JPS61294453A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain a stable picture quality having a less tendency for an image flow by laminating each specific an electric charge blocking layer, an electric charge transfer layer, an electric charge generating layer, an intermediate layer and a surface reforming layer in order on a substrate. CONSTITUTION:The photosensitive body 39 is laminated the P<+> type electric charge blocking layer 44 composed of a-Si:H which is heavily doped with an element belonging to the group IIIa of the periodic table of the element, and contains one of the atoms of C, N, and O, and the electric charge transfer layer 42 composed of a-Si:H which is made an intrinsic, by lightly doping it with an element belonging to the group IIIa of the periodic table of the element, and contains atoms N and O in order on the drum shaped conductive substrate 41 composed of Al. The titled body is constituted by laminating the electric charge generating layer 43 composed of a-Si:H, the intermediate layer 46 composed of a P<+> or N<+> type amorphous hydrogenated silicon which is heavily doped with an element belonging to the group IIIa of Va of the periodic table of the element, and the surface reforming layer 45 composed of an amorphous hydrogenated silicon which is made to a P<+> type or an N<+> type or an intrinsic by doping it with an element belonging to the group IIIa or Va of the periodic table of the element, and contains one of atoms of N, C and O atoms.

Description

[Detailed description of the invention]

B. Industrial Application Field The present invention relates to a photoreceptor, for example, an electrophotographic photoreceptor. Conventional technology Conventionally, as an electrophotographic photoreceptor, Se or As is added to Se.
Photoreceptor doped with 're% 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 (a-3i) as a matrix have been proposed in recent years. a-3i has a so-called dangling bond in which the bond of Si-3i is broken, and many localized levels exist within the energy gap due to this defect. For this reason, hopping conduction of thermally excited carriers occurs, resulting in a small dark resistance, and photoexcited carriers are trapped in localized levels, resulting in poor photoconductivity. Therefore, by compensating for the above defects with hydrogen atoms (H) and bonding H to St,
Filling of dangling bonds is performed. Such amorphous hydrogenated silicon (hereinafter referred to as a-3
It is called i:H. ) has a resistivity in the dark of 108 to 10
9Ω-b, which is about 1 compared to amorphous Se.
It's even lower than 1/10,000. Therefore, a photoreceptor made of a single layer of a-3i:H has problems in that the dark decay rate of the surface potential is high and 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. Figure 8 shows a-3t using the above a-3i:H as the base material.
An electrophotographic copying machine incorporating a photosensitive system 9 is shown. According to this copying machine, a glass document holder 3 on which a document 2 is placed and a platen cover 4 that covers the document 2 are disposed in the upper part of a cabinet 1. Below the document table 3,
An optical scanning table consisting of a first mirror unit 7 equipped with a light R5 and a first reflecting mirror 6 is provided so as to be movable in a straight line in the horizontal direction of the drawing, and the optical path length between the document scanning point and the photoreceptor is kept constant. The second mirror unit 2° moves according to the speed of the first mirror unit, and the reflected light from the document table 3 passes through the lens 21 and the reflection mirror 8 onto the photosensitive drum 9 as an image carrier. It is designed to enter in a slit shape. Around the drum 9, a corona charger 10,
A developing device 11, a transfer section 12, a separation section 13, and a cleaning section 14 are arranged, and the copy paper 18 fed from the paper feed box 15 via each paper feed roller 16, 17 is further processed after the toner image on the drum 9 is transferred. The image is fixed by the fixing unit 19 and then ejected to the tray 35. In the fixing section 19, the developed copy paper is passed between a heating roller 23 containing a heater 22 and a pressure roller 24 to perform a fixing operation. However, photoreceptors with a-5i:H surfaces have problems with surface chemical stability, such as the effects of long-term exposure to the atmosphere or moisture, and the effects of chemical species generated by corona discharge. , has not been sufficiently investigated so far. For example, items that have been left for more than a month will be affected by moisture.
It is known that the receptor potential is significantly reduced. On the other hand, amorphous hydrogenated silicon carbide (hereinafter a-SiC:H
It is called. ), its manufacturing method and existence” Ph11
．． Mag, Vol. 35'' (1978), etc., and its characteristics include high heat resistance and surface hardness, and high dark resistivity (compared to a-3i:H).
