U.S. patent number 3,890,525 [Application Number 05/370,446] was granted by the patent office on 1975-06-17 for photoconductive target of an image pickup tube comprising graded selenium-tellurium layer.
This patent grant is currently assigned to Hitachi, Ltd., Nippon Hoso Kyokai. Invention is credited to Naohiro Goto, Tadaaki Hirai, Kiyohisa Inao, Yukinao Isozaki, Eiichi Maruyama, Keiichi Shidara, Teruo Uchida, Hideaki Yamamoto.
United States Patent |
3,890,525 |
Hirai , et al. |
June 17, 1975 |
Photoconductive target of an image pickup tube comprising graded
selenium-tellurium layer
Abstract
A photoconductive target of an image pickup tube comprising a
light-transmitting substrate, an N-type conductive layer deposited
on the substrate and a P-type conductive layer making a rectifying
contact with the N-type conductive layer, in which the P-type
conductive layer includes at least selenium and tellurium, the
composition of the P-type layer changes along the direction of the
thickness of the layer, the average content of selenium in the
P-type conductive layer is not less than 50 atomic percent, the
content of tellurium at both surfaces of the P-type conductive
layer is not more than 10 atomic percent, and the maximum tellurium
content of 10 to 40 atomic percent is located on a plane in the
P-type conductive layer nearer to the N-type conductive layer than
the middle plane of the P-type conductive layer.
Inventors: |
Hirai; Tadaaki (Koganei,
JA), Maruyama; Eiichi (Kodaira, JA), Inao;
Kiyohisa (Hachioji, JA), Yamamoto; Hideaki
(Kokubunji, JA), Goto; Naohiro (Machida,
JA), Isozaki; Yukinao (Machida, JA),
Shidara; Keiichi (Tokyo, JA), Uchida; Teruo
(Tokyo, JA) |
Assignee: |
Hitachi, Ltd. (BOTH OF,
JA)
Nippon Hoso Kyokai (BOTH OF, JA)
|
Family
ID: |
26400561 |
Appl.
No.: |
05/370,446 |
Filed: |
June 15, 1973 |
Current U.S.
Class: |
313/386;
252/501.1 |
Current CPC
Class: |
H01L
31/00 (20130101); H01J 29/456 (20130101); H01J
9/233 (20130101) |
Current International
Class: |
H01J
29/45 (20060101); H01J 29/10 (20060101); H01L
31/00 (20060101); H01j 029/45 (); H01j
031/38 () |
Field of
Search: |
;313/386,385,384,65A |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Segal; Robert
Attorney, Agent or Firm: Craig & Antonelli
Claims
What we claim is:
1. A photoconductive target of an image pickup tube comprising a
light-transmitting substrate, a first N-type conductive layer
deposited on said substrate and a P-type conductive layer making a
rectifying contact at a first surface thereof with said first
N-type conductive layer and having a second outer surface to be
scanned by electrons, said P-type conductive layer including at
least selenium and tellurium, the composition of said P-type
conductive layer being different along the direction of the
thickness thereof, the average content of selenium in said P-type
conductive layer being not less than 50 atomic percent, the content
of tellurium at said first and second surfaces of said P-type
conductive layer being not more than 10 atomic percent, the maximum
tellurium content of 10 to 40 atomic percent being located on a
plane in said P-type conductive layer between said first N-type
conductive layer and the middle plane of said P-type conductive
layer.
2. A photoconductive target of an image pickup tube according to
claim 1, wherein said first N-type conductive layer is a
transparent conductive film including one substance selected from
the group consisting of an oxide of tin, indium, and titanium as a
main component.
3. A photoconductive target of an image pickup tube according to
claim 1, wherein a second N-type conductive layer formed of one
substance selected from the group consisting of CdS, CdSe, ZnS,
ZnSe and the mixture thereof is interposed between said P-type
conductive layer and said first N-type conductive layer or a
translucent metal electrode constituting the surface portion of
said lighttransmitting substrate on the side of said first N-type
conductive layer.
4. A photoconductive target of an image pickup tube according to
claim 1, wherein said P-type conductive layer contains one
substance selected from the group consisting of As, Sb, P, Bi, Ge,
Si and the mixture thereof in addition to selenium and
tellurium.
5. A photoconductive target of an image pickup tube according to
claim 4, wherein the concentration of said one substance in said
P-type conductive layer is substantially uniform therethrough.
