injection of carriers from the substrate, and since the dark resistance of other layers is high, it is possible to maintain the charged potential and reduce dark decay. Residual potential and charging characteristics can be further improved by hydrogenation and/or by specifying the thickness range of the fluorosilicon carbide layer. The invention will now be illustrated in detail with reference to the drawings. As shown in FIG. 1, a recording medium according to the present invention, for example a photoreceptor, includes a conductive support substrate 1, a third a-8iC:n layer 5 doped with the above-mentioned mA group element, and optionally an mA group element. The second a-8iC doped with an element: the n layer 2, the m
A photoconductive layer 3 consisting of a-8i:H doped with an A-group element;
8iC: It may consist of a book in which the n-layers 4 are sequentially laminated. The third a-8iC:n layer 5 greatly contributes to preventing the injection of carriers from the substrate 1 and maintaining a sufficient surface potential, and for this purpose, it contains P type (even P It is important that the type (type) k conversion is performed. In addition, its thickness is 50^~1-μm (further h4ooX~
5000×) is desirable. The second a-8iC:n layer 2 mainly has the functions of holding potential, transporting charges, and improving adhesion to one substrate 1, and
0001~80μm (more preferably 5μm~+μm)
It should be formed to a thickness of . The photoconductive layer generates charge phase bodies (carriers) in response to light irradiation, and its thickness is 2soo! ~1oμm (especially 5ooo
~5 μm) is desirable. Furthermore, the first a-8i
C: H1 scrap 4 improves the surface potential characteristics of this photoreceptor, maintains the potential characteristics over a long period of time, maintains environmental resistance (prevents the effects of humidity, atmosphere, and chemical species generated by corona discharge), and improves surface hardness. It has functions such as improving printing durability due to its high K content, improving heat resistance when using a photoreceptor, and improving thermal transferability (adhesive transferability in %), and functions as a surface modification layer. a-8tc of this fMl::[(The thickness of layer 4 is 50 to 20
It is extremely important to make it as thin as 00X, preferably 4ooX to teooA. What should be noted about this photoreceptor is the above-mentioned a
S%C/h-8i:H/A-8iC not only has the features of the laminated structure, but also has the 30th a-8iC:
The H layer becomes P type (
In addition, it has been converted to P type by heavy doping), so
Injection of carriers (electrons) from the substrate side during positive charging is effectively prevented. Moreover, in addition to this, the first a-8iC:H layer 4 is set to a much thinner thickness range than conventional ones, and the dark resistance is increased by doping with the mA group element of the periodic table together with the photoconductive layer. This greatly contributes to improving each electrostatic property as described below. In addition, since the photoreceptor shown in Figure 1 has the above-mentioned laminated structure, it retains a high potential with a thinner film than the conventional Se photoreceptor, and is resistant to light in the visible and infrared regions. A-8i thermal photosensitive material (for example, for electrophotography) that exhibits excellent sensitivity, good heat resistance, printing durability, and stable polarity.
can be provided. Next, an apparatus (glow discharge apparatus) that can be used to manufacture a photoreceptor according to the present invention will be described with reference to FIG. this device

[1] Inside the empty coffin 12, the substrate 1 is fixed on the substrate holding part 14, and the substrate 1 is stretched so that the heater 15 can heat the substrate 1 to a predetermined temperature. A high frequency electrode 17 is arranged opposite to the substrate 1, and a glow discharge is generated between the high frequency electrode 17 and the substrate 1. In addition, the title in the figure, 2], n, 23, Sae, 27
, row, wa, (9), 35, part, side is each pulp, 31 is S
iH4 or a source of gaseous silicon compounds, 32 is CH
4 or a source of gaseous carbon compound, 33 is Ar or 1dH
2 is a carrier gas supply source, and 34 is a thiargon diluted diborane gas or phosphine source. In this glow discharge device, first, the surface of a support, for example, an AA substrate 1, is cleaned, and then placed in a vacuum chamber 12.
The valve 1 is evacuated so that the gas pressure in the wafer 2 becomes 10='l'orr, and the substrate 1 is heated and maintained at a predetermined temperature, for example, 200°C. Next, using a high purity inert gas as a carrier gas, a mixed gas prepared by diluting an appropriate amount of 8iHn or a gaseous silicon compound, diborane gas, and a gaseous carbon compound from CHa Matasha is introduced into the vacuum chamber 12.
