U.S. patent number 3,839,084 [Application Number 05/310,209] was granted by the patent office on 1974-10-01 for molecular beam epitaxy method for fabricating magnesium doped thin films of group iii(a)-v(a) compounds.
This patent grant is currently assigned to Bell Telephone Laboratories, Incorporated. Invention is credited to Alfred Yi Cho, Morton B. Panish.
United States Patent |
3,839,084 |
Cho , et al. |
October 1, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
MOLECULAR BEAM EPITAXY METHOD FOR FABRICATING MAGNESIUM DOPED THIN
FILMS OF GROUP III(A)-V(A) COMPOUNDS
Abstract
In a molecular beam epitaxy method of fabricating a Mg doped
thin film of a compound of the form Al.sub.x B.sub.1.sub.-x C,
where B is a Group III(a) element and C is a Group V(a) element,
the sticking coefficient of magnesium is a nonlinear, monotonically
increasing function of the amount of aluminum. P-type thin films of
Al.sub.x B.sub.1.sub.-x C:Mg having a predetermined carrier
concentration are fabricated by including in the molecular beam(s)
an appropriate amount of aluminum determined from said
function.
Inventors: |
Cho; Alfred Yi (New Providence,
NJ), Panish; Morton B. (Springfield, NJ) |
Assignee: |
Bell Telephone Laboratories,
Incorporated (Murray Hill, NJ)
|
Family
ID: |
23201456 |
Appl.
No.: |
05/310,209 |
Filed: |
November 29, 1972 |
Current U.S.
Class: |
117/105; 438/918;
117/106; 117/954; 117/955; 117/108; 438/936; 148/DIG.18;
148/DIG.65; 148/DIG.169; 257/609; 148/DIG.20; 257/102 |
Current CPC
Class: |
C30B
23/02 (20130101); C30B 29/40 (20130101); Y10S
438/936 (20130101); Y10S 148/169 (20130101); Y10S
438/918 (20130101); Y10S 148/018 (20130101); Y10S
148/065 (20130101); Y10S 148/02 (20130101) |
Current International
Class: |
C30B
23/02 (20060101); B44d 001/18 () |
Field of
Search: |
;148/175
;117/200,201,215,217,227,107,16A ;317/235AQ,235N |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weiffenbach; Cameron K.
Attorney, Agent or Firm: Urbano; M. J.
Claims
1. A method for epitaxially growing upon a surface a p-type thin
film of a material having a composition Al.sub.x B.sub.1.sub.-x C,
where 0 < x .ltoreq. 1, Al is aluminum, B is a Group III(a)
element and C is a Group V(a) element, comprising the steps of:
a. reducing the background pressure to a subatmospheric
pressure;
b. directing at least one molecular beam comprising a p-type
dopant, said aluminum, said Group III(a) element and said Group
V(a) element, upon said surface for a time period sufficient to
effect growth of a p-type film of Al.sub.x B.sub.1.sub.-x C, 0 <
x .ltoreq. 1, of the desired thickness;
c. preheating said surface to a temperature effective to allow
atoms impinging thereon to migrate to surface sites to form said
epitaxial film and effective to produce congruent evaporation of
said Group III(a) elements and said Group V(a) element:
d. maintaining the relative proportions of the constituents of said
at least one molecular beam so that at said surface there is an
excess of said Group V(a) element with respect to aluminum and said
Group III(a) element, and characterized in that:
1. said p-type dopant is magnesium;
2. the sticking coefficient of magnesium on said surface, and hence
the carrier concentration of said thin film, increases in
accordance with a determinable relationship with increasing amounts
of aluminum in said thin film; and
3. aluminum is included in said at least one molecular beam in an
amount determined from said relationship effective to produce a
desired carrier
2. The method of claim 1 wherein said background pressure is
reduced to at
3. The method of claim 1 wherein a first layer containing a first
amount of Al is grown on said surface with the Mg flux in said at
least one beam maintained at a first level, then a second layer
containing a second amount of Al is grown, and during the growth of
said second layer the Mg flux is changed to compensate for the
change in the Mg sticking
4. The method of claim 1 wherein said surface is preheated to a
temperature
5. The method of claim 4 wherein said thin film comprises a
material selected from the group consisting of Al.sub.x
Ga.sub.1.sub.-x As and
6. The method of claim 5 wherein said thin film comprises Al.sub.x
