Photosensitive member for electrophotography.

BACKGROUND OF THE INVENTION

1. Field of the Invention

0001The invention relates to an electrophotographic photosensitive member used in electrophotographic imaging processes, and more particularly to a electrophotographic photoreceptor for xerographic systems.

2. Description of the Prior Art

0002Recently, an amorphous silicon nitride containing H, amorphous silicon carbide containing H or amorphous silicon oxide containing H, each hereinafter called as a-SiN, a-SiC or a-SiO photoconductive film, is ex­pected to utilize for a photoconductive layer of an electrophotographic photoreceptor. Because, the photo­receptor composed of such photosensitive members shows (1) long life, (2) harmless to men and (3) high photo­sensitivity.

0003a-SiN, a-SiC or a-SiO photoconductive film has been prepared by plasma CVD method or sputtering method, where H content in these films has been limited to be in the range of 10 - 40 atomic % (see USP 4,471,042).

0004Each of the a-SiN, a-SiC and a-SiO photoconductive films can do, only by prescribing the specific amount of N, C or O in the film and by doping B, reach dark conductivity of about 10⁻¹³Ω⁻¹cm⁻¹ to be usable for photosensitive member. The a-SiC and a-SiO photocon­ductive films surely have an lower dark conductivity but simultaneously lower photosensitivity, so that practical use has been hindered in this regard. Also, the a-SiN photoconductive film has been revealed through the inventor's experiments that in its repeat operation on next charging process after exprosure or photo-discharge, the surface potential lowers 20% or more of an initial value. In other words, the conventional type photorecep­tor using a-SiN film as a photoconcuctive layer is quite poor in dark decay characteristics to thereby be not suitable for practical use. This is considered that gap states such as dangling bond density of Si and the like increas due to the incorporation of N, so that carriers excited by exposure and photo-discharge will be trapped into the gapstates and then will be released from them by the electric field applied on a next charging process thereby removing the surface charges.

0005In addition, the plasma CVD method or sputtering method has been adopted to prepare the conventional a-SiC, a-SiN and a-SiO photoconductive films, which inevitably caused to yield a polymeric powder of (SiH₂)_n which adsorbs on a film surface during deposition to thereby hinder a normal growth of film, and also needed a long time for the film formation due to low deposition rate thereof to thereby remain a drawback for cost saving.

0006Besides, in prior art, it is not obtained the a-SiC, a-SiO and a-SiN photoconductive films possessing sufficient photosensitivety to be used for electrophotographic photosensitive member and containing H content of 40 or more atomic %.

0007A preparation method for amorphous silicon films utilizing the electron cyclotron resonance (ECR) method has been proposed (see USP 4,532,199).

SUMMARY OF THE INVENTION

0008A photosensitive member for electrophotography which comprises a conductive substrate and a photoconductive layer in which the photoconductive layer is an amorphous silicon containing 40 - 50 atomic % of hydrogen and/or halogen and at least one chemical modifier selected from carbon, nitrogen and oxygen and fabricated by elctron cyclotron resonance method.

0009The electrophotographic photosensitive members of the present invention show very low in dark conductivity and sufficient photosensitivity to be put into practical use, and also are superior in dark decay characteristics upon repeat operation.

0010Furthermore, according to the manufacturing method of the present invention it can economically provide the photosensitive members because of high deposition rate and high productivity.

BRIEF DESCRIPTION OF THE DRAWINGS

0011<ul id="ul0001" list-style="none"><li>Fig. 1 is the relationship between H content (atomic %) in a-SiN films fabricated by ECR method and gas pressure during deposition,</li><li>Fig. 2 is the relationship between photo conductivity at 565 nm and gas pressure during deposition with respect to the a-SiN films of Fig. 1,</li><li>Fig. 3 is the relationship between dark conductivity and gas pressure during deposition with respect to a-SiN films,</li><li>Figs. 4 - 6 are the relationships between gas pressure during the deposition of a-SiC film by ECR method, and hydrogen content, photo conductivity at 565 nm or dark conductivity, respectively,</li><li>Figs. 7 - 9 are the relationships between gas pressure during the deposition of a-SiO films and hydrogen content, photo conductivity at 565 nm or dark conductivity, respectively,</li><li>Fig. 10 is the relationships between the film composition, i.e., the atomic ratio of Si atom to C atom and photo conductivity and dark conductivity, with respect to a-SiC films by ECR method,</li><li>Fig. 11 is the relationships between the film com­position, i.e., the atomic ratio of Si atom to O atom and photo conducivity and dark conductivity, with respect to a SiO films by ECR method.</li></ul>