．． High frequency power is applied to the high frequency power source 16 under a reaction pressure of 01 to 10 Torr. As a result, each of the above reaction gases is decomposed by glow discharge, and P-type a-8iC containing hydrogen:
The above-mentioned H layer 5 is deposited on the substrate 1. Chapter 10a
When forming the -8iC:H layer 2 and the 20th a-8iC:H layer 4, diborane gas is similarly supplied. By appropriately adjusting the flow rate ratio of silicon compound and carbon compound and substrate temperature, a-8ix-xcx:H (for example, up to about 0.9 for X) having a desired composition ratio and optical energy gap can be deposited. a that can be produced and precipitated
-8tC:H at a speed of xoooX/min or more without significantly affecting the electrical characteristics of -8iC:H
It is possible to deposit seeds. Furthermore, a-8i:H(
In order to deposit the above photosensitive layer 3), a suitable amount of a gaseous compound of a group HA element of the periodic table, such as BzHs, is added together with a silicon compound without supplying a carbon compound, and both gases are decomposed by glow discharge. , a-81:H can be improved in photoconductivity and its resistance can also be increased. Both the first and 20a-818:H layers described above need to contain hydrogen, but if they do not contain hydrogen, the charge retention characteristics of the photoreceptor will not be practical. Therefore, the hydrogen content is l ~40 ato
mic to (and even 10 to 30 atoms)
96) is desirable. The hydrogen content in the photoconductive layer 3 is essential to compensate for dangling bonds and improve photoconductivity and charge retention, and is usually 1 to 40 atomic %, and 3.5 to 40 atomic %. 20at
More preferably, it is omic%. When forming each layer by glow discharge decomposition in this way, especially the a-8iC:H layers 5 and 4 (and if necessary, the a-8iC:H layers 5 and 4)
Regarding the iC:H layer 2) and the photoconductor 93, it is necessary to appropriately select the flow rate ratio of diborane gas and silicon compound gas (for example, monosilane). Figure 3 shows that when impurity (nIA group) doping is performed on the 1 to 8iC:H layer 5.4 or 2, the non-doped a-8iC:H generally has a resistivity of 1012Ω-somewhat on an inverted plate. It exhibits an N-type conductivity type, but when doped with boron, the impurities are compensated.
When the amount of boron doping is further increased, it is converted into a P-type state. According to the results shown in Fig. 3, if the flow rate ratio (BzHs/5iH4) is appropriately selected at 1F to achieve the purpose of the present invention, ρD
is set to 101Ω-false or higher, and furthermore, a-8iC:H can be substantially made intrinsic to make ρD higher than 1014Ω-d, and if the above flow rate ratio is set to Zoo ppm or higher, it becomes P type (or even P type). It can be converted to . In particular, the above flow rate ratio is 100 ppm-100,000p
pm, the a-8iC:H layer 5 is made into a P type (furthermore, by increasing the above flow rate Kti and making ρD below 10'Ω-Fu, it is made into a P type by K). It functions as a blocking layer that effectively blocks injection of carriers (electrons) from the substrate side during charging. Further, since boron is added to the a-8iC:H layer 2 or 4, the initial charge amount increases and electrophotographic properties such as dark decay can be improved. In particular, if ρ0 is set to 1014Ω-ω or more, further improvement in performance can be expected. On the contrary,
ρD is less than 10139 (if not doped with boron, less than 5 x 1012 Ω) BzHs/SiH4
When the flow rate ratio is 0 to ippm), the characteristic 6 described above is satisfied.
No improvement could be obtained, and it is not sufficient as a photoreceptor. a-8iC: The boron content of the H layer 5 is as described above/
It is necessary to make SiH4≧100 ppm, 100~
100,000 ppm is good. In addition, the boron content of the a-8iC:H scrap 2 or 4 must be appropriately selected in order to obtain the above dark resistance value, and from Fig. 3, Ba)Is/8iH4 = 10~500
ppm is desirable, and about 20 to 300 ppm is more desirable. The flow rate ratio can be 10 to 500 ppm depending on the type of gas used. Figure 4 shows ρ due to the flow rate ratio of BzHs/8iH4 when the a-8tCH layer is doped with 3KmA group elements.
The change in D is shown, and it can be seen from this K that if the flow rate ratio is set to 20 to 300 ppm, ρD can be increased to 10 10 Ω-F or more, and the object of the present invention can be achieved. If the above flow rate ratio is further selected, the a-8l:H layer 3 is substantially made intrinsic, and ρD becomes 10119-1019-1, or even 1012
Ω - Can be raised to the top of the board. Depending on the type of reaction gas used, the above flow rate ratio may vary from 10 to 500.
It is also possible to set it as ppm. As described above, the photoreceptor according to this embodiment includes the a-8iC:H layer 5 which has been made P-type by impurity doping, the a-8iC:H layers 2 and 4 whose dark resistance has been sufficiently increased, and
-8S:T (layer 3), the combination of these layers synergistically improves the surface potential retention, dark resistance, and charging characteristics of the photoreceptor. FIG. 5 shows a vapor deposition apparatus used for producing a photoreceptor according to the present invention by vapor deposition. ) and thereby connect the inside of the perger 41, for example, from 10-3 to 10-
The substrate 1 is placed in the Pel jar 41 and heated to a temperature of 1 by the heater 45.
While heating to 50 to 500°C, preferably 250 to 450°C, the substrate 1 is heated to θ to -10KV by DC power supply 46.
, preferably a negative DC voltage of -1 to -6 KV is applied to the Pelger 41 so that the outlet faces the substrate 1.
