JPH0426466B2 - - Google Patents
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- Publication number
- JPH0426466B2 JPH0426466B2 JP59040938A JP4093884A JPH0426466B2 JP H0426466 B2 JPH0426466 B2 JP H0426466B2 JP 59040938 A JP59040938 A JP 59040938A JP 4093884 A JP4093884 A JP 4093884A JP H0426466 B2 JPH0426466 B2 JP H0426466B2
- Authority
- JP
- Japan
- Prior art keywords
- photoconductive
- layer
- surface protective
- protective layer
- concentration
- 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.)
- Expired - Lifetime
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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 or 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Description
＜技術分野＞
本発明は光に対して感受性を有する光導電材に
関するものである。
＜従来技術＞
従来、電子写真用像形成部材や原稿読取装置等
における光導電層を構成する光導電材料として
は、セレンSe，硫化カドミウムCdS，酸化亜鉛
ZnO等の無機光導電材料若しくはPVK（ポリビニ
ルカルバゾール），TNF（トリニトロフルオレノ
ン）等の有機光導材料が使用されていた。
しかるに、上記材料は光導電材料として要求さ
れる光感度，分光感度，SN比（明抵抗／暗抵抗）
或いは耐久性、人体への安全性（危険度）におい
て必ずしも満足がいくものではなく、ある程度、
条件を緩和して、個々の状況に対応して用いられ
ている。
一方、ａ−Si（アモルフアスシリコン）光導電
材料は、高光感度、高耐久性及び無公害等の長所
を期待できるため、近年、活発な研究がなされて
いる。しかし、現状では暗抵抗が低く、充分な
SN比が得られないこと、又、耐湿性に代表され
る耐環境特性並びに経時的安定性等においてまだ
まだ大きく改良されなければならない。
＜発明の目的＞
本発明は上記の事項に鑑み成されたもので、そ
の目的は特に経時安定性、耐環境性の優れた光導
電材を提供することである。
さらに、本発明の他の目的は表面が硬く、基板
との密着性に優れた光導電材を提供することであ
る。
さらに、本発明の他の目的は耐刷性に優れ、長
波長光にも充分実用に耐え得る感度を具備する光
導電材を提供することである。
＜実施例＞
本発明の構成を述べる。
本発明の光導電材は導電性支持部材、光導電層
及び表面保護層が順次積層された３層構造を有し
ている。
上記の表面保護層は、耐環境特性、経時安定性
の特性改良の要請上、シリコンカーバイド〔ａ−
SixC(1-x)〕、シリコンナイトライド〔ａ−Six
N(1-x)〕又はシリコンオキサイド〔ａ−SixO(1-x)〕
（０＜ｘ＜１）等の安定膜であるが、光導電層の
上（表面）に設けるため、
(イ) 光感度を損ねないこと。
即ち、光導電層に光感度の優れた可視光吸収係
数の大きな材料が使用される関係上、その表面保
護層としては可視光を透過し可視光吸収係数の小
さな物性を有していなければならない。
及び
(ロ) 帯電能力を損ねないこと。
つまり、表面保護層は電気抵抗が大きくなけれ
ばならない。
に留意しなければならない。
上記の比率（組成比の割合）ｘは、その値が大
きいと吸収係数が大きく、可視光に対して透明で
なくなり、又、安定性も良くない。逆に、上記の
比率ｘが小さいと可視光に透明となり、環境特
性、経時安定性等の諸特性が良好になることが判
明した。
さて、前記条件(イ)，(ロ)及び耐環境性、経時安定
性が同時に満足されれば、光感度が高く、電荷保
持能力が大きく、耐刷枚数に優れ、耐環境特性及
び経時安定性に優れた光導電材が得られる。
そこで、光感度を高くするため、吸収係数が大
きく光学的バンドギヤツプ（Band Gap；量子状
態のエネルギー準位のギヤツプ）の小さい光導電