6. A photoconductive target of an image pickup tube according to
claim 1, wherein the minimum concentration of said selenium in said
P-type conductive layer is located at the location of said maximum
tellurium content in said P-type conductive layer.
7. A photoconductive target of an image pickup tube according to
claim 1, wherein said P-type conductive layer contains Cd in
addition to selenium and tellurium.
8. A photoconductive target of an image pickup tube according to
claim 7, wherein the maximum concentration of said Cd in said
P-type conductive layer is located at the location of said maximum
tellurium content in said P-type conductive layer.
9. A photoconductive target of an image pickup tube according to
claim 1, wherein the absolute rate of increase of the tellurium
content in said P-type conductive layer as the location of said
maximum tellurium content is approached is equal to the absolute
rate of decrease of the tellurium content as the location of said
maximum tellurium content is passed.
10. A photoconductive target of an image pickup tube according to
claim 1, wherein the absolute rate of increase of the tellurium
content in said P-type conductive layer as the location of said
maximum tellurium content is approached is greater than the
absolute rate of decrease of the tellurium content as the location
of said maximum tellurium content is passed.
Description
The present invention relates generally to the construction of a
photoconductive layer used for the target of an image pickup tube
of the vidicon type, or more particularly to a photoconductive
layer with a rectifying contact which has an increased sensitivity
and an improved spectral sensitivity to red light.
Sb.sub.2 S.sub.3, PbO and Si are widely used as materials of
photoconductive layers for the target of the vidicon type image
pickup tube. Among these materials, Sb.sub.2 S.sub.3 constitutes a
photoconductive layer of injecting contact type, while PbO and Si
are used for the photoconductive layers of rectifying contact or
junction type. The advantages of the photoconductive layer of
rectifying contact or junction type over that of injection type are
a higher response speed, small dark current and higher sensitivity.
However, the photoconductive materials capable of forming a
rectifying contact successfully used as a target of the image
pickup tube are limited, and it is difficult to obtain a
photoconductive material with properties suitable in all
respects.
The peak of spectral sensitivity, for example, is located in the
proximity of infrared range for Si and on the side of visible short
wavelength for PbO, with the result that if they are used for a
color image pickup tube, Si and PbO have insufficient sensitivity
to blue and red respectively. The inventors have found that
amorphous selenium is also capable of forming a rectifying contact
suitable for the target of the image pickup tube, but this material
also has the disadvantage of insufficient sensitivity to red
light.
A method to improve the sensitivity to red light is disclosed in
U.S. Pat. No. 3,350,595. According to this method, a conductive
thin film is deposited on an insulating substrate which is in turn
covered with a photoconductive layer comprising mainly a mixture of
tellurium and selenium. The surface portion of the photoconductive
layer adjacent to the conductive thin film contains selenium of 70
to 80 % by weight while the opposite surface portion thereof
includes selenium of 90 to 100 % by weight, the selenium content
gently changing between both the surface portions. However, the
fact that the tellurium content in the photoconductive layer near
the interface thereof with the conductive thin film is high is
accompanied by the disadvantage of increased dark current. In order
to overcome this disadvantage, U.S. Pat. No. 3,350,595 discloses a
method in which a blocking layer of such metal as cesium with small
work function is interposed between the conductive film and the
photoconductive layer. This method, however, is disadvantageous in
that the manufacturing processes are complicated.
The object of the present invention is to obviate the
above-mentioned disadvantages and to provide a photoconductive
target of an image pickup tube which is high in sensitivity to red
light, small in dark current and is easily manufactured.
In order to achieve the above-mentioned object, the photoconductive
target of the image pickup tube according to the invention
comprises a light-transmitting substrate, a first N-type conductive
layer deposited on said substrate and a P-type conductive layer
making a rectifying contact with said first N-type conductive
layer, said P-type conductive layer including at least selenium and
tellurium, the composition of said P-type conductive layer being
different along the direction of the thickness thereof, the average
content of selenium in said P-type conductive layer being not less
than 50 atomic percent, the content of tellurium at both surfaces
of said P-type conductive layer being not more than 10 atomic
percent, the maximum tellurium content of 10 to 40 atomic percent
being located on a plane in said P-type conductive layer nearer to
said first N-type conductive layer than the middle plane of said
P-type conductive layer. The N-type conductive layer is a
light-transmitting conductive film preferably including as its main
component an oxide of tin, indium or titanium. Further, to prevent
the crystallization of the P-type conductive layer, an N-type
conductive layer formed of one substance selected from the group
consisting of CdS, CdSe, ZnS, ZnSe and a mixture thereof may be
interposed between the P-type conductive layer and the
light-transmitting conductive film or a translucent metal making up
the surface portion of the light-transmitting substrate nearer to
the side of the N-type conductive film. The P-type conductive layer
may include As, Sb, P, Bi, Ge and/or Si in addition to selenium and
tellurium.
