JPH01315758A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH01315758A JPH01315758A JP33557488A JP33557488A JPH01315758A JP H01315758 A JPH01315758 A JP H01315758A JP 33557488 A JP33557488 A JP 33557488A JP 33557488 A JP33557488 A JP 33557488A JP H01315758 A JPH01315758 A JP H01315758A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- layer region
- electrophotographic photoreceptor
- group
- amorphous silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000000737 periodic effect Effects 0.000 claims abstract description 9
- 108091008695 photoreceptors Proteins 0.000 claims description 42
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 29
- 206010034972 Photosensitivity reaction Diseases 0.000 description 19
- 230000036211 photosensitivity Effects 0.000 description 19
- 239000010408 film Substances 0.000 description 18
- 239000004065 semiconductor Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 229910010271 silicon carbide Inorganic materials 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000000969 carrier Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 206010034960 Photophobia Diseases 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 208000013469 light sensitivity Diseases 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- RCYFOPUXRMOLQM-UHFFFAOYSA-N pyrene-1-carbaldehyde Chemical compound C1=C2C(C=O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 RCYFOPUXRMOLQM-UHFFFAOYSA-N 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
- G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
- G03G5/08214—Silicon-based
- G03G5/08221—Silicon-based comprising one or two silicon based layers
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアモルファスシリコンカーバイド光導電層と有
機光半導゛体層を積層して成る電子写真感光体に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrophotographic photoreceptor comprising a laminated layer of an amorphous silicon carbide photoconductive layer and an organic photoconductor layer.
電子写真感光体の光導電材料には、Se、 5e−Te
+^H5,2,znO,CdS、アモルファスシリコン
などの無機材料と各種有機材料がある。そのなかで最初
に実用化されたものはSeであり、次いでZnO、Cd
S、アモルファスシリコンが実用化された。有機材料で
はPVK−TNFが最初に実用化され、その後、電荷の
発生並びに電荷の輸送という機能を別々の材料に分担さ
せるという機能分離型感光体が提案され、この機能分離
型感光体によって有機材料の開発が飛躍的に発展してい
る。Photoconductive materials for electrophotographic photoreceptors include Se, 5e-Te,
+^ There are inorganic materials such as H5,2, znO, CdS, and amorphous silicon, and various organic materials. Among them, Se was the first to be put into practical use, followed by ZnO and Cd.
S.Amorphous silicon has been put into practical use. Among organic materials, PVK-TNF was first put into practical use, and later, a functionally separated photoreceptor was proposed in which the functions of charge generation and charge transport were shared between separate materials. development is progressing rapidly.
また、無機光導電層の上に有機光半導体層を積層した電
子写真感光体も提案された。Furthermore, an electrophotographic photoreceptor in which an organic photoconductive layer is laminated on an inorganic photoconductive layer has also been proposed.
例えばSe層と有機光半導体層の積層型感光体があり、
既に実用化されたが、この感光体によれば、Se自体有
害であり、しかも、長波長側の感度に劣るという欠点も
あった。For example, there is a laminated photoreceptor with a Se layer and an organic optical semiconductor layer.
Although this photoreceptor has already been put into practical use, it has the disadvantage that Se itself is harmful and that the sensitivity is poor on the long wavelength side.
そこで、特開昭56−14241号にはアモルファスシ
リコンカーバイド光導電層と有機光半導体層から成る積
層型感光体が提案されており、この感光体によれば、上
記問題点を解消して無公害性並びに高光感度な特性が得
られた。Therefore, Japanese Patent Application Laid-Open No. 56-14241 proposes a laminated photoconductor consisting of an amorphous silicon carbide photoconductive layer and an organic photoconductor layer, and this photoconductor solves the above problems and is non-polluting. Characteristics of high light sensitivity and light sensitivity were obtained.
上記公報の電子写真感光体によれば、化学式Si機先光
半導体層順次積層された構造から成る。According to the electrophotographic photoreceptor disclosed in the above-mentioned publication, it has a structure in which optical semiconductor layers of the chemical formula Si are sequentially laminated.
しかしながら、本発明者等がこのような電子写真感光体
を製作し、その表面電位及び残留電位を測定したところ
、いずれも未だ満足し得るような特性が得られず、更に
改善を要することが判明した。However, when the present inventors manufactured such an electrophotographic photoreceptor and measured its surface potential and residual potential, it was found that neither of them had satisfactory characteristics, and further improvements were required. did.
従って、本発明は叙上に鑑みて完成されたものであり、
その目的は高い表面電位が得られ、しかも、残留電位を
低減させた電子写真感光体を提供することにある。Therefore, the present invention has been completed in view of the above,
The purpose is to provide an electrophotographic photoreceptor that has a high surface potential and a reduced residual potential.
本発明によれば、導電性基板上にアモルファスシリコン
カーバイド光導電層(以下、アモルファスシリコンカー
バイドをa−SiCと略す)と有機光半導体層が順次積
層された電子写真感光体において、a−5iCi導電層
が第1の層領域と第2の層領域が順次形成された層構成
であり、第1の層領域に周期律表第Va族元素を5.0
00ppmの範囲内で含有させるか、あるいは該層領域
が実質上含有せず、第2の層領域に周期律表第IIIa
族元素を1〜1゜000ppmの範囲内で含有させたこ
とを特徴とする電子写真感光体が提供される。According to the present invention, in an electrophotographic photoreceptor in which an amorphous silicon carbide photoconductive layer (hereinafter amorphous silicon carbide is abbreviated as a-SiC) and an organic photoconductive layer are sequentially laminated on a conductive substrate, an a-5iCi conductive The layer has a layer structure in which a first layer region and a second layer region are sequentially formed, and the first layer region contains 5.0% of Group Va elements of the periodic table.
00 ppm, or the layer region does not substantially contain it, and the second layer region contains the periodic table IIIa.
Provided is an electrophotographic photoreceptor characterized by containing a group element in a range of 1 to 1.000 ppm.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
第1図は本発明電子写真感光体の層構成を示しており、
同図によれば、導電性基板(1)の上にa−3iCi導
電層(2)及び有機光半導体層(3)が順次積層されて
いる。a−3iC光導電N(2)には電荷発生という機
能があり、他方の有機光半導体層(3)には電荷輸送と
いう機能がある。FIG. 1 shows the layer structure of the electrophotographic photoreceptor of the present invention.