層の上に、前記比率ｘが小さく可視光に透明な光
学的バンドギヤツプの大きい表面保護層を設ける
と、両者（光導電層と表面保護層）におけるバン
ド（エネルギー帯）の整合が良好でないため、光
照射により発生する光キヤリアが自由表面
（Free Surface）へ到達できず、残留電位が大き
く、又、画像の流れが発生したり、解像度が悪く
なる。
他方、上記のバンドの整合をとるため、光導電
層に光学的バンドギヤツプの大きな材料を採用す
ると、光感度の悪いものしか得られず、又、表面
保護層に光学的バンドギヤツプの小さな層を採用
すると電荷保持能力に劣り、それゆえ耐環境特
性、経時安定性にも劣つてしまう。
かような観点を考慮し、研究の末、光導電層へ
の不純物ドーピング（Doping）により表面保護
層との界面付近での伝導型を制御し、フエルミ準
位（Fermi level）を適度に選択することで光導
電層に光学的バンドギヤツプが小さく、表面保護
層に光学的バンドギヤツプの大きなものを採用し
ても残留電位が小さく、解像度も高く、且つ、耐
環境特性並びに経時安定性共に優れた光導電材を
得ることができた。
上述の事項を第１図を用いて詳述する。
同図において、７１は基板、７２は光導電層、
７３は表面保護層である。
さて、前述のバンドの不整合というのは、同図
ａの如く、前記光導電層７２と前記表面保護層７
３のバンドギヤツプの差ａが大きい場合に該光導
電層７２と該表面保護層７３の界面近傍で発生す
る光キヤリアが自由に移動できず、前記界面付近
に空間電荷を形成し、それが原因の残留電位若し
くは静電潜像における解像度の低下現象のことで
ある。
そこで、本発明の光導電材においてはバンドの
整合をとるため、同図ｂ，ｃの通り、前記光導電
層７２における第族ｂの不純物元素の膜中濃度
を界面近傍で増加させ、伝導型を適正に制御しつ
つ、伝導帯の界面付近での整合を図つた。
この同図ｂ，ｃの様にすれば、界面付近で発生
したキヤリアは伝導帯、価電子帯の傾斜のためス
ムーズに自由表面に到達することが可能で、残留
電位もなく、静電潜像における高い解像度を成
し、画像の流れもなくなつた。しかも、前記表面
保護層７３には光学的バンドギヤツプの大きい安
定なものが使えるので、この光導電材は電荷保持
能力、耐環境特性、経時安定性に優れたものとな
る。
具体的な本発明の実施例に係る光導電材の構造
を第２図又は第３図に掲げた。
第２図において、１０１が光導電材であり、３
層構造即ち上から表面保護層１０３、光導電層１
０２及び導電性支持材１０４の積層構造を有して
いる。なお、１０６が自由表面である。
第３図の例は、上記３層の他に少なくとも酸
素、窒素又は炭素を含むａ−Siより成る１層を加
えたもので、２０１が光導電材であり、４層構造
即ち上から表面保護層２０３、光導電層２０２、
前記新たに追加された下地層２０５及び導電性支
持材２０４の積層構造を有している。なお、２０
６が自由表面である。この下地層２０５の存在に
より、前記支持体２０４と前記光導電層２０２の
密着が良くなり成膜の剥離を防止でき、又、該支
持体２０４側よりの電荷の注入も防げる。
ここで、本発明の実施例に係る光導電材の製造
方法につき解説する。
第４図に示す装置を用い以下の様にしてａ−Si
層（非晶質シリコン層）を形成した。
クロロセン超音波洗浄槽及び蒸気洗浄槽（図示
せず）にて充分に表面を洗浄した直径140mm、長
さ340mmのアルミニウム支持体２を用意し、該ア
ルミニウム支持体２をドラムヒーター３に固定し
た。該ドラムヒーター３は前記アルミニウム支持
体２の内径に密着する外径を有し、表面を均一加
熱する。
同図にて、９はメカニカルブースタポンプ、１
０はロータリポンプであり、５は小窓、７は駆動
用モーター、１１はリークバルブである。
次に、バルブ８を開き、反応室１内の空気を排
除し、同時に前記ドラムヒーター３をONにし
た。こうして、前記アルミニウム支持体２の表面
が250℃になるまで温度を上昇させ、その後恒温
状態を保持した。
続いて、補助バルブ１２を全開にし、そして、
SiH4ガスの充填されたボンベ２３、H2ガスの充
填されたボンベ２４及びH2ガス中に濃度400ppm
で混合されたB2H6（ジボラン）ガスの充填された
ボンベ２５を、夫々の付属バルブ１８，１９，２
０を開放することにより各ガスを流出させる。そ
の際、前記ボンベ２３，２４，２５に接続された
質量流量調節器１３，１４，１５の設定値を徐々
に上げて各ボンベ２３，２４，２５からガスが所
定量ほど流れる様に調整した。
この時、前記バルブ８の開度を調節することに