Amorphous selenium is generally of P conduction type and forms a
rectifying contact with a variety of N-type materials including
films of single crystals or crystallites of such IV group
semiconductors as Ge and Si, III - V group semiconductors such as
GaAs and GaP and II - VI group semiconductors. Among them, the most
suitable material of N-type conduction to form a photoconductive
layer for the target of an image pickup tube in combination with
selenium are an oxide of tin used for a transparent conductive
film, an oxide of indium, an oxide of titanium, and II - VI group
semiconductors such as ZnS, ZnSe, CdS and CdSe. Although the low
intrinsic resistance of conductive films of the above-mentioned
oxides makes it possible to use them also as an electrode for
taking out a signal from the image pickup tube, the II - VI group
semiconductors cannot be used as such an electrode at the same time
without additional provision of the transparent electrode of any of
the above-mentioned oxides or a translucent metal laid thereon.
The better understanding of the present invention will be gained
from the following description taken in conjunction with the
accompanying drawings in which:
FIG. 1 is a sectional view showing the fundamental construction of
the target of the image pickup tube according to the present
invention; and
FIGS. 2 to 5 are graphs illustrating the distribution of component
elements along the direction of the thickness of the P-type
photoconductive layer.
An embodiment of the invention is shown in FIG. 1. The target of an
image pickup tube according to the invention generally comprises a
glass substrate 1, a transparent electrode 2 extended on the glass
substrate 1, an N-type conductive layer 3 and a P-type conductive
layer 4. Reference numeral 5 shows incident light, and numeral 6 a
scanning electron beam. A rectifying contact is formed between the
N-type conductive layer 3 and the P-type conductive layer 4.
In the case where the transparent electrode 2 is formed of an oxide
of N-type conductivity, the transparent electrode 2 and the N-type
conductive electrode 3 are actually integrated into a single layer.
In the event that amorphous selenium and the above-mentioned oxide
or a II - VI group semiconductor are used as the materials of the
P-type conductive layer and the N-type conductive layer
respectively, sensitization is necessary to improve the sensitivity
to red light since the above-mentioned materials other than CdSe do
not have sensitivity to red light.
A well-known method to improve sensitivity of II - VI group to red
light consists in doping into it Cl, Br, I, In, Ga or other
elements acting as a donor together with Cu, Ag or the like element
forming an acceptor. In the case where a P-type conductive layer
including selenium is involved as in the present invention, the
sensitivity to red light is successfully improved in combination
with the above-mentioned method concerning the sensitization of the
N-type conductive layer of II - VI group semiconductor.
It is also well known that the sensitivity to red light can be
improved by adding Te to amorphous selenium. The electrical
resistance of Se to which Te has been added is sharply reduced,
thereby degrading the characteristics of the target of the image
pickup tube. If, for example, the concentration of Te in the
neighborhood of the interface between N-type conductive layer 3 and
P-type conductive layer 4 is increased, the reverse breakdown
voltage of the rectifying contact is decreased thereby to increase
the dark current in the image pickup tube.
On the other hand, if the Te concentration of the P-type conductive
layer 4 as a whole is increased, the resistance of the P-type layer
is decreased or the carrier mobility in the layer is reduced, with
the result that the dark current is increased or the time response
characteristics are degraded.
The results of research by the inventors show that in improving the
sensitivity of the Se conductive layer to red light by the use of
Te, it is recommended that Te concentration in the Se conductive
layer be made progressively higher toward the side of the N-type
conductive layer rather than uniformly distributing it, and the Te
concentration at and in the vicinity of the interface between
N-type conductive layer and P-type conductive layer is maintained
at a low level, thus making it possible to prevent dark current
from being increased without adversely affecting the
characteristics of the target of the image pickup tube. For this
purpose, it is necessary to limit the Te concentration at and in
the vicinity of the interface to a level ranging from 0 to 10
atomic percent. Also, if there is Te included in a considerable
portion of the P-type conductive layer toward the opposite surface
thereof, the intensity of electric field in such a portion is
decreased for the degradation of the response characteristic
thereof, and therefore it is necessary to maintain the Te
concentration in that portion in the range from 0 to 10 atomic
percent.