It is known that the optical energy gap changes over the range of 1.6 to 2.8 eV depending on the amount of carbon. However, the band width varies depending on the carbon content. There is a drawback that the long wavelength sensitivity is poor due to the widening of the gap.An electrophotographic photoreceptor combining a-3iC:H and a-3i:H has been proposed, for example, in Japanese Patent Laid-Open No. 127083/1983. According to this, a-3i:H
The layer is a charge generation (photoconductive) layer, and below this charge generation layer is a
-3iC:H layer is provided, the upper layer a-3i:H provides photosensitivity in a wide wavelength range, and the lower layer a-3iC:H forming a heterojunction with a-3i:HN reduces the charging potential. We are trying to improve. However, the dark decay of the a-3t:H layer cannot be sufficiently prevented, and the charging potential is still insufficient to be practical.
The presence of the H layer causes poor chemical stability, mechanical strength, heat resistance, etc. On the other hand, JP-A-57-17952 discloses a-3i:
A first a-3iC:HJ! is formed on the charge generation layer made of H. J
is formed as a surface modification layer, and a second a-3iC:H layer is formed on the back surface (support electrode side). In addition, as related to this known technology,
As seen in Japanese Patent No. 23543, a gradient layer (a-S i +-x Cx : H) is provided between the charge generation layer and the first and second a-3iC:H layers. In the inclined layer, a-3i: X = 0 on the H side, a-8
A photoreceptor in which X=0.5 on the iCsH layer side is known. However, when the present inventor conducted a study on the above-mentioned known photoreceptor, it was found that the effect of providing the surface modification layer is not so pronounced, especially in continuous repeated use. In other words, during continuous running of 200,000 to 300,000 times, the a-3iC layer on the surface is mechanically damaged in about 70,000 to 80,000 times, resulting in white streaks and white spots as image defects. is not enough. Furthermore, light resistance fatigue occurs during repeated use, image blurring occurs, and the electrical and optical characteristics are not always stable, and the effects of the use environment (temperature, humidity) cannot be ignored. Furthermore, it is necessary to further improve the adhesion between the surface modified layer and the charge generation layer. C1 Object of the invention The object of the invention is to provide excellent adhesion between the surface modification layer and the charge generation layer, resistance to mechanical damage, and excellent rigidity resistance.
Stable image quality without image blurring is obtained, there is little optical fatigue during repeated use, the residual potential is low, and the characteristics are compatible with the usage environment (
The purpose of the present invention is to provide a photoreceptor that is stable regardless of temperature and humidity. 20 Structure of the invention and its effects, that is, the present invention is characterized in that the present invention is doped with an element of group Ma of the periodic table and at least one of carbon atoms, nitrogen atoms, and oxygen atoms.
a charge blocking layer made of amorphous hydrogenated and/or fluorinated silicon containing nitrogen atoms; a charge transport layer made of amorphous hydrogenated and/or fluorinated silicon which is made intrinsic and contains nitrogen atoms and oxygen atoms; amorphous hydrogen a charge generation layer made of hydrogenated and/or fluorinated silicon; an intermediate layer doped with a group Ma or Va element of the periodic table and made of amorphous hydrogenated and/or fluorinated silicon; carbon atoms, nitrogen atoms, and oxygen atoms; The present invention relates to a photoreceptor in which a surface-modified layer containing at least one of the above and a surface-modified layer made of amorphous hydrogenated and/or fluorinated silicon is laminated in sequence. According to the present invention, since the surface modified layer contains at least one atom of carbon, nitrogen, and oxygen, it is resistant to mechanical damage, and there is no deterioration in image quality due to white streaks, etc., and it is resistant to It has excellent rigidity. In addition, the present invention also includes Ru1.
In this case, since the impurity-doped intermediate layer is provided between the surface modified layer and the charge generation layer, the adhesion between the surface modified layer and the charge generation layer is improved. Furthermore, since the surface modification layer and intermediate layer are provided on the charge generation layer, in addition to the above, it has excellent resistance to light fatigue during repeated use, no image fading, low residual potential, and electrical resistance. It has been confirmed that the optical properties are always stable and unaffected by the usage environment. E. Examples Hereinafter, the present invention will be explained in detail with reference to examples. FIG. 1 shows an a-3i electrophotographic photoreceptor 39 for positive charging according to this embodiment. This photoreceptor 39 is A2
on a drum-shaped conductive support substrate 41 such as A-3i: (a-3i), which is heavily doped with an element of group Ma of the periodic table (e.g., boron) and contains a small amount of C, N, and 0. −S t (C)(N)(0):H) is a P medium charge blocking N44, which is lightly doped with a group Ma element of the periodic table (e.g., boron) and is not made into an intrinsic material. Contains a-3t:H (this is a
-3iNO: Expressed as H. ), a charge generating layer 43 made of a-3i:H (without impurity doping or made intrinsic), and a P+ type or An intermediate layer 46 made of N+ type amorphous hydrogenated silicon and doped with an element of Group Ma or Group Va of the periodic table to make it P type or N type or intrinsic (or without impurity doping).
