U.S. patent number 3,571,646 [Application Number 04/744,743] was granted by the patent office on 1971-03-23 for photoconductive target with n-type layer of cadmium selenide including cadmium chloride and cuprous chloride.
This patent grant is currently assigned to Tokyo Shibaura Electric Co., Ltd.. Invention is credited to Yuji Kiuchi, Kazuo Shimizu, Okio Yoshida.
United States Patent |
3,571,646 |
Kiuchi , et al. |
March 23, 1971 |
PHOTOCONDUCTIVE TARGET WITH N-TYPE LAYER OF CADMIUM SELENIDE
INCLUDING CADMIUM CHLORIDE AND CUPROUS CHLORIDE
Abstract
This photoconductive target comprises a photoconductive member
consisting of two layers: a first layer 0.5 micron minimum thick
formed on a transparent electrode and a second layer 0.6 micron
maximum thick superposed on the first layer so as to be disposed on
the side electron gun. The first layer is solely or mainly made of
cadmium selenide, and the second layer is formed from a high
resistance semiconductor material.
Inventors: |
Kiuchi; Yuji (Yokohama-shi,
JA), Shimizu; Kazuo (Yokohama-shi, JA),
Yoshida; Okio (Kawasaki-shi, JA) |
Assignee: |
Tokyo Shibaura Electric Co.,
Ltd. (Kawasaki-shi, JA)
|
Family
ID: |
12724950 |
Appl.
No.: |
04/744,743 |
Filed: |
July 15, 1968 |
Foreign Application Priority Data
|
|
|
|
|
Jul 17, 1967 [JA] |
|
|
42/45,640 |
|
Current U.S.
Class: |
313/385;
313/366 |
Current CPC
Class: |
H01J
29/456 (20130101) |
Current International
Class: |
H01J
29/10 (20060101); H01J 29/45 (20060101); H01j
039/06 (); H01j 039/18 (); H01j 031/28 () |
Field of
Search: |
;313/94,102 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Segal; Robert
Claims
We claim:
1. A photoconductive target comprising a first N-type layer made of
cadmium selenide containing cadmium chloride and cuprous chloride
formed on a substrate of transparent electrically conductive
material to a thickness of about 0.5 micron minimum and a second
P-type layer made of at least one high resistance semiconductor
material selected from the group consisting of zinc sulfide and
zinc selenide to a thickness of about 0.6 micron maximum.
Description
The present invention relates to a photoconductive target, more
particularly to the high sensitivity and high resistance
photoconductive target of a photoelectric amplifier or
photoconductive image pickup tube (having the same construction as
the one commercially known as Vidicon, Plumbicon, etc.) used in the
television and other fields.
The conventional photoconductive target of a photoconductive image
pickup tube is prepared by depositing a photoconductive layer on a
transparent faceplate disposed at one end of a vacuum vessel and
constituting a light input plane, with a transparent signal
electrode inserted therebetween. While an image pickup tube
provided with, for example, such a photoconductive target is in
operation, the signal electrode is impressed with a positive
voltage (for example, 30 volts), and the surface of the
photoconductive layer is scanned by low velocity electron beams
emitted from an electron gun similarly enclosed in the vacuum
vessel in an opposite relation to said target. The electric
resistance of the photoconductive layer varies with the intensity
of light entering the image pickup tube from the outside thorough
the faceplate, so that when scanned by the electron beam, a signal
current is produced through a load resistance connected to the
transparent electrode in proportion to the intensity of the
incident light.
It has already been often experienced that the properties of the
photoconductive image pickup tube are effected by those of a
photoconductive member forming a photoconductive target. Generally,
the photoconductive layer consists of a porous P-type material such
as antimony trisulfide, lead monoxide, etc. However, these
materials have been unable to display a fully satisfactory effect
as a photoconductive layer. Therefore to ensure the stability and
improved effect of a photoconductive target, it has been attempted,
in the case of antimony trisulfide, for example, to prepare the
target from three layers of the sulfide, namely, a so-called
continuous solid layer--a so-called porous layer--a continuous
solid layer arranged in the order mentioned in the direction of the
thickness of the photoconductive layer thus formed. The term
"porous layer," as used herein, means a loose aggregate of
relatively large particles of the photoconductive material vapor
deposited in low vacuum, for example 10.sup..sup.-3 torr, and the
term "continuous solid layer" means a compact or vitreous layer of
minutely fine particles of said material vapor deposited in high
vacuum, for example 10.sup..sup.-5 torr. It may be generalized that
where the same material is used, a porous layer thereof has a
relatively high apparent resistance to the introduced electrons,
whereas a continuous solid layer thereof has a relatively low
apparent resistance thereto. In fact, therefore, the quality of an
image regenerated by an image pickup tube using such material is
determined by a combination of resistivity measured in the
direction of the thickness of the photoconductive layer and
resistivity measured in a direction perpendicular thereto, namely,
a direction parallel with the surface of said layer.
