U.S. patent number 3,635,705 [Application Number 04/830,031] was granted by the patent office on 1972-01-18 for multilayered halogen-doped selenium photoconductive element.
This patent grant is currently assigned to Xerox Corporation. Invention is credited to Anthony J. Ciuffini.
United States Patent |
3,635,705 |
Ciuffini |
January 18, 1972 |
MULTILAYERED HALOGEN-DOPED SELENIUM PHOTOCONDUCTIVE ELEMENT
Abstract
A xerographic plate having a two-layer photoconductive segment
comprising a highly doped vitreous selenium transport layer of from
about 20 to 200 microns in thickness and an overlaying control
layer of at least about 5 microns thickness which comprises
selenium. The plate is characterized by low residual potential as
well as exhibiting a minimum ghosting effect.
Inventors: |
Ciuffini; Anthony J.
(Rochester, NY) |
Assignee: |
Xerox Corporation (Rochester,
NY)
|
Family
ID: |
25256150 |
Appl.
No.: |
04/830,031 |
Filed: |
June 3, 1969 |
Current U.S.
Class: |
430/58.1; 430/95;
399/159 |
Current CPC
Class: |
G03G
5/0433 (20130101) |
Current International
Class: |
G03G
5/043 (20060101); G03g 005/00 () |
Field of
Search: |
;96/1,1.5 ;252/501 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Schaffert, Electrophotography, 1965, pp. 231-233..
|
Primary Examiner: Lesmes; George F.
Assistant Examiner: Wittenberg; M. B.
Claims
What is claimed is:
1. A xerographic plate including a two-layer photoconductive
segment, said first layer comprising halogen doped vitreous
selenium in a thickness of about 40-80 microns, with the dopant
being present in a concentration of from about about 60-10,000
parts per million, and an undoped substantially clear vitreous
selenium layer of from about 5-20 microns in thickness overlaying
said first layer.
2. The plate of claim 1 wherein the halogen comprises chlorine.
3. The method of imaging comprising
a. providing a xerographic plate having a two-layered
photoconductive segment, said segment comprising a first layer
40-80 microns thick comprising vitreous selenium doped with
60-10,000 parts per million of halogen, and an overlaying layer
about 5 to 20 microns in thickness comprising undoped selenium,
b. forming an electrostatic latent image on said plate, and
c. developing said image to make it visible.
4. The method of claim 3 wherein the latent image is formed by
first uniformly charging the surface followed by exposure to a
pattern of activating radiation.
5. The method of claim 3 wherein the halogen dopant comprises
chlorine in a concentration of from about 60 to 10,000 parts per
million.
Description
BACKGROUND OF THE INVENTION
This invention relates in general to xerography and in particular
to an improved xerographic plate and a method for its use as an
imaging device.
It is the usual practice in the xerographic art to form an
electrostatic image by first evenly distributing electrical charge
on the surface of a photoconductive member and then exposing the
surface to a pattern of activating radiation corresponding to the
desired image. More specifically, a xerographic plate containing a
photoconductive insulating layer is first given a uniform
electrostatic charge in order to sensitize its surface. The plate
is then exposed to an image of activating electromagnetic radiation
such as light, X-ray, or the like which selectively dissipates the
charge in the illuminated areas of the photoconductive insulator
while leaving behind a latent electrostatic image in the
non-illuminated areas. The latent electrostatic image may then be
developed and made visible by depositing finely divided
electroscopic marking particles on the surface of the
photoconductive insulating layer. This concept was originally
disclosed by Carlson in U.S. Pat. No. 2,297,691 and is further
amplified and described by many related patents in the field.
The discovery of the photoconductive insulating properties of
highly purified vitreous selenium has resulted in this material
becoming the standard in reuseable commercial xerographic plates.