amorphous hydrogenated silicon containing at least one of N, C, and 0 (a-S i (C
)(N)(0):H. ) Surface modified layer 4 consisting of
It has a structure in which 5 and 5 are laminated. Charge generation N43
is the dark resistivity ρ. The ratio of resistivity ρ when irradiated with light is sufficiently large as an electrophotographic photoreceptor, and the photosensitivity (particularly to light in the visible and infrared regions) is good. In addition, when the carbon atom content of each of the above layers is in the range of 0 to 70%, as shown in FIG.
Since there is an almost linear relationship with E g, opt),
It can be defined by replacing the carbon atom content with the optical energy gap. In addition, if the carbon atom content of a-3iC:H is appropriately selected, remarkable effects such as an increase in specific resistance and an improvement in charging potential holding ability can be obtained as shown by curve a in FIG. 3. That is, as shown by curve a in FIG. 3, when the carbon atom content is 30
When ~90% a-3iC:H is used, its resistivity varies according to carbon content and is greater than or equal to 1012 ohms. The above tendency is that a-3iN containing N or O instead of carbon
The same applies to :H,, a-3iO:H. The above-mentioned layer 45 is indispensable for modifying the surface of the photoreceptor and making the a-3i-based photoresistance practically excellent. That is, it enables the basic operations of an electrophotographic photoreceptor, such as charge retention on the surface and attenuation of the surface potential due to light irradiation. Therefore, the repetitive characteristics of charging and optical attenuation become very stable, and good potential characteristics can be reproduced even if left for a long period of time (for example, one month or more). On the other hand, in the case of a photoreceptor having a-3i:H as its surface, it is easily affected by humidity, air, ozone atmosphere, etc., and the potential characteristics change significantly over time. In addition, since the layer 45 has a high surface hardness, it has abrasion resistance during processes such as development, transfer, and cleaning, and also has good heat resistance, so it is possible to apply heat-applying processes such as adhesive transfer. In order to comprehensively achieve the above excellent effects, it is important to select the composition of the layer 45. That is, when containing carbon atoms, Si+C=100at
When omic% (hereinafter, atomic% is simply expressed as %), 1% [03590%, furthermore 10%≦
(C) Desirably 570%. Due to this C content, the above-mentioned resistivity becomes the desired value, and the optical energy gap becomes approximately 2.58 square meters or more, and the irradiated light is a- It becomes easier to reach the 3tsH layer (charge generation layer) 43. However, if the C content is 1% or less, disadvantages such as mechanical damage occur, and the specific resistance tends to fall below the desired value.
