Ion mixing of IIIV compound semiconductor layered structures

W. Xia, S. A. Pappert, B. Zhu, A. R. Clawson, P. K. L. Yu, S. S. Lau, D. B. Poker, C. W. White, and S. A.

Schwarz
Citation: Journal of Applied Physics 71, 2602 (1992); doi: 10.1063/1.351079
View online: http://dx.doi.org/10.1063/1.351079
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Ion mixing of Ill-V compound

semiconductor

layered structures

W. Xia, S. A. Pappert, B. Zhu, A. R. Clawson, P. K. L. Yu, and S. S. Lau

Department of Electrical and Computer Engineering, University oj California at San Diego, La Jolla,
California 92093-0407

D. B. Poker and C. W. White

Solid State Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6048

S. A. Schwarz
Bellcore, Red Bank, New Jersey 07701-7040

(Received 11 September 1991; acceptedfor publication 6 December 1991)

Compositional disordering of III-V compound superlattice structures has received
considerableattention recently due to its potential application for photonic devices.The
conventional method to induce compositional disorder in a layered structure is to implant a
moderate dose of impurity ions ( - lO/cm) into the structure at room temperature,
followed by a high-temperature annealing step (this processis referred to as IA here). Ion
irradiation at room temperature alone does not causeany significant intermixing of
layers. The subsequenthigh-temperature annealing step tends to restrict device processing
flexibility. Ion mixing (IM) is capable of enhancing compositional disordering of
layers at a rate which increasesexponentially with the ion irradiation temperature. As a
processingtechnique to planarize devices,ion mixing appearsto be an attractive technology. In
this work, we investigate compositional disordering in the AlGaAs/GaAs and the
InGaAs/InP systemsusing ion mixing. We found that the ion mixing behavior of these two
systems shows a thermally activated regime as well as an athermal regime, similar to
that observedfor metal-metal and metal-semiconductorsystems.Ion mixing is observedto
induce compositional disordering at significantly lower temperaturesthan that for the
IA process.We have compared the two processesin terms of five parameters: (1) irradiation
temperature, (2) dose dependence,(3) dose rate dependence,(4) annealing, and (5)
ion dependence(including electrical effects and mass dependence).We found that the IM
processis more efficient in utilizing the defects generatedby ion irradiation to cause
disordering. Both the physical mechanism of ion mixing and possible device implications will
be discussed.

I. INTRODUCTION
A. Compositional

disordering

The intermixing of elements in structures of III-V

compound quantum wells and superlatticeshas beeninvestigated extensively in recent years.The layered structure
of quantum wells is generally stable thermally; there is
little or no intermixing between individual layers at temperaturesas high as 1000C if proper precautionsare taken
to prevent vaporization. In 1981, researchersat the University of Illinois reported that the disordering of an AlAsGaAs superlattice could be greatly enhancedby diffusing a
p-type dopant, Zn, into the structure at low temperatures
( 5 600 C) .2T3They found that the superlattice was disordered (intermixed to become an alloy of AlGaAs) only in
the region where Zn was diffused into the structure. In
areaswhere Zn was not diffused into the structure, discrete
layers of the superlattice remained intact. It is interesting
to point out that the disordered region stayed as a single
crystal and epitaxial to the surrounding superlattice regions. Since this discovery, impurity disordering in the
temperature range of 600-900 C has been reported in
AlGaAs/GaAs, InGaPAs/GaAs,4 InA1GaP/InGaP,5
InGaAs/GaAs,6 InGaAs/InP,7 GaInP/AlInP,8 and other
systems. Shallow dopants apparently enhancethe interdif2602

J. Appl. Phys. 71 (S), 15 March 1992

fusion of Al and Ga or As and P atoms, causing intermixing of the layered structure of superlattices. The diffusing
dopants can be either n or p type and may occupy either
group III or V lattice sites. Van Vechten has theorized that
for the case of Zn diffusion into an AlAs/GaAs superlattice, the disordering was due to the interaction between
interstitial Zn and antisite defect complexesin conjunction
with the diffusion of As vacancies by nearest-neighbor
hopping.g Tan and Giisele observed phenomenologically
that the enhancedinterdiffusion between Ga and Al under
n-doping conditions is in accordancewith the Fermi-level
effect where the total Ga vacancy concentration, V,,, is
raised by the addition of charged vacanciesto the neutral
vacancies to promote interdiffusion. lo While the detailed
mechanisms of the disordering are still under
investigation,~r2the effectsof enhancedintermixing under
extrinsic conditions have been firmly established.
Compositional disordering can be induced by several
techniques: fi) impurity-induced disordering, where the
impurities are introduced into the structure either by diffusion or by ion implantation; (ii) defect-induceddisordering, where a stripe pattern of SiOz is deposited on the
surface of the sample (usually superlattice structures of
AlGaAs/GaAs); and (iii) disordering induced by solidphase regrowth.13 We will concentrate on impurity-in-

0021-8979/92/062602-09$04.00

@ 1992 American institute of Physics

2602

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duced disordering by ion implantation here.