Other types of xerographic plates are known including, for example,
paper coated with a photoconductive layer of zinc oxide particles
contained in a film forming insulating resin. However, vitreous
selenium xerographic plates still remain the most widely used in
that they are capable of holding an electrostatic charge for long
periods of time when not exposed to light, because they are
relatively sensitive to light compared to other xerographic plates,
and because of their durability to be reused hundreds or even
thousands of times. The vitreous selenium plate, however, is
somewhat limited than its spectral response which is very largely
limited to the blue or near ultraviolet portion of the spectrum. An
improvement in the light sensitivity in response to longer
wavelengths of vitreous selenium is described by Ullrich in the
U.S. Pat. No. 2,803,542, which discloses that the addition of
arsenic to selenium causes a general increase in the light
sensitivity of the xerographic plate and also causes the plate to
be sensitive to longer wavelengths of light. Still another
contribution was made by Straughan in U.S. Pat. No. 3,312,548 which
discloses the addition of halogens to arsenic-selenium alloys
resulting in improved spectral sensitivity of the photoreceptor
layer.
Although the xerographic processes and devices utilizing the
halogen-doped vitreous selenium plates have had highly satisfactory
results, it should be recognized that the doped vitreous selenium
layers, when used as a single layer, are far from ideal with
respect to the electrical properties of dark decay and residual
potential. Dark decay is that phenomenon peculiar to xerographic
plates whereby there is a loss of apparent surface voltage in the
absence of light. When this phenomena is measured per unit of time
it is referred to as the dark decay rate and is an effective
measure of the retention of the latent electrostatic image by the
plate. Hence, a high discharge rate indicates that a plate has
become fatigued, that is, the latent charge image will rapidly
dissipate. Residual potential is the voltage remaining on the plate
after exposure to the erase lamp in a conventional xerographic
cycle using a reuseable xerographic plate. More particularly, when
a sensitized xerographic plate is exposed to light, the electrical
potential undergoes an initial rapid decay, followed by a
relatively slow decay. The plate voltage at the point beyond which
no further light discharge occurs is called the residual potential.
This potential may vary from zero to as much as 20 or 30 percent of
the initial potential. A low residual potential is a desirable
characteristic of xerographic plates because of the greater voltage
contrast obtainable between background and darkened areas of the
copy; that is, sufficient voltage contrast is required so as to
effectively attract the development toner in a well-contrasted
print.
A plate having ideal electrical characteristics would have a low
dark discharge as well as low residual potential. A plate having
low residual potential is always desirable for satisfactory voltage
contrast. In actual practice, however, it has been difficult to
produce a photoconductive material having the aforementioned
electrical characteristics.
The aforementioned desired electrical characteristics become even
more difficult to attain with respect to plates which are to be
used commercially in rapid recycling machines. Because of the speed
used in rapid cycling machines there is insufficient time for the
photogenerated holes in the photoreceptor to be effectively
neutralized. As a result, with each cycle there occurs the
phenomenon of residual potential buildup, or positive residual
buildup, whereby the exposed areas of the plate fail to effectively
discharge and the apparent surface voltage in the exposed area
increases with each cycle.
It has been found that when a vitreous selenium photoreceptor has
been doped with a halogen throughout its bulk at a concentration of
about 20 parts per million p.p.m. there is observed an exceptional
effectiveness in controlling the residual buildup under moderate
speed cycling conditions. Furthermore, when a halogen is used in
excess of 20 parts per million the overall residual potential can
be reduced to zero. However, it has also been found that if the
concentration of the halogen were greater than needed for the
reduction of the residual buildup, that is, in excess of 20 parts
per million, then the light at the surface of the photoreceptor
causes areas of conductivity throughout the vitreous selenium with
subsequently higher dark discharge values which after a number of
cycles results in a persistently electrically conductive conditions
known as "fatigue." Consequently, in the case of long copy runs
where the image is in registration with a drum having a halogen
doped selenium layer an effect called "ghosting" is observed which
is characterized as a positive residual image; that is, the
previous image remains on the plate, and upon recharging, will
recur in subsequent copy runs for a second or different image. An
explanation of this phenomenon lies in the fact that the background
areas of the plate have become fatigued to a point where upon
recharging, the background areas dissipate the charge leaving a
contrast potential with the darkened print areas of the plate.