In addition to the aforementioned antimony trisulfide
photoconductive layer, there has been proposed a lead monoxide
photoconductive target as a more sensitive type. Plumbicon using
this target has recently come to be practically used in color
television cameras. As compared with the image pickup tube of Image
Orthicon type, however, these photoconductive ones still have a
lower photosensitivity. Consequently strong demand has been voiced
for development of a far more sensitive photoconductive target.
In response to this request, the inventors previously developed a
photoconductive target using cadmium selenide as a photoconductive
layer, and disclosed that an image pickup tube comprising this
target had as high a photosensitivity as more than ten times that
of an image pickup tube consisting of the conventional
photoconductive target. This photoconductive target was distinct
from the one in common use not only in respect of the use of a
different material as a photoconductive layer, but also in the fact
that cadmium selenide used as said layer possessed an N-type
electronic conductivity. The operational difference between such
N-type photoconductive target and the previously known P-type
target lies in the fact that in case of N-type conductivity,
scanning electron beams can be freely introduced into a
photoconductive layer to reach the signal electrode. The high
photosensitivity of the N-type target originates with the fact that
photoexcited holes in the layer are immediately caught in the
recombination centers within the layer and that a secondary
photocurrent can continue to flow due to the influx of electron
beams until the captured hole is recombined with a free electron.
However, like a target prepared from the conventional
photoconductive material, the target comprising a cadmium selenide
photoconductive layer still had the drawbacks that it was
impossible to obtain a signal current, unless an appreciably high
target voltage was applied and that there was a limit to the
latitude in which the target could be operated.
The photoconductive target of the present invention consists of a
first photoconductive layer solely or mainly composed of cadmium
selenide formed on a transparent electrode to a thickness of 0.5
micron minimum and a second layer made of a high resistance
semiconductor material superposed on the first layer to a thickness
of 0.6 micron maximum so as to broaden the potential gradient in
that part of the second layer which faces the first layer, and ease
the electron influx from the second layer. Accordingly, the present
photoconductive target produces a signal current at a low target
voltage and is operable over a broad range of voltage.
The present invention can be more understood from the following
detailed description when taken in connection with the accompanying
drawing in which:
FIG. 1 is a schematic sectional view of an image pickup tube fitted
with the photoconductive target according to the present
invention;
FIG. 2 is a schematic sectional view of an embodiment of the
photoconductive target according to the invention; and
FIG. 3 is a curve diagram offered by way of comparing the prior
photoconductive target only provided with a photoconductive layer
mainly consisting of cadmium selenide and the photoconductive
target according to the present invention provided with a
photoconductive layer prepared in the manner shown in FIG. 2,
regarding the capacity of generating a signal current at a given
target voltage, with the target illumination as a parameter, the
currents and voltages of the present invention being the dashed
lines.
There will now be described an embodiment of the present invention
by reference to the appended drawing. As shown in FIG. 1, the
structure of the image pickup tube using the target of the present
invention has the same construction as other common Vidicon-type
tubes except for the target, so there is only given a brief
description of the ordinary Vidicon-type construction. The tube 10
as illustrated comprises a vacuum vessel 11 containing an electron
gun section 12 and a photoconductive target assembly 13. The
electron gun assembly 12 comprises a heater 14, a cathode 15
surrounding the heater, and a control grid electrode 16 and an
accelerating electrode 17 both disposed coaxially with the cathode
15. An electrode 18 is mounted coaxially with said accelerating
electrode 17, and a mesh electrode 19 is disposed so as to face
said cathode at one end of the electrode 18 opposite to the
accelerating electrode 17. The photoconductive target section 13
comprises a transparent glass substrate 20, a transparent
conductive layer 21 deposited on said substrate 20, and a
photoconductive target 22 according to the invention, said target
22 being deposited on the conductive layer 21 to face the mesh
electrode 19.
