Deposition of GaAs Epitaxial Layers by Organometallic

CVD : Temperature and Orientation Dependence

D. H. Reep and S. K. Ghandhi

J. Electrochem. Soc. 1983, Volume 130, Issue 3, Pages 675-680.

doi: 10.1149/1.2119780

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Vol. I30, No. 3 LATTICE P A R A M E T E R C H A N G E S 675

26. H. G. Hicks and P. D. Greene, "Inst. Phys. Conf. 129 (1972).

Ser. #9," 92 (197t).
26. C. M. W o l f e and G. E. Stillman, Appl. Phys. Lett.,
27, 564 (1975).
27. H. Kressel, J. Appl. Phys., 40, 3587 (1969).
28. N. S. B e l y a s k a y a , Soy. Phys. Crystallography, 17,
29. A. Fazzio, L. M. Brescansin, M. J. Caldas, and J. R.
Leito, J. Phys., 12, L831 (1979).
30. P. J. Anthony, J. L. Zilko, V. S w a m i n a t h a n , N. E.
S c h u m a k e r , W. R. Wagner, and J. C. Norberg,
Appl. Phys. Lett., 38, 434 (1981).

Deposition of GaAs Epitaxial Layers by Organometallic CVD

Temperature and Orientation Dependence

D. H. Reep* and S. K. Ghandhi*

Department of Electrical, Computer and Systems Engineering, Rensselaer Polytechnic Institute, Troy, New York 12181

ABSTRACT
Epitaxial layers of GaAs have been grown in an atmospheric organometallic CVD system, for a wide variety of gas phase
reactant partial pressures and over a broad range of temperature (450~176 The growth rates for (100), (100) + 3~--* < 110>,
(110), (111)Ga, and (111)As substrates are reported as functions of temperature and gas composition. Three distinct tempera-
ture d e p e n d e n t regions of growth are identified, corresponding to a mid-temperature mass transport limited range, a low-
temperature kinetic controlled regime, and a high-temperature desorption limited region. The growth rate is studied as a
function of the growth parameters and substrate orientation, and is related to the decomposition of the two reactants tri-
methylgallium and arsine. A model for the epitaxial growth of GaAs by the organometallic process is proposed, based on
these findings.

The g r o w t h of thin e p i t a x i a l l a y e r s of GaAs, b y the in situ etching of the GaAs substrates p r i o r to e p i t a x i a t

o r g a n o m e t a l l i c CVD technique, has received much a t -
tention recently. In p a r t i c u l a r , the use of such l a y e r s
for optoelectronic (1, 2), m i c r o w a v e (3, 4), and high
speed digital circuits (4) has given p r o m i s i n g results.
This technique has also p r o d u c e d l a y e r s a p p r o a c h i n g
the p u r i t y and m o b i l i t y of the best l a y e r s g r o w n b y the
halide or h y d r i d e techniques, and has g e n e r a t e d much
i n t e r e s t due to its simplicity and flexibility.
C o m p a r e d to the h a l i d e and h y d r i d e g r o w t h systems,
little has been p u b l i s h e d in r e g a r d to the mechanisms
of g r o w t h b y the o r g a n o m e t a l l i c process. While it is
considered to be a "simple" p y r o l y s i s of t r i m e t h y l -
g a l l i u m (TMG) and arsine, the g r o w t h of GaAs films
b y this technique c e r t a i n l y involves c o m p l e x processes.
This is, in part, due to the n a t u r e of the p y r o l y t i c r e -
action, which occurs far from e q u i l i b r i u m and p r e -
cludes r e v e r s a l of the deposition reaction. Hence, t h e r e
is no possibility of a n y " r e o r d e r i n g " of the deposited
GaAs film, in the sense of the r e v e r s i b l e h a l i d e / h y d r i d e
reactions, owing to the absence of an etching halogenic
species in the deposition zone. This effect is most p r o -
nounced in t e r m s of the resulting e p i t a x i a l l a y e r m o r -
phology, as d e t a i l e d in our e a r l i e r w o r k (5).
I n this paper, w e r e p o r t on the g r o w t h of GaAs epi-
t a x i a l l a y e r s on a v a r i e t y of s u b s t r a t e orientations
[(100), (100) + 3 ~ --> <110>, (110), ( l l l ) G a , a n d
( l l l ) A s faces], a n d over a wide r a n g e of deposition
t e m p e r a t u r e s and r e a c t a n t p a r t i a l pressures. Vqe
describe t h r e e distinct regions of growth: a m i d - t e m -
p e r a t u r e mass t r a n s p o r t l i m i t e d region, a low t e m p e r a -
ture k i n e t i c a l l y controlled g r o w t h regime, and a high
t e m p e r a t u r e surface species desorption limited range.
The d e p e n d e n c e of the o b s e r v e d GaAs deposition r a t e
on gas phase r e a c t a n t p a r t i a l pressures and s u b s t r a t e
orientations is considered in conjunction with the ac-
tivation energies of deposition that a r e associated with
the t h r e e g r o w t h regions. A simple g r o w t h m o d e l is
proposed, based on these observations.
Experimental Procedure
E p i t a x i a l l a y e r s of GaAs w e r e g r o w n b y the p y r o l y -
sis of a r s i n e a n d TMG, using h y d r o g e n as the c a r r i e r
gas. A n h y d r o u s h y d r o g e n chloride was a v a i l a b l e for
* Electrochemical Society Active Member.
Key words: organometaUic, OMVPE, OMCVD, epitaxy, gallium
arsenide.
l a y e r growth. The layers w e r e deposited at t e m p e r a -
tures r a n g i n g from 450 ~ to 1050~ with the i n p u t TMG
p a r t i a l p r e s s u r e v a r y i n g from 4.6-37 X 10 -5 atm.
A r s i n e flows were also v a r i e d o v e r a wide range, cor-
responding to AsH3/TMG ratios of 4.7-75 at the r e a c t o r
inlet. The h y d r o g e n c a r r i e r gas flow was fixed at 5
l i t e r s / m i n for all of the g r o w t h runs c a r r i e d out for
this study.
The single c r y s t a l s e m i - i n s u l a t i n g G a A s s u b s t r a t e
m a t e r i a l that was used in this s t u d y was o b t a i n e d from
either C r y s t a l Specialties, Incorporated, Monrovia,
California or C a m b r i d g e I n s t r u m e n t s , Incorporated,
Monsey, New Jersey. The wafers w e r e p u r c h a s e d
l a p p e d and c h e m - m e c h a n i c a l I y polished on one side,
and w e r e oriented (100), (100) -}- 3~ < 1 1 0 > , (110),
or ( l l l ) A s .
The ( l l l ) G a substrates w e r e p r e p a r e d at our facil-
ity, b y m e c h a n i c a l l y polishing the r e v e r s e side of
( l l l ) A s wafers w i t h successively finer grits, to a final
0.05 /~m a l u m i n a (Buehler, Limited, L a k e Bluff, I l l i -
nois) polish. A f t e r d e m o u n t i n g from polishing slugs,
the wafers w e r e cleaned s e q u e n t i a l l y in baths of
methanol, acetone, and trichloroethylene. A chemical
polishing etch of 5 rain duration, in a solution consist-
ing of llHNO3 (70%): 49H3PO4 (85%) at 60~ p r o -
duced m i r r o r - l i k e , d a m a g e free (111) Ga surfaces (6).
The (100), m i s o r i e n t e d (100), (110), a n d ( l l l ) A s
wafers w e r e d e g r e a s e d as described earlier, a n d given
a 1 min free etch in hot Caro's acid [3H2SO4 ( 9 7 % ) :
1H202 (30%): 1H20, at 60~ to r e m o v e a n y residual
surface damage. This p r o c e d u r e gave m i r r o r - l i k e s u r -
faces on all of these s u b s t r a t e orientations, and r e -
m o v e d 15-25 ~m from their surfaces.
The e p i t a x i a l reactor consisted of an a t m o s p h e r i c
pressure, horizontal, rf heated, cold w a l l system as
described e a r l i e r (7). Gases w e r e d e l i v e r e d to the 50
m m ID quartz reaction c h a m b e r t h r o u g h 316 stainless
steel or Monel tubing. The s u b s t r a t e t e m p e r a t u r e was
monitored with a type R thermocouple (Pt/Pt-13%
R h ) , sheathed in quartz, and i n s e r t e d into a well in
the back of the g r a p h i t e susceptor.
TMG ( A l p h a Products, Danvers, Massachusetts)
v a p o r was i n t r o d u c e d into the r e a c t o r b y b u b b l i n g h y -
drogen t h r o u g h the liquid, w h i c h was held at 0~ in a
stainless steel bubbler. A n LED grade, 10% m i x t u r e of
 676 J. Electrochem. Soc.: S O L I D - S T A T E SCIENCE AND TECHNOLOGY March I983

