JPS62170966A - Electrophotographic sensitive body - Google Patents

Electrophotographic sensitive body

Info

Publication number
JPS62170966A
JPS62170966A JP1291886A JP1291886A JPS62170966A JP S62170966 A JPS62170966 A JP S62170966A JP 1291886 A JP1291886 A JP 1291886A JP 1291886 A JP1291886 A JP 1291886A JP S62170966 A JPS62170966 A JP S62170966A
Authority
JP
Japan
Prior art keywords
layer
zno
amorphous silicon
crystals
electrophotographic photoreceptor
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.)
Pending
Application number
JP1291886A
Other languages
Japanese (ja)
Inventor
Noboru Ebara
江原 襄
Yoshimi Kojima
小島 義己
Shiro Narukawa
成川 志郎
Hisashi Hayakawa
尚志 早川
Eiji Imada
今田 英治
Toshiro Matsuyama
松山 外志郎
Hideo Nojima
秀雄 野島
Masahiro Fujiwara
正弘 藤原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sharp Corp
Original Assignee
Sharp Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sharp Corp filed Critical Sharp Corp
Priority to JP1291886A priority Critical patent/JPS62170966A/en
Publication of JPS62170966A publication Critical patent/JPS62170966A/en
Pending legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02Charge-receiving layers
    • G03G5/04Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/043Photoconductive layers characterised by having two or more layers or characterised by their composite structure
    • G03G5/0433Photoconductive layers characterised by having two or more layers or characterised by their composite structure all layers being inorganic

Abstract

PURPOSE:To obtain an excellent photosensitive body small in image unsharpness by using photosensitive layers composed of a specified crystalline semiconductor layer of a compound of groups II-IV, and an amorphous silicon layer. CONSTITUTION:The amorphous silicon a-Si layer 2 is formed on a conductive substrate 3 usually by the plasma CVD method, preferably, using SiH4 as a material gas, and then, the layer 1 of II-IV compound semiconductor, such as ZnO, specified in crystal structure, is formed on the layer 2, most favorably, by the sputtering method using ZnO as a target, resulting in growing columnar crystals oriented in parallel to the C axis perpendicular to the substrate. Since the C axis-oriented columnar ZnO crystals are about 10mum long, and arranged densely in honeycombed structure surrounded with grain boundaries, photo carriers travel through the crystals in the columnar direction without enlarging laterally, hindered with the grain boundaries, thus permitting a good-quality sharp image to be obtained without bleeding the image lines.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明はとII−VI族化合物半導体とアモルファスシ
リコンを基本とする電子写真感光体に関する。
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an electrophotographic photoreceptor based on a II-VI group compound semiconductor and amorphous silicon.

(従来技術およびその問題点) 電子写真感光体として最近一般にアモルファスシリコン
(以下、a −S iと云う。)が適していると考えら
れている。a−Siは以前用いられていたアモルファス
セレンまたはその化合物より高感度で、無害であり、し
かも長寿命であるという点から盛んに用いられている。
(Prior Art and its Problems) Recently, amorphous silicon (hereinafter referred to as a-Si) is generally considered to be suitable as an electrophotographic photoreceptor. a-Si is widely used because it has higher sensitivity, is harmless, and has a longer life than amorphous selenium or its compounds that have been used previously.

しかしながら、a −S iは成膜速度が遅く、原料ガ
スが高価であり、かつa −S iの収率か低いことか
ら非常に高価であり、広く一般的電子写真に適用される
には問題がある。
However, a-Si is extremely expensive due to its slow film formation rate, expensive raw material gas, and low yield of a-Si, and is problematic for wide application to general electrophotography. There is.

また、最近有機半導体系の感光体も注目されているが、
寿命の点でまだa −S iには及ばない。置市には酸
化亜鉛を用いた例もあるが必ずしも十分な感光体特性が
得られていない。
Recently, organic semiconductor photoreceptors have also been attracting attention.
It is still not as good as a-S i in terms of lifespan. Although there are some examples of using zinc oxide in Okiichi, sufficient photoreceptor characteristics have not always been obtained.