Ga.sub.1.sub.-x As and said at least one molecular beam is formed
by heating a first source of liquid Ga to produce a first beam of
Ga molecules, by heating a second source of solid Al to produce a
second beam of Al molecules, by heating a third source of As to
produce a third beam of As molecules and by heating a fourth source
of Mg to produce a fourth beam of Mg molecules, said first, second,
third and fourth beams impinging
7. The method of claim 6 wherein said third source comprises
polycrystalline GaAs to produce said third beam comprising
As.sub.2
8. The method of claim 6 wherein the sticking coefficient of said
Mg molecules on said surface increases according to said
determinable relationship from about 10.sup.-5 to about 10.sup.-2
as the amount x of Al in said thin film increases from about 0 to
0.1 and produces a corresponding increase in the carrier
concentration of said thin film from
9. The method of claim 6 wherein said thin film is made to have a
carrier concentration greater than about 5.times.10.sup.17
/cm.sup.3 by adapting the intensity of said aluminum beam to
produce a thin film of Al.sub.x
10. The method of claim 9 wherein said second source of Al is
heated to a temperature greater than about 1,270.degree. K.
Description
BACKGROUND OF THE INVENTION
This invention relates to the epitaxial growth of thin films of
controllable thickness and, more particularly, to a molecular beam
epitaxy technique for fabricating thin films of Group III(a)-V(a)
compounds having p-type conductivity. The Group III(a) and Group
V(a) elements referred to herein are those identified in the
Chemical Rubber Handbook, Vol. 45, page B-2, published by the
Chemical Rubber Company.
Molecular beam epitaxy (MBE), as described in U.S. Pat. 3,615,931
granted to J.R. Arthur, Jr. on Oct. 26, 1971 and assigned to the
assignee hereof, is a comparatively new technique for the epitaxial
growth of semiconductor materials, in which growth results from the
simultaneous impingement of one or more molecular beams of the
constituent elements onto a heated substrate. In MBE the growth
process is governed primarily by kinetics whereas in liquid phase
epitaxy or chemical vapor phase epitaxy growth is governed by near
thermodynamic equilibrium conditions. In MBE, therefore, the
incorporation of doping elements into the grown layers is strongly
dependent on the arrival rate, the adsorption lifetime, and the
condensation coefficient of the element on a particular substrate
surface.
Unfortunately, desirable p-type dopants such as Zn and Cd have such
low sticking coefficients on materials such as GaAs at the growth
temperature (resulting from low condensation coefficients and/or
low adsorption lifetimes) that the incorporation of these elements
as useful dopants into GaAs during MBE growth has not been
successful. However, as described by one of us, A. Y. Cho, in
copending application Ser. No. 127,926 filed on Mar. 25, 1971 (now
U.S. Pat. No. 3,751,310, issued on Aug. 7, 1973) and assigned to
the assignee hereof, other elements having unity sticking
coefficients such as Si, Ge, and Sn have been successfully used to
dope layers grown by molecular beam epitaxy. Both Si and Sn are
preferentially incorporated into GaAs as donors and therefore
produce n-type layers. On the other hand, Ge forms n- or p-type
layers depending on the surface configuration of the GaAs layer
during growth. More specifically, Ge produces a p-type layer when
the molecular beams are adapted to create during growth a
relatively Ga-rich surface. Conversely, Ge produces an n-type layer
when the molecular beams are adapted to create during growth a
relatively As-rich surface. The conditions which must be varied to
produce these two surfaces are the substrate temperature and the
ratio of As.sub.2 /Ga in the molecular beams. The maintenance of a
Ga-rich surface during MBE growth without formation of Ga droplets
is, however, difficult because it requires relatively highly stable
beam intensities (i.e., fluxes) for long periods of time.
Many of the uses of good quality, thin p-type layers are, of
course, obvious, e.g., in the fabrication of p-n junction devices.