arsine in h y d r o g e n ( A i r Products, T a m a q u a , P e n n s y l -
v a n i a ) , was used to p r o v i d e AsH8 in concentrations TEMPERATURE(%)
n e c e s s a r y for good e p i t a x i a l l a y e r growth. A 1% m i x - 1050 950 850 750 650 550 450
ture of electronic grade h y d r o g e n chloride in h y d r o - 1.0 ~,_ I I i I I I I i I I I i I

gen ( A i r Products, Tamaqua, P e n n s y l v a n i a ) was a v a i l -

a b l e for in situ etching of the s u b s t r a t e w h e n required.
U l t r a p u r e h y d r o g e n c a r r i e r gas was obtained b y p a s s -
i n g commercial g r a d e h y d r o g e n ( A i r Products, T a m a -
qua, P e n n s y l v a n i a ) t h r o u g h a P d - A g a l l o y purifier. I n
all cases, t h e r e a c t a n t s w e r e m i x e d j u s t p r i o r to e n t r y
into the reaction chamber.
The s u b s t r a t e s w e r e l o a d e d into the r e a c t o r i m m e d i -
a t e l y a f t e r chemical etching a n d microscopic inspection
of t h e i r surfaces. The r e a c t o r was evacuated, a n d t h e n
p u r g e d w i t h c o m m e r c i a l g r a d e argon ( A i r Products,
Tamaqua, P e n n s y l v a n i a ) , followed b y hydrogen. A f t e r
sufficient purging, the desired flows of h y d r o g e n and
arsine were set. F o r those e x p e r i m e n t s involving a n
in situ etch p r i o r to growth, the susceptor was h e a t e d
a n d allowed to stabilize at the etch t e m p e r a t u r e ,
t y p i c a l l y 945~ A f t e r a period of 5 rain w h i c h was
considered sufficient to r e m o v e a n y oxide on the G a A s
surface left from the chemical free etch (8), the s u b -
strafes w e r e given an in situ etch of the t y p e p r e v i -
ously detailed (9). The susceptor t e m p e r a t u r e was
then reset and a l l o w e d to stabilize at the g r o w t h t e m -
p e r a t u r e for 2 rain p r i o r to the c o m m e n c e m e n t of
TMG flow.
F o r e x p e r i m e n t s w h e r e no in situ etch was p e r -
formed, the susceptor was h e a t e d to the g r o w t h t e m -
perature1 and stabilized for 5 rain, before the TMG flow
was t e r m i n a t e d , a n d the system m a i n t a i n e d at the
g r o w t h t e m p e r a t u r e f o r an a d d i t i o n a l 3 rain. The sus-
ceptor was then a l l o w e d to cool in the A s H J H 2 a t -
mosphere, followed b y an argon p u r g e a f t e r the t e m -
p e r a t u r e fell below 200~
The g r o w t h r a t e of the e p i t a x i a l l a y e r was d e t e r -
m i n e d either b y w e i g h t change, w h e n no in situ etch
was p e r f o r m e d , or b y cleaving and staining, followed
b y optical microscope inspection using N o m a r s k i dif-
f e r e n t i a l i n t e r f e r e n c e contrast. Scanning electron m i -
croscopy was e m p l o y e d to s t u d y the surface m o r -
phol0gy.
The (100) -l- 3 ~ -~ < 1 1 0 > o r i e n t a t i o n is often used in
commercial practice. Consequently, an initial series of
e x p e r i m e n t s w e r e c a r r i e d o u t with s i d e - b y - s i d e g r o w t h
on (100) a n d (100) + 3 ~ --> < 1 1 0 > o r i e n t e d substrates
for purposes of comparison. In all cases, these gave
identical g r o w t h rates and morphology, which were
d e p e n d e n t o n l y on the g r o w t h p a r a m e t e r s . S u b s e -
quently, the r e m a i n i n g e x p e r i m e n t s w e r e conducted
w i t h simultaneous g r o w t h on (110), ( l l l ) G a , and
( I l l ) A s substrates, in addition to the (100) + 3 ~
wafers, since t h e y w e r e m o r e r e a d i l y available for this
study.
Results
A l l of the (100) l a y e r s ( o r i e n t e d as well as mis-
o r i e n t e d ) showed good surface q u a l i t y over a wide
r a n g e of g r o w t h t e m p e r a t u r e s . F u r t h e r m o r e , the m o r -
p h o l o g y was found to be essentially i n d e p e n d e n t of the