より前記反応室１内の圧力を1.5Torrに保つた。
続いて、高周波電源６のスイツチをONにし、
相対向する１対の放電電極４，４′間に周波数
13.56MHzの高周波電圧を印加してグロー放電を
起こし、加熱された前記アルミニウム支持体２上
にａ−Si膜を形成した。なお、成膜時の高周波電
力は常時400Wに制御した。
ところで、上記のａ−Si膜形成の際、B2H6の
濃度はSiH4との濃度比が10-4となる様にH2ベー
スのB2H6ガス流量は前記質量流量調節器１５に
て調整した。このB2H6は膜の伝導型を制御する
ために添加されるが、添加量が多い場合はｐ型、
p+型となり、添加量が少ない場合はｎ型，ｉ型
となる。一方、暗抵抗比及び光感度に関しては、
微量のNH3（アンモニア）ガスを添加することに
より所定の値にできる。これは当業者が、適宜、
所望の膜特性に応じて決定できる事項である。
この状態で約7.5時間成膜を続行し、次いで、
伝導型をよりp+型とするため、B2H6の導入量を
徐々に増加させた。即ち、Ｂ（ホウ素）濃度が均
一分布でなく傾斜を持つ様に前記質量流量調整器
１５，１６の調整つまみを約30分間にわたつて連
続的に流量増加の方向へ回し続けた。その後直ち
に前記高周波電源６のスイツチをOFFにした。
このOFFする直前でのB2H6濃度はSiH4との濃度
比で５×10-3となつていた。
以上の処理を行うと、Ｂ濃度が表面付近で最大
値となり、分布に傾斜のある光導電層が形成され
た。
今度は、表面保護層を形成すべく各ガスの混合
比を変化させる。即ち、NH3（アンモニア）ガス
を添加するためNH3ガスの充填されたボンベ２
７を付属のバルブ２２を開とし、質量流量調節器
１７にて所定量のNH3ガスを前記反応室１へ導
入した。同時に、B2H6の添加量を最適にするた
め、H2ガス中に濃度１％で混合されたB2H6ガス
の充填されたボンベ２６のバルブ２１を開とし、
該ボンベ２６からのB2H6ガスの流量を調節する
質量流量調節器１６及び前記質量流量調節器１５
にて所定量のB2H6ガスを前記反応室１へ導入し
た。
なお、上述の表面保護層の形成の際に導入され
るNH3ガスの量は、絶縁性の高い膜を所望する
場合には、体積比で、
NH3／SiH4＝0.5〜2.0
と設定し、逆に、光導電性の高い膜を所望する場
合には、体積比で、
NH3／SiH4＝0.01〜0.5
と設定すれば良い。
上記の様にして約５分間表面保護層を形成し、
前記高周波電源６のスイツチをOFFとし、各ガ
スのバルブ１３，１４，１６，３０を閉にして、
再び前記反応室１内を真空にして、前記ドラムヒ
ーター３のスイツチをOFFとして徐冷した後、
ａ−Si膜が形成されたところのアルミニウム支持
体２を取り出す。
以上の工程を経て作製された本実施例の光導電
層においてＢ濃度に傾斜のある光導電部材を、従
来の光導電層においてＢ濃度に傾斜のない光導電
部材と、電子写真プロセスにおける電子写真特性
画像特性、耐環境特性及び経時安定性につき調べ
た。その結果、下表の通りとなつた。
<Technical Field> The present invention relates to photoconductive materials sensitive to light. <Prior art> Conventionally, photoconductive materials constituting photoconductive layers in electrophotographic image forming members, document reading devices, etc. include selenium Se, cadmium sulfide CdS, and zinc oxide.
Inorganic photoconductive materials such as ZnO or organic photoconductive materials such as PVK (polyvinylcarbazole) and TNF (trinitrofluorenone) have been used. However, the above materials have the optical sensitivity, spectral sensitivity, and signal-to-noise ratio (bright resistance/dark resistance) required for photoconductive materials.