Ion implantation of different atomic specieshas been
shown to promote compositional disordering.*27 Highefficiency heterostructure lasers have been fabricated as a
result of compositional disordering using MeV oxygen ion
implantation.25 Introduction of impurities by ion implantation is favored due to the control, reproducibility, and
simplicity of the process. The conventional way of disordering is to implant a moderate dose ( 5 lOi cm - 9 of
shallow dopant ions (e.g., Si for n type and Zn for p
type)26 into the sample at room temperature, followed by a
high-temperature annealing step (600-850 C!) to promote
interdiffusion between layers. (This process is referred to
as the IA process.) Ion irradiation at room temperature
alone does not cause any sign$cant

intermixing

of layers,

although defects must have been introduced by the irradiation. A high-temperature annealing step must follow to
cause compositional disordering. It is generally believed
that compositional disordering caused by post-implantation annealings is due to a Fermi-level effect, identical to
that observed in diffused samples discussedpreviously.26
In terms of device processing, high-temperature annealing steps are undesirablebecauseof processingrestrictions and the requirement of a special annealing environment such as overpressure and/or capping. To facilitate
the planarization of photonic devices, a low-temperature
processing technology, such as ion mixing, appears to be
attractive.
B. The ion mixing phenomenon

Ion mixing is a process to induce intermixing between

regions of different atomic composition under the influence
of an ion beam. It has long been recognized28as an alternative to high doseion implantation in metal-superconductor and metal-metal systems29-32for ion beam modification
of materials.3334In tribology, ion mixing is used to improve surface properties of wear, hardness, and
corrosion.35In microelectronics, ion mixing is used to improve contact formation in small areas (i.e., micron size)
and interconnect surface morphology.36,37In photonics,
ion mixing is potentially useful in creating new material
structures suitable for light sources, detectors, and waveguide modulators.3842
The ion mixing (IM) processmay be divided into two
regimes:43the prompt regime (or prompt mixing) and the
delayed regime (or delayed mixing). In the prompt regime, the incident ion transfers its energy to the target
atoms, producing many recoils. The primary collision, producing recoils in the forward direction, is considered to
have less significant contribution to ion mixing.44Mixing in
the prompt regime is mainly due to secondary collisions
which are isotropic (commonly called cascade mixing)
and athermal (temperature independent). Mixing in the
delayed regime is considered to be a process associated
with radiation-enhancedmigration, which is substrate temperature dependent. At low temperatures, radiation-enhanced migration has only a limited contribution to the
transport of atomic species. The prompt mixing process
dominates. As the substrate temperature increases,delayed

mixing becomes more significant and finally becomesthe

dominant mixing process. The ion mixing process, therefore, should generally exhibit two distinct temperature regimes. The temperature dependence of ion mixing efficiency is commonly referred to as a Q-curve.29*45The
quantity Q is usually defined as the square of the diffusion
length divided by the ion dose or Q = Dt/q& where D is the
effective diffusion coefficient, t is the time, and 4 is the
dose. Below a certain transition temperature, T,, the
amount of mixing, Q, is insensitive to the temperature (the
athermal region); above T,, Q increasesexponentially with
the temperature (the thermally activated regime). The Qcurve characteristics of ion mixing have been observed in
metal-semiconductor and semiconductor-semiconductor
systems. The value of T, depends on the system,& but is
typically around room temperature for metal-semiconductor systems, and around 200 C for III-V compound and
IV-IV layered structures.414U* It is, therefore, possible to
induce disordering in III-V compounds using ion mixing in
the thermally activated regime at temperatures substantially lower than those required by conventional ion implantation followed by high-temperature annealing (the IA
process).
In the most simplistic terms, ion mixing is just ion
irradiation at elevated temperatures. What are the differencesbetween ion mixing (IM) and ion implantation followed by a high-temperature annealing (IA)? It was the
primary objective of this investigation to compare these
two processesin terms of five parameters: (i) irradiation
temperature, (ii) dose dependence, (iii) dose rate dependence, (iv) annealing, and (v) ion dependence(including
electrical effects and mass dependence).
II. EXPERIMENT