TMG or arsine flows for these samples as d e t a i l e d
e a r l i e r (5) for film g r o w t h at 700~ However, l a y e r s
g r o w n on (110), ( l l l ) G a , and (111)As faces showed a
strong d e p e n d e n c e of m o r p h o l o g y on both the arsine
and TMG flows. In the e a r l i e r study, it was also shown
t h a t for all g r o w t h conditions, the best m o r p h o l o g y for
these orientations was o b t a i n e d w i t h a gas phase A s H J
TMG ratio at the r e a c t o r inlet in the 18-37 range. Con-
,sequently, the b u l k of the g r o w t h r a t e d a t a r e p o r t e d
here will fall in this r a n g e as well.
The g r o w t h r a t e for the (100), (110), ( l l l ) ' G a , a n d
( l l l ) A s samples, p l o t t e d vs. reciprocal t e m p e r a t u r e ,
can be seen in Fig. 1 for inlet p a r t i a l pressures of TMG
1 A minimum of 700~ was used for the pregrowth heat-treat-
ment, as this is just sufficient to rapidly remove any trace sur-
face oxide (8). Thus, for those depositions performed below
700~ the susceptor temperature was restabiUzed as appropriate
following this deoxidation treatment.
2.2
2,4
v
0.1
,S
L_. 5.0 16-
- - 11 19- j
~--12 22--
F GAAs ORIENTATION '
. . . . . (100),(110)
----- (111)GA
(111)As
(ALLACTIVATIONENERGIESIN KCAL/MOLE
0.7 0.9 1,1 1.3 1,5
1000
T(~
Fig. 1. Growth rate vs. reciprocal temperature for epitaxial layers
on (100), (110), (111)Go, and (111)As oriented GoAs substrates
with PTMG = 1.8 • 10 - 4 arm and PAsHa ---- 3.3 • 10 - ~ a t m
(AsHa/TMG - - 19).
equal to 1.8 • 10-4 arm and AstIa equal to 8.3 • 10 -8
arm ( A s H J T M G _.-- 19). The a p p a r e n t activation e n -
ergies a r e shown for each o r i e n t a t i o n and for each of
the t h r e e distinct g r o w t h regions. These a r e identified
as a m i d - t e m p e r a t u r e mass t r a n s p o r t l i m i t e d region,
a low t e m p e r a t u r e k i n e t i c a l l y controlled regime, and
a high t e m p e r a t u r e desorption l i m i t e d range.
Singling out one p a r t i c u l a r deposition t e m p e r a t u r e
in each of the t h r e e g r o w t h regions, the effect of v a r y -
i n g the TMG o r AsH~ p a r t i a l pressures is seen in Fig.
2-4, as a function of s u b s t r a t e c r y s t a l l o g r a p h i c o r i e n -
tation. Each of these regions will be considered
separately, w i t h the i m p o r t a n t features of each noted.
Mid-temperature, mass transport limited g r o w t h . -
As seen from Fig. 1, the g r o w t h is w e a k l y d e p e n d e n t on
the deposition t e m p e r a t u r e b e t w e e n 600~176 Here,
the a p p a r e n t activation e n e r g y r a n g e s f r o m 1.5 to 2.4
k c a l / m o l as is e x p e c t e d for diffusion controlled mass
t r a n s p o r t limited film g r o w t h (10). A d d i t i o n a l l y , the
g r o w t h r a t e is r e l a t i v e l y insensitive to the s u b s t r a t e
orientation in this t e m p e r a t u r e region, w i t h the m a x i -
m u m v a r i a t i o n b e t w e e n the highest and lowest values
shown being a p p r o x i m a t e l y 20%.
F i g u r e s 2a and b show the g r o w t h r a t e vs. PTMG and
PAsHa, respectively, at 700~ Here, all s u b s t r a t e o r i e n -
tations used show the same l i n e a r v a r i a t i o n in g r o w t h
rate w i t h PTMG, and i n d e p e n d e n c e of g r o w t h r a t e
(within the limits of e x p e r i m e n t a l e r r o r ) on PAsH3, as
has been c o m m o n l y r e p o r t e d in the l i t e r a t u r e (11-13).
Moreover, in this mass t r a n s p o r t l i m i t e d regime, the
n a t u r e of the g r o w t h mechanisms is m a s k e d since the
g r o w t h r a t e is l i m i t e d b y the diffusion of the m i n o r i t y
species in the gas s t r e a m to the g r o w i n g c r y s t a l
surface.
VoL 130, No. 3 GaAs EPITAXIAL LAYERS 677