PREFERRED EMBODIMENT OF THE INVENTION

0012The electrophotographic photosensitive member of the present invention comprises basically a conductive substrate and a photoconductive layer but may provide an intermediate layer therebetween and a surface protecting layer on a free surface of the photoconductive layer.

0013As the conductive substrate, it may be used a con­ventional one available in the field, for example, a plate made from metals such as Al, Cr, Mo, Au, Ir, Nb, Ta, Pa, Pd and the like, or alloys from these metals. Also it may be a film or a sheet made of synthetic resins such as polyesters, polyethylenes, cellulose acetate, polypro­pylenes and the like, and a sheet made of glass, ceramics, those being given a conductive layer on its surface. Any shapes of the substrate may be used suitably for the purpose and is not limited to any particular configuration.

0014The photoconductive layer of the invention contains at least one chemical modifier among C, N and O in amorphous silicaon. N content with respect to Si atom is usually 0.01 - 28 atomic %, preferably 0.2 - 28 atomic %. C con­tent with respect to Si atom is usually 5 - 30 atomic %, preferably 10 - 30 atomic %. And, O content with respect to Si atom is usually 5 - 20 atomic %, preferably 10 - 20 atomic %.

0015Also, the content of hydrogen and/or halogen in the photoconductive layer is preferably at least 40 atomic %, and 60 atomic % at maximum. Such films with high content of hydrogen and/or halogen may be prepared by ECR method. The films with derived content may be obtained mainly by adjusting gas pressure during deposition under the condi­tion of the high microwave power of 2.5 kW and without the substrate heating. Usually, it is preferable that only hydrogen is contained in the photoconductive layer, but only halogen, or hydrogen with halogen may be contained.

0016The thickness of the photoconductive layer is usually 5 - 80 µm, preferably 10 - 50 µm.

0017To be noted is that the photoconductive layer may contain impurities such as P or B. Such impurities may control the dark conductivity and the carrier transport property, so that they may be added when necessary.

0018The intermediate layer serves to prevent the injec­tion of carriers from the conductive substrate to the photoconductive layer, so that it may be provided when necessary. The intermediate layer is preferably formed by amorphous silicon and has usually a thickness of 2.0 - 20 µm.

0019The surface protecting layer may be preferably pro­vided for protecting the photosensitive member from physical or chemical damages such as corona discharge. The surface protecting layer may be amorphous silicon added with the same chemical modifier as that for the photoconductive layer and may preferably use a-SiC whose film thickness is usually 0.2 - 10 µm.

0020ECR method is used for fabricating the photoconduc­tive layer of the present invention.

0021Next, a film preparation method will be described with exemplifying the case of a-SiN film.

0022The ECR plasma CVD equipment is composed of a plasma formation chamber and a specimen chamber. The plasma formation chamber constructs a cavity resonator which is connected with the microwave source (a frequency of 2.45 GHz) through a rectangular waveguide, via microwave intro­ducing window made from quartz. Around the plasma chamber are provided magnetic coils, and they give the electron cyclotron resonance condition and form the divergent magnetic field, which extract the plasma stream to a substrate. The specimen chamber includes a conductive substrate. When the substrate is a cylindrical type, it is supported by a support member to thereby be rotatable. Into the specimen chamber is introduced a material gas of silicon compounds containing H or halogen, such as SiH₄, Si₂H₆, SiF₄, SiCl₄, SiHCl₃, SiH₂Cl₂ and the like or mixture of these material gases. Also, gas for supplying N effec­tively may include NH₃ or N₂ gas. First, the plasma formation chamber and specimen chamber are evacuated to vacuum so as to allow material gases to be introduced thereinto. In this instance, gas pressure is usually set at 10⁻³ Torr - 10⁻⁴ Torr. Then, into the plasma formation chamber is applied a magnetic field and then supplied a microwave power so as to excite plasma, which is directed to the substrate through divergent magnetic field to cause a-SiN to be deposited. Since the support member is rotated, the film is uniformly deposited. The film uniformity can be improved by adjusting the position and the shape of plasma extracting orifice, which is arranged at the end opposite to the microwave introducing window.