(発明の目的) 本発明は優れた特性を有する電子写真感光体を得ること
を目的とする。
(Objective of the Invention) The object of the present invention is to obtain an electrophotographic photoreceptor having excellent characteristics.

(発明の内容) 即ち、本発明は導電性基体上に感光体層を有する電子写
真感光体において、該感光体層が基体に対してC軸が垂
直に配向するヴルツ型のll−ff族化合物半導体層と
アモルファスシリコン層からなる電子写真感光体を提供
する。
(Contents of the Invention) That is, the present invention provides an electrophotographic photoreceptor having a photoreceptor layer on a conductive substrate, in which the photoreceptor layer is a Wurz-type ll-ff group compound in which the C axis is oriented perpendicularly to the substrate. An electrophotographic photoreceptor comprising a semiconductor layer and an amorphous silicon layer is provided.

導電性基体としては通常アルミニウム、銅等が好ましい
。この基体上に通常a−5i層を形成し、次いでn−■
族化合物半導体層を形成する。もちろん、逆に■−■族
化合物半導体層を最初に形成し、次いでa −S i層
を形成してもよい。■−■族化合物半導体としては、Z
nO1ZnSSZnSe。
Aluminum, copper, etc. are usually preferred as the conductive substrate. A layer of a-5i is usually formed on this substrate, and then a layer of n-■
A group compound semiconductor layer is formed. Of course, conversely, the ■-■ group compound semiconductor layer may be formed first, and then the a-Si layer may be formed. As a ■-■ group compound semiconductor, Z
nO1ZnSSZnSe.

Cd01CdS、CdSe等種々のものが挙げられるが
、ZnO;酸化亜鉛が最も好ましい。以下、この酸化亜
鉛を例にとって、説明する。
Various materials such as Cd01CdS and CdSe can be mentioned, but ZnO; zinc oxide is the most preferred. This will be explained below using zinc oxide as an example.

a−Si層は通常プラズマCVD法により形成される。The a-Si layer is usually formed by plasma CVD.

この場合、原料ガスとしてはS i H4であるのが好
ましい。a−Si層は小量のホウ素を含んでも良く、そ
の場合、5IH4ガスにB t Heガスを小量混合す
る。
In this case, the raw material gas is preferably S i H4. The a-Si layer may contain a small amount of boron, in which case a small amount of BtHe gas is mixed with the 5IH4 gas.

本発明では特定結晶構造の酸化亜鉛を用いる。In the present invention, zinc oxide having a specific crystal structure is used.

酸化亜鉛は前述の如く、実はかつて広く電子写真感光体
として用いられ、その材料自体は高い光伝導特性がある
ことが広く知られていたが、この場     色合酸化
亜鉛の粉体を有機樹脂中に分散することにより感光体と
して必要とする1013〜14Ωcmの高抵抗を得てい
る。しかし粉体を有機樹脂に分散した材料は電気抵抗が
高くなると同時に光伝導性も小さくなり、粉体は表面積
が大きく表面電子状態が大幅に増加し光伝導特性や感光
体特性に悪影響を与える。そこで粉体化すること自体、
光伝導特性を劣化し、その点に関しては好ましくないが
帯電特性を上げるために、止むを得ず粉体化し樹脂とコ
ンポジット化を行っている。しかし本発明では、酸化亜
鉛をコン子ジット化することなく、むしろ酸化亜鉛のC
軸配向する結晶化させて、C軸方向に有する分極効果を
利用することにより電子写真に必要な表面帯電電位を容
易に持たせることができる。
As mentioned above, zinc oxide was actually once widely used as an electrophotographic photoreceptor, and the material itself was widely known to have high photoconductive properties. By dispersing it, a high resistance of 1013 to 14 Ωcm, which is required for a photoreceptor, is obtained. However, a material in which powder is dispersed in an organic resin has a high electrical resistance and at the same time a low photoconductivity.The powder has a large surface area, and the surface electronic state increases significantly, which adversely affects the photoconductivity and photoreceptor properties. The pulverization itself is
Although it deteriorates the photoconductive properties and is undesirable in that respect, in order to improve the charging properties, it is unavoidable to turn it into powder and make it into a composite with a resin. However, in the present invention, zinc oxide is not converted into a conjugate, but rather the carbon of zinc oxide is
By axially oriented crystallization and utilizing the polarization effect in the C-axis direction, it is possible to easily provide the surface charging potential required for electrophotography.