0,5 i i i i i i i
0,25 i t i i i i i

500Oc
700~
0,2(3 PAsH3= 3,3x i0-3 ATM
~ 0,40,3PAsH3= 3 , 3 ~ ~
0,15

0.2
010E A A

/ GAALORIENTATI~
Z/ o (lOO) ~.l / ~ o (100)
O'O~F//B o iii~i
0,I ~ m (ii0) L/X ~ (111)GA
v (Ill)As oV , , ,iiiii ;,
0 1,0 2,0 3,0 4.0
I I I ! ' ' '
0 1.0 20. 3,0 4,0 PTMG(x 10-4 ATM)
PTMG(x 10-4 ATM) Fig. 3a. Growth rate vs. partial pressure of TMG for G,As epi-
Fig. 2a. Growth rate vs. partial pressure of TMG for GaAsepi- taxial laye~ at constant PAsHa ---- 3.3 • 10 - a atm and 500~
taxiallaye~ atconstantPAsHs = 3.3 X 10-Satm and 7~~

0,25 I I I I I I I

0.5 , ~ , , i I I 5000C
700~ 0.50 PTMG= 1,8 x 10-4 ATM
0.4 PTMG= 1.8 x 10-4 ATM

0.15
0,3
A V
A A
A
O,10
,S 0,2 GAAs ORIENTATION o~
= o (100)
0 (100) 0,05
[] (110) [] (110)
0,1 A (lll)GA
A (111)GA v (llllAs
V (111)As | ! I I i I I

I I
10 20
PAsH3 (x 10-4 ATM)
Fig. 2b. Growth rate vs. partial pressure of AsH~ for GaAs epi-
taxial layers at constant PTMO: 1.8 • 10 - 4 atm and 700~
Low temperature, kinetic controlled growth.--The
deposition r a t e is k i n e t i c a l l y l i m i t e d at t e m p e r a t u r e s
b e l o w a p p r o x i m a t e l y 600~ (550~ for the ( l l l ) G a
face), showing an o v e r a l l activation e n e r g y for the
deposition process r a n g i n g from 16 k c a l / m o l for the
( l l l ) A s to 22 k c a l / m o l for the ( l l l ) G a (Fig. 1).
F i g u r e 3a shows the effect of v a r y i n g the TMG p a r t i a l
p r e s s u r e while h o l d i n g PAsHa constant at 500~ while
Fig. 3b shows the case for v a r y i n g PAsHa at constant
PTMG again at 500~ F r o m these graphs, one can see
t h a t the (100), (110), and ( l l l ) A s o r i e n t e d l a y e r s all
b e h a v e in a v e r y s i m i l a r m a n n e r , showing a slight s u b -
l i n e a r v a r i a t i o n of g r o w t h r a t e w i t h PTMG and w e a k
d e p e n d e n c e of the deposition on PAsHs. I n c o n t r a s t to
this, the ( l l l ) G a face shows s t r o n g l y n o n l i n e a r b e -
h a v i o r of the g r o w t h r a t e w i t h PTMO, and a significant
d e p e n d e n c e of g r o w t h r a t e on the m a g n i t u d e of PAsHa.
High temperature, desorption limited growth.--For
e p i t a x i a l deposition at t e m p e r a t u r e s g r e a t e r t h a n
850~ t h e g r o w t h r a t e falls off w i t h increasing t e m -
p e r a t u r e at a r a t e w h i c h is h i g h l y o r i e n t a t i o n sensitive
(Fig. 1). The lowest fall off is seen for the ( l l l ) A s face
at 5 k c a l / m o l , w h e r e a s the (100), (110), a n d ( l l l ) G a
faces show a fall-off "activation e n e r g y " of 11-12 k c a l /
tool. The g r o w t h r a t e on the various orientations is
also quite different, w i t h g r o w t h on ( l l l ) A s face b e -
ing a p p r o x i m a t e l y 42% f a s t e r t h a n the ( l l l ) G a at
1000~
I I I I 10 20 30 40
3O 40
PAsH3 (x 10-4 ATM)
Fig. 3b. Growth rate vs. parfiat pressure of AsH~ for GaAs ep|-
taxial layers at constant PTMG -- 1.8 X 10 - 4 atm and 500~
F i n a l l y , Fig. 4a a n d b show the g r o w t h rate vs. PTMG
and PAsHa, respectively, at 1000~ Here, the deposition
r a t e was found to be l i n e a r w i t h PTMG, w i t h g r o w t h
being fastest on the ( l l l ) A s face, a n d slowest for the
( l l l ) G a orientation, w i t h i n t e r m e d i a t e values for the
(100) a n d (110) faces. The deposition r a t e was also
found to be i n d e p e n d e n t of PAsHa at this t e m p e r a t u r e ,
for fixed PTMG, b u t v a r i e d w i t h c r y s t a l l o g r a p h i c o r i e n -
tation in the same o r d e r as above.
Discussion
This section i n t e r p r e t s our e x p e r i m e n t a l results in
terms of classical g r o w t h m e c h a n i s m s which h a v e been
described in the l i t e r a t u r e . F o r simplicity, r e a c t i n g
species a r e w r i t t e n as TMG and AsI-~. However, the
actual surface species which l e a d to G a A s g r o w t h a r e
c o n s i d e r a b l y m o r e complex in o r g a n o m e t a l l i e CVD.
A l t h o u g h t h e i r n a t u r e is uncertain, some conjectures
will be m a d e b a s e d on the a v a i l a b l e studies of d e c o m -
position of the reactants.
I n previous studies, the pyrolysis of TIVIG and AsI-I3
has been m o d e l e d both w i t h a L a n g m u i r - R i d e a l m e c h -
anism (14) w h e r e gas phase g a l l i u m species react w i t h
surface a d s o r b e d arsenic, and b y a L a n g m u i r - H i n s h e l -
wood m e c h a n i s m (15) w h e r e TMG a n d AsHa adsorb on
the surface p r i o r to p a r t i a l decomposition a n d reaction.
These two heterogeneous reaction m e c h a n i s m s should
be distinguishable b y the d e p e n d e n c e of the g r o w t h
r a t e on the p a r t i a l pressures of TMG a n d AsI-Ia in the
gas phase.
 678 J. Electrochem. Soc.: S O L I D - S T A T E S C I E N C E AND T E C H N O L O G Y March 1983