The III-V compound superlattice structures were

grown by either molecular beam epitaxy (MBE) or by
metallorganic chemical vapor deposition (MOCVD) .
Most of the experiments were performed with the
InGaAsAnP and the AlGaAs/GaAs systems. The
AlGaAs/GaAs samples nominally consisted of 100-A
Alc5Gac5As and 100-A GaAs with a total of 16 periods
grown on GaAs substrates. In some cases, samples with
different composition and superlattice structure were also
used in this investigation. The Ine53Gac47As/InP samples
usually consisted of 25-A Ine53Gac47Aswells and 50-A
InP barriers with a total of 50 periods grown on InP substrates. Ion mixing experiments were carried out with various ions at temperatures ranging from 77 to -858 K
( 585 C), and with various energies.The sampleswere analyzed with MeV ion Rutherford backscattering spectrometry (RBS), secondary-ion mass spectrometry (SIMS), xray rocking curve (XRC), cross-sectional transmission
electron microscopy (XTEM), and optical measurements.
Ill. RESULTS AND DISCUSSiON
A. Irradiation

temperature

and dose dependence

The temperature and dose dependenceof the ion mixing behavior of the AlGaAs/GaAs was investigated in de-

2603
J. Appl. Phys., Vol. 71, No. 6, 15 March 1992
Xia et al.
2603
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m
.e
5
L
:
.-c
-.A
2
F
.e
-2
25
x
.e
z
3
-c
0
c
.-(J1
v-l
T
O

Angie

(Degree)

50

100

150

Depth

200

250

300

(nm)

FIG. 1. X-ray rocking curvea (200 reflection) for an Alo,Ga,,,As (100

A)/GaAs (100 A) sample with 16 periods: (a) as-grown, (b) after ion
mixing at 385 C with 1 x IO Ar+ cm- at 190 keV, the time for ion
mixing was about 20 min, (c) after ion mixing at 585 C, and (d) after ion
implantation at room temperature, followed by annealing at 650 C for20
min. Note that the thermal annealing temperature was 65 higher than
that of ion mixing.

FIG. 2. SIMS profiles shown on a linear scale for the four samples shown
in Fig. 1. The profiles showed more mixing at 585 C than at 385 C. The
profile from the sample implanted at room temperature followed by annealing at 650 C! for 20 min has peak-to-valley ratios comparable to the
virgin sample. Ion intensity of AlAs was monitored under 6-keV CJ+
bombardment at 30 off normal incidence.

tail. Figure 1 shows the x-ray rocking curves (XRC) of an

A&GacsAs (100 A)/GaAs ( 100 A) sample with 16 periods before and after ion mixing at 658 K (385 C!) and
858 K (585 C) with Arf ions to a dose of 1 x 1015cmW2
with an energy of 190 keV. The XRC for the as-grown
sample shows satellite peaks (located around hO.25)
characteristic of the superlattice [Fig. 1(a)]. The sharp
peak at 0is the substratepeak and the peak slightly to the
left ( - 0.0s) is the zeroth-order peak of the superlattice.
After ion mixing at 385 C, the integrated intensities of the
satellite peaks decreasein magnitude, indicating compositional disordering has occurred [Fig. 1 (b)]. After ion mixing at 585 C, the satellite peaks are barely detectable,indicating almost complete disordering in the sample [Fig.
l(c)]. A third x-ray peak located around the substrate
peak appearedin the XRC after ion mixing, it is likely to
be the zeroth-order peak of the ion-mixed layer appearing
near the zeroth-order peak of the remaining unmixed superlattice layer. Also shown in Fig. 1(d) is the XRC obtained on a sample implanted at room temperature followed by annealing at 650 C for 20 min (approximately
the sametime period for the sample implanted at 585 C).
It is clear that even annealing at a temperature 65 C
higher than the ion mixing temperature the crystal quality
of this sample is very poor after the IA process,and the
extent of disordering cannot be reasonablyestimatedfrom

XRC measurements.More quantitative analytical techniques such as secondary-ionmass spectrometry (SIMS)

and transmissionelectron microscopy (TEM), are needed
to characterize the mixing phenomenon.Figure 2 shows
the SIMS profiles of the four samplesshown in Fig. 1. The
results show that ion mixing at 585 C! causesmore compositional disordering than at 385 C!. Ion implantation at
room temperature followed by annealing at 650 C for 20
min causesmuch less mixing than direct ion mixing at
585 C. The extent of mixing or interdiffusion is evidenced
by an effect on the peak-to-valley height of the Al oscillations in the SIMS depth profile. Curve (c), corresponding
to ion mixing at 585 C, is unique in that it displays a
significant reduction in peak-to-valley heights with the
greatestreduction occurring in the middle of the film, at a
depth correspondingto the projected rang? An Al diffusion length is estimated to be about 50 A in this case.
Figure 3 shows the cross-sectionalTEM micrographs of
the four samplesshown in Fig. 1. The TEM results confirm
those shown in Figs. 1 and 2.
For well-behavedsystemsthe kinetics of interactions,
such as interdiffusion, between layers in a superlattice
structure can be conveniently monitored by x-ray rocking
curve measurements.48-50
The decay of the normalized intensity, 1, is directly related to the interdiffusion coefficient
Da by

2604

J. Appl. Phys., Vol. 71, No. 6, 15 March 1992

Xia et al.

