U.S. patent number 3,663,320 [Application Number 04/846,062] was granted by the patent office on 1972-05-16 for vapor growth process for gallium arsenide.
This patent grant is currently assigned to Nippon Electric Company, Limited. Invention is credited to Sadao Kikuchi, Mitsuhiro Maruyama, Osamu Mizuno.
United States Patent |
3,663,320 |
Maruyama , et al. |
May 16, 1972 |
VAPOR GROWTH PROCESS FOR GALLIUM ARSENIDE
Abstract
A process is provided for vapor growing a gallium arsenide
single crystal layer on a substrate seed-crystal of gallium
arsenide having a uniform electron concentration profile in the
layer wherein at least two kinds of impurities of the same
conductivity type are employed, one which causes autodoping to
occur in the vapor-grown crystal, the other which tends to inhibit
autodoping.
Inventors: |
Maruyama; Mitsuhiro (Tokyo,
JA), Mizuno; Osamu (Tokyo, JA), Kikuchi;
Sadao (Tokyo, JA) |
Assignee: |
Nippon Electric Company,
Limited (Tokyo, JA)
|
Family
ID: |
13005346 |
Appl.
No.: |
04/846,062 |
Filed: |
July 30, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Aug 2, 1968 [JA] |
|
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43/55672 |
|
Current U.S.
Class: |
438/505;
257/E21.112; 117/96; 438/916; 148/DIG.7; 148/DIG.151; 252/62.3GA;
257/657 |
Current CPC
Class: |
H01L
21/02395 (20130101); H01L 21/02573 (20130101); H01L
21/02546 (20130101); Y10S 148/007 (20130101); Y10S
148/151 (20130101); Y10S 438/916 (20130101) |
Current International
Class: |
H01L
21/02 (20060101); H01L 21/205 (20060101); H01l
007/36 (); H01l 007/00 (); C23c 011/00 () |
Field of
Search: |
;148/174,175,190,191
;117/106,107.2 ;252/62.3,512,518 ;23/204 ;317/234,235 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Saba; W. G.
Claims
What is claimed is:
1. A process for vapor growing gallium arsenide which comprises,
doping a substrate of gallium arsenide single crystal with at least
one impurity selected from the group consisting of tellurium,
selenium and sulfur each in an amount of about 5.times.10.sup.17
cm.sup.-.sup.3 and at least one other impurity from the group
consisting of silicon and tin, each in an amount of less than about
3.times.10.sup.18 cm.sup.-.sup.3, and vapor-growing an n-type
gallium arsenide single crystal having impurity concentration of
less than 5.times.10.sup.16 cm.sup.-.sup.3 on said substrate of
gallium arsenide single crystal.
2. The method of claim 1, wherein one impurity is tellurium, and
wherein the other impurity is silicon.
3. The method of claim 1, wherein one impurity is tellurium, and
wherein silicon and tin together comprise the other impurity.
4. In a process for vapor growing a gallium arsenide single crystal
layer on a substrate seed-crystal of gallium arsenide having a
uniform electron concentration profile in the layer, the
improvement which comprises the steps of doping said substrate
seed-crystal with at least two kinds of impurities having the same
conductivity type, one being able to cause autodoping to occur in
the vapor-grown crystal which is selected from the group consisting
of tellurium, selenium and sulfur each in an amount of about
5.times.10.sup.17 cm.sup.-.sup.3, the other tending to inhibit
autodoping which is selected from the group consisting of silicon,
tin and germanium, and vapor-growing a gallium arsenide single
crystal having impurity concentration of less than
5.times.10.sup.16 cm.sup.-.sup.3 on said substrate seed-crystal of
gallium arsenide single crystal.
Description
This invention relates to a process of incorporating impurities in
a substrate seed-crystal of gallium arsenide in order to attain a
uniform electron concentration profile in the vapor-grown gallium
arsenide epitaxial layer. The resulting gallium arsenide crystal
may be adapted for the fabrication of Gunn effect elements and
other gallium arsenide devices.