According to the figure, an a-3iCi conductive layer (2) and an organic optical semiconductor layer (3) are sequentially laminated on a conductive substrate (1). The a-3iC photoconductive layer (2) has a function of charge generation, and the other organic optical semiconductor layer (3) has a function of charge transport.
本発明は、a−SiC光導電層(2)の内部に第1の層
領域(2a)と第2の層領域(2b)が順次形成されて
おり、第1のN領域(2a)が周期律表第Va族元素(
以下、Va族元素と略す)を所定の範囲内で含有するか
、あるいは実質上含有せず、しかも、第2のN領域(2
b)が周期律表第m’a族元素(以下、IIIa族元素
と略す)を所定の範囲内で含有し、これにより、表面電
位及び残留電位を改善したことが特徴である。In the present invention, a first layer region (2a) and a second layer region (2b) are sequentially formed inside the a-SiC photoconductive layer (2), and the first N region (2a) has a periodicity. Elements of group Va in the Table of Laws (
(hereinafter abbreviated as Va group element) within a predetermined range or substantially free of the second N region (2
b) is characterized in that it contains an element of group m'a of the periodic table (hereinafter abbreviated as group IIIa element) within a predetermined range, thereby improving the surface potential and residual potential.
また、このような層領域を形成したことにより負帯電用
電子写真感光体となることも特徴である。Another feature is that by forming such a layer region, it becomes a negatively charging electrophotographic photoreceptor.
先ず、a−3iCi導電層(2)はアモルファス化した
St元素とC元素並びにこれらの元素のダングリングボ
ンド終端部に導入された水素(H)元素又はハロゲン元
素から成り、その組成式は下記の通りに設定するとよい
。First, the a-3iCi conductive layer (2) consists of an amorphous St element and C element, as well as a hydrogen (H) element or a halogen element introduced at the end of a dangling bond between these elements, and its composition formula is as follows: It is best to set it accordingly.
(Si、□Cつ) +−y A 。(Si, □C) +-y A.
(但し^はH元素又はハロゲン元素)
0.01<x<0.5
好適には 0.05 < x < 0.5最適には 0
.1 < X < 0.40.1 < V < 0.
5
好適には 0.2 < y < 0.5最適には 0.
25 < y < 0.45x値が0.01 < x
< 0.5の範囲内であれば、光導電性が得られ、0.
05 < x < 0.5の範囲内に設定された場合に
は短波長側の光感度が高められ、しかも、光導電性が顕
著に高くなって光キャリアの励起機能が大きくなる。(However, ^ is H element or halogen element) 0.01<x<0.5 Preferably 0.05<x<0.5 Optimally 0
.. 1 < X < 0.40.1 < V < 0.
5 preferably 0.2 < y < 0.5 optimally 0.
25 < y < 0.45x value is 0.01 < x
<0.5, photoconductivity is obtained;
When it is set within the range of 05 < x < 0.5, the photosensitivity on the short wavelength side is increased, and the photoconductivity is significantly increased, so that the excitation function of optical carriers is increased.
また、y値が0.1以下の場合には膜質が低下し、これ
によって光導電性が著しく低下し、0.2<y < 0
.5の範囲内に設定された場合には暗導電率が小さくな
るとともに光導電性が大きくなり、優れた光導電性が得
られ、また、基板との密着性にも優れる。In addition, when the y value is less than 0.1, the film quality deteriorates, resulting in a significant decrease in photoconductivity, and 0.2<y<0.
.. When it is set within the range of 5, the dark conductivity decreases and the photoconductivity increases, resulting in excellent photoconductivity and excellent adhesion to the substrate.
このa−5iC光導電N(2)には水素(I()元素や
ハロゲン元素がダングリングボンド終端用に含有されて
いるが、これらの元素のなかでH元素が終端部に取り込
まれ易く、これによってバンドギャップ中の局在準位密
度が低減化されるという点で望ましい。This a-5iC photoconductive N(2) contains hydrogen (I() element) and halogen element for dangling bond termination, but among these elements, H element is easily incorporated into the termination part, This is desirable in that the local level density in the band gap is reduced.
また、a−3iC光導電層(2)の厚みは0.05〜5
um、好適には0.1〜3μIの範囲内に設定すればよ
く、この範囲内であれば高い光感度が得られ、残留電位
が低くなる。Moreover, the thickness of the a-3iC photoconductive layer (2) is 0.05 to 5
um, preferably within the range of 0.1 to 3 μI; within this range, high photosensitivity can be obtained and the residual potential will be low.
次に第1の層領域(2a)については、Va族元素をO
〜5.OOOppm(なお、Oppmとは実質上含有し
ない場合である)、好適にはO〜3000 ppm含有
させ、これにより、n形半導体となし、a−3iC光導
電層(2)で発生した光キャリア、特に負電荷を基板側
へスムーズに流すことができ、また、基板側のキャリア
がa−3iC光導電層(2)へ流入するのが阻止できる
。即ち、第1の層領域(2a)は基板(1)に対して整
流性を有するという点で非オーミツク接触していると言
える。Next, for the first layer region (2a), the Va group element is replaced with O
~5. OOppm (oppm means substantially no content), preferably O to 3000 ppm, thereby forming an n-type semiconductor, photocarriers generated in the a-3iC photoconductive layer (2), In particular, negative charges can flow smoothly to the substrate side, and carriers on the substrate side can be prevented from flowing into the a-3iC photoconductive layer (2). That is, the first layer region (2a) can be said to be in non-ohmic contact with the substrate (1) in that it has rectifying properties.
従って、この非オーミツク接触により表面電位が高くな
り、残留電位が低減する。Therefore, this non-ohmic contact increases the surface potential and reduces the residual potential.
かかるVa族元素が5.000ppmを越える場合には
、この層領域の内部欠陥が増大して膜質が低下し、表面
電位の低下並びに残留電位の上昇をきたす。If the Va group element exceeds 5.000 ppm, internal defects in this layer region will increase, the film quality will deteriorate, and the surface potential will decrease and the residual potential will increase.
また、第1の層領域(2a)はVa族元素含有量ととも
に、その厚みでもって更に具体的に設定するのが望まし
い。Further, it is desirable that the first layer region (2a) is set more specifically by its thickness as well as the Va group element content.