The silicon evaporation source 48 and the aluminum evaporation source 49, which are provided to face the substrate 1, are heated while introducing active hydrogen and hydrogen ions from the hydrogen gas discharge tube 47, which is connected to the At the same time, each upper shutter S is opened to simultaneously evaporate silicon and aluminum at an evaporation rate such that the evaporation rate ratio is, for example, 1:0.01 to 0.2. This results in aluminum doped a
-8tSH layer 3 (see FIG. 1) is formed. Further, with the shutter S on the aluminum evaporation source 49 open, methane gas activated between the discharge tubes is introduced into the Pelger 41, thereby causing the a-8iC:H layer 5 (the first 1) is formed on the substrate 1. Also when forming the first and second a-8iC:H layers 4 and 2, antimony or aluminum may be evaporated. For example, the structure of the discharge tube 47 is shown in the discharge tube 47, as shown in FIG. , between a discharge space member 64 made of, for example, cylindrical glass surrounding the discharge space B, and another ring-shaped electrode member provided at the other end of this discharge space member 64 and having an outlet portion; By applying a DC or AC voltage between the electrode member 62 and the other electrode member, for example, hydrogen gas supplied through the gas inlet 61 flows into the discharge space 6.
At 3, a glow discharge is generated, whereby active hydrogen and ionized hydrogen ions constituted by hydrogen atoms or molecules activated by simulonic energy are discharged from the outlet section. The illustrated example of the discharge space member has a double pipe structure and is configured to allow cooling water to flow therethrough, and 67 and glaze indicate the cooling water inlet and outlet. 69 is a cooling fin for one electrode member 62. The distance between the electrodes in the hydrogen gas discharge tube 47 is 10 to 15 mm, and the applied voltage is 600 V.
, the pressure in the discharge space 63 is approximately 10-3 Torr. Also in the photoreceptor produced by the vapor deposition apparatus shown in FIGS. 5 and 6, a-8iC:H layers 2 and 4, a-8i:
The H layer 3 is made highly resistive (and substantially made intrinsic) by doping with aluminum or antimony.
As a result, -0 has been improved in the same way as described above. For this reason, K is 10 to 500 ppm of aluminum vapor to silicon vapor during vapor deposition, and even 20 to 500 ppm of aluminum vapor to silicon vapor during vapor deposition.
A concentration of 300 ppm is preferred. Also, a-8i
The C:H layer 5 is also doped with Group IIIA elements, and during vapor deposition, impurity vapor is added to silicon vapor at 100 to 10' ppm.
(＼.Next, each layer of the photoreceptor according to the present invention will be explained in more detail. And a-
This is indispensable in order to make the 8t-based bad sensitivity practically excellent. In other words, charge retention on the surface, surface lightning attenuation due to light irradiation, and (1) basic operation as an electrophotographic photoreceptor are possible.Therefore, the repetitive characteristics of charging and light attenuation are It is extremely stable9, and good potential characteristics can be reproduced even if it is left for a long period of time (for example, over 1 month).On the contrary, in the case of a photoreceptor with a-8i:H as a surface, is easily affected by humidity, air, ozone atmosphere, etc., and the potential characteristics change significantly over time.Also, a-8iC:
Because of its high surface hardness, IC1 development, transfer, and
It has good abrasion resistance in processes such as coating, and also has good heat resistance, so processes that apply heat such as adhesive transfer can be applied. In order to achieve such excellent effects comprehensively, K is a-
It is extremely important to select the thickness of the 8iC:H layer 4 within the range of 5oλ to 2000^ as described above. That is, if the film thickness is 2000λ or more, the residual potential becomes too high and the sensitivity decreases, resulting in the loss of good characteristics as an A-81 photoreceptor. In addition, when the film thickness is less than 50λ, the charge is not charged on the surface due to the tunnel effect, so the a-8iC2H
The film thickness balance between layer 4 and a-8i:H layer 3 causes an increase in dark attenuation and a significant decrease in photosensitivity. Therefore, the film thickness of the a-sic:H layer 4 is less than 200OA, 50OA
It is essential that the value be X or higher. Furthermore, it has been found that it is also important to select the carbon composition of this a-8tC:H layer 4 in order to exhibit the above-mentioned effects. If the composition ratio is expressed as a-8it-xcx:H, then
atomic%) is desirable. That is, 0
．． If 4≦X, the optical energy gap is t!
J 2.3 e V or more, as shown in Figure 7, it is substantially photoconductive to visible and infrared light (where ρD is the resistivity in the dark, and ρL is the resistivity when irradiated with light). with resistivity of ρ
Due to the so-called optically transparent window effect, most of the irradiated light is a-8i.
