Journal of Crystal Growth 248 (2003) 108113

MOVPE homoepitaxial growth used to study the effect of

aging and chemical treatment on GaAs substrates
Dan Allwooda, Nigel Masona, Andrew Mowbrayb, Ruth Palmerb,*
a

Clarendon Laboratory, Department of Physics, University of Oxford, Oxford OX1 3PU, UK

b
Wafer Technology Ltd, 34 Maryland Road, Tongwell, Milton Keynes MK15 8HJ, UK

Abstract
Epiready GaAs substrates have been studied to establish the effect of aging and chemical treatment on the wafer
surface. A 6-month aging trial was carried out by growing homoepitaxial layers on the substrates by MOVPE and
analysing the morphology of the layers by optical microscopy and AFM. The study has shown that the chemical nature
of the native oxide changes over time leading to degradation in the quality of homoepitaxial growth. As the on-axis
substrates age, growth quality can deteriorate after 4 weeks or 12 weeks, depending on the growth conditions used;
growth quality on vicinal wafers was good throughout the 24-week period. The aging effect can be reduced by careful
choice of growth conditions, substrate orientation and chemical treatments. Epiready wafers have been compared to
wafers prepared using two different chemical treatments: HCl/H2O and NH4OH/H2O2/H2O. It is recommended that
wafers are stored in their original packaging until just prior to use and storage at reduced temperature will prolong the
lifetime of an epiready wafer.
r 2002 Elsevier Science B.V. All rights reserved.
PACS: 78.66.Fd; 81.15.Gh; 81.40.Cd; 81.65.
b
Keywords: A1. Atomic force microscopy; A1. Aging; A1. Surface treatments; A3. Metalorganic vapor phase epitaxy; B1. Oxides;
B2. Semiconducting gallium arsenide

1. Introduction
Successful epitaxial growth of high quality
semiconductor layers demands that the substrates
used provide a perfect template for epitaxy. A
GaAs wafer has a thin oxide layer present on the
surface covering the underlying bulk GaAs [1,2].
This oxide must be of controlled composition and
thickness in order for it to be removed easily
*Corresponding author. Tel.: +44-1908-210444; fax: +441908-210443.
E-mail address: rpalmer@wafertech.co.uk (R. Palmer).

before growth takes place, leaving the underlying

surface at and free from contamination. Wafers
provided by the manufacturer in this state are
known as epiready [3], intended for use straight
from the packaging with no need for additional
surface preparation for most applications.
Previous research by the MOVPE group at
Oxford University and Wafer Technology [4] has
indicated that the age of a GaAs substrate relates
directly to the quality of epitaxial layers that can
be grown upon it. Some wafer manufacturers only
guarantee their products as being epiready for 3
months. The epireadiness of InP with age has been

0022-0248/03/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 2 ) 0 2 0 4 3 - 2

D. Allwood et al. / Journal of Crystal Growth 248 (2003) 108113

studied [5], but no equivalent study of GaAs

substrates exists.
There is currently an array of different chemical
etches [6,7] and treatments used to pretreat even so
called epiready wafers prior to growth. These
treatments may be used because the growth
process is not tuned for the use of the epiready
substrate or just to follow a historic recipe and
may in some cases do more harm than good. In
this study MOVPE growth quality on substrates
prepared with two different chemical treatments
has been compared with growth on epiready
wafers.
The aim of this paper is to assess the effect of
wafer aging on epitaxial growth over a 6-month
period. The role of the reactor ambient conditions
in the pregrowth stages is unknown but is expected
to affect the quality of grown layers. The selection
of substrate orientation and the effect of commonly used wet chemical treatments on the wafer
surface are considered. Recommendations for
prolonging the lifetime of epiready wafers by
considering the storage conditions used are also
presented.