即ち、第1の層領域(2a)の厚みは0.05〜5μm
、好適には0.1〜3μIの範囲内に設定するとよく、
この範囲内であれば残留電位を低減できるとともに感光
体の耐電圧を高めることができるという点で有利である
。That is, the thickness of the first layer region (2a) is 0.05 to 5 μm.
, preferably set within the range of 0.1 to 3 μI,
If it is within this range, it is advantageous in that the residual potential can be reduced and the withstand voltage of the photoreceptor can be increased.
しかも、第1のNeM域(2a)はVa族元素含有量及
び厚みとともに、そのSiC組成比を下記の通りに設定
するのが望ましい。Moreover, it is desirable that the SiC composition ratio of the first NeM region (2a) is set as follows, as well as the Va group element content and thickness.
即ち、組成式St、、 C、で表した場合、0.1〈x
< 0.5の範囲内に設定するとよく、この範囲内で
あれば、表面電位を高め、基板との密着性を高めること
ができる。That is, when expressed by the composition formula St,, C, 0.1<x
It is preferable to set it within the range of <0.5, and within this range, the surface potential can be increased and the adhesion with the substrate can be improved.
また、上記のようにC元素比率を設定するに当たって、
その比率を第2のN jl域(2b)に比べて大きくす
るとよく、これは表面電位を高め、基板との密着性を高
めることができる点で有利である。In addition, in setting the C element ratio as described above,
It is preferable to make the ratio larger than that in the second N jl region (2b), which is advantageous in that the surface potential can be increased and the adhesion with the substrate can be improved.
上記Va族元素にはN、 P、^s、Sb、[liがあ
るが、P元素が共有結合性に優れて半導体特性を敏感に
変え得る点で、その上、優れた帯電能と光感度が得られ
るという点で望ましい。The Va group elements mentioned above include N, P, ^s, Sb, and [li, and the P element has excellent covalent bonding properties and can sensitively change semiconductor properties, and also has excellent charging ability and photosensitivity. This is desirable in that it provides the following.
第2の層領域(2b)については、IIIa族元素を1
〜1 、 OOOppm、好適には30〜300ppn
含有させ、これにより、a−SiC光導電層(2)内部
の有機光導電層(3)側にP形半導体層を形成し、この
層(2)で発生した光キャリア、特に正電荷を有機光半
導体層(3)へスムーズに流すことができ、その結果、
表面電位が高くなり、残留電位が低減する。For the second layer region (2b), 1 group IIIa element is added.
~1, OOOppm, preferably 30-300ppn
As a result, a P-type semiconductor layer is formed on the organic photoconductive layer (3) side inside the a-SiC photoconductive layer (2), and the photocarriers generated in this layer (2), especially positive charges, are transferred to the organic photoconductive layer (2). It can flow smoothly to the optical semiconductor layer (3), and as a result,
The surface potential increases and the residual potential decreases.
かかるUia族元素がippm未満の場合には帯電能を
向上させることができず、1 、000ppmを越える
場合には光励起キャリアの発生能力が劣り、光感度が低
下する。If the amount of the Uia group element is less than ippm, the charging ability cannot be improved, and if it exceeds 1,000 ppm, the ability to generate photoexcited carriers is poor and the photosensitivity is reduced.
また、第2のN領域(2b)はIIIa族元素含有量と
ともに、その厚みでもって更に具体的に設定するのが望
ましい。Further, it is desirable that the second N region (2b) is set more specifically by its thickness as well as the IIIa group element content.
即ち、第2の層領域(2b)の厚みは0.05〜5μm
、好適には0.1〜3μmの範囲内に設定するとよく、
この範囲内であれば、高い光感度が得られ、残留電位が
低くなる。That is, the thickness of the second layer region (2b) is 0.05 to 5 μm.
, preferably set within the range of 0.1 to 3 μm,
Within this range, high photosensitivity can be obtained and residual potential will be low.
上記■a族元素にはB、AI、Ga、 In等があるが
、8元素が共有結合性に優れて半導体特性を敏感に変え
得る点で、その上、優れた帯電能および光感度が得られ
るという点で望ましい。The above Group A elements include B, AI, Ga, In, etc., and the eight elements have excellent covalent bonding properties and can sensitively change semiconductor properties.In addition, they have excellent charging ability and photosensitivity. It is desirable in that it can be done.
上記の通り、本発明の電子写真感光体によれば、a−3
iC光導電層(2)にp−n接合が形成され、そのため
、この層(2)で発生したキャリアのうち、正孔は有機
光半導体N(3)へ向かい、電子は基板(1)へ向かう
。従って、負帯電型の電子写真感光体となる。As described above, according to the electrophotographic photoreceptor of the present invention, a-3
A p-n junction is formed in the iC photoconductive layer (2), so that among the carriers generated in this layer (2), holes go to the organic photoconductor N (3), and electrons go to the substrate (1). Head towards. Therefore, it becomes a negatively charged electrophotographic photoreceptor.
このような負帯電型電子写真感光体においては、有機光
半導体層(3)に電子供与性化合物が選ばれ、この化合
物には例えば高分子量のものとして、ポリ−N−ビニル
カルバゾール、ポリビニルピレン、ポリビニルアントラ
セン、ピレン−ホルムアルデヒド縮重合体などがあり、
また、低分子量のものとしてオキサジアゾール、オキサ
ゾール、ピラゾリン、トリフェニルメタン、ヒドラゾン
、トリアリールアミン、N−フェニルカルバゾール、ス
チルベンなどがあり、この低分子物質は、ポリカーボネ
ート、ポリエステル、メタアクリル樹脂、ポリアミド、
アクリルエポシキ、ポリエチレン、フェノール、ポリウ
レタン、ブチラール樹脂、ポリ酢酸ビニル、ユリア樹脂
などのバインダに分散されて用いられる。In such a negatively charged electrophotographic photoreceptor, an electron-donating compound is selected for the organic photosemiconductor layer (3), and this compound includes, for example, a high molecular weight compound such as poly-N-vinylcarbazole, polyvinylpyrene, There are polyvinyl anthracene, pyrene-formaldehyde condensation polymers, etc.