The n-type impurities with which the substrate seed-crystals of
gallium arsenide used for the vapor growth of gallium arsenide are
doped are the elements of the Group VI of the Periodic Table, such
as tellurium, sulfur and selenium and the Group IV elements, such
as silicon and tin.
BACKGROUND OF THE INVENTION
In order to reduce the resistivity of the substrate, it is
desirable to dope the substrate with as much impurity as is
feasible. However, if an epitaxial layer is grown from the vapor
phase on a tellurium-doped substrate with electron concentration
more than 10.sup.18 cm.sup.-.sup.3, for example, the electron
concentration profile of the growth layer is influenced by
substrate autodoping. The autodoping makes it almost impossible to
ensure a uniform electron concentration profile throughout the
grown layer. With regard to the phenomenon of "autodoping",
reference is made to C.O. Thomas D. Kahng and R.C. Manz, J.
Electrochem, Soc. 109(1962) 1055. If the tellurium concentration of
the substrate is made low enough to prevent or inhibit the
influence of the autodoping, the resistivity of the substrate is
often too high for practical applications. Further, when a silicon-
or tin-doped substrate is used for the vapor growth, low electron
concentration and an electrically high resistance region appear in
the growth layer in the vicinity of the layer-substrate interface,
with the result that the grown layer thus obtained also does not
have a uniform electron concentration profile.
It is thus the object of the invention to provide a process for
growing a gallium arsenide single crystal layer on a substrate
seed-crystal of gallium arsenide having a uniform electron
concentration profile in the layer.
Other objects will more clearly appear from the following
disclosure and the accompanying drawing, wherein:
FIG. 1 is a graph showing typical electron concentration profiles
of gallium arsenide epitaxial layers grown from the vapor phase on
a conventional substrate seed-crystal; and
FIG. 2 is a graph showing exemplary electron concentration profile
of a grown layer on a substrate seed-crystal according to the
present invention .
General Statement of the Invention
The present invention is directed to a process for doping a
substrate seed-crystal of gallium arsenide with impurities, which
overcomes the difficulties above mentioned and makes it possible to
obtain a vapor grown layer having a uniform impurity concentration
profile.
The essence of the present invention is as follows: A substrate
seed-crystal is employed for vapor growth which is doped with two
kinds of impurities having the same conductivity type, one impurity
being the type that causes autodoping into the grown layer from the
substrate, the other being such as to inhibit autodoping. The
concentration of the first impurity which causes autodoping is
sufficiently restricted so as to preclude autodoping during the
growth process, while the concentration of the other impurity that
inhibits autodoping is made as high as possible. Thus, an epitaxial
layer with uniform impurity concentration profile and of
sufficiently low resistance is grown on the substrate.
The impurities that can cause autodoping into a grown layer are the
n-type tellurium, selenium and sulfur and the p-type impurity zinc.
The other kind of impurities which tends to inhibit autodoping
includes silicon, tin and germanium as n-type impurities, germanium
being also a p-type impurity, since the germanium conductivity type
is amphoteric. There appears to be a critical concentration for
tellurium, selenium and sulfur above which the substrate autodoping
into the grown layer occurs, and below which the high resistance
region in the growth layer in the vicinity of the layer-substrate
interface appears. The critical value is not affected by the
conditions of the vapor growth of gallium arsenide and is about
5.times.10.sup.17 cm.sup.-.sup.3. There is no critical value for
silicon and tin. The high resistance region always appears in the
growth layer in the vicinity of the layer-substrate interface, even
if heavily silicon- or tin-doped substrate is used, although the
electron concentration of the substrate has an upper limit of about
3.times.10.sup.18 cm.sup.-.sup.3.