0023By the deposition apparatus mentioned above, experi­ments have been made at some gas pressures with the material gases of SiH₄ and NH₃. In this case, the material gas flow rate is (SiH₄ + NH₃ = 120 sccm), gases ratio is (SiH₄/(SiH₄ + NH₃) = 0.96), microwave power is 2.5 kW, and substrate is not heated.

0024Figs. 1, 2 and 3 show H content in the film, photo conductivity (η µ τ) at 565 nm, and dark conductivity (σ_d) dependent on gas pressure with respect to the obtained a-SiN films. As shown in Fig. 1 - 3, when the gas pressure is selected to provide a-SiN film with H content of more than 40 atomic %, the dark conductivity becomes less than 10⁻¹⁵Ω⁻¹cm⁻¹ without having boron doped and the photo conductivity is high (photosensitivity is high). In the range where photo conductivity (η µ τ) becomes larger, the dark conductivity (σ_d) shows smaller. The dark conductivity is proportional to drift mobility µ, so that in this region, it can be understood that lifetime τ becomes larger. It is well known that the τ and dangl­ing bond density have a good correlation (i.e., when dangling bond density decreases, τ becomes larger). Hence, it was found that dangling bond density due to Si atom can be mainly reduced in the a-SiN film with H content of 40 or more atomic %, fabricated by ECR method. It is pointed out that the a-SiN film having less than 10⁻¹⁴ - 10⁻¹⁵Ω⁻¹cm⁻¹ of dark conductivity and in addition high photo conductivity (high photosensitivity) without doping of boron could not be obtained in prior art, that is, the a-SiN films prepared by a conventional method could not reach the said characteristics.

0025In the method for fabricating the a-SiN films mentioned above, no formation of (SiH₂)_n powder is recognized. In this instance, the deposition rate and gas usage efficiency largely depend on gas pressure, so that gas pressure is selected to be obtained a considerable higher (6 - 10 times higher) deposition rate and gas usage efficiency in com­parison with the conventional art. Furthermore, it has been observed that at a specific gas pressure where H con­tent becomes more than 40 atomic%, i.e., at gas pressure 2 - 3.5 m Torr) where it is possible to provide a-SiN film having dark conductivity more than 10⁻¹⁴- 10⁻¹⁵Ω⁻¹cm⁻¹ and a high photo conductivity (high photosensitivity), the deposition rate and gas usage efficiency preferably show a higher value. On the contrary, a-SiN films de­posited by a conventional method generally have such tendency that photosensitivity is deteriorated in the range of higher deposition rate. Also in this respect, the present invention has a superior feature to those in the conventional art.

0026It is natural that when a silicon compound contain­ing halogen is introduced as material gas, it requires that a total amount of H and halogen in the film is more than 40 atomic %. From additional experiments, it has been observed that when the amount of H and/or halogen in the film is set to be more than 60 atomic %, optical band gap of the film becomes too larger, so that this feature is not suitable for photoconductive layer for electrophotographic photosensitive member requiring photosensitivity with respect to visible light. In detail, a relevant content of H and/or halogen in the film is 40 - 60 atom %, preferably 43 - 55 atomic %.