In addition, there are low molecular weight substances such as oxadiazole, oxazole, pyrazoline, triphenylmethane, hydrazone, triarylamine, N-phenylcarbazole, and stilbene. ,
It is used dispersed in a binder such as acrylic epoxy, polyethylene, phenol, polyurethane, butyral resin, polyvinyl acetate, or urea resin.
また、前記基板(1)には銅、黄銅、SO5、AI等の
金属導電体、あるいはガラス、セラミックス等の絶縁体
の表面に導電体薄膜をコーティングしたものがあり、就
中、AIがコスト面並びにa−SiC層との密着性とい
う点で有利である。In addition, the substrate (1) includes a metal conductor such as copper, brass, SO5, AI, etc., or an insulator such as glass or ceramics coated with a conductive thin film on the surface. It is also advantageous in terms of adhesion to the a-SiC layer.
かくして本発明によれば、a−5iC光導電層にVa族
元素及びIIIa族元素が所定の範囲内で含有した1!
ipi域を形成したことにより、表面電位及び残留電位
が改善され、そして、そのSiC元素比率を所定の範囲
内に設定して光感度が高められる。Thus, according to the present invention, the a-5iC photoconductive layer contains the Va group element and the IIIa group element within a predetermined range.
By forming the ipi region, the surface potential and residual potential are improved, and the photosensitivity is increased by setting the SiC element ratio within a predetermined range.
本発明の電子写真感光体においては、第1の層領域(2
a)と第2の層領域(2b)のそれぞれのVa族元素含
有量及び[I[a族元素含有量を層厚方向に亘って変化
させてもよい。その例を第6図〜第15図に示す。In the electrophotographic photoreceptor of the present invention, the first layer region (2
The Va group element content and the [I[a group element content] of each of a) and the second layer region (2b) may be varied in the layer thickness direction. Examples are shown in FIGS. 6 to 15.
これらの図において、横軸は層厚方向であり、Sは基板
(1)と第1の層領域(2a)の界面、tは第1の層領
域(2a)と第2の層領域(2b)の界面、Uは第2の
層領域(2b)と有機光半導体層(3)の界面を表し、
また、縦軸はVa族元素又はIIIa族元素の含有量を
表わす。In these figures, the horizontal axis is the layer thickness direction, S is the interface between the substrate (1) and the first layer region (2a), and t is the interface between the first layer region (2a) and the second layer region (2b). ), U represents the interface between the second layer region (2b) and the organic optical semiconductor layer (3),
Moreover, the vertical axis represents the content of the Va group element or the IIIa group element.
このように第1の層領域(2a)又は第2の層領域(2
b)で層厚方向に亘ってそれぞれVa族元素又はIII
a族元素の含有量を変えた場合には、その元素含有量は
それぞれの層領域(2a) (2b)全体当たりの平均
含有量に対応する。In this way, the first layer region (2a) or the second layer region (2a)
In b), Va group element or III is added in the layer thickness direction.
When the content of the group a element is changed, the element content corresponds to the average content of each layer region (2a) (2b) as a whole.
また、上記の通りにVa族元素又はIIIa族元素の含
有量を変えた場合、第1の層領域(2a)と第2の層領
域(2h)の間に真性半導体層が形成される場合がある
。Furthermore, when the content of the Va group element or the IIIa group element is changed as described above, an intrinsic semiconductor layer may be formed between the first layer region (2a) and the second layer region (2h). be.
次に本発明電子写真感光体の製法を述べる。Next, a method for manufacturing the electrophotographic photoreceptor of the present invention will be described.
a −S’i C層を形成するにはグロー放電分解法、
イオンブレーティング法、反応性スパッタリング法、真
空蒸着法、CVD法などの薄膜形成方法がある。To form the a-S'i C layer, glow discharge decomposition method,
There are thin film forming methods such as an ion blasting method, a reactive sputtering method, a vacuum evaporation method, and a CVD method.
グロー放電分解法を用いる場合、Si元素含有ガスとC
元素含有ガスを組合せ、この混合ガスをプラズマ分解し
て成膜形成する。このSi元素含有ガスには5i11a
+5izH□5iJs+SiF4,5iC14+5il
lCIt等々があり、また、C元素含有ガスにはCL、
C2H4,Czl12+C3H11等々があり、就中、
C,H2は高速成膜性が得られるという点で望ましい。When using the glow discharge decomposition method, Si element-containing gas and C
A film is formed by combining element-containing gases and plasma decomposing the mixed gas. This Si element-containing gas has 5i11a
+5izH□5iJs+SiF4,5iC14+5il
lCIt, etc., and C element-containing gases include CL,
There are C2H4, Czl12+C3H11, etc., among others,
C and H2 are desirable in that they provide high-speed film formation.
本実施例に用いられるグロー放電分解装置を第2図によ
り説明する。The glow discharge decomposition device used in this example will be explained with reference to FIG.
図中、第1タンク(4)、第2タンク(5)、第3タン
ク(6)、第4タンク(7)、第5タンク(8)にはそ
れぞれSiH4+CzHz、PH:++BzH6(PH
:+ガス及びBZH&ガスはいずれも水素ガスで希釈さ
れている)及びH2が密封され、これらのガスは各々対
応する第1調製弁(9)、第2調製弁(10) 、第3
調製弁(11)、第4調製弁(12)及び第5調製弁(
13)を開放することにより放出される。この放出ガス
の流量はそれぞれマスフローコントローラ(14) (
15) (16) (17) (18)により制御され
、各々のガスは混合されて主管(19)へ送られる。尚
、(20) (21)は止め弁である。In the figure, SiH4+CzHz, PH:++BzH6(PH
:+ gas and BZH & gas are both diluted with hydrogen gas) and H2 are sealed, and these gases are respectively
Regulating valve (11), fourth regulating valve (12) and fifth regulating valve (
13) is released by opening. The flow rate of this released gas is determined by the mass flow controller (14) (
15) (16) (17) (18), each gas is mixed and sent to the main pipe (19). Note that (20) and (21) are stop valves.