0,5 I I I I I I I where the terms are analogous to those defined for the
L a n g m u i r : R i d e a l case, and
1000~ 3 ~ v
0,4 PAsH3 = 3,3x10-3 ATM K2flAsHsflTMGPAsH3PTMG
R:
(i + ~AsHaPAsH3) (I+ #TMGPTMG)
"~ 0,3 SO that the predicted growth rate is sublinear in both
T M G and Asl-l~. This equation also assumes no hinder-
0,2 ing effect of desorption of reaction by-products such
~- / / / GAAa as CI-14 as has been experimentally verified (16).
/ / / ~ / ORIENTATION
Mid-temperature, mass transport limited region.--
/p/./ n (110) I n the t e m p e r a t u r e range from 600~176 the ob-
served growth rate is l i n e a r l y d e p e n d e n t on the TMG
v (Ill)As partial pressure and i n d e p e n d e n t of the AsHa partial
I 1 I I I I I pressure. This is as expected for growth which is l i m -
1,0 2,0 3,0 LL0
ited b y diffusion of the less a b u n d a n t species to the
PTMG (x 10-4 ATM) crystal surface. Moreover, the surface reactions pro-
ceed faster t h a n this diffusion process, so that i n f o r m a -
Fig. 4a. Growth rate vs. partial pressure of TMG for GaAs epi- tion on the growth rate gives little insight with respect
taxial layers at constant PAsH3 = 3.3 X 10 - 3 arm and 1000~ to the mechanisms of reaction in this t e m p e r a t u r e
range. I n d e p e n d e n c e of growth rate on crystallographic
o r i e n t a t i o n is also observed, since the surface de-
0,5 I I I i I I I p e n d e n t processes are effectively masked by the n a t u r e
of the mass t r a n s p o r t limited growth.
lO00~
PTMG = i,8 x 10.4 ATM
Low temperature, kinetically controlled g r o w t h . -
0,4 Our results show that, over this t e m p e r a t u r e range,
the growth of GaAs is s u b l i n e a r with respect to both
TMG and AsH~ for all substrate orientations (Fig. 3a
0,3 and b). Thus, the L a n g m u i r - H i n s h e l w o o d model can
~ W W
V be used to describe the growth process. Here, the ad-
D sorption of both arsenic a n d g a l l i u m species plays a
[] o role i n this deposition. However, we propose that p r o :
A cesses associated with arsenic adsorption dominate,
since the growth rate on the ( l l l ) G a face is higher
0,i GAAS ORIENTATION t h a n that on the ( l l l ) A s face.
O (i00) A (III)GA I n this region, the m e a s u r e d activation e n e r g y for
[] (110) V (Ill)As the deposition of GaAs on the (111)Ga face is 22 k c a l /
0 l l l l l I l tool. Since this is very n e a r l y the same as the e n e r g y
i0 20 30 40 measured for the heterogeneous decomposition of AsHa
(23.2 kcal/mol, (17)) corresponding to rapid removal
PAsH3 (x 10.4 ATM) of the first H atom s u b s e q u e n t to adsorption, we postu-
late that the adsorption and rapid decomposition of ar-
Fig. 4b. Growth ratevs, partml pressu~ofAsH3forGaAsepi- sine on the growing surface is the d o m i n a n t process.
taxiallayersatconstantPT~G = 1.8 X 1 0 - 4 a r m and 1000~ Further, the lower value for the activation energy on
the ( l l l ) A s face (15 kcal/mol) suggests that the pres-
For the L a n g m u i r - R i d e a l case, a s s u m i n g AsHa is ad- ence of the G a - b e a r i n g reactant enhances the p r o b a b i l -
sorbed prior to decomposition, the growth rate, R, is ity of chemisorption of ASH2, p r o b a b l y as a result of
given b y coordination with these species. We expect this coordi-
R -- K1 9ASH3PTMG nation to follow the gas phase partial pressure of the
m i n o r i t y species (TMG), such that the decomposition
where Ks is a rate constant, PTMC is the gas phase TMG r e m a i n s a strong function of the m i n o r i t y reactant, as
p a r t i a l pressure, a n d #ASH3 is the surface coverage of is verified by the e x p e r i m e n t a l results of Fig. 3a.
arsine as predicted by the L a n g m u i r adsorption iso- The availability of m a n y coordination sites for AsI-I3
t h e r m (after (10)) on the (111)Ga face should result in the growth being
~AsH3PAsH3 a function of the AsH3 partial pressure, as seen in Fig.
OAsH3 "-- 3b. On the ( l l l ) A s face, however, the growth should
1 q- flAsHaPAsH3 be relatively i n d e p e n d e n t of the AsH~ overpressure,
Here, PAsHa is the arsine gas phase partial pressure since this surface provides an a b u n d a n c e of As atoms.
and #AsHa is the ratio of the rate constant for adsorp- I n the previous study (15), a n activation energy of
tion of arsine to the rate constant for desorption. If 13 k c a l / m o l was measured for the low temperature,
#AsH3 PAsH~ > > 1 due to strong arsine adsorption, then surface catalyzed reaction of TMG a n d AsHa, where
this equation reduces to no oriented single crystal substrate was present. A
value of 13 __. 5 k c a l / m o l was reported previously (14),
R = K1 PTMG for the growth on (100)GaAs substrate material. Both
of these values compare favorably with our results.
SO that the predicted growth rate is l i n e a r l y d e p e n d e n t Thus, the growth of GaAs films at ]ow t e m p e r a t u r e s
on the partial pressure of TMG, and i n d e p e n d e n t of the is aided by the adsorption of both reactants leading to