The Te concentration of as little as 10 atomic percent in the
P-type conductive layer cannot achieve sufficient improvement in
sensitivity to red light. In view of this, the most effective
method to improve the sensitivity to red light is to provide a
portion between the surfaces of the P-type conductive layer with
the main component of Se where the Te concentration is maximum. If
the excitation of carriers is to be effected satisfactorily at the
point of high Te concentration, it is desirable that such a portion
be located at a position the nearest possible to the plane of
incidence of a light signal into the P-type conductive layer, that
is, the interface thereof with the N-type conductive layer. In
other words, the portion of maximum Te concentration should be
located on a plane in the P-type conductive layer nearer to the
N-type conductive layer than the middle plane of the P-type
conductive layer.
Since an excessively high Te concentration in that portion results
in an increased dark current, the maximum value of Te concentration
should preferably be between 10 to 40 atomic percent. As will be
explained later with reference to an embodiment, Te is not
necessarily required to be smoothly distributed in the P-type
conductive layer, but it may consist of a laminated structure of a
multiplicity of films each about 10 A thick comprising films of
high Te concentration and films of low Te concentration laid one on
another. For this reason, it should be noted that the
above-mentioned range of Te concentration from 10 to 40 atomic
percent represents an average value in the region several hundred A
thick including the portion of maximum Te concentration.
The progressive change in Te concentration in the transverse
direction of the P-type conductive layer may be abrupt in the
microscopic order of, say, several tens of A. Somewhat
macroscopically, however, the curve of the change should preferably
be gentle in the order of several hundreds of A. If macroscopically
there is a portion where the Te concentration is discontinued, the
burning effect of the image pickup tube may be promoted.
The disadvantage of the photoconductive layer with Se as a main
component resides in that the layer is easily crystallized by heat,
with the result that the picture produced is accompanied by defects
in the form of white dots. By a well-known method to prevent the
defects, an element such as As, Sb, P, Bi, Ge or Si is added to the
material for the layer thereby to increase the viscosity thereof
and delay the speed of crystallization. This principle also applies
to the present invention, wherein the life of the target may be
lengthened by adding such an element to the P-type conductive layer
thereby to reduce the speed of crystallization. The addition of
excessive amount of the element adversely affects the response
characteristic of the target, the desirable amount of the element
to be added being less than 20 atomic percent.
When the element for prevention of the crystallization coexists
with tellurium for improving the sensitivity, the maintaining of
superior dark current and response characteristics require that
selenium accounts for at least 50 atomic percent.
The fact that the emission of secondary electrons from the
photoconductive layer containing much Se used as a target is
comparatively great disturbs the landing of the scanning beam and
often causes abnormal phenomena including the distortion of an
image and the reversal of a polarity of a video signal at a high
target voltage.
An effective method to prevent the above-mentioned phenomena is to
deposit by vacuum or gaseous evaporation on the P-type conductive
layer a film of Sb.sub.2 S.sub.3, As.sub.2 Se.sub.3 or As.sub.2
S.sub.2 approximately 1000 A thick.
Embodiments of the invention will be explained below.
Embodiment 1
Se, Ge and Te contained in different evaporation boats of tantalum
are deposited simultaneously by evaporation in the vacuum of 3
.times. 10.sup.-.sup.6 Torr on a transparent N-type conductive
layer with tin oxide as a main component which is formed on a glass
substrate. In this way, a P-type photoconductive layer as thick as
3 .mu.m is produced.
The compositional profile of the P-type photoconductive layer is
adjusted by controlling the current in each boat so as to be in
consistence with the graph as shown in FIG. 2. Further, an Sb.sub.2
S.sub.3 film approximately 1000 A thick is deposited by evaporation
on the surface of the P-type photoconductive layer in the
low-pressure argon of 5 .times. 10.sup.-.sup.2 Torr thereby to
improve the landing characteristic of the scanning beam for the
target of an image pickup tube.
Embodiment 2
A transparent N-type layer consisting mainly of indium oxide is
deposited on a glass substrate. A CdSe film 2000 A thick is further
deposited in the vacuum of 2 .times. 10.sup.-.sup.6 Torr at the
substrate temperature of 200.degree.C, on the surface of a
transparent N-type conductive layer by evaporation. On the other
hand, a first photoconductive material of Se containing Te of 40
atomic percent and a second photoconductive material of Se
containing As of 10 atomic percent are prepared in a quartz ampule.