主管(19)を通して流れるガスは反応管(22)へ流
入されるが、この反応管(22)の内部には容量結合型
放電用電極(23)が設置され、また、筒状の成膜用基
板(24)が基板支持体(25)の上に載置され、基板
支持体(25)がモータ(26)により回転駆動され、
これに伴って基板(24)が回転される。そして、電極
(23)に電力50w 〜3Kw 、周波数1〜50M
H2の高周波電力が印加され、しかも、基板(24)が
適当な加熱手段により約200〜400℃、好適には約
200〜350℃の温度に加熱される。また、反応管(
22)は回転ポンプ(27)と拡散ポンプ(28)に連
結されており、これにより、成膜形成時に所要な減圧状
態(放電時のガス圧0.01〜2.0Torr)が維持
される。The gas flowing through the main pipe (19) flows into the reaction tube (22), and a capacitively coupled discharge electrode (23) is installed inside this reaction tube (22), and a cylindrical film-forming electrode (23) is installed inside the reaction tube (22). A substrate (24) is placed on a substrate support (25), the substrate support (25) is rotationally driven by a motor (26),
Along with this, the substrate (24) is rotated. Then, the electrode (23) has a power of 50w to 3Kw and a frequency of 1 to 50M.
A high frequency power of H2 is applied, and the substrate (24) is heated by suitable heating means to a temperature of about 200-400°C, preferably about 200-350°C. In addition, the reaction tube (
22) is connected to a rotary pump (27) and a diffusion pump (28), thereby maintaining the required reduced pressure state (gas pressure during discharge of 0.01 to 2.0 Torr) during film formation.
このような構成のグロー放電分解装置を用いて基板(2
4)の上にa−SiC層を形成する場合、第1調製弁(
9)、第2調製弁(10) 、第3調製弁(11)及び
第5調製弁(13)を開いてSil+4.CJz、Pl
h+)Izの各々のガスを放出し、その放出量をマスフ
ローコントロ−ラ(14) (15) (16) (1
8)により制御し、各々のガスは混合されて主管(19
)を介して反応管(22)へ流入する。そして、反応管
内部の真空状態、基板温度及び電極印加用高周波電力を
所定の条件に設定するとグロー放電が発生し、ガスの分
解に伴ってP元素含有のa−SiC膜が基板上に高速に
形成する。The substrate (2
4) When forming an a-SiC layer on top of the first regulating valve (
9), open the second regulating valve (10), the third regulating valve (11), and the fifth regulating valve (13) to obtain Sil+4. CJz, Pl
h+) Iz, and the amount of the released gas is controlled by the mass flow controller (14) (15) (16) (1
8), each gas is mixed and sent to the main pipe (19
) into the reaction tube (22). Then, when the vacuum state inside the reaction tube, the substrate temperature, and the high-frequency power applied to the electrodes are set to predetermined conditions, a glow discharge occurs, and as the gas decomposes, an a-SiC film containing P element is deposited on the substrate at high speed. Form.
上述した通りの薄膜形成方法によりa−5iC層が形成
すると、次に有機光半導体層を形成する。After the a-5iC layer is formed by the thin film forming method as described above, an organic optical semiconductor layer is then formed.
有機光半導体層は浸漬塗工方法又はコーティング法によ
り形成し、前者は感光材が溶媒中に分散された塗工液の
中に浸漬し、次いで、一定な速度で引上げ、そして、自
然乾燥及び熱エージング(約150℃、約1時間)を行
うという方法であり、また、後者のコーティング法によ
れば、コーター(塗機)を用いて、溶媒に分散された感
光材を塗布し、次いで熱風乾燥を行う。The organic photosemiconductor layer is formed by a dip coating method or a coating method, in which the photosensitive material is immersed in a coating solution in which it is dispersed in a solvent, then pulled up at a constant speed, and then air-dried and heated. According to the latter coating method, a photosensitive material dispersed in a solvent is applied using a coater, and then dried with hot air. I do.
次に本発明の実施例を述べる。 Next, examples of the present invention will be described.
(例1)
第2図のグロー放電分解装置を用いて、SiH4ガスを
200secmの流量で、lhガスを270secmの
流量で、そして、C2H2ガスの流量を変化させ、また
、ガス圧を0.6Torr 、高周波電力を150W、
基板温度を250℃に設定し、グロー放電によってa−
5jC膜(膜要約1μm)を形成した。(Example 1) Using the glow discharge decomposition apparatus shown in Fig. 2, the flow rate of SiH4 gas is 200 sec, the lh gas is 270 sec, and the flow rate of C2H2 gas is changed, and the gas pressure is 0.6 Torr. , high frequency power of 150W,
The substrate temperature was set at 250℃, and a-
A 5jC film (film diameter: 1 μm) was formed.
このようにa−5iC膜のカーボン含有比率を変え、そ
して、膜中のカーボン量をXMA法により測定し、また
、光導電率及び暗導電率を測定したところ、第3図に示
す通りの結果が得られた。When the carbon content ratio of the a-5iC film was changed in this way, the amount of carbon in the film was measured by the XMA method, and the photoconductivity and dark conductivity were also measured, the results were as shown in Figure 3. was gotten.
第3図中、横軸はカーボン含有比率、即ちSi+−XC
Xのy値であり、縦軸は導電率を表わし、○印は発光波
長550nm(光量50μ−/cm”)の光に対する光
導電率のプロットであり、・印は暗導電率のプロットで
あり、また、a、bはそれぞれの特性曲線である。In Figure 3, the horizontal axis is the carbon content ratio, i.e., Si+-XC
It is the y value of , and a and b are respective characteristic curves.
上記各a−5iC膜について、その水素含有量を赤外吸
収測定法により求めたところ、第4図に示す通りの結果
が得られた。When the hydrogen content of each of the above a-5iC films was determined by infrared absorption measurement, the results shown in FIG. 4 were obtained.
第4図中、横軸はSi+−x CXのy値であり、縦軸
は水素含有量、即ち(Sil□C,)、−、IIVのy
値であり、○印はSi原子に結合した水素量のプロット
であり、・印はC原子に結合した水素量のプロットであ
り、また、c、dはそれぞれの特性曲線である。In Fig. 4, the horizontal axis is the y value of Si+-x CX, and the vertical axis is the hydrogen content, i.e., the y value of (Sil□C,), -, IIV.
The ◯ mark is a plot of the amount of hydrogen bonded to the Si atom, the * mark is the plot of the amount of hydrogen bonded to the C atom, and c and d are the respective characteristic curves.
第4図より明らかな通り、本例のa−SiC膜はいずれ
もy値が0.3〜0.4の範囲内にあることが判る。As is clear from FIG. 4, it can be seen that the a-SiC films of this example all have y values within the range of 0.3 to 0.4.