While it is possible to control residual buildup with halogen
doping in an amount of up to about 20 parts per million and still
retain a minimum dark discharge rate in machines of moderate
cycling speeds, unfortunately the residual buildup of such a doped
photoreceptor increases with the speed of cycling. Therefore the
sensitivity of a doped plate will decrease with the increased
cycling, i.e., the ability of the plate to contrast low-density
subjects will be lessened by the increased cycling speed. It
therefore becomes imperative in the case of modern fast copying
machines when using a halogen-doped selenium plate to use a highly
doped plate which has the characteristics of low residual buildup
even under conditions of high speed.
OBJECTS OF THE INVENTION
As a result of the aforementioned problems it is an object of the
present invention to provide a new halogen doped xerographic plate
which has a relatively low residual potential and exhibits a
minimum ghosting effect.
It is a further object of this invention to provide a xerographic
plate having improved physical and electrical properties.
It is another object of this invention to provide a system
utilizing a xerographic plate containing a halogen-doped vitreous
selenium layer having improved light fatigue characteristics.
It is yet a further object of this invention to provide an improved
xerographic plate which exhibits a minimum residual potential.
SUMMARY OF THE INVENTION
These and other objects are obtained in accordance with the present
invention by preparing a xerographic plate having a double-layered
photoconductive segment comprising a lower transport layer of
vitreous selenium doped with a halogen and a relatively thin
overlayer which consists of undoped vitreous selenium. The
concentration of halogen in the lower transport layer ranges from
about 60 to 10,000 p.p.m.
DESCRIPTION OF THE DRAWINGS
Further objects of the invention, together with additional features
contributing thereto will be apparent from the following
description of one embodiment of the invention when read in
conjunction with the accompanying drawings wherein:
FIG. 1 is a schematic sectional view of one embodiment of a
xerographic plate contemplated by the instant invention.
FIGS. 2 and 3 illustrate characteristic discharge curves for doped
vitreous selenium at different recycling speeds.
FIG. 4 illustrates discharge curves for a halogen-doped vitreous
selenium and an overcoated vitreous selenium plate of the instant
invention.
FIG. 1 illustrates one embodiment of an improved xerographic plate
10 according to this invention. Reference character 11 designates a
substrate or mechanical support. The substrate may comprise a metal
such as brass, aluminum, gold, platinum, steel, or the like. It may
be of any convenient thickness, rigid or flexible, in the form of a
sheet, web, cylinder, or the like, and may be coated with a thin
layer of plastic. It may also comprise such other materials as
metallized paper, plastic sheets covered with a thin coating of
aluminum or copper iodine, or glass coated with a thin layer of
chromium or tin oxide. It is usually preferred that the support
member be somewhat electrically conductive or have a somewhat
conductive surface and that it be strong enough to permit a certain
amount of handling. In certain instances, however, support 11 need
not be conductive or may be even dispensed with entirely.
Reference character 12 designates a storage layer which comprises
high-purity vitreous selenium heavily doped with a halogen such as
chlorine, fluorine, bromine, or iodine. The halogen is present in
relatively large amounts which are measured in parts per million.
For the purposes of this invention concentrations from about 60 to
10,000 p.p.m. are preferred in order to obtain an effectively doped
vitreous selenium layer. As heretofore indicated halogen dopant
below 20 p.p.m. results in a residual buildup at high cycling
speeds while concentrations above 10,000 are unnecessary to achieve
the electrical properties desired in the instant invention.
Storage layer 12 may be in any suitable thickness used for
conventional photoconductive layers. Typical thicknesses range from
about 20 to 200 microns. A range of from about 40 to 80 microns is
preferred since these are the thicknesses that are generally used
in conventional xerographic machines.
Overlaying control layer 13 comprises undoped vitreous selenium in
a thickness of from about 5 to 20 microns. Thicknesses below about
5 microns fail to effectively overcome the high dark discharge
characteristics of the heavily halogenated vitreous selenium
transport layer while thicknesses above 20 microns effectively
masks the lower transport layer so that the chlorine doped selenium
fails to function as a low residual photoreceptor.
It can thus be seen that the photoconductive portion of the plate
of FIG. 1 is divided into two functional layers: (1) a highly doped
transport layer which functions to prevent positive residual
buildup during rapid cycling discharge, thereby ensuring charge
contrast, and; (2) an overlaying control layer of more than 5
microns which effectively shields the highly halogenated layer from
harmful radiation and thus prevents excessively high dark discharge
in the halogen-doped layer.