AsI-I8 overpressure. significant deposition even at low temperatures, where
The L a n g m u i r - H i n s h e l w o o d model for n o n c o m p e t i - homogeneous AsI-i3 decomposition cannot take place to
tive adsorption of TMG and AsHa2 followed by sur- a n y significant extent (18). Finally, comparison of the
face reaction predicts that value for the third GaCH3 bond dissociation energy
R : K26AsH8 8TMG (77.5 k c a l / m o l ) (19) and the observed activation e n -
ergy of GaAs deposition indicates that no gas phase re-
~Noncompetitive surface adsorption is expected, due to the actions are expected to occur in this t e m p e r a t u r e range.
strong Lewis acid-Lewis base interaction of AsH3 with a Ga sur-
face atom, or of an As surface atom with TMG. Thus, a two site High temperature, desorption limited region.--In
adsorption mechanism is probable, as a result of this complexing
of the reactants with the surface (16). this region (>850~ the growth rate falls off with i n -
VoL I30, No. 3 GaAs EPITAXIAL LAYERS
creasing t e m p e r a t u r e . This can be caused b y gas phase
d e p l e t i o n effects (which w e r e not o b s e r v e d at the flow
rates used in o u r e x p e r i m e n t s ) or b y increased d e s o r p -
tion of r e a c t a n t species. We note, however, t h a t the
g r o w t h r a t e varies l i n e a r l y w i t h PTMG and is i n d e -
p e n d e n t of the arsine o v e r p r e s s u r e to t e m p e r a t u r e s as
high as 1050~ This w o u l d indicate t h a t the d o m i n a n t
factor controlling g r o w t h in the high t e m p e r a t u r e
r a n g e is the desorption of the g a l l i u m species and not
the arsenic species (14). F o l l o w i n g this line of r e a -
soning, we would expect the g a l l i u m species to be
m o r e s t r o n g l y a d s o r b e d on the ( l l l ) A s face, resulting
in a slower fall off w i t h t e m p e r a t u r e t h a n for the
( l l l ) G a orientation. Moreover, we would expect the
g r o w t h rate to be h i g h e r on the ( l l l ) A s face due to
the l a r g e r n u m b e r of a v a i l a b l e g a l l i u m k i n k sites. Both
of these observations w e r e noted in o u r e x p e r i m e n t s
(see Fig. 1 and 4).
A l t h o u g h desorption of the g a l l i u m species is the
controlling factor, an i m p o r t a n t consideration is that
g r o w t h takes place in an excess arsenic overpressure.
Thus, the o b s e r v e d g r o w t h b e h a v i o r m a y be e x p l a i n e d
b y the L a n g m u i r - H i n s h e l w o o d m o d e l (both species
surface adsorb p r i o r to reaction), w h e r e
~AsH3 PAsRS > > 1 and flTMGPTMG < < 1
U n d e r these conditions of r e l a t i v e l y strong As a d s o r p -
tion, a n d i n c r e a s i n g Ga-species desorption
R ~---K2 PTMG
as seen in o u r e x p e r i m e n t a l results.
We have r u l e d out depletion reactions as a cause for
the o b s e r v e d high t e m p e r a t u r e g r o w t h rate fall off for
t h r e e reasons. First, we o b s e r v e d no gas phase reaction
products either in the gas s t r e a m or on the reactor
walls in the v i c i n i t y i m m e d i a t e l y p r e c e d i n g the hot
susceptor, at the gas flows used in our w o r k (total flow
5 l i t e r s / m i n ) . Second, we o b s e r v e d no dependence
of the fall off in g r o w t h r a t e on the AsI-I~ p a r t i a l p r e s -
sure. This rules out gas phase TMG-AsH3 coordination
reactions of the t y p e r e p o r t e d for the g r o w t h of
GaInAs, w h e r e depletion of In from the gas phase in-
creased m o n o t o n i c a l l y w i t h PAsHa (20). Third, the pos-
sibility of p a r t i a l gas phase decomposition of TMG
l e a d i n g to p o l y m e r s of t h e f o r m (GaCH3)n seems u n -
likely, since these p o l y m e r s should react r e a d i l y w i t h
AsH3 at l o w t e m p e r a t u r e s (15, 16).
Nature of the surface species.--The f o r m of the g a l -
l i u m and arsenic b e a r i n g species on the c r y s t a l surface
has not y e t been e x p l i c i t l y d e t e r m i n e d . However,
s e v e r a l studies of the kinetics of TMG decomposition
(19), the decomposition of arsine (17), the interaction
of TMG with an arsenic film (21), a n d the surface in-
teraction of TMG w i t h AsH3 (15, 16) can be used to
gain some insight into t h e i r nature.
The s t u d y of the decomposition kinetics of TMG (19)
gave dissociation activation energies of 59.5, 35.4, and
77.5 k c a l / m o l for t h e first, second, a n d t h i r d GaCtt8
bonds, respectively. F o r the t e m p e r a t u r e r a n g e of
400~176 decomposition led to only f o r m a t i o n of
G a - b e a r i n g polymers, p r e s u m a b l y (GaCH3)., in a d d i -
tion to CH4, C2Hs, a n d to a much s m a l l e r extent, s e v -
e r a l m o r e c o m p l e x hydrocarbons. Moreover, the rate
constant for the dissociation of the first GaCH3 bond
was c o n s i d e r a b l y h i g h e r t h a n that of the second bond,
even t h o u g h its activation e n e r g y was higher. Thus,
the r a t e l i m i t e r for the t h e r m a l decomposition of TMG
is in all p r o b a b i l i t y the b r e a k i n g of the last GaCHs