また、第3図より明らかな通り、カーボン含有比率Xが
0.2 < X < 0.5の範囲内であれば、光導電
率と暗導電率の比率が顕著に大きくなり、優れた光怒度
が得られることが判る。Furthermore, as is clear from Fig. 3, if the carbon content ratio X is within the range of 0.2 < It can be seen that the degree is obtained.
(例2)
次に本例においては、Si)+4ガスを200secm
の流量で、C,H2ガスを20secmの流量で、H2
ガスをO〜101000scの流量で導入し、そして、
高周波電力を50〜300W、ガス圧を0.3〜1.2
Torrに設定し、グロー放電によりa−SiC膜(膜
要約1μm)を形成した。(Example 2) Next, in this example, Si)+4 gas is heated for 200 sec.
C, H2 gas at a flow rate of 20 sec, H2 gas
Gas is introduced at a flow rate of O~101000sc, and
High frequency power 50~300W, gas pressure 0.3~1.2
Torr was set, and an a-SiC film (film thickness: 1 μm) was formed by glow discharge.
かくして、カーボン含有比率Xを0.3に設定し、そし
て、水素含有量yを変化させた種々のa−5iCMを形
成し、各々の膜について光導電率及び暗導電率を測定し
たところ、第5図に示す通りの結果が得られた。In this way, various a-5iCMs were formed with the carbon content ratio X set to 0.3 and the hydrogen content y varied, and the photoconductivity and dark conductivity of each film were measured. The results shown in Figure 5 were obtained.
第5図中、横軸は水素含有量、即ち[5il−x C8
]1□N、のy値であり、縦軸は導電率を表し、○印は
発光波長550nm (光量50μW/cm2)の光に
対する光導電率のプロットであり、・印は暗導電率のプ
ロットであり、また、e、fはそれぞれの特性曲線であ
る。In FIG. 5, the horizontal axis represents the hydrogen content, that is, [5il-x C8
]1□N, the vertical axis represents the conductivity, the circle mark is a plot of photoconductivity for light with an emission wavelength of 550 nm (light intensity 50 μW/cm2), and the mark is a plot of dark conductivity. , and e and f are respective characteristic curves.
第5図より明らかな通り、y値が0.2を超えた場合、
高い光導電率並びに低い暗導電率が得られることが判る
。As is clear from Figure 5, when the y value exceeds 0.2,
It can be seen that high photoconductivity as well as low dark conductivity are obtained.
(例3)
グロー放電分解装置の反応管内部に表面研磨したアルミ
ニウム製平板(25mm X 50mm)を設置し、そ
の平板の上に第1表に示す成膜条件により順次第1の層
領域(2a)と第2の層領域(2b)を形成する。(Example 3) A flat aluminum plate (25 mm x 50 mm) with a polished surface was installed inside the reaction tube of a glow discharge decomposition device, and layer area 1 (2a ) and a second layer region (2b) are formed.
次いで、真空蒸着法により円板状(3mmφ)のアルミ
ニウム電極を形成し、第16図に示す通りの光導電部材
を製作した。同図中、(29)及び(3o)はそれぞれ
平板及びアルミニウム電極である。Next, a disk-shaped (3 mmφ) aluminum electrode was formed by vacuum evaporation to produce a photoconductive member as shown in FIG. 16. In the figure, (29) and (3o) are a flat plate and an aluminum electrode, respectively.
(以下余白)
このようにして成膜した第1の層領域(2a)及び第2
の層領域(2b)について、それぞれのカーボン量をX
MA法により、また、P元素含有量及びB元素含有量を
二次イオン質量分析法により測定したところ、第2表に
示す通りの結果が得られた。(Left below) The first layer region (2a) and the second layer region (2a) formed in this way
For layer region (2b), each carbon amount is
When the P element content and B element content were measured by the MA method and by secondary ion mass spectrometry, the results shown in Table 2 were obtained.
第2表
かくして得られたa−3iC光導電部材を第16図に示
す通りアルミニウム電極(30)側に電圧を印加し、平
板(29)をアース側に導電させ、これによって電圧−
電流特性を測定したところ、第17図に示す通りの結果
が得られた。Table 2 The a-3iC photoconductive member thus obtained is applied with a voltage on the aluminum electrode (30) side as shown in FIG.
When the current characteristics were measured, the results shown in FIG. 17 were obtained.
また、本例においては、第1の層領域を形成するに当た
ってPH3ガスを導入せず、しかも、第2の層領域を形
成するに当たってB 、 I! 、ガスを導入せず、そ
の他は本例と全く同じ成膜条件に設定し、これにより、
P元素及びB元素を含有しないa−3iC光導電部材を
製作し、これを比較例とし、その電圧−電流特性も測定
した。Furthermore, in this example, PH3 gas is not introduced when forming the first layer region, and B, I! gas is not introduced when forming the second layer region. , no gas was introduced, and the other conditions were exactly the same as in this example, and as a result,
An a-3iC photoconductive member containing neither P element nor B element was manufactured and used as a comparative example, and its voltage-current characteristics were also measured.
第17図中、横軸はアルミニウム電極(30)に印加す
る電圧であり、縦軸は電流値であり、○印は本発明に係
るa−3iC光導電部材の測定プロット、・印は比較例
のa−5iC光導電部材の測定プロットであり、g浦は
それぞれの特性曲線である。In FIG. 17, the horizontal axis is the voltage applied to the aluminum electrode (30), the vertical axis is the current value, the circle mark is a measurement plot of the a-3iC photoconductive member according to the present invention, and the mark is a comparative example. Figure 3 is a measurement plot of the a-5iC photoconductive member, and gura is the respective characteristic curve.
第17図より明らかな通り、本発明に係るa−3iC光
導電部材によれば、アルミニウム電極(30)に負の電
圧を印加しても電流がほとんど流れないが、その電極(
30)に正の電圧を印加した場合には著しく大きな電流
が流れる。As is clear from FIG. 17, according to the a-3iC photoconductive member according to the present invention, almost no current flows even when a negative voltage is applied to the aluminum electrode (30);
When a positive voltage is applied to 30), a significantly large current flows.