2. Experimental procedure
The substrates used in the aging trial were 2-in
diameter VGF grown GaAs, doped with silicon.
Wafers were supplied by Wafer Technology,
350 mm thick and single side polished. Half were
(1 0 0)70.11 orientation (termed on-axis) and
half were cut 21 from (1 0 0) towards 1% 10 (termed
vicinal). Chemical treatments used Ashland
cleanroom grade solutions: HCl (36%), NH4OH

109

(29%) and H2O2 (30%) and 18 MO cm deionised

water.
We have used two treatments to improve the
wafer surface before growth. Wafers were stored in
uoroware trays inside nitrogen lled bags in
cleanroom conditions at 201C and tested at time
intervals shown in Table 1. Epiready wafers have
been given Wafer Technologys proprietary polish
and epiready treatment. The chemical treatments
that have been developed were carried out
immediately after polishing. APM etch, NH4OH/
H2O2/H2O of composition 2:1:40 was found to be
a smooth, controllable etch which maintained the
mirror nish of the polished wafers while removing
1 mm of GaAs per minute. An etch time of 30 s was
previously found to be sufcient to remove the
surface anisotropy [8]. The HCl treatment, using
HCl/H2O 1:1 for 1 min, is not an etch as only the
oxides are removed. Clean wafers were achieved
by quenching the HCl with owing deionised
water, resulting in regrowth of the oxide.
In this work, growth has been carried out under
hydrogen in a horizontal reactor cell, details of the
set-up are provided elsewhere [4]. The ow rate of
hydrogen through the reactor was 16 min
1 at
1000 mbar and the precursors used were tBAs,
Mochem, 51C, 60 Torr and TMGa, Epichem,

91C, 42 Torr. All wafers were tested with two
types of homoepitaxy and two types of deoxidation, the conditions are given in Table 2. These
were used in order to assess the effect on growth
quality of aging and treatments before and after
growth and to establish the role of tBAs or H2 in
the pregrowth stages.
Ex situ analysis was carried out using optical
microscopy and AFM. Samples were photo-

Table 1
Summary of samples included in each run at each time interval
Orientation

Treatment

Growth A

Growth B

Deox

Anneal

On-axis

APM
HCl
Epiready

0,1,4,12,24
0,1,4,12,24
0,1,4,12,24

0,1,4,12,24
0,1,4,12,24
0,1,4,12,24

0,1,4,12,24
0,1,4,12,24
0,1,4,12,24

0,1,4,12,24
0,1,4,12,24
0,1,4,12,24

Vicinal

APM
HCl
Epiready

0,1,4,12,24
0,1,4,12,24
0,1,4,12,24

12,24
12,24
12,24

12,24
12,24
12,24

12,24
12,24
12,24

The week at which a type of growth run was carried out on a sample is given. All treatments carried out at time zero.

D. Allwood et al. / Journal of Crystal Growth 248 (2003) 108113

110

Table 2
Conditions for the growth and deoxidation runs investigated. Growth rate was approximately 2 mm per hour
Run