The need for such layers has become significantly greater with the
recent devleopment of the GaAs-AlGaAs double heterostructure (DH)
junction laser, the only semiconductor laser at this time which is
capable of c.w. operation at room temperature. The ability of some
types of DH laser to operate c.w. at room temperature is dependent
to a large extent upon the inclusion in the device of an active
layer less than 1 .mu.m thick. Thus, the fact that MBE permits
reproducible growth of thin layers of controllable thickness less
than 1 .mu.m, renders this growth technique particularly suitable
to the fabrication of the thin GaAs-AlGaAs layers of the DH laser.
However, there is still a need for a technique for incorporating a
p-type dopant into MBE layers of compounds of the form Al.sub.x
B.sub.1.sub.-x C, where Al is aluminum, B is a Group III(a) element
and C is a Group V(a) element. To avoid the formation of Ga
droplets previously mentioned, it is preferred that the p-type
dopant be incorporated while maintaining a surface condition which
is stabilized in the Group V(a) element (e.g., an As-rich surface
condition when growing AlGaAs layers).
Atoms of a Group II element usually enter the lattice of a
III(a)-V(a) compound by substituting for atoms of the Group III(a)
element to give acceptor centers. However, as already mentioned, we
have been unsuccessful in our attempts to incorporate useful
amounts of Zn and Cd, for example, into GaAs by the MBE method. On
the other hand, we have been able to incorporate relatively small
amounts of Mg as a p-type dopant in GaAs only by using a relatively
high Mg beam flux (e.g., an arrival rate of 10.sup.14 /cm.sup.2
sec) to compensate for its low sticking coefficient (about
10.sup.-.sup.5 at 560.degree. Centigrade). Evan at high beam
fluxes, however, the carrier concentration of the grown layers is
only about 10.sup.16 /cm.sup.3, whereas in many devices (e.g., the
p-type active region of a double heterostructure laser) it is
preferable that the carrier concentration be about
5.times.10.sup.17 to 5.times.10.sup.18 /cm.sup.3.
Summary of the Invention
During the process of growing MBE layers of Al.sub.x
Ga.sub.1.sub.-x As doped with Mg, we have discovered that the
sticking coefficient of magnesium, and hence the carrier
concentration of the layers, increases monotonically with x, the
mole fraction of AlAs in Al.sub.x Ga.sub.1.sub.-x As. More
specifically, for an illustrative substrate temperature of about
560.degree. Centigrade, we have found that as aluminum is added to
the grown layer so that x increases from 0 to 0.2, the sticking
coefficient of Mg rapidly increases by nearly three orders of
magnitude from about 10.sup..sup.-5 to about 10.sup..sup.-2.
Correspondingly, the carrier concentration of the grown layers
increases from about 10.sup.16 /cm.sup.3 to about 10.sup.19
/cm.sup.3. Concentrations of 5.times.10.sup.17 /cm.sup.3 to
5.times.10.sup.18 /cm.sup.3 are attained with x in the range 0.02
to 0.08 approximately.
The increase by three orders of magnitude in the sticking
coefficient of Mg and therefore the increase in the carrier
concentration in the grown layers has several important
implications. First, we have been able to grow p-type MBE layers
having carrier concentrations in the 10.sup.18 /cm.sup.3 range
which are suitable for double heterostructure junction lasers,
whereas priorly the maximum Mg doping level attained was only
10.sup.16 /cm.sup.3. Moreover, the amount of aluminum (x = 0.02 to
0.08) to produce the higher concentrations is also suitable for
creating in a DH laser the necessary refractive index steps which,
as in now well known, produce both optical and carrier
confinement.
Secondly, the ability to vary the sticking coefficient of Mg by
controlling the intensity of the Al beam (i.e., the Al arrival
rate) means that, for a given carrier concentration in the layer
grown, a lower Mg beam flux may be used by increasing the amount of
Al in the layer, i.e., by increasing the intensity of the Al
beam.