Or, it is not necessarily satisfactory in terms of durability and safety (danger level) to the human body, and to some extent,
Conditions are relaxed and used in response to individual situations. On the other hand, a-Si (amorphous silicon) photoconductive materials have been actively researched in recent years because they are expected to have advantages such as high photosensitivity, high durability, and no pollution. However, at present, the dark resistance is low and sufficient
The SN ratio cannot be obtained, and the environmental resistance properties represented by moisture resistance and stability over time still need to be greatly improved. <Objective of the Invention> The present invention was made in view of the above-mentioned matters, and its object is to provide a photoconductive material particularly excellent in stability over time and environmental resistance. Furthermore, another object of the present invention is to provide a photoconductive material that has a hard surface and excellent adhesion to a substrate. Furthermore, another object of the present invention is to provide a photoconductive material that has excellent printing durability and has sufficient sensitivity to long wavelength light for practical use. <Example> The configuration of the present invention will be described. The photoconductive material of the present invention has a three-layer structure in which a conductive support member, a photoconductive layer, and a surface protection layer are sequentially laminated. The above surface protective layer is made of silicon carbide [a-
Si x C (1-x) ], silicon nitride [a-Si x
N (1-x) ] or silicon oxide [a-Si x O (1-x) ]
Although it is a stable film such as (0<x<1), since it is provided on the top (surface) of the photoconductive layer, (a) it must not impair photosensitivity. That is, since a material with excellent photosensitivity and a large visible light absorption coefficient is used for the photoconductive layer, the surface protective layer must have physical properties that transmit visible light and have a small visible light absorption coefficient. . and (b) not to impair charging ability. In other words, the surface protective layer must have high electrical resistance. must be kept in mind. When the value of the above ratio (compositional ratio) x is large, the absorption coefficient is large, the film is not transparent to visible light, and the stability is also poor. On the contrary, it has been found that when the above ratio x is small, the film becomes transparent to visible light and has good environmental properties, stability over time, and other properties. Now, if the above conditions (a) and (b), environmental resistance, and stability over time are satisfied at the same time, the photosensitivity is high, the charge retention capacity is large, the number of printing sheets is excellent, and the environment resistance and stability over time are satisfied. A photoconductive material with excellent properties can be obtained. Therefore, in order to increase photosensitivity, an optical layer with a small ratio When a surface protective layer with a large band gap is provided, the bands (energy bands) of the two (photoconductive layer and surface protective layer) do not match well, so light carriers generated by light irradiation cannot reach the free surface. First, the residual potential is large, image blur occurs, and resolution deteriorates. On the other hand, if a material with a large optical bandgap is used for the photoconductive layer in order to match the above bands, only poor photosensitivity will be obtained, and if a layer with a small optical bandgap is used as the surface protective layer. It has poor charge retention ability, and therefore poor environmental resistance and stability over time. Taking these points into consideration, after research, we controlled the conduction type near the interface with the surface protective layer by doping impurities into the photoconductive layer, and selected an appropriate Fermi level. As a result, even if the photoconductive layer has a small optical bandgap and the surface protective layer has a large optical bandgap, the residual potential is small, the resolution is high, and the photoconductive material has excellent environmental resistance and stability over time. I was able to get The above matters will be explained in detail using FIG. In the figure, 71 is a substrate, 72 is a photoconductive layer,
73 is a surface protective layer. Now, as shown in FIG.
When the bandgap difference a in No. 3 is large, optical carriers generated near the interface between the photoconductive layer 72 and the surface protective layer 73 cannot move freely, and space charges are formed near the interface. This refers to the phenomenon of reduced resolution in residual potential or electrostatic latent images. Therefore, in the photoconductive material of the present invention, in order to achieve band matching, the concentration of the group b impurity element in the photoconductive layer 72 is increased near the interface, as shown in FIGS. Through appropriate control, we achieved matching near the conduction band interface. By doing as shown in b and c in the same figure, the carriers generated near the interface can smoothly reach the free surface due to the slope of the conduction band and valence band, and there is no residual potential, resulting in an electrostatic latent image. This resulted in high resolution and no image flow. Moreover, since a stable material with a large optical bandgap can be used for the surface protective layer 73, this photoconductive material has excellent charge retention ability, environmental resistance characteristics, and stability over time. The structure of a photoconductive material according to a specific example of the present invention is shown in FIG. 2 or 3. In FIG. 2, 101 is a photoconductive material, and 3
Layer structure: from top to bottom: surface protective layer 103, photoconductive layer 1
02 and a conductive support material 104. Note that 106 is a free surface. In the example shown in FIG. 3, one layer made of a-Si containing at least oxygen, nitrogen, or carbon is added in addition to the above three layers, 201 is a photoconductive material, and the four-layer structure includes a surface protective layer from above. 203, photoconductive layer 202,
It has a laminated structure of the newly added base layer 205 and the conductive support material 204. In addition, 20
6 is the free surface. The presence of the base layer 205 improves the adhesion between the support 204 and the photoconductive layer 202, preventing peeling of the formed film, and also prevents charge injection from the support 204 side. Here, a method for manufacturing a photoconductive material according to an embodiment of the present invention will be explained. Using the apparatus shown in Figure 4, a-Si was prepared as follows.