本発明の特定結晶構造の酸化亜鉛層はイオン工学的製法
、例えばスパッタリング等を用いて形成される。ZnO
をターゲットとするスパッタリングが最も好ましい。こ
のようなイオン工学的製法によれば基体に垂直にC軸配
向した柱状結晶が成長し、亜鉛イオンからなる層と酸素
から成る層が交互に積層した形になり、これらの正と負
イオンの層の有する電気的分極が積み重って大きな分極
をC軸方向に示す。この分極が帯電保持する。
The zinc oxide layer of the present invention having a specific crystal structure is formed using an ion engineering method, such as sputtering. ZnO
Sputtering targeting is most preferred. According to such an ion engineering method, columnar crystals with C-axis oriented perpendicular to the substrate grow, forming a structure in which layers consisting of zinc ions and layers consisting of oxygen are alternately stacked, and these positive and negative ions are The electrical polarizations of the layers stack up to exhibit large polarization in the C-axis direction. This polarization maintains the charge.

感光体層の製造時には酸化亜鉛の他に他の元素のイオン
、例えばリチウムイオン、銅イオン、カリウムイオンま
たはこれらの混合を含むのが好ましい。これらの元素の
イオンは感光体に必要な高抵抗を得るために酸化亜鉛中
に小量添加される。
When manufacturing the photoreceptor layer, it is preferable to include ions of other elements in addition to zinc oxide, such as lithium ions, copper ions, potassium ions, or a mixture thereof. Ions of these elements are added in small amounts to zinc oxide to obtain the high resistance required for the photoreceptor.

これらのイオン供給源として添加される化金物としては
CuCQ等が挙げられる。添加最は酸化亜鉛に対して0
.OI〜数wt、%である。
Examples of the metal compound added as a source of these ions include CuCQ. Addition is 0 for zinc oxide
.. OI ~ several wt, %.

(発明の作用・効果) 本発明の作用効果を図面に基づいて説明する。(Action/effect of invention) The effects of the present invention will be explained based on the drawings.

第1図は本発明による電子写真感光体の構造を示す図で
ある。
FIG. 1 is a diagram showing the structure of an electrophotographic photoreceptor according to the present invention.

上層(1)のZnOはLi又はCuを少量添加すること
により高い抵抗を有する。しかし、エネルギーバンド幅
は約3.4eVであり、ZnO自体秀れた光伝導体であ
るが、紫外光に近辺の短波長光にのみ感度を宵する。可
視光の露光光線はZnO層を通過して下のa−9i:8
層(2)に照射するが、a−5i:8層は可視光に対し
て量子効率がほとんど1と高い効率で光キャリアーを発
生する。感光体表面は正に帯電せしめ、a −S i層
で発生した光キャリアーの電子はZnO層を通り表面に
到り、表面帯電電位と中和する。一方、a−Si中で発
生した光キャリアーの正孔は基体金属(3)へ流出する
。この場合、ZnO層(1)中の電子の移動度は結晶化
して居る場合的3000m2/v−3ecと太きくa−
Si:H中のそれが高々1 cm”/ V−sec、の
程度であることと比較して大いに有利である。
The ZnO of the upper layer (1) has high resistance by adding a small amount of Li or Cu. However, the energy band width is about 3.4 eV, and although ZnO itself is an excellent photoconductor, it is sensitive only to short wavelength light near ultraviolet light. The visible light exposure beam passes through the ZnO layer and forms the a-9i:8 layer below.
Layer (2) is irradiated, and the a-5i:8 layer generates photocarriers with high efficiency, with a quantum efficiency of almost 1 for visible light. The surface of the photoreceptor is positively charged, and electrons of photocarriers generated in the a-Si layer reach the surface through the ZnO layer and are neutralized with the surface charging potential. On the other hand, holes of photocarriers generated in a-Si flow to the base metal (3). In this case, the mobility of electrons in the ZnO layer (1) is as large as 3000 m2/v-3ec when it is crystallized.
This is a great advantage compared to that in Si:H, which is of the order of at most 1 cm"/V-sec.