bond.
A s t u d y p e r f o r m e d on the decomposition of AsH~
(17) suggested that the r a t e l i m i t e r in this case is the
r e m o v a l of the first h y d r o g e n atom or the e n e r g y for
direct chemisorption onto the surface. Moreover, the
chemisorption onto an As surface
AsH3 (g) --> ASH2* + H*
679
( w h e r e the * denotes s u r f a c e - a d s o r b e d species) has
been found to proceed w i t h a r e l a t i v e l y low activation
e n e r g y of 23.2 k c a l / m o l , w i t h subsequent h y d r o g e n r e -
lease being more rapid. In a l a t e r study (16), AsH3 was
found to decompose over GaAs at 172~ b y a surface
catalyzed reaction, lending support to the notion of its
easy chemisorption followed b y r a p i d decomposition.
A recent s t u d y d e t a i l i n g the homogeneous b r e a k -
down of AsI-Ia using mass spectroscopy showed that the
p r e v a l e n t b r e a k d o w n products are As and H2 below
620~ with As2 and As4 f o r m a t i o n occurring o n l y at
h i g h e r t e m p e r a t u r e s (22). A s t u d y of the AsH3 content
of the gas s t r e a m of a cold w a l l o r g a n o m e t a l l i c CVD
reactor n e a r the end of the decomposition zone has also
d e m o n s t r a t e d significant amounts of undecomposed
AsH3 a r e p r e s e n t for a susceptor t e m p e r a t u r e of 70O~
(23). This s t u d y p r o v i d e d a d d i t i o n a l evidence of e n -
hanced AsH3 b r e a k d o w n in the presence of a GaAs
substrate. Thus, at the g r o w t h t e m p e r a t u r e s c o m m o n l y
used for o r g a n o m e t a l l i c deposition of GaAs, the limited
communication b e t w e e n the gas s t r e a m and hot sus-
ceptor at typical flow rates combined with the surface
catalyzed b r e a k d o w n of AsH8 w o u l d suggest that the
a m o u n t of As2 and As4 p r e s e n t will be less than t h a t
predicted by thermodynamics.
The interaction of TMG and AsI-I3 enhances the
b r e a k d o w n of the G a - b e a r i n g reactant. S u p p o r t of this
comes from the o b s e r v a t i o n t h a t h e a t e d m i x t u r e s of
TMG and AsH3 give products of the form (CH3)3-~-
G a A s H s - y which e v e n t u a l l y evolve to GaAs b y 420~
(15). Moreover, these p a r t i a l decomposition p r o d u c t s
react w i t h AsH3 at t e m p e r a t u r e s as low as 364~ to
give GaAs (16), and TMG b r e a k s down in the presence
of an a r s e n i c - c o a t e d surface at t e m p e r a t u r e s in the
vicinity of 285~ (21). In contrast, the decomposition of
TMG to g a l l i u m in the absence of an A s - b e a r i n g
species has not been o b s e r v e d b e l o w 800~ (19).
Based on these observations, we propose t h a t the
most p r o b a b l e situation is t h a t GaCI5~* and AsH* are
the p r i m a r y r e a c t a n t species on the g r o w i n g surface.
Moreover, the a b u n d a n c e of h y d r o g e n (PH2 ~ 1 a t m )
in our system should lead to a large surface p o p u l a -
tion of ASH*, and p r o m o t e dissociation of Ass and As,
species. The deposition reaction m a y follow
GaCH3* + AsH* --> (CH~Ga -- A s H ) *
(CH~Ga -- AsH) * --> GaAs(s~ + CH4(g~
Thus, at g r o w t h t e m p e r a t u r e s above 420~ the se-
quential d e m e t h y l a t i o n of ( C H s ) 8 - z G a A s H s - y seems
unlikely, in v i e w of the p r o b a b l e surface c a t a l y z e d
f o r m a t i o n of CHsGa-AsH.
A n a l t e r n a t e v i e w p o i n t is that GaCH3* is chemi-
sorbed on the surface and diffuses to a g a l l i u m k i n k
site w h e r e it e v e n t u a l l y forms GaAs. This process is
enhanced b y the presence of arsenic, so that this r e a c -
tion most p r o b a b l y proceeds as follows
AsH* -> ASAs + H*
GaCH3* + ASAs + H* --> GaAscs~ + CH~cg~
w h e r e AsAs denotes arsenic on an arsenic lattice site.
Finally, the reaction m a y be aided b y the f o r m a t i o n of
C2H6, as detected both in the absence of AsH~ (19) as
well as in its presence (24). This w o u l d correspond to
2ASH* --> 2AsAs + H2r
2GaCHs* + 2ASAs--> 2GaAs~s~ +4- C2H6~g~
We note, however, that this situation is less p r o b a b l e
t h a n the previous, since TMG is the lesser r e a c t a n t and
much less a b u n d a n t t h a n h y d r o g e n . Moreover, the e x -
cess of the As-species w o u l d suggest t h a t interaction
of the a d s o r b e d G a - and A s - b e a r i n g r e a c t a n t s w o u l d
occur f a s t e r t h a n the G a - s p e c i e s w o u l d find a l a t t i c e
k i n k site. The distinction h e r e is w h e t h e r mobile G a -
a n d A s - b e a r i n g r e a c t a n t s diffuse to t h e i r a p p r o p r i a t e
k i n k sites p r i o r to decomposing, or w h e t h e r these
680 J. EZectrochem. Soc.: S O L I D - S T A T E SCIENCE AND TECHNOLOGY
species interact to form a mobile (CH~Ga-AsH)*
complex 3 which diffuses to the growing crystal step.
Neither of these cases greatly alters the growth model,
as both should fit a Langmuir-Hinshelwood type reac-
tion and will be indistinguishable based on studies of
the reactant input partial pressures and overall deposi-
tion process.