In addition, a portion of the light is absorbed by the surface layer 45, and the photosensitivity of the photoreceptor tends to decrease. In addition, if the C content exceeds 90%, the amount of carbon in the layer increases, and semiconductor properties are likely to be lost, and the deposition rate when forming the a-3iC:H film by the glow discharge method is likely to decrease. The C content is preferably 90% or less. Similarly, in the case of the layer 45 containing nitrogen or oxygen, 1% [N3590%, (furthermore 10%≦(N)570%)
is good, 0%≦

[0]≦70% (even 5%≦

[0]≦
30%) is good. In order to improve the charging ability, the surface modified layer 45 may have a high resistance. For this purpose, the surface modified layer may be made intrinsic. When used with positive or negative charging, in order to facilitate the injection of electrons or holes from the intermediate layer into the surface-modified layer and to minimize the residual potential, the surface-modified layer may be of P or N type. good. The amount of impurity doped in each case (at the time of glow discharge decomposition described later) may be as follows. Intrinsic: Bt H& / s i H4F Type: B
z Hb / S 1H4N type: PH3/5iH4 1-1000 (preferably 50-500) (SiNO
:H(F), 5iCO:H(F) common) Also, layer 45
is a-3ico, a-31NOsa-3iO1a-3i
It may consist of Q2, etc., and the film thickness should be 400 people≦t≦
It is also important to select within the range of 5,000 people (in particular, 400≦t<2,000 people. In other words, if the film thickness exceeds 5,000 people, the residual potential (6) will become too high and the photosensitivity will decrease. also occurs, a-5
It is easy to lose the good characteristics as a t-type bad sensitivity. Furthermore, if the film thickness is less than 400, charges will not be charged on the surface due to the tunnel effect, resulting in an increase in dark decay and a decrease in photosensitivity. Regarding the intermediate layer 46, in order to reduce the residual potential, the intermediate layer may be of P or N type to enable charge injection from the charge generation layer. The doping amount for 4-electrode control is
It may be the same as the surface modified layer. The thickness of this intermediate layer is preferably 50 to 5,000 people, but if it exceeds 5,000 people, the same phenomenon as described above is likely to occur, and if it is less than 50 people, the effect as an intermediate layer is poor (preferably). , 100 Å or more and 1000 Å or less. Regarding charge generation N43, in order to improve charging ability,
The resistance of the charge generation layer may be increased. For this purpose, the charge generation layer may be made intrinsic. For this intrinsicization, Bz
It is preferable that Hb/S iH* = 1 to 20 volumes t pp m. Further, the charge generation layer has a thickness of 1 to 10 μm, preferably 5 to 7 μm.
It is preferable to set it to μm. If the thickness of the charge generation layer 43 is less than 1 μm, the photosensitivity will not be sufficient, and if it exceeds 10 μm, the residual potential will increase, which is insufficient for practical use. Regarding the charge transport layer 42, it is necessary to make it intrinsic in order to optimize charging ability and sensitivity. The doping amount for making it intrinsic is CBZ Hb ) / (S i H4) = 1 to 2
000 capacitance ppm is optimal. However, since the above value depends on the N concentration, it is not necessarily limited to the above value. The thickness of the charge transport layer is preferably 10 to 30 μm. The composition of the charge transport layer is preferably 1% <[83530%, preferably 10%≦(N)530%, and less than 0% [O
] 510%, preferably 0% < [O] 61%. Furthermore, in order to sufficiently prevent the injection of electrons from the substrate 41 and to improve sensitivity and charging ability, the charge processing/7 king layer 44 must be able to decompose elements of group Ma of the periodic table (for example, poron) by glow discharge decomposition. It is doped to become P type (or even P+ type). The doping amount is controlled by the composition of the blocking layer as follows. a-3iC or a-3iCO: P type (P''); Bz Hb / S i H42
0-5000 Capacity ppm a-3iN or a-3iNO: P type (P +); Bt H6/SI H410
00-5000 ppm by volume The prof tip layer may be a compound such as SiOs SiOz. Further, the thickness of the blocking layer 44 is preferably 500 μm to 2 μm. If it is less than 500, the blocking effect will be weak, and if it exceeds 2 μm, the charge transport ability will tend to deteriorate. The composition of blocking FJ44 is preferably as follows. That is, 1%〈[03590%, preferably 10%≦(C)570%, and 1%〈 [N] 5
90%, preferably 10% [N3570%, θ
%≦(0)570%, preferably 0%≦(0)530%
It is better to Note that each of the above layers needs to contain hydrogen. In particular, the hydrogen content in the charge generating JW43 is essential for compensating for dangling bonds and improving photoconductivity and charge retention, and is preferably 10 to 30%. This content range also applies to the surface modification layer 45, blocking M44, and charge transport layer 42. Further, as an impurity for controlling the conductivity type of the blocking layer 44, in addition to boron, Al, Ga, In,
Periodic table ma group elements such as TJ can be used. For N-type conversion, in addition to phosphorus, periodic table Va such as A S % S b etc.