layer (amorphous silicon layer) was formed. An aluminum support 2 having a diameter of 140 mm and a length of 340 mm whose surface had been thoroughly cleaned in a chlorocene ultrasonic cleaning tank and a steam cleaning tank (not shown) was prepared, and the aluminum support 2 was fixed to a drum heater 3. The drum heater 3 has an outer diameter that closely contacts the inner diameter of the aluminum support 2, and uniformly heats the surface. In the same figure, 9 is a mechanical booster pump, 1
0 is a rotary pump, 5 is a small window, 7 is a drive motor, and 11 is a leak valve. Next, the valve 8 was opened to remove the air in the reaction chamber 1, and at the same time the drum heater 3 was turned on. In this way, the temperature of the surface of the aluminum support 2 was raised to 250° C., and then a constant temperature state was maintained. Next, the auxiliary valve 12 is fully opened, and
A cylinder 23 filled with SiH 4 gas, a cylinder 24 filled with H 2 gas, and a concentration of 400 ppm in the H 2 gas.
The cylinder 25 filled with B 2 H 6 (diborane) gas mixed with
By opening 0, each gas flows out. At that time, the set values of the mass flow rate regulators 13, 14, 15 connected to the cylinders 23, 24, 25 were gradually increased so that a predetermined amount of gas would flow from each cylinder 23, 24, 25. At this time, the pressure inside the reaction chamber 1 was maintained at 1.5 Torr by adjusting the opening degree of the valve 8. Next, turn on the switch of high frequency power supply 6,
Frequency between a pair of discharge electrodes 4 and 4' facing each other
A high frequency voltage of 13.56 MHz was applied to cause glow discharge, and an a-Si film was formed on the heated aluminum support 2. Note that the high frequency power during film formation was always controlled to 400W. By the way, during the above a-Si film formation, the H 2 -based B 2 H 6 gas flow rate is controlled by the mass flow controller 15 so that the concentration ratio of B 2 H 6 to SiH 4 is 10 -4 . Adjusted. This B 2 H 6 is added to control the conductivity type of the membrane, but if it is added in a large amount, it will cause p-type,
It becomes p + type, and when the amount added is small, it becomes n type and i type. On the other hand, regarding dark resistance ratio and photosensitivity,
A predetermined value can be achieved by adding a small amount of NH 3 (ammonia) gas. This is determined by a person skilled in the art, as appropriate.
This is a matter that can be determined depending on the desired film characteristics. Film formation continued in this state for about 7.5 hours, and then
In order to make the conductivity type more p + type, the amount of B 2 H 6 introduced was gradually increased. That is, the adjustment knobs of the mass flow rate regulators 15 and 16 were continuously turned in the direction of increasing the flow rate for about 30 minutes so that the B (boron) concentration was not uniformly distributed but had a slope. Immediately thereafter, the high frequency power source 6 was turned off.
The concentration of B 2 H 6 immediately before turning off was 5×10 −3 in terms of concentration ratio with SiH 4 . When the above treatment was carried out, the B concentration reached its maximum value near the surface, and a photoconductive layer with a sloped distribution was formed. Next, the mixing ratio of each gas is changed to form a surface protective layer. That is, cylinder 2 filled with NH 3 gas to add NH 3 (ammonia) gas.
7 was opened to open the attached valve 22, and a predetermined amount of NH 3 gas was introduced into the reaction chamber 1 using the mass flow controller 17. At the same time, in order to optimize the amount of B 2 H 6 added, the valve 21 of the cylinder 26 filled with B 2 H 6 gas mixed with H 2 gas at a concentration of 1% is opened.
A mass flow controller 16 and the mass flow controller 15 that adjust the flow rate of B 2 H 6 gas from the cylinder 26.