: It reaches the H layer (charge generation layer) 3. On the contrary x
(If it is 0.4, part of the light will be absorbed by the surface layer 4,
The photosensitivity of the photoreceptor tends to decrease. Furthermore, if X exceeds 0.9, most of the layer becomes carbon, and not only the semiconductor properties are lost, but also the deposition rate when forming the a-8iC:H film by the glow discharge method decreases. It is preferable that ≦0.9. 20th a-sic: a layer This a-8iC:H layer 2 has both functions of charge, potential retention and charge transport, and has improved dark resistivity by doping with the above impurity and has high electric field resistance. Since the potential held per unit film thickness is high, and the electrons or holes injected from the photosensitive layer 3 exhibit large mobility and lifetime, charge carriers are efficiently transported to the support 1 side. Further, since the size of the energy gap can be adjusted by changing the composition of carbon, charge carriers generated in the photosensitive layer 3 in response to light irradiation can be injected efficiently without creating a barrier. 1, this second a-8iC:H layer 2II'i support 1 also has the property of good adhesion and film formation with, for example, an At electrode. Therefore, this a-8i(::=H layer 2 maintains a high surface potential at a practical level, and a-8t:H
It has the function of efficiently and quickly transporting the charge carriers generated in the layer 3, resulting in a photoreceptor with high sensitivity and no residual potential. However, since this layer 2 has a sufficient thickness as described below, it exhibits good potential holding ability and charge transport ability even if the v resistivity is not necessarily increased as described above by impurity doping. In order to achieve these functions, the thickness of the a-8iC:H layer 2 is desirably 5000× to 80 μm in order to apply a dry deposition method using the Carlson method, for example. If this film thickness is less than 5000 A, it is too thin and the surface potential necessary for development cannot be obtained, and if it exceeds 80 μm, the surface potential becomes high and the removability of attached toner becomes poor, making it difficult to develop with two-component system. The carrier of the agent also adheres to the surface. However, even if the film thickness of this a-8iC:H layer is made thinner (for example, 10-odd μm) than that of the Se photoreceptor, a surface potential at a practical level can be obtained. Moreover, this a-8iC:H layer 2 is a-3it-xcx
: When expressed as H, 0.1≦X≦0.9 (carbon atom content is 10 atomic % to 90 atomic
%, preferably 30 to 90 atomic 4 ). If 0.1≦X, a-8iC:H
Layer 3 can be completely different from layer 3, and 0, 9 (if x, most of the layer will be carbon) will not only lose its semiconductor properties but also reduce the deposition rate during film formation. This is because in order to prevent this, it is better to set X≦0.9. Third a-8iC:H layer This layer forms an energy gap between the substrate and the substrate that can sufficiently prevent the injection of carriers (especially electrons) from the substrate 1. It has the function of eliminating the sum phenomenon and maintaining the surface potential and, ultimately, the charging characteristics well. For this reason, it is desirable that the a-sic:u layer 5 be made into a P type (or even a P+ type) by doping with impurities as described above. Further, the film thickness is preferably selected from 50X to 1 μmK. If it is less than 50X, there is no effect, and if it exceeds 1 μm, the charge transport property tends to deteriorate. In addition, its carbon content is 10 to 90 atoms, similar to the above a-stc:u layer 2.
It is better if it is ie*. a-8i: H layer (photoconductive layer or photosensitive layer) a-8i:
The H layer 3 has high photoconductivity for visible light and infrared light, and as shown in FIG.
For red light near m, ρD/ρL is the maximum ~104. By using this a-8i:IH as a photosensitive layer, it is possible to create a photoreceptor that is highly sensitive to light in the entire visible region and in the infrared region. Furthermore, the specific resistance is increased by doping with the mA group element of the periodic table, and ρD is improved accordingly, so that both the charging potential and the dark decay are good. In order to absorb visible light and infrared light without wasting it and generate charge carriers, the film thickness of 5-8i:HN3 should be 2500X to 10μ.
It is desirable to do m. If the film thickness is less than 2500X, all of the irradiated light will not be absorbed and some of it will be absorbed by the underlying a-
8iC: Since the H layer reaches 2IC, the photosensitivity decreases significantly. Also, it is not necessary to make the a-8i:1 layer 3 thicker than the thickness required for light absorption between the photosensitive layer and L7, and the thickness is at most 10 μm.
It is sufficient. In the example explained above, in order to compensate for dangling bonds, fluorine is introduced into a-8t in place of (2) above, or in combination with H, and a-8i:F
, a-8i:H:F, e, -8iC:F, a-
It can also be 8iC:H:F. In this case, the amount of fluorine is preferably 0.01 to 20 atom ic%, and 0.01 to 20 atom ic%.
5 to 10 atomic units is more desirable. Note that the above manufacturing method is based on the glow discharge decomposition method or the vapor deposition method, but in addition to this, there are also sputtering methods,
Aeon play 1. The above-mentioned photoreceptor can also be manufactured by a printing method or the like. Reaction gas used K other than 3iH4
4Si2HQ, 5iHFs or its derivative gases, lower hydrocarbon gases other than CH4 (7) C2H6, Cs1(s, etc.) can be used.In addition, impurities to be doped include gallium in addition to the above boron and aluminum. , other Group HA elements of the periodic table such as indium, and other Group VA elements of the periodic table such as arsenic other than phosphorus and antimony.Next, Examples in which the present invention is applied to an electrophotographic photoreceptor Example 1 An electrophotographic photoreceptor having the structure shown in Fig. 1 was prepared on an AL support by a glow discharge decomposition method.First, a clean At support with a smooth surface was placed in a glow discharge device. It was placed in a reaction (vacuum) tank.The inside of the reaction tank was evacuated to a high vacuum level of 10-6 Torr, and after heating the support to 200°C, high-purity Ar gas was introduced, and the back pressure was set to 0.5 Torr. Pressure source frequency 1
3.56 MH! , high-frequency power with a power density of 0.04 W/cd was applied, and preliminary discharge was performed for 15 minutes. Then,
A reaction gas consisting of SiH4 and CHa was introduced, and the flow rate ratio of (Ar+5iHa) was 3:1:0.5~0.05.
