U.S. patent number 3,870,558 [Application Number 05/368,309] was granted by the patent office on 1975-03-11 for process for preparing a layer of compounds of groups ii and vi.
This patent grant is currently assigned to Tokyo Shibouro Electric Co., Ltd.. Invention is credited to Satoshi Aihara, Kazuo Shimizu, Kazuo Terakawa, Okio Yoshida.
United States Patent |
3,870,558 |
Shimizu , et al. |
* March 11, 1975 |
Process for preparing a layer of compounds of groups II and VI
Abstract
A process for preparing a layer of compounds of Groups II and VI
characterized in that a layer of the compounds is formed on the
surface of a substrate, and the formed layer is heat-treated in an
atmosphere comprising an inert gas, 0.1-10% by volume of oxygen on
the basis of said inert gas and vapour of at least one element
selected from a group consisting of sulfur, selenium and tellurium
so that uniform grain growth with a narrow range grain size
distribution is effected.
Inventors: |
Shimizu; Kazuo (Yokohama,
JA), Yoshida; Okio (Yokohama, JA),
Terakawa; Kazuo (Tokosuka, JA), Aihara; Satoshi
(Yokohama, JA) |
Assignee: |
Tokyo Shibouro Electric Co.,
Ltd. (Kawasaki-shi, JA)
|
[*] Notice: |
The portion of the term of this patent
subsequent to February 19, 1991 has been disclaimed. |
Family
ID: |
26868101 |
Appl.
No.: |
05/368,309 |
Filed: |
June 8, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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172454 |
Aug 17, 1971 |
3793069 |
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Current U.S.
Class: |
427/255.26;
257/E21.462 |
Current CPC
Class: |
C30B
1/02 (20130101); C30B 29/48 (20130101); H01L
21/02631 (20130101); H01L 21/0256 (20130101); H01L
21/02557 (20130101) |
Current International
Class: |
H01L
21/02 (20060101); C30B 1/00 (20060101); C30B
1/02 (20060101); H01L 21/363 (20060101); B44d
001/02 () |
Field of
Search: |
;117/16A,62,215,201,16R |
References Cited
[Referenced By]
U.S. Patent Documents
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|
3793069 |
February 1974 |
Shimizu et al. |
|
Primary Examiner: Weinblatt; Mayer
Attorney, Agent or Firm: Kemon, Palmer & Estabrook
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This is continuation-in-part of the U.S. patent No. application
Ser. No. 172,454 filed on Aug. 17, 1971, now U.S. Pat. No.
3,793,069.
Claims
What we claim is:
1. A process for preparing a composite layer consisting of a CdS
layer and a CdSe layer which comprises forming said composite layer
on a substrate plate and heat-treating it in an atmosphere
comprising an inert gas, 0.1-10% by volume of oxygen on the basis
of said inert gas and vapour selected from the group consisting of
selenium, sulfur and mixtures of sulfur with selenium, whereby
uniform-grain growth with narrow range grain size distribution is
effected.
2. A process for preparing a layer of Group II-VI compound which
comprises forming a layer of cadmium selenide on a substrate plate
and heat-treating it in an atmosphere comprising an inert gas,
0.1-10% by volume of oxygen on the basis of said inert gas and
vapour of sulfur or mixtures of sulfur with selenium, whereby
uniform grain growth with narrow range grain size distribution is
effected.
3. A process for preparing a layer of a Group II-VI compound which
comprises forming a layer of cadmium sulfide on a substrate plate
and heat-treating it in an atmosphere comprising an inert gas,
0.1-10% by volume of oxygen on the basis of the inert gas and
vapour of selenium or mixtures of selenium with sulfur, whereby
uniform grain growth with narrow grain size distribution is
effected.
4. A process for preparing a layer of a Group II-VI compound which
comprises forming a layer of cadmium sulfoselenide on a substrate
plate and heat-treating it in an atmosphere comprising an inert
gas, 0.1-10% by volume of oxygen on the basis of the inert gas and
vapour selected from the group consisting of selenium, sulfur and
mixtures thereof, whereby uniform grain growth with narrow grain
size distribution is effected.
5. The process of claim 2 wherein said atmosphere consists
essentially of an inert gas selected from the group consisting of
nitrogen and argon, 0.1-10% by volume of oxygen on the basis of the
inert gas and vapour of sulfur or mixtures of sulfur with
selenium.