In FIG. 2 there is a dramatic illustration of the effect of
increased speed on the residual potential of a single layer
vitreous selenium having moderate amounts of halogen. Here, the
residual buildup of a vitreous selenium monolayer photoreceptor
containing 20 p.p.m. chlorine dopant was measured by exposure to a
cool white fluorescent light source at speeds of 5, 20, and 50
r.p.m. on an oxidized aluminum substrate in the form of a
cylindrical drum approximately 4.75 inches in diameter by 10.2
inches long. The residual potential was measured after the plate
reached its maximum residual buildup which generally occurred after
30 to 40 cycles. Exposure values ranged from 0.03 to 30 foot-candle
seconds at each speed. As is apparent from FIG. 2 a concentration
of 20 p.p.m. of chlorine is adequate at a drum rotation speed of 5
r.p.m. in that the selenium layer does not attain a maximum
residual potential; that is, there is no apparent voltage after
about 1.87 foot-candle seconds of exposure. However, as the speed
of the drum is increased a maximum residual potential results and
successively increases as the speed is increased from 20 r.p.m. to
50 r.p.m. Consequently at high speeds there will be lessened
contrast potential for a given amount of light or, in other words,
a decrease in sensitivity which will become apparent in the
effectiveness of low density copyability.
By contrast, FIG. 3 graphically demonstrates the advantages of
using a highly doped vitreous selenium photoreceptor plate in rapid
recycling machines. Here the residual potential of a vitreous
selenium monolayer photoreceptor containing 100 p.p.m. chlorine is
measured by discharging at speeds of 5, 20, and 50 r.p.m. in the
manner as described for FIG. 2. It can be clearly seen that
discharge at each speed results in total dissipation of the surface
charge effectively eliminating residual potential. The curves of
FIG. 3 clearly indicate the utility of the highly doped
photoreceptor in rapid recycling machines.
The effect of the overcoating of the instant invention on the
discharge characteristics of highly doped vitreous selenium layer
is demonstrated in FIG. 4. Here the discharge characteristics of a
vitreous selenium monolayer doped with 60 p.p.m. chlorine is
graphically compared to the same monolayer overcoated with a
5-micron layer of pure selenium in accordance with the present
invention. It can be seen from FIG. 4 that the selenium overcoating
has not altered the discharge characteristics to any great extent
thus indicating that the selenium overcoating does not adversely
affect the sensitivity of highly doped vitreous selenium
photoreceptors.
In preparing xerographic plates of the instant invention, selenium
may be conveniently purchased to specification with the desired
concentration of dopant already present. Canadian Copper Refiners
is one source of predoped selenium. If desired, the selenium may be
doped by any conventional laboratory technique such as physically
mixing the dopant with the selenium and vacuum evaporating the
mixture onto the conductive substrate. Bromine may be added in the
form of liquid drops to the selenium which has been precooled.
Chlorine or fluorine may be added by admitting chlorine or fluorine
gas to an evacuated tube containing selenium, which has been
precooled, and maintaining the flow of gas until the selenium
contains the desired amount of dopant. Suitable doping techniques
such as those listed above, which may be used are disclosed in U.S.
Pat. No. 3,312,548 to Straughan. It should also be pointed out that
the halogen may be added to the selenium in the form of a compound
of the selenium or with other compounds such as silver halides.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Two halogen-doped vitreous selenium plates were prepared in order
to illustrate the dark discharge characteristics of highly doped
plates. Each plates contains a 50-micron-thick photoreceptor layer
of halogen doped vitreous selenium and are chlorine doped to a
concentration of 66 p.p.m. In one embodiment illustrative of the
instant invention, plate 2 is overcoated with a 5-micron layer of
undoped selenium.