+CH4) a -8iC that prevents carrier injection by glow discharge decomposition of mixed gas and BIH6 gas
: H layer, and a- which plays the role of potential retention and charge transport function.
An 8iC:H layer was deposited at a deposition rate of 350 A/min. Once the reaction tank was evacuated, 5tH4 and BzHs were added using Ar as a carrier gas without supplying Cuttf.
was decomposed by discharge to form a poron-doped a-8i:H photosensitive layer, CH4 and f3*Hs were supplied again, and this time (Ar+5iHa+CH4
) The mixed gas is decomposed by glow discharge and boron-doped A-8
A tC:H surface modification layer was further provided to complete the electrophotographic photoreceptor. The optical energy gap of this a-, SiC:H surface modified layer was 2.5 to 2 OeV. Also,
Analysis showed that the carbon composition was ~20 atomic%. When the thus prepared photoreceptor was subjected to a positive corona discharge of 6 KV, the surface was charged to a positive potential. After 6 seconds of dark decay, the surface potential decayed almost linearly with 1 lux light irradiation. At this time, the half-decreased exposure amount was very low, there was almost no residual potential, and the charging/exposure repetition characteristics were also very good. Comparative Example 1 Ka-8iC was produced on an At support by the same manufacturing method as in Example 1 except that f3tHg was mixed as a reaction gas.
H layer 5 was formed. a-8iC: H layer 2.4, a-8i
:) The i-layer 3 was also formed in the same manner as in Example 1, except that BzHg was mixed or not. Example 1 using this photoreceptor
I conducted a similar test. As a result, the dark decay is large,
The half-life exposure amount also increased, and the performance during image formation was such that the maximum image density was low and the sensitivity was insufficient. Example 2 An aluminum doped a-8iC:H layer 5 and an aluminum doped a-8t:H:A/ layer 3 as a photoconductive layer were formed on an At substrate 1 using the vacuum evaporation tank 41 shown in FIG. Formed. Above and below this photoconductive layer are antimony-doped a
-8iC: a-8iC without H layer 4 and doped foot:
The H layer 2 was formed by the method described above. That is, the tank 41 is opened by a vacuum pipe.
The discharge device 47 shown in FIG. 6 is installed in this tank 41.
Hydrogen gas (100cc/min) activated by discharge using
The silicon evaporation source 48 and the At evaporation source 49 are heated with an electron gun to evaporate them, and the silicon evaporation amount and A
10' without detecting the amount of evaporation with the crystal monitor:
The ratio of 1 (the concentration of evaporation amount of AL to the amount of evaporation of St is 11
00pp or higher), and the substrate voltage -2
KV and a substrate temperature of 300 DEG C. to form an aluminum doped a-8iC:n layer 5, an a-8i:H-:At layer 3, and a doped g-8iCrH layer 4. a-8iC: When forming the n layer 2, methane gas was heated at 30 ec.
A photoreceptor of the present invention was obtained by forming an a-sic:n layer in the same manner as described above, except that At was introduced at a flow rate of /mlri and the shutter of the At evaporation source was closed if necessary to block evaporation. . Comparative Example 2 Next, for comparison, a-8 with and without antimony doping
iC: combined with n layer 5, a-8i: n layer 3 or a-8
When the tC:n layer 2 or 4 was not doped with At, it was formed in the same manner as above without evaporating At, and this was used as a photoreceptor for comparison. The photoconductor according to the present invention and the photoconductor for comparison were electrometer fI1g manufactured by Kawaguchi Electric Co., Ltd. and U-BixV-2.
The results of a performance test using the modified machine are shown below. (The following is a blank space, continued on the next page) In the above table, the electrostatic characteristic V is the initial charging potential ΔV/V
is the dark decay rate of the charge 6 seconds after the end of charging, EIA is the half-decreased exposure amount (unit: lux·see), and Vyt is the residual potential. These results show that the photoreceptor according to the present invention has a sufficient charging potential, a slightly low dark decay rate, and high sensitivity. Furthermore, clear, high-density images can be obtained even after repeated copying over 75,000 times. On the other hand, it can be seen that the comparative example has poor potential, dark decay, and photosensitivity, and is also significantly inferior in repeatability. Example 3 Layer configuration according to the same manufacturing method as in Example 1, i.e. 2000 X co BtHs/5iH4 thick on an At support.
a-8iC:H layer (blocking layer) doped with 10,000 ppm and 10 μm B2He/5iH4
Doped with 100ppm, resistivity 3.6 x 10”
After forming an a-8iC:H potential-holding layer of Ω-ring and an a-8i:H photosensitive layer with a specific resistance of 2.5 x 1012 Ω-m doped with BzH+s/5iH4100ppm with a thickness of 1.0 μm, K B 2 Hs / S 1
In a photoreceptor with a laminated H4100a-8iC:H surface modification layer, the thickness of the a-8iC:H surface layer was 0.05 t.