Looked at in another way, the latter feature of our invention
permits fabrication of MBE multilayered devices in a controlled
fashion. Consider, for example, that one skilled in the art desires
to grow by MBE contiguous layers of p-type GaAs and p-type
Al.sub.0.1 Ga.sub.0.9 As both doped with Mg and both having the
same carrier concentration. Ordinarily, one would adjust the Mg
beam to produce a predetermined, but fixed, arrival rate. To his
chagrin, the worker would find that the carrier concentration of
the GaAs:Mg layer was only about 10.sup.16 /cm.sup.3 whereas that
in the Al.sub.0.1 Ga.sub.0.9 As layer was about 10.sup.19
/cm.sup.3. Our discovery, on the other hand, indicates that for x =
0.1 the Mg sticking coefficient is nearly three orders of magnitude
higher than for x = 0 (i.e., pure GaAs). Consequently, when growing
the Al.sub.0.1 Ga.sub.0.9 As layer, the Mg beam should be adjusted
to produce an arrival rate three orders of magnitude smaller.
Brief Description of the Drawing
Our invention, together with its various features and advantages,
can be easily understood from the following more detailed
description taken in conjunction with the accompanying drawing, in
which:
FIG. 1 is a partial cross-sectional view of illustrative apparatus
utilized in practicing our invention; and
FIG. 2 is a graph of carrier concentration and Mg sticking
coefficient versus AlAs mole fraction in Al.sub.x Ga.sub.1.sub.-x
As.
DETAILED DESCRIPTION
Apparatus
Turning now to FIG. 1, there is shown apparatus for growing by MBE
epitaxial films of Group III(a)-V(a) compounds, and mixed crystals
thereof, of controllable thickness and conductivity type.
The apparatus comprises a vacuum chamber 11 having disposed therein
a gun port 12 containing illustratively three cylindrical guns 13a,
13b and 13c, typically Knudsen cells, and a substrate holder 17,
typically a molybdenum block. In FIG. 1 the guns 13 are shown to be
disposed in a vertical plane for clarity of illustration. Holder 17
is adapted for rotary motion by means of shaft 19 having a control
knob 16 located exterior to chamber 11. Also shown disposed within
chamber 11 is a cylindrical liquid nitrogen cooling shroud 22 which
surrounds the guns and a collimating frame 23 having a collimating
aperture 24. Substrate holder 17 is provided with an internal
heater 25 and with clips 26 and 27 for affixing a substrate member
28 thereto. Additionally, a thermocouple is disposed in aperture 31
in the side of substrate 28 and is coupled externally via
connectors 32-33 in order to sense the temperature of substrate 28.
Chamber 11 also includes an outlet 34 for evacuating the chamber by
means of a pump 35.
A typical cylindrical gun 13a comprises a refractory crucible 41
having a thermocouple well 42 and a thermocouple 43 inserted
therein for the purpose of determining the temperature of the
material contained in the gun source chamber 46. thermocouple 43 is
connected to an external detector (not shown) via connectors 44-45.
Source material (e.g., bulk GaAs) is inserted in source chamber 46
for evaporation by heating coil 47 which surrounds the crucible.
The end of crucible 41 adjacent aperture 24 is provided with a
knife edge opening 48 (typically about 0.17cm.sup.2) having a
diameter preferably less than the average mean free path of atoms
in the source chamber.
General MBE Technique
The first step in a typical MBE technique involves selecting a
single crystal substrate member, such as GaAs, which may readily be
obtained from commerical sources. One major surface of the GaAs
substrate member is initially cut along the (001) plane and
polished with diamond paste, or any other conventional technique,
for the purpose of removing the surface damage therefrom. An
etchant such as a bromine-methanol or hydrogen peroxide-sulphuric
acid solution may be employed for the purpose of further purifying
the substrate surface subsequent to polishing.
Next, the substrate is placed in an apparatus of the type shown in
FIG. 1, and thereafter, the background pressure in the vacuum
chamber is reduced to less than 10.sup..sup.-6 Torr and preferably
to a value of the order of about 10.sup.-8 to 10.sup..sup.-10 Torr,
thereby precluding the introduction of any deleterious components
onto the substrate surface. Since, however, the substrate surface
may be subject to atmospheric contamination before being mounted
into the vacuum chamber, the substrate is preferably heated, e.g.,
to about 600.degree. Centigrade, to provide an automically clean
growth surface, (i.e., desorption of contaminants such as CO and
H.sub.2 O). The next steps in the process involve introducing
liquid nitrogen into the cooling shround via entrance port 49 and
heating the substrate member to the growth temperature which
typically ranges from about 450 to 650 degrees Centigrade dependent
upon the specific material to be grown, such range being dictated
by considerations relating to arrival rates and surface
diffusion.