As shown in FIG. 2, the photoconductive target of the present
invention consists of a first layer 23 mainly composed of cadmium
selenide formed on a transparent electrode 21 and a second layer 24
made of high resistance semiconductive material such as antimony
trisulfide superposed on the first layer 23. In the FIG., the arrow
.alpha. denotes the direction from which light is projected and the
arrow .beta. shows the direction in which electron beams are
introduced.
There will now be described an example of the method of
manufacturing a photoconductive target in accordance with the
present invention. On a transparent electrode 21 on a transparent
substrate is vapor deposited in as high vacuum as 1 or
2.times.10.sup..sup.-5 mm. Hg a layer of cadmium selenide about 1
micron thick. Prior to vapor deposition, there are added in advance
to cadmium selenide, for example, 20 percent by weight of cadmium
chloride and 0.05 percent by weight of cuprous chloride. The layer
thus laminated by vapor deposition is further sintered, for
example, by heating 15 minutes at a temperature of 600.degree. C.
in a nitrogen atmosphere. The mass is then subjected to heat
treatment in a selenium atmosphere, for example, 30 minutes at a
temperature of 500.degree. C., to obtain a high resistivity
photoconductive layer. This layer is named a first layer 23 for
convenience. On the first layer 23 is vapor deposited in the
aforesaid high vacuum of 10.sup..sup.-5 mm. Hg a layer of antimony
trisulfide 24 having a thickness of 0.4 micron to form the
photoconductive target of the present invention. Addition of
cuprous chloride in this process is intended to elevate the
photoconductivity of the layer obtained. And inclusion of cadmium
chloride in heat treatment after vapor deposition aims at the
acceleration of growth of cadmium selenide crystals. In this case,
cadmium selenide alone, of course, fully serves the purpose.
Further, the cadmium selenide component may consist of a solid
solution or mixture containing a proper amount of cadmium sulfide
(for example, weight ratio of cadmium sulfide to cadmium selenide =
1:2). Further, the added impurities may include in addition to
copper one or more of silver, gold, thallium, indium, gallium,
aluminum, halogens, tellurium, antimony, bismuth, lead, tin, alkali
metals, and alkali earth metals.
An image pickup tube containing a target consisting of the first
and second layers prepared by the aforementioned process has, as
shown in FIG. 3, far more excellent properties than the prior
target which lacked the second layer of antimony trisulfide. FIG. 3
compares the present and prior targets with the signal current
value (logarithmic scale) represented by the ordinate and the
target voltage value (logarithmic scale) denoted by the abscissa,
using the target illuminations (0.8 lux, 0.3 lux and
nonillumination) as a parameter. The solid curves of FIG. 3
indicate the properties of the prior target and the dashed curves
denote those of the present target.
As seen from the FIG., the present target uses a far lower voltage
than the prior one in obtaining the same signal current. This is
particularly prominent where there is only required a minute signal
current. Moreover, the application of such a low target voltage
does not affect the dark current value. The photoconductive target
according to the invention permits the target voltage to be chosen
over a broader range than in the prior art device. For example,
based on 0.8 lux illumination, the prior art ranges in target
voltage between about 40 volts and about 25 volts, whereas the
present invention ranges from about 45 volts to about 8 volts.
While the present invention has such good effect as may be
understandable from FIG. 3, it has a further advantage of reducing
the afterimage. Let us take a case, for example, where a
photoconductive image pickup tube is operated and a test pattern is
illuminated one minute thereon and after removal of said pattern it
is exposed to a white light. Then the initial test pattern remains
with the prior target only using a first layer of cadmium selenide.
However, a photoconductive image pickup tube containing the target
of the present invention does not substantially present any
afterimage when it undergoes the same operation. Namely, this image
pickup tube not only possesses the high sensitivity and
panchromatism of the prior image pickup tube simply provided with
cadmium selenide as a first layer, but also is more improved in
various undesirable transitory properties associated with an image
produced, thus offering a greater practical use.