C軸に配向するZnOは約lOμ程度の大きさの六角柱
の形状を有し、それらがダレインバラングリ−(粒界)
で囲まれてぎっしり蜂の巣状に並んでいることはよく知
られていることであるが、フォトキャリアーはこの柱状
の結晶の中を柱の方向に走行し、グレンバウンダリー(
粒界)に防げられて層方向に広がり画像の滲を作ること
はないので良好な画質を得ることが出来る。
ZnO oriented along the C-axis has a hexagonal prism shape with a size of about 10μ, and these form grain boundaries.
It is well known that the photocarriers are surrounded by crystals and arranged in a tightly honeycomb pattern, and the photocarriers travel in the direction of the pillars within these columnar crystals, forming a grain boundary (
Since it is prevented from spreading in the layer direction and causing blurring of the image due to grain boundaries), good image quality can be obtained.

(実施例) 実施例1 本発明を実証すべ(0,2mm厚さのアルミニウムフォ
イル上に約3μmのボロンを微量添加してP−型半導体
としたa−9i:H(B)をP−CVD法により成膜し
たものの上に、マグネトロンスパッタリング装置により
Z no (L i)を15μm成模し九0この場合a
−8iの成膜条件は、SiH,ガスを30sec+nと
水素に0,3%希釈したB t Hsを23ccm流し
、約80Wの13.56MHzの高周波電力を印加して
15cm径の電極間のプラズマ放電を行せしめA児基板
を約235℃に保持して成膜した。このa−9i:H(
B)の上にマグネトロンスパッタリングによりZ nO
(L i)をターゲットとしてアルゴンと酸素を各50
%づつ混合せるガスを約0 、 I Torr導入した
反応槽内で約150℃に基体温度を保持してZnO層を
約15μm形成した。このマグネトロンスパッタ装置の
ターゲット径は10cmであり、13.56MHzの高
周波を印加した。
(Example) Example 1 To demonstrate the present invention (a-9i:H(B) was made into a P-type semiconductor by adding a small amount of boron of about 3 μm onto an aluminum foil with a thickness of 0.2 mm by P-CVD. On the film formed by the method, a 15 μm thick layer of Z no (L i) was formed using a magnetron sputtering device.90 In this case, a
-8i film formation conditions were SiH gas for 30 sec + n, B t Hs diluted 0.3% with hydrogen flowing at 23 ccm, approximately 80 W of 13.56 MHz high frequency power applied, and plasma discharge between 15 cm diameter electrodes. The A substrate was held at about 235° C. to form a film. This a-9i:H(
B) ZnO by magnetron sputtering on top
Argon and oxygen were added at 50% each using (L i) as a target.
A ZnO layer having a thickness of about 15 .mu.m was formed by maintaining the substrate temperature at about 150.degree. C. in a reaction tank into which a gas to be mixed at a rate of about 0.1 Torr was introduced. The target diameter of this magnetron sputtering device was 10 cm, and a high frequency of 13.56 MHz was applied.

このようにして作られた感光体の特性は、6000V正
のコロナ放電で約400vの帯電電位を示しその暗減衰
時間は約6秒あり、光感度は容色光の蛍光燈光源に対し
て約1 、5 Jlux sccと認められたが、今後
の改良の余地は大きいと考える。
The characteristics of the photoreceptor made in this way are that it has a charging potential of about 400V with a positive corona discharge of 6000V, its dark decay time is about 6 seconds, and its photosensitivity is about 1. , 5 Jlux scc, but I think there is a lot of room for future improvement.