A predetermined amount of B 2 H 6 gas was introduced into the reaction chamber 1. Note that the amount of NH 3 gas introduced during the formation of the above-mentioned surface protective layer is set at a volume ratio of NH 3 /SiH 4 =0.5 to 2.0 when a highly insulating film is desired. Conversely, if a film with high photoconductivity is desired, the volume ratio of NH 3 /SiH 4 may be set to 0.01 to 0.5. Form a surface protective layer for about 5 minutes as above,
Turn off the switch of the high frequency power supply 6, close the valves 13, 14, 16, 30 of each gas,
After evacuating the reaction chamber 1 again and turning off the drum heater 3 for slow cooling,
The aluminum support 2 on which the a-Si film is formed is taken out. The photoconductive member in the photoconductive layer of this example produced through the above steps has a gradient in B concentration, the photoconductive member in the conventional photoconductive layer without a gradient in B concentration, and the photoconductive member in the electrophotographic process. Characteristics Image characteristics, environmental resistance characteristics, and stability over time were investigated. The results were as shown in the table below.
【表】
なお、上記の電子写真プロセスとは、第５図の
通り、光導電部材が表面にコーテイングされたド
ラム５０８上に１次帯電器（6.0KV）５０１にて
電圧を印加し、前記ドラム５０８上にレンズ５０
２を通過した像を露光して、該露光像を現像器５
０３にて現像し、その像を転写紙５０４に転写用
帯電器５０５により転写する工程及び転写後該ド
ラム５０８をクリーニング装置５０６で清掃する
こと並びに除電光源５０７にて除電を行う工程の
ことである。
ここで、光導電層及び表面保護層における望ま
しいＢ（ホウ素）濃度及びＮ（窒素）濃度の膜厚方
向の分布を第６図を用いて説明する。
同図ａ，ｂ，ｃ，ｄ，ｅ，ｆにおいて横軸は膜
厚距離（膜厚方向に沿つた移動長さ）であり、Ｘ
端が基板、Ｙ端が自由表面である。又、縦軸の単
位は任意である。
同図において、各グラフの実線ＰはＢ濃度を、
破線ＱはＮ濃度を表わしており、いずれのグラフ
にても、Ｎ濃度が表面保護層において高く、Ｂ濃
度に関しては表面保護層と光導電層の界面近傍で
最大値となり且つ基板側へ向かつて低下する傾斜
（表面保護層に向かつて上昇する傾斜）を持つ折
線（曲線）となつている。
もちろん、このＢ濃度の傾斜は特定の傾きを持
つ直線状であつても若しくは一定の曲率を持つ曲
線状であつても構わない。又、Ｎ濃度についても
下地層、表面保護層及び光導電層の界面付近で傾
斜を有していても良い。
なお、上記下地層についてはその作製方法を述
べなかつたが、基本的に表面保護層を形成する処
理と同様な方法でできる。この下地層は支持体と
光導電層の間に介在させても良い。
＜効 果＞
以上の様に本発明によれば、光導電層に第族
ｂの元素、特にホウ素(B)を不純物として含有させ
る際、光導電層の膜厚方向に窒素を含む表面保護
層側の界面に近付くにしたがい徐々にホウ素濃度
が高くなるように、その分布に傾斜が生じるべく
光導電層を形成したことで、光導電層と表面保護
層との整合性が良くなり、経時安定性、耐環境特
性、電荷保持能力、残留電位及び画像の流れ特性
に優れた光導電材が得られる。[Table] As shown in FIG. 5, the above electrophotographic process involves applying a voltage with a primary charger (6.0KV) 501 to a drum 508 whose surface is coated with a photoconductive member, and Lens 50 on 508
2 is exposed to light, and the exposed image is transferred to a developing device 5.