6. The process of claim 3 wherein said atmosphere consists
essentially of an inert gas selected from the group consisting of
nitrogen and argon, 0.1-10% by volume of oxygen on the basis of the
inert gas and vapour of selenium or mixtures of selenium with
sulfur.
7. The process of claim 4 wherein said atmosphere consists
essentially of an inert gas selected from the group consisting of
nitrogen and argon, 0.1-10% by volume of oxygen on the basis of the
inert gas and vapour selected from the group consisting of
selenium, sulfur and mixtures thereof.
Description
FIELD OF THE INVENTION
This invention relates to a process for preparing a layer of Groups
II-VI compounds with narrow grain size distribution.
DESCRIPTION OF THE PRIOR ART
A film of a large area of a compound or a film of a compound
separately distributed over a large area is useful as a
light-electricity transducer in a wide range of technical fields,
such as solar cells, solid state photosensors for image pickup
application, photoconductive film for image pickup tubes, etc. Such
films should be furnished not only with electrical properties
satisfactory enough for desired performance, but also with
uniformity in such properties over a wide area. For instance, local
unbalance in photosensitivity or intensity of luminescence of a
film element not only abates the commercial value thereof, but
constitutes a fatal factor which restricts the life of the film
element.
Usually such a film is formed by vacuum evaporation or gaseous
phase reaction on the surface of a substrate plate. In order to
improve the electrical properties thereof, however, heat treatment
is necessary after film formation in many cases. Such heat
treatment is generally accompanied by growth of grains which
constitute the film. Therefore the characteristics of a film
element, especially uniformity of the characteristics over a wide
area is often influenced by the grain growth during the heat
treatment. In order to secure desirable grain growth in the heat
treatment, it is important to select a suitable temperature, but
the maximum temperature may be limited because of heat resistance
of the substrate material, possible decomposition of the compound
constituting the film, etc. Therefore, fluxes are widely employed
in such heat treatment.
A typical example of such fluxes used in the heat treatment is
cadmium chloride, which is employed in the treatment of cadmium
sulfide used for photoconductive elements. Cadmium chloride is
effective for cadmium selenide or cadmium sulfoselenide film, too.
To make the effect of the heat treatment satisfactory,
consideration is paid to making the flux concentration as uniform
as possible. However, when cadmium chloride is used in the heat
treatment of cadmium sulfide or cadmium selenide photoconductive
films, a large quantity of chlorine penetrates into the
photoconductive film and in some cases the concentration thereof
reaches as high as 10.sup.20 atoms/cm.sup.3. This chlorine builds
up a shallow doner level in the cadmium sulfide or selenide. The
existence of such high concentration of a shallow doner level
impairs photosensitivity of the films and in some other cases
retards response to light.
The advantage of the above-mentioned heat treatment in which the
flux is used is that grain size is rather uniform after grain
growth. In contrast, in methods in which flux is not used, but, for
instance, simply temperature is raised for promotion of grain
growth, the grain growth rate varies from part to part and a film
with a wide range distribution of grain size results. This is the
cause of non-uniformity in film thickness and causes fatal defects
such as pinhole, peeling-off of film, etc.
In order to carry out the uniform grain growth of a film which
comprises amorphous or extremely fine grains, it is necessary in
general to generate a suitable number of uniformly distributed
nuclei on the surface of the film.
SUMMARY OF THE INVENTION
In accordance with this invention, such uniformly distributed
nuclei which lead to a film of a uniform structure with narrow
range grain size distribution are provided on the surface of a film
of Groups II-VI compounds by carrying out the heat treatment of
said film in an atmosphere comprising an inert gas and 0.1-10% by
volume of oxygen on the basis of said inert gas and the vapour of
at least one element selected from a goup consisting of sulfur,
selenium and tellurium.
BRIEF DESCRIPTION OF THE DRAWING
This invention can be more fully understood from the following
detailed description when taken with reference to the accompanying
drawings, in which:
FIG. 1 is a diagram showing the grain size distribution
characteristic of the film obtained in accordance with this
invention in comparison with those of the prior art films;
FIG. 2 is a photomicrograph (x 5,000) of a film obtained by the
process of this invention; and
FIG. 3 is a photomicrograph of a film obtained by the prior art
process at the same magnification.