Im So, 2 am, 0.5 μm, 1, and 9 μm were prepared, and their charging and optical attenuation characteristics were compared. After charging the surface of the photoreceptor with a +6KV corona discharge, 1 lux of light was irradiated, and the results of the optical attenuation characteristics were as shown in the table below and FIG. 8 (data plotted). Here, E1/2 is the half-reduced exposure amount (lux e see
), VR is the residual potential (volt). As is clear from this result, for a-8iC:H, the thickness of the surface layer is 0.
When the length was 211 m or more, a significant decrease in photosensitivity and an increase in residual potential were observed. Further, the initial charging potential was +760 volts for those with a surface layer thickness of 0.2 μm, and for the thicker ones, the initial charging potential was improved by the residual potential shown in the above table. As shown in the above table and FIG. 8, a=Si:H and a-
8iC:H is easily injected into the hole 1ja-8iC:H layer among the charge carriers generated in the a-8t:H photosensitive layer at the interface between the a-8i:H layer and the a-8iC:H layer. In contrast, electrons form a barrier and have an energy level that makes it difficult to inject them, which is thought to have caused a decrease in photosensitivity and a residual potential. As described above, making the thickness of the a-8iC,:H surface modification layer less than 0.2 μm makes it easier for electrons to be injected, neutralizing the surface negative charge, and making it easier for holes to reach the substrate side. ), which was important in obtaining good optical attenuation characteristics. Also,
The a-8iC:H surface layer had a thickness of 0.15 μm, but when a carbon composition of 20 atomic % was used, the half-attenuation exposure amount was 1.21 ux-see. In this case, the optical energy gap of the a-8iC:H layer with this composition is 2. Since it was OeV and a part of the irradiated light was absorbed by the surface layer, the photosensitivity decreased as a result. In this way, a-8iC:I (the composition of the surface layer is 40 atoms or more as shown in FIG. 7 and has photoconductivity to visible and infrared light),
It was important to make it optically transparent.

[Brief explanation of drawings]

The drawings illustrate the present invention, in which FIG. 1 is a cross-sectional view of a part of an electrophotographic photoreceptor, FIG. 2 is a schematic cross-sectional view of a glow discharge device for manufacturing the photoreceptor, and FIG. 3 is a doped a -B* when forming a film of 8iC:H
A graph showing the dark resistance change depending on the He/SiH4 flow rate ratio, Fig. 4 is a graph similar to Fig. 3 when forming a film of doped a-8i:H, Fig. 5 is a schematic cross-sectional view of the vapor deposition apparatus, Fig. 6 The figure is a cross-sectional view of the discharge part. Figure 7 is a graph showing the photoconductivity of e-8i:H and a-8sd:H of each composition. Figure 8 is the electrostatic characteristics depending on the thickness of the 10a-8iC:H layer. It is a graph showing changes in. In addition, in the symbols shown in the drawings, 1...
...Support (substrate) 2... Second a- doped with impurities
8iC:H layer 3... Impurity doped a-gt:H photosensitive layer (photoconductive layer) 4... 10a-8iC:H layer 11...
......Glow discharge device 17...
High frequency electrode 31... Gaseous silicon compound supply source 3
2... Gaseous carbon compound supply source...
...Carrier gas supply source 34...
・B2H6 or PHs supply source 41... Vapor deposition tank 47, Seki... Discharge section 48... Silicon evaporation source 49...・
...Aluminum is an antimony evaporation source. Agent Patent Attorney Hiroshi Aisaka Figure 1 Figure 21 η BzH1 Group 4 (ρ- B”G'SiH4 (PPm) No. 50 3, 6th day seal procedure amendment 1. Indication of the case 1982 Patent No. 102417 No. 2, Record of the name of the invention 3, Relationship with the case of the person making the amendment Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name:
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Number of inventions increased by amendment 7, Claims column, Detailed explanation of the invention column, and brief explanation of drawings of the specification subject to amendment Column 8, ? In the correct iR content (2), "station unit" on page 6, line 8 of the specification letter is corrected to "localized level." (3), "Fluorinated carbonization" in the fourth line from the bottom of page 9 is corrected to "Fluorinated carbonization." (4), "20" in the fourth line from the bottom of page 10 of the same page is replaced with "30"
I apologize. (5), ra-8iCJ (2 places) on page 11, line 13 is corrected to "a-8iC:HJ". (6), r vs. environment on page 12, line 9. I corrected it to "environmental resistance." (7), page 13, lines 3-4, “34 is...--
・Correct "Supply" to "34 is diborane gas supply." (8), "3.5-20" in the first line of page 15 is changed to "10".
~30” I corrected it. (9), page 19, line 5, ro, o1~0.2'' is r
I will correct it as lO'J. (II, ``Antimony or'' in the 13th line of page 19 of the same book is deleted. 11 Delete ``or antimony'' in the 4th line from the bottom of the Shu page of the same book. 6th page, 12-13 of the same page, 22 pages. Row ra-SiC:
Delete "by H......-" and cough. □ (I3, page n, lines 5-8, “Substantially...