Heat up

Growth A
Growth B
Deox
Anneal

To
To
To
To

6001C
6001C
6001C
6001C

Deoxidation
over
over
over
over

25 min
25 min
25 min
25 min

with
with
with
with

tBAs and H2
H2
tBAs and H2
H2

At
At
At
At

6001C
6001C
6001C
6001C

for
for
for
for

5 min
5 min
5 min
5 min

Growth

Cool down

At 5801C for 30 min

At 5801C for 30 min

To
To
To
To

201C
201C
201C
201C

over
over
over
over

45 min
45 min
45 min
45 min

graphed with a Leitz Laborlux 12Me microscope

at  200 magnication and were given a value for
defect level, graded from 1 for no defects to 9
indicating many defects. The Park Scientic
Instruments Thermomicroscope Autoprobe M5
AFM was operated in the non-contact mode.
The roughness of samples was measured from
average Ra (average roughness) values calculated
from 5 lines drawn across the AFM image.
2.1. Aging trial
When ideal growth conditions were used with
tBAs, as in growth A, high quality epitaxial
growth was observed for the rst 3 months on all
wafers. tBAs decomposes at above 4101C in the
deoxidation stage, providing both arsenic and
atomic hydrogen. This aids oxide desorption [9]
and limits the desorption of arsenic from the bulk,
leaving a smooth surface for subsequent growth.
Layers produced exhibited atomic terracing, a
typical example is shown in Fig. 1(a). Growth A
begins to deteriorate at week 12, Fig. 1(b). Growth
is nucleated at defects on the terraces left after
deoxidation in preference to the step edges,
causing the rough epitaxial layer shown. The
change in growth mode from step ow growth to
island type growth [10] is demonstrated in Table 3
where the defect level and Ra roughness increases
with age.
When only molecular hydrogen was present in
the heatup in Growth B, the growth quality had
begun to deteriorate by week 4, Table 3. Heatup in
a molecular hydrogen atmosphere simulates deoxidation conditions when insufcient cracking of
the group V precursor has taken place. This
suggests aging issues may be more important
when growth conditions are such that the arsenic

Fig. 1. AFM images showing: (a) growth A on the APM

treated wafer at week 1 showing atomic terraces (3 mm), (b)
growth A on the epiready sample at week 12 (10 mm), (c) deox
on the epiready sample at week 12 (10 mm), and (d) anneal on
the APM etched sample at week 12 (10 mm).

precursor has not fully pyrolysed to arsenic and

atomic hydrogen in the pregrowth stage.
The advantages of the presence of tBAs at this
stage are again shown from the Deox results given
in Table 3. Throughout the aging period, a smooth
surface with consistently low Ra values is obtained
after Deox, Fig. 1(c). However, this highlights the
limits of AFM for predicting good growth because
results from Growth A show a degradation in the
surface at week 12, possibly due to organic
contamination.
Annealed samples deoxidised in molecular
hydrogen clearly show that a smooth surface does
not result when tBAs is absent in the heatup.

D. Allwood et al. / Journal of Crystal Growth 248 (2003) 108113

111

Table 3
Growths A and B and anneal results for on-axis samples treated with APM at time zero
Run

Analysis

12

24

Growth A

Defect level
Ra roughness

2
0.2

3
0.2

2
4.0

6
4.5

Growth B

Defect level
Ra roughness

2
0.2

2
0.2

5
3.3

5
5.1

5
4.7

Deox

Ra roughness

0.1

0.1

0.2

0.2

0.1

Anneal

Droplet count

22

29

Data indicating surface quality are given for runs carried out at intervals over the 6-month storage trial. Defect level is given on a low
(1) to high (9) scale. Average Ra roughness values are in nm. Gallium droplet count is per 10 mm square image. (Conditions were not
optimised for Growth A week 0.)

Large droplets of gallium [11] appeared on the

annealed surface after 12 weeks, Fig. 1(d), which
could then act as nucleation sites for island growth
leading to the rough surfaces seen. The droplet
counts in Table 3, which proved a good measure of
aging and growth quality, were calculated by
averaging counts over nine 10 mm AFM images.
Results for the time interval at which poor
growth morphology was rst observed are given in
Table 4 for growth A and B and on-axis and
vicinal samples. Growth on the vicinal wafers
resulted in smooth layers and few defects throughout because these substrates have more abundant
nucleation sites for growth at step edges as the
terrace width is much lower than for on-axis
substrates. When vicinal substrates are used, the
optimisation of reactor conditions is less crucial.
At each time interval in the trial, the quality of
growth on the APM treated sample was better
than the HCl treated sample and this was better
then the epiready sample. As an example, week 12
data is shown in Table 5. The APM etch produces
the best growth morphology because the etching
action removes any defects or impurities at the
oxide bulk interface and polishes the surface. The
oxide after HCl treatment is chemically different to
the epiready sample. Treatment removes the
hydroxyl groups present on epiready wafer surfaces [12] that can result in an increase in oxidation
rate in the wafer packaging. XPS analysis [13] has
revealed a higher level of arsenic present on HCl
treated wafers.