0027Next, it has been observed that when the H content in the film is fixed in a range of 43 - 46 atomic % and a gaseous ratio of SiH₄ and NH₃ is changed to vary N con­tent in the film. In the case of N content less than 0.01 atomic %, there is no effect of decrease in the dark conductivity. It is considered that nitrogen acts as a donor and it causes the dark conductivity to be larger. Therefore, in this region, a-SiN films are not proper for photoconductive layer for electrophotographic photosensi­ tive member. Also, in the case of N content more than 28 atomic %, the photosensitivity to visible light is drastically lowered, which feature is also not suitable for photoconductive layer for electrophotographic photo­sensitive member. In other words, a usual value of N content with respect to Si atom is to be 0.01 - 28 atomic %, preferably 0.2 - 28 atomic %.

0028Next, the details of a-SiC film and a-SiO film will be described. The preparation apparatus to be used is the same as that for the a-SiN films. Material gases to be introduced are silicon compounds containing H or halogen such as SiH₄, Si₂H₆, SiF₄ SiCl₄, SiHCl₃ SiH₂Cl₂ and the like or mixture of these material gases. Also, gases for C source may be such as CH₄, C₂H₆ or C₂H₄, and gases for O source may be CO₂, N₂O or O₂.

0029Figs. 4 - 9 show H content in the film, photo conduc­tivity (η µ τ) at 565 nm, dark conductivity (σ_d) dependent on gas pressure during deposition for a-SiC films and a-SiO films. The preparation conditions for these films are as follows. For a-SiC films, SiH₄ + CH₄ = 145 sccm, SiH₄/­(SiH₄ + CH₄) = 0.83, microwave power = 2.5 kW, and the substrate is not heated. In the case of a-SiO films, SiH₄ + O₂ = 145 sccm, SiH₄/(SiH₄ + O₂) = 0.83, microwave power = 2.5 kW, and the substrate is not heated. As seen from Figs. 4 - 9, similarly with the a-SiN films, only when gas pressure is selected to set H content to be more than 40 atomic %, it is possible to provide a sufficient photo conductivity (η µ τ) and dark conductivity (σ_d) for electrophotographic photosensitive member.

0030Figs. 10 and 11 show the relationships between photo conductivity (η µ τ), and dark conductivity (σ_d), and the film composition of a-SiC films or a-SiO films which were prepared in varying the flow rates of SiH₄ and CH₄, or SiH₄ and O₂, respectively. The other preparation conditions are the same as those of the films shown in Figs. 4 - 9 except for gas pressure fixed at 3.0 m Torr.

0031As seen in Figs. 4 - 9, in the a-SiC films and a-SiO films with low dark conductivity and high photo conductivity, the content of H and/or halogen is to be 40 - 60 atomic %. To be noted is that when H content is more than 60 atomic %, H is bonded with Si in polymeric configuration of (SiH₂)_n to thereby deteriorate photo conductivity. The H and/or halogen content in these films is preferably 43 - 55 atomic %. From Fig. 10, in the SiC films with C content more than 30 atomic %, photo conductivity (η µ τ) shows less than 10⁻⁷ cm²/v, and less than 5 atomic %, dark conductivity (σ_d) is not drastically changed comparison with that of the film with no C content. The films with said characteristic is the object of the present invention. In other words, the C content in the a-SiC films is to be 5 - 30 atomic %, preferably 10 - 30 atomic %. Also, from Fig. 11, the O content in the a-SiO films is to be 5 - 20 atomic %, preferably 10 - 20 atomic % on the same reason mentioned above for said C content.

0032The photoconductive films according to the present invention are most suitably usable for a photosensitive device adapted to convert optical informations to electrical signals, such as those provided in electrophotography, image sensor or display in a coupled configuration with a liquid crystal. The invention is also applicable to such a device as solar battery, thin film transister.

0033Next examples are given for the embodiments of the preparation of a-SiN film, a-SiC film, a-SiO film having H and/or halogen content at more than 40 atomic % in the film and their use in photoconductive layer of electro­photographic photosensitive member.

Example 1

0034A cylindrical conductive substrate made of Al is mounted in the specimen chamber. SiH₄ gas of 120 sccm and B₂H₆ gas of 20 sccm (diluted by H₂ to 3000 ppm) are fed into the specimen chamber, so that an intermediate layer comprised of a-Si of 2.5 µm thickness is fabricated on the conductive substrate by ECR method under the condition of gas pressure of 3.0 m Torr and microwave power of 2.5 kW.