DESCRIPTION OF PREFERRED EMBODIMENTS
Now the invention is explained in detail with respect to an
embodiment pertaining to a preparation of a photoconductive
element. A thin film of cadmium selenide, 5.mu. thick for instance,
is deposited on the surface of a substrate plate kept at
150.degree.C in vacuo by vacuum evaporation technique. The thus
obtained film is heat-treated in an inert gas such as nitrogen
containing 5% by volume of oxygen at 500.degree.C for 1 hour,
wherein selenium vapour exhibiting saturation vapour pressure at
500.degree.C co-exists. This selenium vapour can be mixed with the
oxygen prior to the heat treatment or can be generated in situ by
suitable means. By this heat treatment, the grain size of the
originally deposited film which is about 1000A grows to about
1.5.mu. and a film having grain size which is quite uniform is
obtained. This grain growth is the same as the grain growth which
results from a process in which 20 mole percent of cadmium chloride
is mixed with cadmium selenide when the substrate plate is treated
therewith and the deposited film is heat-treated in a nitrogen
atmosphere.
The effect and advantage of this invention is now given below on
the basis of the above-described embodiment. The point of this
invention is that limited volume of oxygen is employed in
combination with selenium vapour in the heat treatment atmosphere.
To heat-treat cadmium selenide in a selenium vapour has been known
and practiced in the prior art. However, this is a treatment for
the purpose of filling the selenium vacancies in cadmium selenide
film, and is carried out so as to modify the electrical properties
of a film. Also heat treatment in air is frequently employed as the
treatment in an oxygen-containing atmosphere. Air is regarded as a
mixture of oxygen and nitrogen. Japanese Pat. Publication No.
23456/65 refers to nitrogen atmosphere containing 0.2-1.7% oxygen
as the atmosphere containing limited amount of oxygen. However, the
invention of this reference relates to a process of heat treatment
in which cadmium selenide is heat-treated together with a flux, and
the atmosphere comprises oxygen, nitrogen and cadmium halide
vapour, whereby grain growth is effectuated with the cadmium halide
flux, and oxygen is added for filling selenium vacancies merely as
an auxiliary agent.
In accordance with this invention, as illustrated in the above
example, oxygen and selenium vapour must co-exist in the atmosphere
during the heat treatment. That is, if the atmosphere lacks either
of the two, no such film as is aimed at in this invention can be
obtained. For instance, if the operation of the above-mentioned
working example is carried out in an atmosphere which contains no
selenium vapour, grain growth does not proceed as shown by
comparison of Curve 1 in FIG. 1, which represents the grain size
distribution before the heat treatment, and Curve 2, which
represents the grain size distribution after the heat treatment. On
the other hand, when oxygen is omitted from the atmosphere, the
grain size distribution after the treatment is represented by Curve
3 in FIG. 1. In this case, the range of grain size distribution is
much enlarged.
In contrast, Curve 4 represents the grain size distribution when a
film is heat-treated in an atmosphere in which oxygen and selenium
vapour co-exist in accordance with this invention. Comparison of
FIGS. 2 and 3, which show electron photomicrographs of the film of
this invention and that of the prior art, shows how superior the
film of this invention is to that of the prior art in the grain
size and the grain size distribution. Thus, the photoconductive
film of this invention, as represented by FIG. 2, is free from
unevenness in photoelectric sensitivity.
Now the reason why such effect is achieved by this invention is
discussed with particular reference to the above-mentioned
embodiment. In the course of the heat treatment, when the
temperature of the substrate plate is raised, oxygen and selenium
from the atmosphere and cadmium from the film react on the surface
of the film to form an intermediate oxide, for instance, cadmium
selenite (CdSeO.sub.3), which is a salt of an oxyacid. This
compound is redecomposed at higher temperatures, and therefore,
transient formation and decomposition of the intermediate oxide
takes place in the course of temperature raise. This gives nuclei
which become sites where grain growth is initiated, and
rearrangement of structure begins at the surface and it proceeds
into the inner parts. Such intermediate steps promote grain growth
and bring about narrow distribution of grain size.