(例4)
(例3)と同じa−3iC光導電層をアルミニウム基板
上多こ形成し、次いで、ポリカーボネートにヒドラゾン
系化合物を分散させた有機光半導体層(膜要約15μm
)を形成し、電子写真感光体とした。(Example 4) The same a-3iC photoconductive layer as in (Example 3) was formed in multiple layers on an aluminum substrate, and then an organic photoconductive layer (film size: 15 μm
) was formed and used as an electrophotographic photoreceptor.
かくして得られた電子写真感光体の特性評価を電子写真
特性測定装置により測定したところ、優れた光感度及び
表面電位が得られ、しかも、低い残留電位が得られた。When the properties of the electrophotographic photoreceptor thus obtained were measured using an electrophotographic property measuring device, it was found that excellent photosensitivity and surface potential were obtained, as well as a low residual potential.
(例5)
上記(例4)の電子写真感光体を作製するに当たって、
(例3)の比較例をa−5iC光導電層とし、更に同じ
有機光半導体層を形成して成る電子写真感光体を製作し
た。(Example 5) In producing the electrophotographic photoreceptor of the above (Example 4),
As a comparative example of (Example 3), an electrophotographic photoreceptor was manufactured by using an a-5iC photoconductive layer and further forming the same organic photoconductor layer.
この電子写真感光体の光感度を測定したところ、(例4
)の電子写真感光体に比べて約10χ低下しており、ま
た、残留電位は約7χ大きくなった。When the photosensitivity of this electrophotographic photoreceptor was measured, (Example 4
), the residual potential was about 10χ lower than that of the electrophotographic photoreceptor, and the residual potential was about 7χ higher.
(例6)
本例においては、第3表に示す成膜条件により第1の層
領域にP元素を含有しないa−SiC光導電層を形成し
、その他の成膜条件を(例3)及び(第4)と同様に設
定し、電子写真感光体とした。(Example 6) In this example, an a-SiC photoconductive layer containing no P element is formed in the first layer region under the film forming conditions shown in Table 3, and other film forming conditions are set as in (Example 3) and The same settings as in (4th) were made to obtain an electrophotographic photoreceptor.
また、上記により得られたa−5iC光導電層のカーボ
ン量及びB元素含有量を測定したところ、第4表に示す
通りの結果が得られた。Furthermore, when the carbon content and B element content of the a-5iC photoconductive layer obtained above were measured, the results shown in Table 4 were obtained.
第4表
かくして得られた電子写真感光体についても、優れた光
感度及び表面電位が得られ、しかも、低い残留電位が得
られた。Table 4 The electrophotographic photoreceptor thus obtained also had excellent photosensitivity and surface potential, and also had a low residual potential.
(例7)
また本発明者等は(例4)の電子写真感光体を製作する
に当たって、PH,ガス流量とB、H,ガス流量を変化
させ、これにより、第5表に示す通りに第1の層領域の
P元素含有量並びに第2の層領域のB元素含有量を変え
た15種類の電子写真感光体(感光体へ〜0)を作製し
た。(Example 7) In manufacturing the electrophotographic photoreceptor of (Example 4), the present inventors changed the PH, gas flow rate, B, H, and gas flow rate, and thereby, as shown in Table 5, Fifteen types of electrophotographic photoreceptors (from photoreceptor to 0) were produced in which the P element content in the first layer region and the B element content in the second layer region were changed.
これらの電子写真感光体の光感度、表面電位並びに残留
電位を測定したところ、第5表に示す通りの結果が得ら
れた。When the photosensitivity, surface potential and residual potential of these electrophotographic photoreceptors were measured, the results shown in Table 5 were obtained.
同表中、光感度は相対評価により◎印、0印、△印及び
x印の4段階に区分し、◎印は最も優れた光感度が得ら
れた場合であり、O印は幾分価れた光感度が得られた場
合であり、Δ印は他に比べてわずかに劣る光感度になっ
た場合であり、×印は光感度が最も低下した場合である
。In the same table, photosensitivity is classified into four levels based on relative evaluation: ◎, 0, △, and x. ◎ indicates the best photosensitivity, and O indicates a somewhat higher The Δ mark is a case where the photosensitivity is slightly inferior to the others, and the x mark is the case where the photosensitivity is the lowest.
表面電位の特性評価も◎印、○印、Δ印及びX印の4段
階に区分し、■印は最も高い表面電位が得られた場合で
あり、O印は幾分高い表面電位が得られた場合であり、
Δ印は他に比べて高い表面電位が認められなかった場合
であり、x印は表面電位が最も低下した場合である。Characteristic evaluation of surface potential is also divided into four stages: ◎, ○, Δ, and If
The Δ mark indicates a case where a higher surface potential was not observed compared to the others, and the x mark indicates a case where the surface potential decreased the most.
また、残留電位についても4段階に相対評価しており、
■印は残留電位が最も小さくなった場合であり、0印は
残留電位の低下が幾分認められた場合であり、Δ印は他
に比べて残留電位の低減が認められなかった場合であり
、X印は残留電位が最も高くなった場合である。In addition, the residual potential is also evaluated relative to 4 levels.
The mark ■ indicates the case where the residual potential is the smallest, the mark 0 indicates the case where a slight decrease in the residual potential is observed, and the mark Δ indicates the case where the reduction in the residual potential is not observed compared to the others. , X marks are the cases where the residual potential is the highest.
*印の感光体は本発明の範囲外のものである。Photoreceptors marked with * are outside the scope of the present invention.
第1表より明らかな通り、感光体A −C、感光体E−
Lは優れた光感度が得られ、しかも、表面電位が高く、
残留電位の低減が認められた。As is clear from Table 1, photoconductor A-C, photoconductor E-
L has excellent photosensitivity, and has a high surface potential.
A reduction in residual potential was observed.
然るに、感光体り、M、Nは光感度及び表面電位が劣り
、また、感光体Oは光感度、表面電位並びに残留電位の
いずれの特性も改善されていないことが判る。However, it can be seen that the photosensitivity and surface potential of photoreceptors L, M, and N are poor, and that photoreceptor O has not been improved in any of the characteristics of photosensitivity, surface potential, and residual potential.
以上の通り、本発明の電子写真感光体によれば、B−3
iC光導電層の内部にVa族元素とIIIa族元素を所
定の範囲内で含有された各N領域を形成したことにより
優れた光感度が得られ、表面電位を高め、しかも、残留
電位を低減させることができた。As mentioned above, according to the electrophotographic photoreceptor of the present invention, B-3
Excellent photosensitivity is obtained by forming each N region containing Va group elements and IIIa group elements within a predetermined range inside the iC photoconductive layer, increasing the surface potential and reducing residual potential. I was able to do it.