This invention is advantageous where the impurity concentration of
the grown layer is 5.times.10.sup.16 cm.sup.-.sup.3 or less if the
grown layer is of the n-type. In the case where a vapor-grown layer
has an impurity concentration of more than 5.times.10.sup.16
cm.sup.-.sup.3, the low electron concentration region in the
vicinity of the layer-substrate interface does not appear, even if
silicon- or tin-doped substrate is used; and, therefore, a
substrate simply containing an impurity that does not cause
autodoping results. This has nothing to do with the present
invention. It is considered that there may be a similar
concentration limit for p-type grown layer.
The invention will be more fully described hereunder with reference
to the accompanying drawings.
DETAILS OF THE INVENTION
FIG. 1 graphically illustrates an example of electron concentration
profile of an n-type vapor-grown layer on a conventional substrate
of n-type gallium arsenide. The curve 11 represents the electron
concentration profile of a substrate. The curve 13 is the electron
concentration profile of the layer grown on a substrate doped with
1.times.10.sup.18 cm.sup.-.sup.3 tellurium, which shows occurrence
of autodoping of tellurium into the grown layer, while the curve 14
represents the profile of the layer grown on a substrate doped with
1.times.10.sup.18 cm.sup.-.sup.3 silicon, which shows the
appearance of low electron concentration region near the
layer-substrate interface.
In an embodiment of the invention, a substrate seed-crystal of
n-type gallium arsenide doped with both 5.times.10.sup.17
cm.sup.-.sup.3 tellurium and 1.times.10.sup.18 cm.sup.-.sup.3
silicon is employed. Referring to FIG. 2, lines 21 and 22 represent
electron concentrations in the substrate seed-crystal due to
silicon and tellurium, respectively, while the hatched portion
represents the amount of electron concentration due to silicon in
excess of that due to tellurium. On this substrate, an n-type
gallium arsenide layer is grown by feeding arsenic trichloride
(AsCl.sub.3) gas with hydrogen gas as a carrier gas into a reaction
system in which gallium heated at 850.degree. C. and the substrate
heated at 750.degree. C. are placed. Line 23 of FIG. 2 represents
the electron concentration profile of the layer thus obtained.
Thus, by doping the substrate seed-crystal with tellurium of the
critical amount, or 5.times.10.sup.17 cm.sup.-.sup.3, that avoids
the autodoping of tellurium from the substrate into the grown
layer, it is possible to obtain a vapor-grown layer with a uniform
electron concentration profile. In addition to tellurium doping, by
doping said substrate seed-crystal with 1.times.10.sup.18
cm.sup.-.sup.3 silicon that inhibits autodoping, it is possible to
prevent increase in the resistivity of the substrate.
Doping the substrate seed-crystal with not only both
5.times.10.sup.17 cm.sup.-.sup.3 tellurium and 1.times.10.sup.18
cm.sup.-.sup.3 silicon but also with not less than
1.times.10.sup.18 cm.sup.-.sup.3 tin will, like silicon, induce no
autodoping, while reducing the resistivity of the substrate still
further. Simultaneous doping with other different impurities may be
employed to reduce the substrate resistivity or control the
autodoping as desired.
For example, doping with silicon and tin both within the limit of
concentration of about 3.times.10.sup.18 cm.sup.-.sup.3 would make
it possible to enhance the electron concentration of the substrate
to 6.times.10.sup.18 cm.sup.-.sup.3. Additional doping with
tellurium and selenium both in the concentration of
5.times.10.sup.17 cm.sup.-.sup.3 would enable increasing the
electron concentration of the substrate up to 7.times.10.sup.18
cm.sup.-.sup.3 without autodoping occuring in the grown layer.
A described above, the present invention makes it possible to
obtain easily a vapor-grown layer of gallium arsenide having a
uniform impurity concentration profile and to control, as desired,
the impurity concentration profile in the growth layer near the
layer-substrate interface by varying the kinds and concentration of
the impurities doped in the substrate seed-crystal.
It should be understood that the present invention is not limited
to the embodiment above described, but, of course, many other
applications are possible without departing from the spirit of this
invention.
* * * * *