尚残留電位は約80Vであった。これらの値は従来の感
光体よりも高い感度でかつ安価に無公害の光感度や波長
特性などのa−9t系感光体の長所を有する感光体も安
価に得ることか可能となり、かつ画像のボケの少ない秀
れた感光体を作ることが可能となった。
Note that the residual potential was about 80V. These values make it possible to obtain a photoconductor that has the advantages of the A-9T photoconductor, such as light sensitivity and wavelength characteristics, with higher sensitivity than conventional photoconductors, is non-polluting, and has the advantages of a-9T photoconductors at low cost. It has become possible to create an excellent photoreceptor with less blur.

【図面の簡単な説明】[Brief explanation of drawings]

第1図は本発明による電子写真感光体の構造を示す図で
ある。図中、(1)は金属基体、(2)はa−Si層お
よび(3)は酸化亜鉛層を示す。
FIG. 1 is a diagram showing the structure of an electrophotographic photoreceptor according to the present invention. In the figure, (1) shows a metal substrate, (2) shows an a-Si layer, and (3) shows a zinc oxide layer.

Claims (1)

【特許請求の範囲】 1、導電性基体上に感光体層を有する電子写真感光体に
おいて、該感光体層が基体に対してC軸が垂直に配向す
るヴルツ型のII−IV族化合物半導体層とアモルファスシ
リコン層からなる電子写真感光体。 2、II−IV族化合物半導体層が酸化亜鉛からなる第1項
記載の電子写真感光体。 3、II−IV族化合物半導体層が酸化亜鉛の他に、銅また
はリチウムイオンを含む第1項記載の電子写真感光体。 4、アモルファスシリコンが水素化され、かつ微量のホ
ウ素を含む第1項記載の電子写真感光体。 5、導電性基体上にアモルファスシリコン層を形成し、
次いでII−IV族化合物半導体層を形成する第1項記載の
電子写真感光体。
[Claims] 1. In an electrophotographic photoreceptor having a photoreceptor layer on a conductive substrate, the photoreceptor layer is a Wurz-type II-IV group compound semiconductor layer in which the C axis is oriented perpendicularly to the substrate. An electrophotographic photoreceptor consisting of an amorphous silicon layer. 2. The electrophotographic photoreceptor according to item 1, wherein the II-IV group compound semiconductor layer is made of zinc oxide. 3. The electrophotographic photoreceptor according to item 1, wherein the II-IV group compound semiconductor layer contains copper or lithium ions in addition to zinc oxide. 4. The electrophotographic photoreceptor according to item 1, wherein the amorphous silicon is hydrogenated and contains a trace amount of boron. 5. Forming an amorphous silicon layer on the conductive substrate,
2. The electrophotographic photoreceptor according to item 1, wherein a group II-IV compound semiconductor layer is then formed.
JP1291886A 1986-01-22 1986-01-22 Electrophotographic sensitive body Pending JPS62170966A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1291886A JPS62170966A (en) 1986-01-22 1986-01-22 Electrophotographic sensitive body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1291886A JPS62170966A (en) 1986-01-22 1986-01-22 Electrophotographic sensitive body

Publications (1)

Publication Number Publication Date
JPS62170966A true JPS62170966A (en) 1987-07-28

Family

ID=11818718

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1291886A Pending JPS62170966A (en) 1986-01-22 1986-01-22 Electrophotographic sensitive body

Country Status (1)

Country Link
JP (1) JPS62170966A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0296178A (en) * 1988-08-17 1990-04-06 Fuji Xerox Co Ltd Electrophotographic sensitive body

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0296178A (en) * 1988-08-17 1990-04-06 Fuji Xerox Co Ltd Electrophotographic sensitive body

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