These two types of photoconductive materials are crushed and put
into different evaporation boats of tantalum and then they are
simultaneously deposited on the CdSe layer in the vacuum of 3
.times. 10.sup.-.sup.6 Torr. In the process, the speed of
evaporation of the first and second photoconductive materials is
continuously changed to form a film 4 .mu.m thick with the
composition distribution of Se, Te and As as shown in the graph of
FIG. 3. On the surface of the resulting P-type conductive layer is
deposited by evaporation a film of As.sub.2 Se.sub.3 approximately
500 A thick in the vacuum of 3 .times. 10.sup.-.sup.6 Torr. This
As.sub.2 Se.sub.3 film is further covered by a similar method with
an As.sub.2 Se.sub.3 film about 500 A thick in the low-pressure
argon of 5 .times. 10.sup.-.sup.2 Torr. This double layer of
As.sub.2 Se.sub.3 is formed for the purpose of improving the
landing characteristic of the scanning electron beam.
Embodiment 3
A translucent Al film is formed on a glsss substrate in the vacuum
of 1 .times. 10.sup.-.sup.6 Torr at the substrate temperature of
150.degree.C, and then on this translucent Al film is deposited a
CdS film 3000 A thick in the vacuum of 5 .times. 10.sup.-.sup.6
Torr at the substrate temperature of 150.degree.C.
Subsequently, thin films of Se, As.sub.2 Se.sub.3 and Te are
deposited one after another on the CdS film in a rotary vacuum
evaporator of 5 .times. 10.sup.-.sup.6 Torr. As a result, a film 5
.mu.m thick comprising 3000 to 6000 layers of Se, As.sub.2 Se.sub.3
and Te each having the average thickness of 10 A or less is
obtained.
During the process of forming the multiple layer, the current in
the Te boat or the opening of a slit interposed between the Te
evaporation boat and the substrate is controlled continuously
thereby to produce a macroscopic profile of transverse distribution
of composition as shown in FIG. 4. On this multiple layer is
further deposited an As.sub.2 S.sub.3 film about 500 A thick in the
vacuum of 2 .times. 10.sup.-.sup.6 Torr thereby to improve the
landing characteristic of the scanning electron beam.
Embodiment 4
Films of CdSe, CdTe and Se are deposited one after another in the
vacuum of 5 .times. 10.sup.-.sup.6 Torr on a transparent N-type
conductive electrode with tin oxide as a main component which is in
turn deposited on a glass substrate. In this way, a multiple layer
2 .mu.m thick comprising 2000 to 4000 films of CdSe, CdTe and Se
each having the average thickness of 10 A or less is obtained. In
the process of forming the multiple layer, the macroscopic
composition of the elements in the transverse direction of the
layer is controlled by similar means to those employed in the
preceding embodiment thereby to obtain the profile of composition
as shown in FIG. 5.
An excessive amount of Cd tends to be included in the CdSe film by
the ordinary method of production thereof, often resulting in the
CdSe film having an N-type of conduction. This problem is overcome
by adding Se as in the embodiment under consideration thereby to
obtain an intrinsic or nearly P-type layer. On this layer is
further deposited an Sb.sub.2 S.sub.3 film approximately 1000 A
thick in the low-pressure argon of 5 .times. 10.sup.-.sup.2 Torr
for improving the landing characteristic of the scanning beam.
It will be understood from the above explanation of the embodiments
that according to the invention the sensitivity especially to red
light is improved without adverse effect on the rectifying contact
with the N-type photoconductive layer by distributing Te in a
P-type photoconductive layer containing Se or 50 or more atomic
percent in such a manner that the maximum Te content is located on
a plane in the P-type conductive layer nearer to the N-type
conductive layer than the middle plane of the P-type conductive
layer. The spectral sensitivity of the P-type conductive layer is
thus changed greatly, making it possible to produce a
photoconductive layer suitable for a specific purpose. Although the
above explanation of the embodiments involves a light-receiving
film of the target for the image pickup tube, it is possible to use
the above-mentioned photoconductive layer for a solid-state
light-receiving element, solid-state image pickup element or the
like by employing an appropriate metal electrode in place of an
electron beam.
* * * * *