Group elements can be used. Next, a method for manufacturing the above-mentioned photoreceptor (for example, drum-shaped) and an apparatus therefor (glow discharge apparatus) will be explained with reference to FIG. A drum-shaped substrate 41 is set rotatably vertically in a vacuum chamber 52 of this device 51, and a heater 55 is used to rotate the substrate 41.
can be heated to a predetermined temperature from the inside. A cylindrical high frequency electrode 57 with a gas outlet 53 is disposed around and facing the substrate 41, and a glow discharge is generated between the electrode 57 and the substrate 41 by a high frequency power source 56. In addition, 62 in the figure is a supply source of S i H4 or a gaseous silicon compound, 63 is a supply source of hydrocarbon gas such as CH4, 64 is a supply source of nitrogen compound gas such as N2, and 65 is an oxygen compound such as Offi. 66 is a carrier gas supply source such as Ar, 67 is an impurity gas (for example, Bz Hb) supply source, and 68 is each flow meter. In this glow discharge device, first a support, for example Aj! After cleaning the surface of the substrate 41, it is placed in a vacuum chamber 52, the gas pressure in the vacuum chamber 52 is adjusted to 10-6 Torr, and the air is evacuated. C. (preferably 150 to 300 C.). Then,
Using high-purity inert gas as a carrier gas, S i H
a or gaseous silicon compound, CHa, Nt, Ox
etc. are appropriately introduced into the vacuum chamber 52, for example, o, oi to 10
A high frequency voltage (for example, 13.56 MHz) is applied by a high frequency power supply 56 under a reaction pressure of Torr. As a result, each of the above reaction gases is decomposed by glow discharge between the electrode 57 and the substrate 41, pP type a-3iC:H, i-type 5tNO:
H. aS i: H% P+ or Nt type a-3t:H
. a-5iC:H above layer 44.42.43.46.4
5 in succession (i.e., corresponding to the example of FIG. 1, for example). In the above manufacturing method, the support temperature is set at 100 to 350°C in the step of forming the a-3t layer on the support, so it is possible to improve the film quality (especially the electrical properties) of the photoreceptor. In addition, when forming the above a-3i photoreceptor photosensitive layer,
In order to compensate for dangling bonds, fluorine is introduced in the form of SiFa or the like instead of or in combination with H to form a-8i:F. a-3i:H:F% a-5iN:F. a-3iN:H:F, a-3iC:F. It can also be a-3iC:H:F. In this case, the amount of fluorine is preferably 0.5 to 10%. The above manufacturing method is based on the glow discharge decomposition method, but there are also sputtering methods, ion blating methods, and methods in which Si is evaporated while introducing activated or ionized hydrogen in a hydrogen discharge tube ( In particular, Japanese Patent Application Laid-Open No. 56-78413 (Japanese Patent Application No. 1524-1983) filed by the present applicant
The above photoreceptor can also be manufactured by the method of No. 55). Hereinafter, the present invention will be described with reference to specific examples. By glow discharge decomposition method, the first
An electrophotographic photoreceptor having the structure shown in the figure was manufactured. That is, first, after cleaning the surface of a support, for example, a drum-shaped Al substrate 41 having a smooth surface, it is placed in a vacuum chamber 52 in FIG. 4, and the gas pressure in the vacuum chamber 52 is set to 10-'
Torr, and exhaust the air, and keep the substrate 41 at a predetermined temperature, particularly 100 to 350°C (preferably 150 to 350°C).
Heat and maintain at 300°C. Next, high-purity Ar gas was introduced as a carrier gas, and high-frequency power at a frequency of 13.56 MHz was applied under a back pressure of Q, 5 Torr to perform a preliminary discharge for 10 minutes. Next, a reaction gas consisting of 5iH and BtH was introduced, and the flow rate ratio was 1:1:1:(1,5xlO-
') of (A r + S i H4+ CH4 or N
z + B z Hb) By glow discharge decomposition of the mixed gas, P+ type a which plays a charge blocking function
-3iC:H layer 44 and a-3tNO:H charge transport layer (BzHb/SiHa = 500% by volume,
(N) = 12%, (0) = 1000 ppm (S
For i)) and 42 were sequentially formed to a predetermined thickness at a deposition rate of 6 pm/hr. Continuing, Bz H, and CH
4 was stopped, S i H, was decomposed by discharge, and the thickness was 5μ.