The guns 13a, 13b and 13c employed in the system have previously
been filled with the requisite amounts of the constituents of the
desired film to be grown (e.g., gun 13a contains a Group
III(a)-V(a) compound such as a GaAs in bulk form; gun 13b contains
a Group III(a) element such as Ga; and gun 13c contains a dopant
such as Mg in bulk form). In the practice of our present invention,
a fourth gun (not shown) containing Al is also used. Following,
each gun is heated to a temperature (not necessarily all the same)
sufficient to vaporize the contents thereof to yield (with shutter
14 open) a molecular beam (or beams); that is, a stream of atoms
manifesting velocity components in the same direction, in this case
toward the substrate surface. The atoms or molecules reflected from
the surface strike the interior surface 50 of the cooled shroud 22
and are condensed, thereby insuring that only atoms or molecules
from the molecular beam impinge upon the substrate surface.
For the purpose of the present invention, the amount of source
materials (e.g., Ga, Al and GaAs) furnished to the guns and the gun
temperatures should be sufficient to provide an excess of the Group
V(a) element (As) with respect to the Group III(a) elements (Al and
Ga); that is, the surface should be As-rich (also referred to as
As-stabilized). This condition arises from the large differences in
sticking coefficient at the growth temperature of the several
materials; namely, unity for Ga and Al and about 10.sup.-2 for
As.sub.2 on a GaAs surface, the latter increasing to unity when
there is an excess of Ga (and/or Al) on the surface. Therefore, as
long as the As.sub.2 arrival rate is higher than that of Ga and/or
Al, the growth will be stoichiometric. Similar considerations apply
to Ga and P.sub.2 beams impinging, for example, on a GaP
substrate.
Growth of the desired doped epitaxial film is effected by directing
the molecular beam generated by the guns at the collimating frame
23 which functions to remove velocity components therein in
directions other than those desired, thereby permitting the desired
beam to pass through the collimating aperture 24 to effect reaction
at the substrate surface. Growth is continued for a time period
sufficient to yield an epitaxial film of the desired thickness.
This technique permits the controlled growth of films of thickness
ranging from a single monolayer (about 3 Angstroms) to more than
100,000 Angstroms. Note, that the collimating frame serves also to
keep the vacuum system clean by providing a cooled surface on which
molecules reflected from the growth surface can condense. If the
effusion cell provides sufficient collimation of the beams,
however, the collimating frame is not essential to the growth
technique.
The reasons which dictate the use of the aforementioned temperature
ranges can be understood as follows. It is now known that Group
III(a)-V(a) elements, which are adsorbed upon the surface of single
crystal semiconductors, have different condensation and sticking
coefficients as well as different adsorption lifetimes. Group V(a)
elements typically are almost entirely reflected in the absence of
III(a) elements when the substrate is at the growth temperature.
However, the growth of stoichiometric III(a)-V(a) semiconductor
compounds may be effected by providing vapors of Group III(a) and
V(a) elements at the substrate surface, an excess of Group V(a)
element being present with respect to the III(a) elements, thereby
assuring that the entirety of the III(a) elements will be consumed
while the nonreacted V(a) excess is reflected. In this connection,
the aforementioned substrate temperature range is related to the
arrival rate and surface mobility of atoms striking the surface,
i.e., the surface temperature must be high enough (e.g., greater
than about 450 degrees Centigrade) that impinging atoms have enough
thermal energy to be able to migrate to favorable surface sites
(potential wells) to form the epitaxial layer. The higher the
arrival rate of these impinging atoms, the higher must be the
substrate temperature. On the other hand, the substrate surface
temperature should not be so high (e.g., greater than about 650
.degree. Centigrade) that noncongruent evaporation results. As
defined by C. D. Thurmond in Journal of Physics Chem. Solids, 26,
785 (1965), noncongruent evaporation is the preferential
evaporation of the V(a) elements from the substrate eventually
leaving a new phase containing primarily the III(a) elements.
Generally, therefore congruent evaporation means that the
evaporation rate of the III(a) and V(a) elements are equal. The
temperatures of the cell containing the III(a) element and the cell
containing the III(a)-V(a) compound, which provides a source of
V(a) molecules, are determined by the desired growth rate and the
particular III(a)-V(a) system utilized.