The gas phase complexing of AsH3 with TMG has
not been detected (15); however, the possibility of
such a complex diffusing to the crystal surface and
heterogeneously decomposing cannot be entirely ruled
out.
In summary, therefore, the actual gas phase and sur-
face reaction processes are quite complex. However,
the primary result of these processes is the strong ad-
sorption of GaCH~* and AsH* on the surface of the
gallium arsenide over the useful practical range of
growth temperatures.
Conclusions
We conclude that the deposition of GaAs epitaxial
layers by the pyrolysis of TMG and AsH~ most prob-
ably occurs following a Langmuir-Hinshelwood type
reaction. That is, both the gallium- and arsenic-bearing
reactants are expected to adsorb on the growing crystal
face prior to reaction. Furthermore, such a reaction is
heterogeneous in nature, and no evidence of gas phase
reactions was found even in the high temperature
range.
Three distinct growth regions were identified as the
deposition temperature was increased from 450 ~-
1050~ The low temperature kinetically controlled
growth regime was characterized by an orientation
dependent deposition rate and activation energy that
suggest the chemisorption and subsequent decomposi-
tion of the As-bearing species is essential to the growth
in that region. Furthermore, the deposition in this
range was found to vary sublinearly with the gas
phase partial pressures of both the Ga- and As-bearing
reactants, as predicted by the Langmuir-Hinshelwood
model. From approximately 600~ a mass trans-
port limited growth region was observed. Here, the
apparent activation energy for the deposition of GaAs
epitaxial layers corresponded to growth which was
limited by reactant diffusion through a stagnant
boundary layer. Finally for temperatures above 850~
a decrease in the layer growth rate with increasing
temperature was noted. This was explained on the
basis of GaCH8 desorption, since even in that region,
the growth was independent of the gas Stream partial
pressure of ASH3. The substrate orientation depen-
dence of the observed high temperature fall off in
deposition rate was used to provide evidence of a lack
of significant depletion effects for our reported flow
conditions, and to give further support to the Lang-
muir-Hinshelwood growth model.
3This ease is essentially analogous to that suggested to explain
experimental results for the halide growth of GaAs, where AsGaC1
is thought to be the mobile reactant responsible for deposition
(25).
March 1983
Acknowledgments
The authors wish to thank R. Reep and A. Hayner
for manuscript preparation. This work was supported
by the Solar Energy Research Institute, Golden,
Colorado, under Contract No. XS-0-9002-4.
Manuscript submitted Sept. 3, 1982; revised manu-
script received Oct. 22, 1982.
Any discussion of this paper will appear in a Dis-
cussion Section to be published in the December 1983
JOURNAL. All discussions for the December 1983 Dis-
cussion Section should be submitted by Aug. 1, 1983.
Publication costs of this article were assisted by
Rensselaer Polytechnic Institute.
REFERENCES
1. R. R. Bradley, J. Cryst. Growth, 55, 223 (1981).
2. J. P. Andrd, P. Guittard, J. HaUais, and C. Piaget,
ibid., 55, 235 (1981).
3. M. Bonnet, N. Visentin, G. Bessonneau, and J. P.
Duchemin, ibid., 55, 246 (1981).
4. T. Nakanisi, T. Udagawa, A. Tanaka, and K. Kamei,
ibid., 55, 255 (1981).
5. D. H. Reep and S. K. Ghandhi, ibid., Submitted.
6. D. J. Stirland and B. W. Straughan, Thin Solid
Films, 31, 139 (1976).
7. K. P. Pande, D. H. Reep, S. K. Shastry, A. S.
Weiner, J. M. Borrego, and S. K. Ghandhi, IEEE
Trans. Electron Devices, ed-27, 635 (1980).
8. M. Otsubo, T. Oda, S. Mitsui, and H. Miki, This
Journal, 124, 1907 (1977).
9. R. Bhat, B. J. Baliga, and S. K. Ghandhi, ibid., 122,
1378 (1975).
19. D. W. Shaw, in "Crystal Growth," Vol. I, C. H. L.
Goodman, Editor, p. 1, Plenum Press, New York
(1974).
11. H. M. Manasevit and W. I. Simpson, This Journal,
116, 1725 (1969).
12. A. L. Lin, V. Dao, and L. F. Donaghey, in "Chemical
Vapor Deposition 1977," L. F. Donaghey, P. Rai-
Choudhury, and R. N. Tauber, Editors, p. 264,
The Electrochemical Society Softbound Proceed-
ings Series, Princeton, NJ (1977).
13. S. J. Bass, J. Cryst. Growth, 31, 172 (1975).
14. W. H. Petzke, V. Gottschalch, and E. Butter, Krist.
Tech., 9, 763 (1974).
15. D. J. Schlyer and M. A. Ring, This Journal, 124,
569 (1977).
16. D. J. Schlyer and M. A. Ring, J. Organomet. Chem.,
114, 9 (1976).
17. K. Tamaru, J. Phys. Chem., 59, 777 (1955).
18. V. S. Ban, This Journal, 118, 1473 (1971).
19. M. G. Jacko and S. J. W. Price, Can. J. Chem., 41,
1560 (1963).
20. J. S. Whiteley and S. K. Ghandhi, Submitted to This
Journal.
21. D. J. Schlyer and M. A. Ring, J. Organomet. Chem.,
71, C25 (1974).
22. A. R. Calawa, Appl. Phys. Lett., 38, 701 (1981).
23. M. R. Leys and H. Veenvliet, J. Cryst. Growth, 55,
145 (1981).
24. N. N. Travkin, B. G. Gribov, C. P. Rumyantseva,
I. G. Tonoyan, and E. N. Zorina, J. Gen. Chem.
USSR, 45, 316 (1975).
25. J. L. LaPorte, M. Cadoret, and R. Cadoret, J. Cryst.
Growth, 50, 663 (1980).