0035Then, into the specimen chamber is introduced SiH₄ gas of 115 sccm, NH₃ gas of 5 sccm, B₂H₆ gas of 12.5 sccm (diluted by H₂ to 30 ppm), so that a photoconductive layer comprised of a-SiN of 28 µm thickness is fabricated by ECR method under the condition of gas pressure of 3.2 m Torr and microwave power of 2.5 kW.

0036Furthermore, into the specimen chamber is introduced SiH₄ gas of 30 sccm and CH₄ gas of 1000 sccm, so that a surface protecting layer comprised of a-SiC of 0.3 µm thickness is prepared by ECR method under the condition of gas pressure of 3.0 m Torr and microwave power of 2.5 kW.

0037The N content (N/Si) and the hydrogen content in the a-SiN photoconductive layer is 11 atomic % and 48 atomic %, respectively.

0038In the preparation process of the electrophotographic photoreceptor, there is no formation of polymeric powder of (SiH₂)_n, and deposition rate and gas usage efficiency have a considerable higher (6 - 10 times higher) value in comparison with those in the conventional art. Additionally, the obtained electrophotographic photo­ receptor showed a superiority in dark decay character­istics, particularly upon repeat operation. Furthermore, the electrophotographic photoreceptor was evaluated in a commercially available duplicator and provided a favourable image quality.

Example 2

0039Under the same preparation conditions as that used in the example 1 except that gas pressure is changed to 2.7, 3.3, 3.6, 4.2 and 4.8 m Torr upon fabrication of a-SiN photoconductive layer, that is, five electrophoto­graphic photoreceptors were made. The Table 1 shows the results of the image quality and the dark decay characteristics upon repeat operation for the obtained five electrophotographic photoreceptors. Also, the hydrogen content, photo conductivity and dark resistivity of the photoconductive layers dependent on gas pressure are as shown in Figs. 3, 4 and 5. As shown in these figures, at gas pressure of 2.7 m Torr and 3.3 m Torr, an excel­lent electrophotographic photosensitive members can be obtained, wherein hydrogen content in the photoconductive layers is more than 40 atomic %. In this instance, N content (N/Si) was 9 - 12 atomic %. <tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="6" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Gas pressure (m Torr)</entry><entry namest="col2" nameend="col2" align="right">2.7</entry><entry namest="col3" nameend="col3" align="right">3.3</entry><entry namest="col4" nameend="col4" align="right">3.6</entry><entry namest="col5" nameend="col5" align="right">4.2</entry><entry namest="col6" nameend="col6" align="right">4.8</entry></row><row><entry namest="col1" nameend="col1" align="left">Dark decay characteristics</entry><entry namest="col2" nameend="col2" align="right">ⓞ</entry><entry namest="col3" nameend="col3" align="right">ⓞ</entry><entry namest="col4" nameend="col4" align="right">Δ</entry><entry namest="col5" nameend="col5" align="right">×</entry><entry namest="col6" nameend="col6" align="right">×</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Image quality</entry><entry namest="col2" nameend="col2" align="right">ⓞ</entry><entry namest="col3" nameend="col3" align="right">ⓞ</entry><entry namest="col4" nameend="col4" align="right">×</entry><entry namest="col5" nameend="col5" align="right">×</entry><entry namest="col6" nameend="col6" align="right">×</entry></row></tbody></tgroup></table></tables>

Example 3

0040Under the same preparation conditions as that in the example 1 except that phosphorus in place of boron is doped into photoconductive layer and intermediate layer, a negative charge electrophotographic photoreceptor was made. The flow rates of PH₃ upon the fabrication of the intermediate layer and photoconductive layer are 1.5 sccm (diluted by H₂ to 3000 ppm) and 1.2 sccm (diluted by H₂ to 30 ppm), respectively.

0041Measurement of the obtained electrophotographic photo­receptor showed a superiority in dark decay characteristics particularly upon repeat operation. Also, the photoreceptor was evaluated in a commercially available duplicator for negative charge and could provide a favourable image quality.