Table 4
Time interval at which poor morphology is observed in the
aging trial
Orientation

Growth A

Growth B

On-axis
Vicinal

12 weeks
>24 weeks

4 weeks
24 weeks

Table 5
Growth A and B and anneal results for on-axis samples at 12
weeks after chemical treatment showing improvement in
growth by chemical treatment
Run

Analysis

APM

HCl

Growth A

Defect level
Ra roughness

2
4.0

4
4.1

6
5.4

Growth B

Defect level
Ra roughness

5
5.1

6
5.4

6
6.0

Anneal

Droplet count

22

25

Epiready

32

Defect level is given on a low (1) to high (9) scale. Average Ra

roughness values are in nm. Gallium droplet count is per 10mm
square image.

2.2. Change in chemical composition of oxide with

time
The growth quality on all on-axis wafers
degrades over time due to a change in the chemical
composition of the oxide [11]. This results in
incomplete desorption of the oxide during the

D. Allwood et al. / Journal of Crystal Growth 248 (2003) 108113

112

Table 6
Average gallium droplet counts over a 10 mm scan after annealing for samples from the storage trial. Fig. 1(d) is a typical example of
such a scan
Conditions

Ambient

Ambient

Furnace

Furnace

Freezer

Fridge

N2

Air

Time
Droplet count

1 week
10

2 years
105

10 h
50

29 h
120

2 years
15

2 years
20

20 weeks
10

20 weeks
59

deoxidation stage of growth unless high deoxidation temperatures are used, but this can roughen
the surface due to arsenic loss.
Initially the major component of the native
oxide coating on GaAs is As2O3. This oxide is not
passivating, it is unstable in the presence of GaAs.
As the substrate ages, an internal change in the
chemical nature of the oxide occurs [14]:
2GaAs As2 O3 -4As Ga2 O3 :

This degrades the oxide/bulk interface and

generates gallium oxide which is more difcult to
remove before growth than the arsenic oxide.
If Ga2O3 is not removed before growth it can
be reduced to gallium which coalesces to form the
droplets seen, inducing an island growth mode
leading to a roughened layer.
2.3. Storage trial
Storage of wafers at elevated temperatures
produces droplets of gallium after annealing at a
rate much faster than in ambient storage conditions. Post-anneal gallium droplet counts from
epiready samples stored at room temperature for
periods up to 2 years were compared with samples
stored in a mufe furnace at 2001C for up to 30 h.
As the gallium droplet formation is related to the
amount of Ga2O3 on the surface, these results were
used to calculate an estimated activation energy
for the formation of Ga2O3 (Eq. (1)) of
34.7 kJ mol
1. High temperature storage may be
used as an accelerated aging method and the
activation energy may be used to calculate
estimated lifetimes of substrates stored at different
temperatures. Storage at reduced temperatures
should slow the aging process.
Wafers stored for 2 years in a freezer at 201C
showed little sign of aging compared to samples of

the same age stored at ambient temperature.

Smoother epitaxial layers were produced by both
Growth A and B on the freezer stored sample.
Table 6 shows droplet counts after anneal for fresh
epiready wafers, freezer stored samples and 2-yearold epiready samples. Storage in a fridge at 21C
also showed great improvement over the quality of
grown layers on wafers stored at room temperature. Storage at reduced temperature is recommended to extend the lifetime of epiready wafers.
Results from comparisons between wafers
stored in nitrogen lled bags and those stored in
air (Table 6) shows slower aging when wafers are
stored in inert conditions. This limits the amount
of As2O3 on the wafer surface and therefore
reduces the amount of Ga2O3 that can be
produced through Eq. (1), leading to the recommendation that wafers are stored as received in
their original packaging until just before use.

3. Conclusion
This work has found that when a ow of tBAs
was used in the oxide thermal desorption stage of
growth, good morphology of the grown layer was
maintained for longer than when tBAs was not
present. In a comparison of substrate orientation,
layers grown on vicinal substrates maintained a
good morphology throughout the trial, whereas
the quality of the growth upon on-axis substrates
was seen to degrade. At each time interval in the
trial, samples chemically treated at time zero were
found to produce smoother epitaxial growth with
fewer defects than the epiready sample. An
investigation into storage conditions has shown
that at elevated temperatures the aging effects
observed are accelerated and at reduced temperatures they are attenuated.

D. Allwood et al. / Journal of Crystal Growth 248 (2003) 108113

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