If the atmosphere in which there is to be conducted the desired
reaction should contain larger proportions of oxygen than
prescribed for concomitance with vapours of selenium, for example,
if the reaction is performed in the ordinary air, then oxidation
will proceed in excess. This will cause to form an intermediate
oxide whose growth should originally stop with the formation of a
nucleus prominently to settle on the treated layer to constitute an
objectionable surface deposit, with the resultant deterioration of
the electric properties of said layer. This is the reason why the
amount of oxygen in the heat treatment atmosphere must be limited
when the synergistic effect of oxygen and selenium is expected.
This limit is 10% by volume on the basis of the volume of base or
carrier gas such as argon or nitrogen. It is needless to say that
too small an amount of oxygen does not work. In order to effectuate
smooth creation of grain growth nucleus sites, at least 0.1% by
volume of oxygen is necessary.
On the other hand it is rather difficult to determine a suitable
amount of concentration of selenium vapour, since the partial
pressure of selenium vapour in the heat treatment atmosphere is
related to the electrical properties of finished products, but at
least 1 mm Hg will suffice. A temperature of at least 450.degree.C
for the heat treatment is required since the treatment is carried
out without the aid of a flux.
The invention has been explained above with respect to cadmium
selenide layer in particular. However, this invention is
effectively applicable to compounds of Groups II and VI in general
such as cadmium sulfide, cadmium telluride, zinc sulfide, zinc
selenide, zinc telluride, and a mixture (solid solution or
heterogeneous mixture), and films of multi-layer structure of these
compounds, too. Layers of these compounds may contain known
impurities. The inert gases which constitute the main component of
the heat treatment atmosphere are argon, nitrogen or a mixture
thereof. In conclusion, the process of this invention is
characterized in that nuclei necessary for uniform grain growth are
provided on the surface of a film to be treated by causing
formation and decomposition of intermediate oxide, such as salt of
an oxyacid, on the surface of the film in the course of the heat
treatment.
According to this invention, grain growth is effected without using
any flux, the film to be treated is not contaminated with the flux,
and therefore, control of impurity content is much simplified.
EXAMPLE 1
A cadmium sulfoselenide of 3.mu. in thickness was vapour formed in
an atmosphere of argon pressure of 0.5 mm Hg onto a substrate kept
at 250.degree.C. Then, the film was heat treated for 15 minutes at
600.degree.C in a gaseous nitrogen atmosphere including 2% of
volume of oxygen and under coexistence with a solenium vapour as
indicating one half of a saturated vapour pressure at 600.degree.C.
The vapour formed film had a grain size of about 2000A. After the
heat treatment, however, the grain size of the film was grown to
2.mu. and a film with uniform grain size distribution was
obtained.
The cadmium sulfoselenide film was prepared from a composition of
cadmium sulfide and cadmium selenide whose molar ratio was
preliminarily adjusted to be 1:2. That is, the composition ratio
was preliminarily adjusted so that a wavelength present at a peak
position of the spectral sensitivity of the film is in a range
between about 5000A constituting the fundamental absorption edge of
cadmium sulfide and 7000A constituting the fundamental absorption
edge of cadmium selenide. The composition ratio, however, can be
varied according to the usage of the adjusted film.
EXAMPLE 2
A cadmium sulfoselenide film of about 2.mu. in thickness prepared
from a composition of cadmium sulfide and cadmium selenide whose
molar ratio was preliminarily adjusted to be, for example, 1:2 was
vapour formed, in an atmosphere of an inert gas, for example, an
argon pressure of 0.8 mm Hg, onto a substrate kept at 250.degree.C.
Then, the film was heat treated for 15 minutes at 550.degree.C in
an inert gas atmosphere of, for example, nitrogen or argon,
including 1.5% by volume of oxygen and under coexistence with a
sulfur vapour as indicating one half of a saturated vapour pressure
at 550.degree.C.
The vapour formed film had a grain size of about 2000 A. After the
heat treatment, however, the grain size of the film was grown to
about 1.mu. and a film with uniform grain size distribution was
obtained.
EXAMPLE 3
A cadmium sulfoselenide film of about 2.mu. in thickness prepared
from cadmium sulfide and cadmium selenide whose molar ratio is
preliminarily adjusted to be, for example, 1:2 was vapour formed in
an atmosphere of an argon pressure of 0.8 mm Hg onto a substrate
kept at 250.degree.C. The film was heat treated for 15 minutes at
580.degree.C in an inert gas atmosphere of nitrogen or argon
including 2% by volume of oxygen and under coexistence with a
selenium vapour and a sulfur vapour as both showing one half of a
saturated vapour pressure. The vapour formed film had a grain size
of about 2000 A. After the heat treatment, however, the grain size
of the film was grown to about 1.mu. and a film with uniform grain
size distribution was obtained.