The doped plates are then tested to measured their dark discharge
rate under both rested and fatigued conditions. Both plates were
rested overnight and mounted on an aluminum testing fixture in the
form of a cylindrical drum approximately 4.75 inches by 10.2 inches
long. For dark discharge values in the rested condition the plate
was charged to an initial potential of 800 volts by means of a dual
corotron and the rate of dark discharge measured at intervals of 4,
10, and 30 seconds. For fatigued values the mounted plates were
exposed by means of a cool white fluorescent light source to 1,550
foot-candle seconds for 5 cycles. The fatigued plates were then
charged to 800 volts on the sixth cycle and the dark discharge
values measured in the same manner described above for the rested
plates. The results are presented in table I.
---------------------------------------------------------------------------
TABLE
Dark discharge values Rested (sec.) Fatigued (sec.) 4 10 30 4 10 30
__________________________________________________________________________
Plate I 4% 10% 21% 8% 18% 38% (Vitreous selenium con- taining 66
p.p.m. chlorine) Plate II 4% 8.5% 19% 5% 11% 22% (Vitreous selenium
con- taining 66 p.p.m. chlorine over- coated with 5 microns on non-
halogenated selenium)
__________________________________________________________________________
An examination of the dark discharge values in table I indicates
the following: First, in accordance with what has hereinbefore
mentioned with regard to highly doped vitreous selenium
photoreceptors there in a prominent increase of the dark discharge
rate of plate 1 going from the rested to the fatigued plates was
decreased by the application of the selenium overcoating as
indicated by the values of plate 2. The difference in the discharge
values between the rested and fatigued plates accounts for the
positive residual image, i.e., ghosting, of the uncoated highly
doped plate. This can be conceptualized if one realizes that in
measuring the rested plate the dark discharge of print or dark
areas of a copy is actually being measured while the dark discharge
of a fatigued plate effectively measured that of the background of
a copy. Hence, if there is enough percentage difference between
them then upon recharging a contrast potential will exist such that
there is a printout or ghost when the plate is developed.
An illustration of the effectiveness of this selenium overcoating
is set forth in the following examples.
EXAMPLE I
An oxidized aluminum drum approximately 4.75 inches in diameter by
10.2 inches long having an arsenic-selenium photoreceptor with 66
p.p.m. chlorine was prepared and placed in a Xerox 813 Office
Copier. An off-on switch was placed in series with the white light
expose lamp and the preclean corotron and erase lamp were
disconnected. With the drum rested overnight three exposures were
made and the expose lamp shut off. In cycling without the exposure
lamp a ghost image of the original copy appeared thereby indicating
that the background areas had become persistently conductive and
thereby contrasted with the darkened areas of the copy.
EXAMPLE II
This same drum was then overcoated with a 5-micron layer of pure
undoped selenium and the above test repeated. The resultant copy
showed virtually no ghosting after the expose lamp has been shut
off thereby indicating that the pure selenium overcoating prevented
the contrast between the background and darkened areas of the
copy.
The plates of the instant invention may be prepared by any of the
well-known conventional techniques such as those set forth in U.S.
Pat. No. 2,803,542 to Ullrich, U.S. Pat. No. 2,822,300 to Mayer et
al., or U.S. Pat. No. 3,312,548 to Straughan. Briefly, such
techniques involve forming suitable mixtures of selenium, arsenic
and halogen in a container and reacting said elements at elevated
temperatures. The resulting alloy is then cooled and applied to a
suitable conductive supporting base by vacuum evaporation.
Similarly, the transport layer is also evaporated onto the
conductive substrate by any conventional technique such as those
shown by U.S. Pat. No. 2,753,278 to Bixby et al. and U.S. Pat. No.
2,970,906 to Bixby. If desired, both the transport layer and
control layer may be evaporated sequentially without breaking the
vacuum. This avoids the possible danger of contaminating the
surface of the plate.
Although special components and proportions have been stated in the
above description of the preferred embodiments of the selenium
overcoated highly chlorinated xerographic plate, other suitable
materials, as listed above, may be used with similar results. In
addition, other materials, such as sensitizers, may be added to
enhance synergize, or otherwise modify the properties of the novel
plate contemplated by this invention.
While the invention has been described with reference to a
preferred embodiment, it will be understood by those skilled in the
art that various changes and equivalence may be substituted for
elements thereof without departing from the true spirit and scope
of the invention. Such modifications are intended to be included
within the scope of this invention.
* * * * *