...not shown," will be deleted. 04, Delete "mostly" from lines 8 to 9 of the same page 0 6 Sieve, "Surface potential..." from lines 2 to 4 of page 25
・・・－・・・I end up doing it. "ra-8i: The rate of charge carriers generated in the H layer 3 reaching the support 1 is reduced. ” I am corrected. ae, page 25, lines 10-11, “, preferably 30
~90 atomic '16 J will be deleted. (In, same No. 26) mouth lines 4 and 188 r pv
Correct J to "ρ0". In turn 6, on page 26, line 14, "-L" is corrected to "pL". 091 r 5iHFs'J on page 4, second line from the bottom
Corrected to siHFs, 5iFa J. Kan, "Gas" in the first line of the same survey is corrected to "Gasya CF4 J. --),""Shita." in the third line of page 29 of the same survey is changed to "Shita. This a.
7 SiC: The result of Auger electron spectroscopy analysis of carbon particles contained in the H layer was 15 atomic-. ” I am corrected. ), delete "K as carrier gas" on page 9, line 4. 2), in the 6th line from the bottom of page 9, we have corrected ``Gyoto ζro'' to ``Gyonai''. (c), "6 seconds" in the fifth stroke from the bottom of the fourth page is corrected to "2 seconds". ), page 4-5, ", a-8i: H layer 3
”. ), "Antimony-doped! L-8iC:) I layer 4 and T-pad" in line 30jj 15-16 is changed to "Aluminum doped A-8iC: H layer 4 and aluminum doped board". Correct. ), page 31, lines 4-5 r 10': t...
・・・・・・・・・・・・Delete. ), "doped" on page 31, line 8 is corrected to "aluminum doped". ), on page 31, line 15, "antimony" is corrected to "aluminum". ), page 31, line 16, RA-8i:H layer 3 or''
Delete. C11), "Electrometer" in the first line of page 32 is corrected to [Electrometer 5P-428J]. (b) The table on pages 33-34 of the same is revised as follows. (The following margin is continued on the next page.) (B) Correct "6 seconds later" in the second line of page A of the same page to "2 seconds later." (b), p. 37, lines 2 to 10 [The above song can be considered. ”. (C), "Surface negative charge" on page 37, line 12 is corrected to [Surface positive charge, 1]. ), in line 3864, "It was important." is corrected to "It was favorable." (b) The following statement is added between lines 8 and 9 on page 39. ``5......Third a-SiC:H scrap doped with impurities''), page 39, line 14 [or delete PHm J]. (b) Delete "or antimony" on page 39, line 18. 1 or more - 1, consisting of a third amorphous hydrogenated and/or fluorinated silicon carbide layer, a second amorphous hydrogenated and/or fluorinated silicon carbide layer, and an amorphous hydrogenated and/or fluorinated silicon The third amorph 7 comprises a laminate in which a photoconductive layer and a first amorphous hydrogenated and/or fluorinated silicon carbide layer are sequentially stacked on a substrate. The hydrogenated and/or fluorinated silicon carbide layer is converted to P-type by containing an element from group 111A of the periodic table, and the photoconductive layer is made to contain an element from group HA of the periodic table. Therefore, the first amorphous hydrogenated and/or fluorinated silicon carbide layer exhibits a dark resistivity of 10*@Ω-m or more, and has a resistivity of 50A to 2000Ω.
1. A recording medium having a film thickness of 2. The recording medium according to claim 1, wherein the third amorphous hydrogenated and/or fluorinated silicon carbide layer is a P+ type layer with a high impurity concentration. 3. The dark resistivity of the photoconductive layer is 4011 Ω-m or more,
A recording medium according to claim 1 or 2. 4. The first amorphous hydrogenation and/or), the dark resistivity of the pruned silicon carbide layer is 10140-m or more, as described in any one of claims 1 to 3. record body. 5. The second amorphous hydrogenated and/or fluorinated silicon carbide layer also exhibits a dark resistivity of 1 ojlΩ-m or more by containing an element of group A of the periodic table.
A recording medium according to any one of claims 1 to 4. 6. Ioo to 100,000 ppm of the second reaction gas that supplies the HA group element of the periodic table to the first reaction gas that supplies silicon and hydrogen atoms and/or fluorine atoms.
, and the third amorphous hydrogenated and/or fluorinated silicon carbide layer is formed by glow discharge decomposition of both reaction gases.
A recording medium described in any one of item 5. 7. To the first reaction gas that supplies silicon and hydrogen atoms and/or fluorine atoms, a second reaction gas that supplies an element of group 1rIA of the periodic table is supplied at a concentration of 10 to 500 ppnl, and both of these reactions are performed. Any one of claims 1 to 6, wherein the first or second amorphous hydrogenated and/or fluorinated silicon carbide layer or photoconductive layer is formed by glow discharge decomposition of the gas. Records listed in section. 8. The concentration of vapor of group 1rIA elements of the periodic table is 100 to 100.000 ppyn to silicon vapor,
Any one of claims 1 to 5, wherein the third amorphous hydrogenated and/or fluorinated silicon carbide layer is formed by performing the vapor deposition in the presence of hydrogen atoms and/or fluorine atoms. The recording medium described in Section 1. 9. With respect to silicon vapor, vapor of the first TIA group element of the periodic table is made to have a concentration of 10 to 500 ppm, and vapor deposition is performed in the presence of hydrogen atoms and/or fluorine atoms.Thus, the first or second amorphous A recording body according to any one of claims 1 to 5 or claim 8, on which a hydrogenated and/or fluorinated silicon carbide layer or a photoconductive layer is formed. 10. The thickness of the third amorphous hydrogenated and/or fluorinated silicon carbide layer is 50' to 1/1 m), the second
The thickness of the first amorphous hydrogenated and/or fluorinated silicon carbide layer is 5000×~80 pm, the thickness of the photoconductive layer is 21500×~10/jm, and the first amorphous hydrogenated and/or fluorinated silicon carbide layer is 5000×~80 pm. The recording medium according to any one of claims 1 to 9, wherein the silicon carbide layer has a thickness of 50X to 2000X. 11. The thickness of the third amorphous hydrogenated and/or fluorinated silicon carbide layer is 400X to 5000X, and the thickness of the second amorphous hydrogenated and/or fluorinated silicon carbide layer is 5pyH-2 pm. The thickness of the photoconductive layer is 5000 A to 5 μm, and the thickness of the first amorphous hydrogenated and/or fluorinated silicon carbide layer is 4 μm.