Example 5

0042An intermediate layer comprised of a-Si with 2.5 µm thick­ness was fabricated on the cylindrical conductive support member made of Al by ECR method under such conditions as microwave power of 2.5 kW, gas pressure of 2.7 m Torr and SiH₄ gas of 120 sccm, B₂H₆ gas of 22 sccm (diluted by H₂ to 3000 ppm), and NO gas of 12 sccm.

0043Then, a photoconductive layer comprised of a-SiC with 28 µm thickness was made on the intermediate layer by ECR method under such conditions as microwave power of 2.5 kW, gas pressure of 2.7 m Torr and SiH₄ gas of 120 sccm, CH₄ gas of 25 sccm and B₂H₆ gas of 40 sccm (diluted by H₂ to 30 ppm).

0044Furthermore, a surface layer comprised of a-SiC with 0.3 µm thickness was fabricated on the photoconductive layer under such conditions as microwave power of 1.5 kW, gas pressure of 0.8 m Torr and SiH₄ gas of 10 sccm and CH₄ gas of 18 sccm, whereby an electrophotographic photoreceptor could be obtained.

0045In the case, the carbon content in the photoconductive layer was 20 atomic %, and the hydrogen content was 43 atomic %. Also, it was found that the deposition rate for the photoconductive layer was about 23 µm/hour which notably improved in comparison with the case of that (about 10 µm/hour) of the conventional plasma CVD method. Upon the preparation process, the conductive support member was not heated and there observed no formation of polymeric powder of (SiH₂)_n. Measurement of the obtained electrophotographic photoreceptor for positive charge showed a favourable photosensitivity, less amount of residual potential, and is superior particularly in dark decay characteristics. Also, the electrophotographic photoreceptor was evaluated in a commercially available duplicator for positive charge and could provide a favour­able image quality without having fogging.

Example 6

0046Under the same preparation conditions as that in the Example 5 except that O₂ gas of 25 sccm in place of CH₄ gas was introduced upon the fabrication of a-SiO photoconductive layer by ECR method, an electrophotographic photoreceptor was made. In the a-SiO photoconductive layer, the oxygen content was 12 atomic %, and the hydrogen content was 47 atomic %. In this case, the deposition rate was 23 µm/hour. Measurement of the obtained electrophotographic photoreceptor for positive charge showed the same results as in the Example 5, that is, it has a favourable photosensitivity, less residual potential and is superior in dark decay charac­teristics. Furthermore, the electrophotographic photo­receptor was evaluated in a commercially available duplicator for positive charge and could provide a favourable image quality without having fogging.

Example 7

0047Under the same preparation conditions as that in the Example 5 except that PH₃ gas of 12 sccm (diluted by H₂ to 2000 ppm) in place of B₂H₆ gas was introduced upon the fabrication of the intermediate layer and B₂H₆ gas was not introduced upon the fabrication of the photoconductive layer, an electrophotographic photoreceptor was made. Measure­ment of the obtained electrophotographic photoreceptor for negative charge showed that it has a favourable photosensi­tivity, less residual potential and is superior particularly in dark decay characteristics, as the same results in the Example 5 except for polarity. Furthermore, the electro­photographic photoreceptor was evaluated in a commercially available duplicator for negative charge and could provide a favourable image quality without having fogging.

Example 8

0048Under the same preparation conditions as that in the Example 6 except that PH₃ gas of 12 sccm (diluted by H₂ to 2000 ppm) in plade of B₂H₆ gas was introduced upon the fabrication of the intermediate layer and B₂H₆ gas was not introduced upon the fabrication of the photoconductive layer, an electrophotographic photoreceptor was made. Measurement of the obtained electrophotographic photo­receptor showed that it has a favourable photosensitivity, less residual potential and is superior particularly in dark decay characteristics, as the same results in the Example 5 except for polarity. Furthermore, the electrophotographic photoreceptor was evaluated in a commercially available duplicator for negative charge and could provide a favour­able image quality without having fogging.