Example: Doping AlGaAs with Mg
This example describes a process for the growth by MBE of p-type
layers of Al.sub.x Ga.sub.1.sub.-x As doped with Mg.
In guns 13a, 13b and 13c there were placed, respectively, 1 gram of
Al, 3 grams of polycrystalline GaAs and 3 grams of Ga. In a fourth
gun (not shown for simplicity) was placed 0.5 gram of Mg. Each of
the guns was made from aluminum oxide lined with spectroscopically
pure graphite except for the Al gun which was made from pyrolytic
BN in order to reduce the likelihood of aluminum oxides
forming.
The vacuum in the chamber of FIG. 1, was reduced to about 5 .times.
10.sup.-.sup.8 Torr which is primarily As.sub.2 background
pressure.
Next, the substrate 28, comprising Si-doped n-type GaAs with its
(001) surface facing the guns, was placed about 5cm from the guns
and was heated to about 560.degree. Centigrade. The latter
temperature was chosen because layers grown at 560.degree.
Centigrade have exhibited higher photoluminescent (PL) efficiency
than layers grown at other temperatures in the range 450.degree. to
650.degree. Centigrade. High PL efficiency is one of the
prerequisites for the active region of a DH laser.
The guns were then heated to a suitable temperature effective to
produce desired arrival rates at the growth surface. Thus, the Al
gun 13a was heated to temperatures ranging from about 1200.degree.
to 1400.degree. Kelvin to produce Al arrival rates ranging from
about 10.sup.13 to 10.sup.15 Al/cm.sup.2 sec; the GaAs gun 13b was
heated to about 1180.degree. Kelvin to produce an As.sub.2 arrival
rate of about 5 .times. 10.sup.15 As.sub.2 /cm.sup.2 sec; the Ga
gun 13c was heated to about 1,250.degree. Kelvin to produce a Ga
arrival rate of about 10.sup.15 Ga/cm.sup.2 sec; and the Mg gun
(not shown) was heated to about 680.degree. Kelvin to produce a Mg
arrival rate of about 10.sup.14 Mg/cm.sup.2 sec.
With constant temperatures maintained for the Ga and GaAs guns as
specified above, we fabricated a multilayered structure on the GaAs
substrate to determine the doping profile in the several layers.
The temperature of the Mg gun was the same for all layers except in
two layers where Mg was omitted altogether. The temperature of the
Al gun was changed from one layer to the next, but was constant
during the growth of each particular layer. Eight layers were
sequentially grown as follows with the temperatures in parenthesis
being the Al gun temperature: (1) GaAs:Mg (850.degree. Kelvin which
produces negligible evaporation of Al) (2) Al.sub.0.20 Ga.sub.0.80
As: Mg (1,340.degree. Kelvin); (3) Al.sub.0.10 Ga.sub.0.90 As: Mg
(1,325.degree. Kelvin); (4) Al.sub.0.04 Ga.sub.0.96 As: Mg
(1,270.degree. Kelvin); (5) Al.sub.0.02 Ga.sub.0.98 As: Mg
(1,225.degree. Kelvin); (6) Al.sub.0.01 Ga.sub.0.99 As: Mg
(1,200.degree. Kelvin); (7) GaAs: Mg (Al gun unheated); and (8)
GaAs: undoped (Al gun unheated).
Several single-layered structures were also grown on Cr-doped
semi-insulating GaAs substrates for the purpose of marking Hall
effect measurements. All of the layers of the latter structure were
grown with constant Mg, Ga and As.sub.2 beam fluxes, but with
varying Al beam intensities.
The epitaxial film properties were studied in situ with a
reflection high energy electron diffraction (HEED) system
commercially available from Varian Associates, Palo Alto,
California and by Auger spectroscopy with a PHI cylindrical mirror
electron spectrometer commercially available from physical
Electronic Industries, Inc., Edina, Minnesota. Subsequent to
growth, tests were also made with ion sputtering mass spectrometry
(IMS) and Hall measurements. The arrangement of the in situ
analysis instruments in the vacuum system of FIG. 1 is well known
in the art and is therefore omitted here for simplicity and clarity
of illustration.