Claim 12, wherein the carbon atom content of the first amorphous hydrogenated and/or fluorinated silicon carbide layer is from 40 atoms to 90R.
tomief), and the carbon atom content of the second and third amorphous hydrogenated and/or fluorinated silicon carbide layers is 10 atomic % to 90 atomic-
The recording medium according to any one of claims 1 to t411.

Claims (1)

[Claims] 1. A third amorphous hydrogenated and/or fluorinated silicon carbide layer, a second amorphous hydrogenated and/or fluorinated silicon carbide layer, and an amorphous hydrogenated and/or fluorinated silicon carbide layer. and a first amorphous hydrogenated and/or fluorinated silicon carbide layer are sequentially stacked on a substrate, the third amorphous hydrogenated and/or fluorinated silicon carbide layer is P due to the inclusion of Group HA elements of the periodic table.
The photoconductive layer is converted to a periodic table of hydrogenated and/or fluorinated silicon carbide layers of 50X to 20
It has a film thickness of 00λ and contains Group A elements of the periodic table, making it a 10" body. 2. The third amorphous hydrogenated and/or fluorinated silicon carbide layer is a P+ type layer with a high impurity concentration. A recording body according to claim 1 or 2. A recording body according to any one of claims 1 to 3. 5. Second amorphous hydrogen Indicates the change and/or company fusi element,
A recording medium according to any one of claims 1 to 4. 6. 100 to 100,000 ppm of the second reaction gas that supplies the qmA group element of the periodic table to the first reaction gas that supplies silicon and hydrogen atoms and/or fluorine atoms.
The third amorphous hydrogenated and/or fluorinated carbonized 7917 layer is formed by supplying the reaction gas at a concentration of The recording medium described in Section 1. 7. To the first reaction gas that supplies silicon and hydrogen atoms and/or fluorine atoms, a second reaction gas that supplies the mA group element of the periodic table is supplied at a concentration of 10 to 500 ppm, and both of these reactions are performed. Any one of claims 1 to 6, wherein the first or second amorphous hydrogenated and/or fluorinated silicon carbide layer or photoconductive layer is formed by glow discharge decomposition of the gas. Records listed in section. 8. The concentration of the vapor of group mA element of the periodic table is 100 to 100,000 ppm to the silicon vapor, and the 3rd φ The recording medium according to any one of claims 1 to 5, in which a fluorinated and/or fluorinated silicon carbide layer is formed. 9. The first step is performed by adding vapor of Group HA elements of the periodic table to silicon vapor at a concentration of 10 to 500 ppm and performing vapor deposition with hydrogen atoms and/or fluorine atoms mixed in.
or a recording body according to any one of claims 1 to 5 or 8, on which a second amorphous hydrogenated and/or fluorinated silicon carbide layer or a photoconductive layer is formed. . 10. The thickness of the third amorphous hydrogenated and/or fluorinated silicon carbide layer is 50X to 1 μm, and the thickness of the second amorphous hydrogenated and/or fluorinated silicon carbide layer is 50X to 80 μm. , the photoconductive layer has a thickness of 2500× to 10 μm, and the first amorphous hydrogenated and/or fluorinated silicon carbide layer has a thickness of 50 μm.
The recording medium according to any one of claims 1 to 9, which has a wavelength of λ~2000 A. 11. The thickness of the third amorphous hydrogenated layer/or fluorinated silicon carbide layer is 400λ to 5000X,
The second amorphous hydrogenated and/or fluorinated silicon carbide layer has a thickness of 5 μm to 20 μm, the photoconductive layer has a thickness of 500λ to 5 μm, and the first amorphous hydrogenated and/or fluorinated silicon carbide layer has a thickness of 5 μm to 20 μm. Thickness is 4oo
A recording medium according to claim 10, which has a weight of A to 1600 k. The carbon atom content of the amorphous hydrogenated and/or fluorinated silicon carbide layer of 12.941 is between 40 atomic and 90 atomic, the second and third amorphous hydrogenated and/or fluorinated silicon carbide layers. The carbon atom content of is 10 atomic % ~ 90 atom
ic %, the recording medium according to any one of claims 1 to 11.