03, and the image is transferred to a transfer paper 504 by a transfer charger 505; after the transfer, the drum 508 is cleaned by a cleaning device 506; and the charge is removed by a charge removal light source 507. . Here, the desired distribution of B (boron) concentration and N (nitrogen) concentration in the film thickness direction in the photoconductive layer and the surface protection layer will be explained using FIG. In a, b, c, d, e, and f of the same figure, the horizontal axis is the film thickness distance (movement length along the film thickness direction), and
The end is the substrate and the Y end is the free surface. Further, the unit of the vertical axis is arbitrary. In the same figure, the solid line P in each graph represents the B concentration,
The broken line Q represents the N concentration, and in both graphs, the N concentration is high in the surface protective layer, and the B concentration reaches its maximum value near the interface between the surface protective layer and the photoconductive layer, and increases toward the substrate side. It is a broken line (curved line) with a decreasing slope (increasing slope toward the surface protective layer). Of course, the gradient of the B concentration may be linear with a specific slope or curved with a constant curvature. Further, the N concentration may also have a gradient near the interface between the underlayer, the surface protective layer, and the photoconductive layer. Although the method for producing the base layer has not been described, it can be basically produced by the same method as that for forming the surface protective layer. This underlayer may be interposed between the support and the photoconductive layer. <Effects> As described above, according to the present invention, when the photoconductive layer contains a Group B element, particularly boron (B), as an impurity, a surface protective layer containing nitrogen is added in the thickness direction of the photoconductive layer. By forming the photoconductive layer so that the boron concentration gradually increases as it approaches the side interface, the distribution of the photoconductive layer has a slope, which improves the consistency between the photoconductive layer and the surface protective layer, resulting in stability over time. A photoconductive material having excellent properties such as durability, environmental resistance, charge retention ability, residual potential, and image flow properties can be obtained.
第１図ａ，ｂ，ｃは光導電材を形成する光導電
層と表面保護層のエネルギー帯を示す図、第２図
及び第３図は本発明の適用される積層構造の光導
電材の側断面図、第４図は本発明の実施例に係る
光導電材の製造器具のブロツク図、第５図は本発
明の実施例に係る光導電材の使用される電子写真
装置のプロセス説明に供する図、第６図ａ，ｂ，
ｃ，ｄ，ｅ，ｆは本発明の光導電材の特定の元素
の濃度分布のグラフ図である。
１……反応室、２……アルミニウム支持体、３
……ドラムヒーター、４，４′……放電電極、５
……小窓、６……高周波電源、７……駆動用モー
ター、８……バルブ、９……メカニカルブースタ
ポンプ、１０……ロータリポンプ、１１……リー
クバルブ、１２……補助バルブ、１３，１４，１
５，１６，１７……質量流量調整器、１８，１
９，２０，２１，２２……付属バルブ、２３，２
４，２５，２６，２７，２８……ボンベ、２９…
…付属バルブ、３０……質量流量調整器、３１…
…補助バルブ、７１……基板、７２……光導電
層、７３……表面保護層、１０１……光導電材、
１０２……光導電層、１０３……表面保護層、１
０４……導電性支持材、１０６……自由表面、２
０１……光導電材、２０２……光導電層、２０３
……表面保護層、２０４……導電性支持材、２０
５……下地層、５０１……帯電器、５０２……レ
ンズ、５０３……現像器、５０４……転写紙、５
０５……転写用帯電器、５０６……クリーニング
装置、５０７……除電光源。
Figures 1a, b, and c are diagrams showing the energy bands of the photoconductive layer and surface protective layer forming the photoconductive material, and Figures 2 and 3 are side cross-sections of the photoconductive material with a laminated structure to which the present invention is applied. 4 is a block diagram of a photoconductive material manufacturing apparatus according to an embodiment of the present invention, and FIG. Figure 6 a, b,
c, d, e, f are graphs of concentration distributions of specific elements in the photoconductive material of the present invention. 1...Reaction chamber, 2...Aluminum support, 3
...Drum heater, 4,4'...Discharge electrode, 5
...small window, 6 ... high frequency power supply, 7 ... drive motor, 8 ... valve, 9 ... mechanical booster pump, 10 ... rotary pump, 11 ... leak valve, 12 ... auxiliary valve, 13, 14,1
5, 16, 17... Mass flow regulator, 18, 1
9, 20, 21, 22... Attached valve, 23, 2
4, 25, 26, 27, 28...Cylinder, 29...
...Attached valve, 30...Mass flow regulator, 31...
... Auxiliary bulb, 71 ... Substrate, 72 ... Photoconductive layer, 73 ... Surface protective layer, 101 ... Photoconductive material,
102...Photoconductive layer, 103...Surface protection layer, 1
04... Conductive support material, 106... Free surface, 2
01...Photoconductive material, 202...Photoconductive layer, 203
... Surface protective layer, 204 ... Conductive support material, 20
5... Base layer, 501... Charger, 502... Lens, 503... Developer, 504... Transfer paper, 5
05... Transfer charger, 506... Cleaning device, 507... Static elimination light source.