また、この電子写真感光体によれば、a−3iC光導電
層が基板に対して非オーミツク接触であり、これにより
、−流樋能が高められ、高い表面電位並びに低い残留電
位の負帯電用電子写真感光体が提供できた。In addition, according to this electrophotographic photoreceptor, the a-3iC photoconductive layer is in non-ohmic contact with the substrate, which increases the -flow ability and enables negative charging with high surface potential and low residual potential. We were able to provide an electrophotographic photoreceptor.
第1図は本発明電子写真感光体の層構成を表わす断面図
、第2図は実施例に用いられるグロー放電分解装置の概
略図、第3図はカーボン含有比率と導電率の関係を示す
線図、第4図はカーボン含有比率と水素含有量の関係を
示す線図、第5図は水素含有量と導電率の関係を示す線
図であり、また、第6図、第7図、第8図、第9図、第
10図、第11図、第12図、第13図、第14図及び
第15図はアモルファスシリコンカーバイド光導電層の
層厚方向に亘るVa族元素含有量及びIIIa族元素含
有量を表わす線図である。第16図は光導電部材の電圧
−電流特性を測定するための説明図、第17図は電圧−
電流特性を示す線図である。
1・・・導電性基板
2・・・アモルファスシリコンカーバイド光導電層
2a・・・第1の層領域
2b・・・第2の層領域
3 ・・・有機光半導体層
第4図
第5図
0 0.1 0.2 0,3 0.4 0.57K I
I量(S」)
5 t u
S と シ手続補正書
平成1年6月23日FIG. 1 is a cross-sectional view showing the layer structure of the electrophotographic photoreceptor of the present invention, FIG. 2 is a schematic diagram of a glow discharge decomposition device used in Examples, and FIG. 3 is a line showing the relationship between carbon content ratio and electrical conductivity. 4 is a diagram showing the relationship between carbon content ratio and hydrogen content, FIG. 5 is a diagram showing the relationship between hydrogen content and electrical conductivity, and FIGS. 8, 9, 10, 11, 12, 13, 14, and 15 show the Va group element content and IIIa in the thickness direction of the amorphous silicon carbide photoconductive layer. It is a diagram showing group element content. Fig. 16 is an explanatory diagram for measuring the voltage-current characteristics of a photoconductive member, and Fig. 17 is an explanatory diagram for measuring the voltage-current characteristics of a photoconductive member.
FIG. 3 is a diagram showing current characteristics. 1... Conductive substrate 2... Amorphous silicon carbide photoconductive layer 2a... First layer region 2b... Second layer region 3... Organic optical semiconductor layer Fig. 4 Fig. 5 0 0.1 0.2 0.3 0.4 0.57K I
I amount (S”) 5 t u
S and C procedural amendment June 23, 1999
Claims (2)
光導電層と有機光半導体層が順次積層された電子写真感
光体において、前記アモルファスシリコンカーバイド光
導電層が第1の層領域と第2の層領域が順次形成された
層構成であり、第1の層領域に周期律表第Va族元素を
5,000ppm以下の範囲内で含有させ、第2の層領
域に周期律表第IIIa族元素を1〜1,000ppmの
範囲内で含有させたことを特徴とする電子写真感光体。(1) In an electrophotographic photoreceptor in which an amorphous silicon carbide photoconductive layer and an organic photoconductive layer are sequentially laminated on a conductive substrate, the amorphous silicon carbide photoconductive layer has a first layer region and a second layer region. It has a layer structure formed in sequence, with the first layer region containing an element from group Va of the periodic table in a range of 5,000 ppm or less, and the second layer region containing an element from group IIIa of the periodic table in a range of 1 to 500 ppm. An electrophotographic photoreceptor characterized in that the content is within a range of 1,000 ppm.
光導電層と有機光半導体層が順次積層された電子写真感
光体において、前記アモルファスシリコンカーバイド光
導電層が第1の層領域と第2の層領域が順次形成された
層構成であり、第1の層領域は周期律表第Va族元素を
実質上含有せず、第2の層領域に周期律表第IIIa族元
素を1〜1,000ppmの範囲内で含有させたことを
特徴とする電子写真感光体。(2) In an electrophotographic photoreceptor in which an amorphous silicon carbide photoconductive layer and an organic photoconductive layer are sequentially laminated on a conductive substrate, the amorphous silicon carbide photoconductive layer has a first layer region and a second layer region. It has a layer structure formed in sequence, with the first layer region containing substantially no Group Va elements of the periodic table, and the second layer region containing elements of Group IIIa of the periodic table in a range of 1 to 1,000 ppm. An electrophotographic photoreceptor comprising:
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63335574A JP2789100B2 (en) | 1988-03-24 | 1988-12-28 | Electrophotographic photoreceptor |
US07/392,936 US5529866A (en) | 1988-03-11 | 1989-03-10 | Electrophotographic sensitive member |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7026088 | 1988-03-24 | ||
JP63-70260 | 1988-03-24 | ||
JP63335574A JP2789100B2 (en) | 1988-03-24 | 1988-12-28 | Electrophotographic photoreceptor |
Publications (2)
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JPH01315758A true JPH01315758A (en) | 1989-12-20 |
JP2789100B2 JP2789100B2 (en) | 1998-08-20 |
Family
ID=26411425
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JP63335574A Expired - Fee Related JP2789100B2 (en) | 1988-03-11 | 1988-12-28 | Electrophotographic photoreceptor |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5614241A (en) * | 1979-07-16 | 1981-02-12 | Matsushita Electric Ind Co Ltd | Electrophotographic receptor |
JPS5821256A (en) * | 1981-07-30 | 1983-02-08 | Seiko Epson Corp | Electrophotographic receptor |
-
1988
- 1988-12-28 JP JP63335574A patent/JP2789100B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5614241A (en) * | 1979-07-16 | 1981-02-12 | Matsushita Electric Ind Co Ltd | Electrophotographic receptor |
JPS5821256A (en) * | 1981-07-30 | 1983-02-08 | Seiko Epson Corp | Electrophotographic receptor |
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