The vital point of a composite target according to the present
invention is that its first layer consists of cadmium selenide
which itself possesses a sufficient photosensitivity. If the first
layer has a poor photosensitivity, a composite target, though
prepared pursuant to the invention, would offer no advantage. It
will be apparent that the method of manufacturing this first layer
is not limited to the aforementioned embodiment. For instance,
prior to heat treatment in a selenium atmosphere, it is possible to
carry out the vapor deposition of the required layer in an inert
atmosphere in as low vacuum as 10.sup..sup.-1 mm. Hg instead of
10.sup..sup.- 5 mm. Hg as previously described.
From the standpoint of allowing the first layer to have a full
photosensitivity, it is preferred that the first layer be 0.5
micron minimum thick. The reason is that if the first layer is too
thin, it will result in the reduction of photosensitivity and
increase of a dark current and failure to produce high quality
television pictures.
There will now be described the second layer involved in a
composite target with antimony trisulfide taken as an example. In
the foregoing embodiment, antimony trisulfide forms a continuous
solid layer 0.4 micron thick. If the thickness increases over 0.6
micron, there will only be obtained an instantaneous regenerated
picture at the time of pickup. Thus the regenerated picture at the
time of pickup. Thus the regenerated image will disappear at once,
rendering the image pickup tube quite useless. From the
aforementioned operating principle of the first layer, this is
considered due to the fact that such a thick second layer will
obstruct the inflow of electron beams to stop the flow of a
secondary photocurrent. In other words, the second layer formed on
the first layer should not be so thick as appreciably to prevent
the inflow of scanning electron beams. The materials of the second
layer may include in addition to the aforesaid antimony trisulfide
other high resistance semiconductor materials such as antimony
triselenide, arsenic trisulfide, arsenic triselenide, bismuth
trisulfide, bismuth triselenide, cadmium telluride, lead monoxide,
selenium, zinc sulfide and zinc selenide. When the second layer
consisted of any of the above-listed materials the same results
were obtained as in the preceding embodiment. Since these materials
have different specific resistances, the upper limit to the
thickness of a layer prepared therefrom varies according to whether
it is formed into a continuous solid layer or porous one. For
instance, where arsenic trisulfide having a relatively high
specific resistivity is used as a second layer, it is preferably
formed into a continuous solid layer in consideration of the ease
of controlling the layer thickness in vapor deposition. And in the
case of a material having a relatively low specific resistivity
such as antimony triselenide it is desirable to form it into a
porous layer also in the sense of preventing the degradation of the
resolving capability of the layer thus prepared. While the second
layer may of course consist of one or more layers, the total
thickness thereof should not exceed 0.6 micron in any case.
The spectroscopic photosensitivity of the first layer mainly
consisting of cadmium selenide prevails all over the visible ray
region from the blue to the red. In other words, the layer has a
great absorption coefficient over the entire region of visible
light beams. Accordingly the light which has been transmitted
through the first layer is considerably reduced in the power of
exciting the second layer. The second layer used in the present
invention is only prepared by vapor deposition, requiring no
further special treatment.
Since the above-listed second layer materials include P-type
materials, it may be imagined that there will be formed a
back-biased PN junction between the first layer (N-type layer) and
the second layer (P-type layer). As seen from FIG. 3, however, the
characteristics of the composite target according to the present
invention are such that while the whole range of the operating
voltage of the target rather shifts toward the low voltage side,
the target displays substantially analogous current-voltage
properties to those of a target only provided with a first layer.
Therefore the composite target does not display a current saturated
condition due to the presence of a PN junction as generally
supposed. This fact proves that the photoelectric converting
properties of the target according to the present invention are
quite independent of the problem of special contact between the
first and second layers. The second layer is only intended to ease
the inflow of electron beams by locally providing a sharp potential
gradient on the scanned surface of the first layer. In other words,
the second layer acts to reduce a large number of levels present on
the surface of the first layer, which behave traps to charge
carriers. This effect comes from the fact that the transitory
properties of the target, for example, the undesirable afterimage
originates with the trapping of a charge carrier by these surface
levels.
While the invention has been described in connection with some
preferred embodiments thereof, the invention is not limited thereto
and includes any modifications and alterations which fall within
the scope of the invention as defined in the appended claims.
* * * * *