Claims (1)
れたところの少なくとも水素を含む非晶質シリコ
ンより成る光導電層と、前記光導電層の表面に設
けられた表面保護層を有する光導電材において、 上記光導電層は不純物として少なくとも第族
ｂの元素を含む、該不純物は上記導電性支持部材
の表面に略平行な面内では実質的に均一で該光導
電層の膜厚方向に徐々に前記表面保護層の界面側
に多く存在する濃度分布を示し、 上記表面保護層は、少なくとも窒素を含む非晶
質シリコンより成り、該窒素は少なくとも前記光
導電層の窒素濃度より多いことを特徴とする光導
電材。 ２ 前記支持部材と前記光導電層との間に少なく
とも酸素、窒素若しくは炭素を含む非晶質シリコ
ンより成る層を介在させたことを特徴とする特許
請求の範囲第１項記載の光導電材。 ３ 上記第族ｂの元素はホウ素であることを特
徴とする特許請求の範囲第１項記載の光導電材。 ４ 自由表面が正に帯電し、感光性を有すること
を特徴とする特許請求の範囲第１項記載の光導電
材。 ５ 電子写真法が適用されることを特徴とする特
許請求の範囲第１項記載の光導電材。[Scope of Claims] 1. A conductive support member, a photoconductive layer formed on the support member and made of amorphous silicon containing at least hydrogen, and a surface protection provided on the surface of the photoconductive layer. In the photoconductive material having a layer, the photoconductive layer contains at least a Group B element as an impurity, and the impurity is substantially uniform in a plane substantially parallel to the surface of the conductive support member, and the impurity is substantially uniform in the photoconductive layer. The concentration distribution gradually increases in the film thickness direction toward the interface side of the surface protective layer, and the surface protective layer is made of amorphous silicon containing at least nitrogen, and the nitrogen concentration is at least equal to the nitrogen concentration of the photoconductive layer. A photoconductive material characterized by more. 2. The photoconductive material according to claim 1, wherein a layer made of amorphous silicon containing at least oxygen, nitrogen, or carbon is interposed between the support member and the photoconductive layer. 3. The photoconductive material according to claim 1, wherein the element of group b is boron. 4. The photoconductive material according to claim 1, wherein the free surface is positively charged and has photosensitivity. 5. The photoconductive material according to claim 1, to which an electrophotographic method is applied.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4093884A JPS60184256A (en) | 1984-03-02 | 1984-03-02 | Photoconductive member |
| DE19853506657 DE3506657A1 (en) | 1984-02-28 | 1985-02-26 | PHOTO-CONDUCTIVE DEVICE |
| DE3546544A DE3546544C2 (en) | 1984-02-28 | 1985-02-26 | |
| US06/706,669 US4632894A (en) | 1984-02-28 | 1985-02-28 | Photoconductive device having photoconductive layer containing hydroxyl radicals |
| US06/786,046 US4683186A (en) | 1984-02-28 | 1985-10-10 | Doped amorphous silicon photoconductive device having a protective coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4093884A JPS60184256A (en) | 1984-03-02 | 1984-03-02 | Photoconductive member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60184256A JPS60184256A (en) | 1985-09-19 |
| JPH0426466B2 true JPH0426466B2 (en) | 1992-05-07 |
Family
ID=12594439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4093884A Granted JPS60184256A (en) | 1984-02-28 | 1984-03-02 | Photoconductive member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60184256A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0786693B2 (en) * | 1992-08-31 | 1995-09-20 | スタンレー電気株式会社 | Electrophotographic photoconductor |
| US7378219B2 (en) | 2002-11-26 | 2008-05-27 | Genencor International, Inc. | Optical information carrier comprising immobilized proteorhodopsin |
| JP5694896B2 (en) * | 2011-10-28 | 2015-04-01 | 株式会社ハシモト商会 | Catalytic CVD method and apparatus therefor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59165066A (en) * | 1983-03-11 | 1984-09-18 | Fuji Electric Corp Res & Dev Ltd | Electrophotographic sensitive body |
-
1984
- 1984-03-02 JP JP4093884A patent/JPS60184256A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60184256A (en) | 1985-09-19 |
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|---|---|---|---|
| EXPY | Cancellation because of completion of term |