HEED was used to observe the surface structures of the outermost
atomic layers during growth. We observed a new surface structure,
GaAs (001) - 2.times.2 -Mg when the Mg beam was used to dope the
various epitaxial layers. As the Mg beam impinged on a GaAs or
Al.sub.x Ga.sub.1.sub.-x As surface, the (001) - 2.times.2 --Mg
surface structure was formed independent of whether the initial
surface was As-stabilized or Ga-stabilized.
Auger electron spectroscopy was used in situ to study the elemental
composition of the top few monolayers of the grown epitaxial
layers. this technique can be used to determine the substrate
cleanliness, contamination (if any) of the layers during growth,
and, to some extent, the chemical compositions of the Al.sub.x
Ga.sub.1.sub.-x As layers.
IMS was used to determine the doping profile of the multi-layer
structure and Hall effect measurements were used to determine the
carrier concentrations and mobilities in the layers. The room
temperature Hall mobilities varied from 215 cm.sup.2 /V sec for a
carrier concentration (N.sub.A -N.sub.D) = 2.5.times.10.sup.16
/cm.sup.3 to 30 cm.sup.2 /V sec for (N.sub.A -N.sub.D) = 10.sup.19
/cm.sup.3. Since the Mg beam flux was kept constant during the
growth of the layers on the Cr-doped substrate, we conclude that
the increase in carrier concentration corresponds to an increase in
the sticking coefficient of Mg brought about by the presence of Al
in the layers.
The results of our work are summarized in FIG. 2, a graph of
carrier concentration (N.sub.A -N.sub.D) and Mg sticking
coefficient versus x, the mole fraction of AlAs in Al.sub.x
Ga.sub.1.sub.-x As. Although the data presented in FIG. 2
correspond to a substrate temperature of 560 degrees Centigrade, we
expect similar results within the typical range of substrate
temperatures suitable for epitaxial growth by MBE (i.e., about
450.degree. to 650.degree. Centigrade). The graph vividly depicts
the drastic (three orders of magnitude) increase in Mg sticking
coefficient from about 1.times.10.sup.-.sup.5 to
4.times.10.sup.-.sup.3 as the amount of aluminum in the grown
layers (i.e., the mole fraction x) increases from about 0 to 0.1.
The corresponding increase in carrier concentration is from about
2.5.times.10.sup.16 /cm.sup.3 to about 8.times.10.sup.18 /cm.sup.3.
For x between 0.1 and 0.2 the increase is much more gradual: the
sticking coefficient increases to about 6.times. 10.sup.-.sup.3 and
the corresponding carrier concentration increases to about
1.5.times.10.sup.19 /cm.sup.3.
As mentioned previously, there are several ramifications of FIG. 2
which are important to the fabrication of devices by MBE.
First, we have demonstrated that Mg incorporates into MBE layers as
a p-type dopant under As-stabilized surface conditions.
Consequently, larger spurious variations of the As.sub.2 /Ga ratio
in the molecular beams can be tolerated without seriously affecting
the Mg doping level. Moreover, because growth on a Ga-stabilized
surface is not necessary to obtain p-type conductivity (contrast
the Ge situation), the likelihood that Ga droplets will form on the
surface and disrupt the homogeneity of the layers is substantially
reduced.
Secondly, we have demonstrated that the addition of aluminum to the
molecular beam drastically increases the sticking coefficient of Mg
and consequently the carrier concentration of the p-type layers
grown. We can fabricate Mg doped AlGaAs layers with carrier
concentrations as high as 10.sup.19 /cm.sup.3 whereas only about
10.sup.16 /cm.sup.3 was attainable priorly. P-type layers doped in
the 5.times.10.sup.17 to 5.times.10.sup.18 /cm.sup.3 range find
important application in many semiconductor devices. A device of
particular significance is the double heterostructure (DH) junction
laser. Illustratively, the DH laser comprises an n-type GaAs
substrate on which are grown sequentially the following layers: a
n-Al.sub.x Ga.sub.1.sub.-x As layer; a p-Al.sub.y Ga.sub.1.sub.-y
As layer and a p-Al.sub.z Ga.sub.1.sub.-z As layer with y < x
and z. The middle layer of Al.sub.y Ga.sub.1.sub.-y As forms the
active region of the device where radiative recombination of holes
and electrons occurs to produce a coherent light output. For
efficient recombination to occur the carrier concentration is
typically about 10.sup.18 /cm.sup.3. The condition y < x and z
creates a pair of heterojunctions at the interfaces with the middle
layer. These heterojunctions confine injected carriers and optical
photons to the middle layer and enable c.w. operation at room
temperature if the thickness of the middle layer is less than about
1 .mu.m. To this end, the other layers should also be thin (e.g.,
1-2 .mu.m) in order to facilitate the extraction of heat from the
device.