EXAMPLE 4
A cadmium selenide film of 2.mu. in thickness was vapour formed in
an atmosphere of an argon pressure of 1 mm Hg onto a substrate
keept at 250.degree.C. The film was heat treated for 15 minutes at
550.degree.C in an atmosphere of an inert gas, for example,
nitrogen or argon, including 1% by volume of oxygen and under
coexistence of a sulfur vapour as indicating one half of a
saturated vapour pressure at 550.degree.C. The vapour formed film
had a grain size of about 2000 A. After the heat treatment,
however, the grain size of the film was grown to about 1.mu. and a
film with uniform grain size distribution was obtained.
To prevent an excess replacement of the surface of a cadmium
selenide film by cadmium sulfide, the heat treatment may be made,
in this case, under coexistence with both said sulfur vapour and a
selenium vapour as indicating a saturated vapour pressure at the
heat treating temperature.
EXAMPLE 5
A cadmium sulfide film of 2.5.mu. in thickness was vapour formed in
vacuum onto a substrate kept at 120.degree.C. Then, the film was
heat treated for 20 minutes at 580.degree.C in an inert gas
atmosphere of, for example, nitrogen or argon including 3% by
volume of oxygen and under coexistence with a selenium vapour as
indicating one half of a saturated vapour pressure at 580.degree.C.
The vapour formed film had a grain size of 1000 A. After the heat
treatment, however, the grain size of the film was grown to about
1.5.mu. and a film with uniform grain size distribution was
obtained.
To prevent an excess replacement of the surface of a cadmium
sulfide film by cadmium selenide, the heat treatment may be
effected, in this case, under coexistence of both said selenium
vapour and a sulfur vapour as indicating a saturated vapour
pressure.
EXAMPLE 6
A cadmium sulfide film of 1.mu. in thickness was vapour formed in
an atmosphere of an argon pressure of 0.8 mm Hg onto a substrate
kept at 200.degree.C. Then, a cadmium selenide film of 2.5.mu. in
thickness was vapour formed onto the cadmium sulfide film. The
composite film was heat treated for 10 minutes at 620.degree.C in
an inert gas atmosphere of nitrogen or argon including 1.5% by
volume of oxygen and under coexistence with a selenium vapour as
indicating a saturated vapour pressure at the heat treating
temperature. The vapour formed composite film had a grain size of
about 2000 A. After the heat treatment, however, the grain size of
the composite film was grown to 1.mu. and a film with uniform grain
size distribution was obtained.
EXAMPLE 7
A cadmium sulfide film of 2.mu. in thickness was vapour formed in
an atmosphere of an argon pressure of 0.8 mm Hg onto a substrate
kept at 200.degree.C. Then, a cadmium selenide film of 2.mu. in
thickness was vapour formed onto the cadmium sulfide film. The
composite film was heat treated for 15 minutes at 600.degree.C in
an inert gas atmosphere of, for example, nitrogen or argon
including 1% by volume of oxygen and under coexistence with a
sulfur vapour as indicating one half of a saturated vapour pressure
at 600.degree.C. The vapour formed composite film had a grain size
of about 2000 A. After the heat treatment, however, the grain size
of the composite film was grown to about 1.mu. and a film was
uniform grain size distribution was obtained.
EXAMPLE 8
A cadmium sulfide film of 2.mu. in thickness was vapour formed in
an atmosphere of an argon pressure of 0.8 mm Hg on a substrate kept
at 200.degree.C. Then, a cadmium selenide film of 2.mu. in
thickness was vapour formed onto the cadmium sulfide film. The
composite film was heat treated for 10 minutes at 600.degree.C in
an inert gas atmosphere of, for example, nitrogen or argon
including 1.5% by volume of oxygen, and under coexistence with a
selenium vapour and a sulfur vapour as both indicating a saturated
vapour pressure at the heat treating temperature. The vapour formed
composite film had a grain size of about 2000 A. After the heat
treatment, however, the grain size of the composite film was grown
to about 1.mu. and a film with uniform grain size distribution was
obtained.
* * * * *