a-3i of m:) 1 layer 43 was formed. Subsequently, glow discharge decomposition is performed by changing the flow rate ratio of the impurity gas to form an intermediate layer 46 with a varying film thickness, and further a
A -5iCO:H or a-3iNO:H surface protective layer 45 was further provided to complete the electrophotographic photoreceptor. As a comparative example, a photoreceptor without an intermediate layer was prepared. The structure of the photoreceptor thus produced was summarized as follows. (1) 0 surface modified layer: a-3iNO:H or a-3iCO:H (Bz H&
/S i Hs -100 volume iJppm) (2),
Intermediate layer: doping amount, film thickness change (see Figure 5) (3), a-3i: H charge generation layer: film thickness = 5μ
m (4), a-3iNo: H charge transport layer: film thickness = 1
5 μm N content = 12% O content = 11000 pp For positive charging - B doped glow discharge decomposition method (5), a-3i C: H or a-5i N:H charge blocking layer: Film thickness = 1 μm Carbon content Amount=12% For positive charging: B doped (6) Support: Al cylinder (mirror polished finish) Next, various tests were conducted using each of the above photoreceptors as follows. ■ As shown in Figure 6, the 0,
Apply a load W to the 3R diamond needle 70 and morph the photoreceptor 71
Rotate and scratch the electrophotographic copying machine U-
B 1x1600 (manufactured by Konishiroku Photo Industry Co., Ltd.) An image is produced using a modified machine, and the scratch strength (g) of the photoreceptor is determined by the load at which white streaks appear on the image. The photoreceptor was allowed to acclimate for 24 hours in a modified electrophotographic copying machine U-B 1x4500 (manufactured by Konishiroku Photo Industry Co., Ltd.) under an environment of IL standard temperature of 33°C and relative humidity of 80%, and then the developer, paper,
After 1000 copies were made without contact with the blade, an image was produced and the degree of image blurring was determined based on the following criteria. ◎: There is no image blurring at all, and the reproducibility of 5.5-point alphabetic characters and thin lines is good. ○: 5.5 point alphabetic characters are slightly thicker. △: 5.5 point letters are crushed and difficult to read. X: 5.5 point English letters are illegible. - Standing Vl (v) U -B Potential measurement using 1x2500 modified machine, 4
Static elimination light 301 with a peak at 00nm! ux-sec
The surface potential of the photoreceptor that remains even after irradiation. Vo(v) U-B 1x2500 modified machine (manufactured by Konishiroku Photo Industry ■)
The surface potential immediately before development was measured using a 360SX electrometer (manufactured by Trek) under the conditions of a photoconductor inflow current of 200 μA and no exposure. 'E l1zcl ux 0see) Using the above device, a guichroic mirror (manufactured by Koshin Kogaku Co., Ltd.)
The exposure amount required to sharply cut long wavelength components of 620 nm or more of the image exposure wavelength and halve the surface potential from 500 V to 250 V. (The exposure amount was measured using a 550-1 light meter (manufactured by EGandG)) The results are summarized in FIG. 7. These results show that if a photoreceptor is prepared according to the present invention, a photoreceptor with excellent performance for electrophotography can be obtained.

[Brief explanation of drawings]

1 to 7 show embodiments of the present invention.
Graph showing the optical energy gap of iC, FIG. 3 is a graph showing a-3iCO resistivity, FIG. 4 is a schematic cross-sectional view of the glow discharge device, FIG. 5 is a table showing the layer structure of each photoreceptor, FIG. 6 is a schematic diagram of a scratch strength tester, and FIG. 7 is a table showing the characteristics of each photoreceptor. FIG. 8 is a schematic sectional view of a conventional electrophotographic copying machine. In addition, in the reference numerals shown in the drawings, 39...a-3L type adverse photosensitive 41...support (substrate) 42...charge transport layer 43...charge generation layer 44... . . . Charge blocking layer 45 . . . Surface modification layer 46 . . . Intermediate layer. Agent Patent Attorney Hiroshi Aisaka Figure 1 Figure 2 a-5ir-x Cx: Hx Figure 3 Coalwood content (at□m1Co/,) Figure 6 Figure 4 Figure 7

Claims (1)

[Claims] 1. A carbon atom doped with a group IIIa element of the periodic table,
a charge blocking layer consisting of amorphous hydrogenated and/or fluorinated silicon containing at least one of nitrogen atoms and oxygen atoms; an amorphous hydrogenated and/or fluorinated silicon that is intrinsic and contains nitrogen atoms and oxygen atoms; a charge transport layer made of silicon; a charge generation layer made of amorphous hydrogenated and/or fluorinated silicon; and an intermediate layer doped with a Group IIIa or Va element of the periodic table and made of amorphous hydrogenated and/or fluorinated silicon. and a surface-modified layer containing at least one of carbon atoms, nitrogen atoms, and oxygen atoms and made of amorphous hydrogenated and/or fluorinated silicon, which are sequentially laminated.