Consequently, MBE, with its ability to grow extremely thin layers
of controllable thickness, is particularly suited to the
fabrication of DH lasers. As discussed in the copending application
of A. Y. Cho (Case 2) supra, Sn or Si may be used in MBE to produce
the n-type A1.sub.x Ga.sub.1.sub.-x As layer in which typically x =
0.1. In accordance with one aspect of our invention, the layers of
Al.sub.y Ga.sub.1.sub.-y As and Al.sub.z Ga.sub.1.sub.-z As can be
made p-type by doping with Mg, and a predetermined carrier
concentration in each can be attained by controlling the amount of
Al incorporated into the layers, i.e., by controlling the
temperature of the Al and Mg guns during MBE growth.
Thus, for example, to enhance photoluminescent efficiency the
substrate is maintained at about 560.degree. Centigrade. To produce
a carrier concentration of about 1.5.times.10.sup.18 /cm.sup.3 in
the middle layer, the Al content should be about y = 0.04 which is
attained when the Al gun is heated to about 1,270.degree. Kelvin.
With the Mg gun heated to a suitable temperature sufficient to
evaporate Mg molecules (e.g., to 680.degree. Kelvin), a p-type
Al.sub..04 Ga.sub..96 As:Mg layer about 1 .mu.m thick is formed
after about 60 minutes of growth time. Thinner layers may be
fabricated by growing for shorter periods of time (growth is
readily terminated by sliding the shutter 14 in front of aperture
24 of collimating frame 23).
A fourth aspect of our invention relates again to our discovery
that in Mg doped layers the carrier concentration is a function of
the amount of Al in the layer. Thus, where it is desired to grow
successive (not necessarily contiguous) layers of AlGaAs, for
example, having different amounts of Al but the same carrier
concentration, then the Mg beam flux must be adjusted to compensate
for the changed Mg sticking coefficient. Illustratively, in the
n-p-p DH laser discussed above, it might be desired that the
p-Al.sub..04 Ga.sub..96 As middle layer (y =0.04) and the p-
Al.sub..10 Ga.sub..90 As outer layer (z =0.10) have the same
carrier concentrations, e.g., about 1.5.times.10.sup.18 /cm.sup.3.
But y = 0.04 produces a Mg sticking coefficient of about
6.times.10.sup.-.sup.4 whereas x = 0.10 produces a coefficient of
about 3.times. 10.sup.-.sup.3, five times higher. Consequently,
when growing the p-Al.sub..10 Ga.sub..90 As layer the temperature
of the Mg gun should be lowered to produce a Mg arrival rate about
five times smaller than that used for growing the p-Al.sub..04
Ga.sub..96 As layer.
It is to be understood that the above-described arrangements are
merely illustrative of the many possible specific embodiments which
can be devised to represent application of the principles of our
invention. Numerous and varied other arrangements can be devised in
accordance with these principles by those skilled in the art
without departing from the spirit and scope of the invention. In
particular, although in the last-mentioned aspect of our invention
the Mg flux was adjusted to produce the same carrier concentration
in contiguous p-type layers of AlGaAs, it is of course apparent to
one skilled in the art that our technique is generally applicable
to producing different carrier concentrations by predetermining the
requisite Al content and/or Mg beam intensity. Moreover, our
invention is not limited in its application to AlGaAs only, but is
also suitable to other III(a)-V(a) compounds containing Al, e.g.,
AlGaP, a material particularly attractive for use in GaP-AlGaP
spontaneously emitting heterostructure diodes (LEDs).
* * * * *