2604

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FIG. 3. Cross-sectional TEM micrographs

of the four samples shown in Fig. 1. The
top of the figure is the surface of the sample
(a) as-grown, (b) after ion mixing at
385 C, (c) after ion mixing at 585 C, and
(d) after ion implantation at room temperature followed by annealing at 650 C.

cohesiveenergy,52the calculated transition temperaturefor

this system is around 300 C. This temperature dependent
0
behavior (i.e., the Q-curve characteristics) is consistent
where A is the superlattice
period and IO is the normalized
with that observedfor metal/Si systems.44Using the same
intensity before interdiffusion occurs. It was found that low
procedure, the Q curve for the InGaAsAnP system was
angle peaks around (000) as well as satellite peaks about
determined [Fig. 5(b)]. The activation energywas found to
(400) [or (200)] can be used for the measurements.4g150
If
be about 0.24 eV (similar to that observed in metal/Si
the ion mixing processis a diffusion-like process,the varisystems33)with a transition temperature of about 185C.
able t (diffusion time) in Eq. ( 1) can be replacedby 4 (the
ion dose). In this case, Eq. ( 1) can be rewritten as
B. Dose-rate dependence
-f&n

=+DL,

(1)

(2)

where K is a constant and D is the effective diffusion coefficient for ion mixing. The conventional diffusion length,
(Dt) 12, can be replacedby (04) 12. A plot of ln(I/Io) vs
4 should yield a straight line with a slope proportional to
D, since in ion mixing the amount of mixing is depth dependent. (O#> I measuredby this method is an average
quantity along depth. Figure 4 shows the plot of hr(l/lo)
vs 4 at various temperaturesfor the same AlGaAs/GaAs
sample shown in Fig. 1, implanted with Si + with an energy of 180 keV. It can be seenthat a linear relationship is
reasonably observed at different temperatures, indicating
that ion mixing is a diffusion-like process.The amount of
intermixing, A (usually defined as the characteristic diffusion length), is proportional to $.5 (i.e., A(r4.5). On the
other hand, the IA processshows an ion dose dependence
of the form A@.3 for dosesup to about 3 x 10*5/cm2for
the AlGaAs/GaAs system.23v24These observations suggest

Figure 6 shows the x-ray rocking curves of an

Alo.5Gae5As(100 A)/GaAs ( 100 A) sample with 16 periods after ion mixing at 585 C with 1 X lOI5Ar cm - ions
at 190 keV with different dose rates [Fig. 6(a)] and after
ion implantation and annealingfor different times at 585 C!
[Fig. 6(b)]. It can be seenby comparing the top and mid-

g.

that the IM process is more eficient in utilizing the ions in

causing interdzflusion (compare curves c and d in Fig. 1,

and the SIMS profiles in Fig. 2).

The temperaturedependenceof ion mixing rate (or the
Q curve) for this sample is shown in Fig. 5 (a). The parameter Q is proportional to KD (the slope of the straight
lines shown in Fig. 4). The mixing rate indicates a thermally activated regime with an activation energy of -0.46
eV. The activation energy for pure thermal diffusion is - 6
eV. The transition temperature between the thermally
activated and the athermal regime is -250 C!. Using the
correlation betweentransition temperatureand the average
2605

J. Appi. Phys., Vol. 71, No. 6, 15 March 1992

1 o-'

-8
0

2 Dose

71 04)6

FIG. 4. elln (I/1e) vs dose for Al,,sG~,,As/GaAs

samples implanted at
various temperatures. These samples (similar to those shown in Fig. 1)
were implanted with Sif ions with an energy of 180 keV.
Xia et

al.

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Ea=0.46ev

-0.4

(a)

lo12

Angle (Degree)
(4

-0.2

0.0

0.2

0.4

Angle (Degree)
(b)

1000/T
FIG. 6. X-ray rocking curves (200 reflection) for AlO,,G%h,As/GaAs
with 16 periods: (a) IM process, (b) IA process. In Fig. 6(a) the bottom
spectrum is for the as-grown sample, the middle spectrum is for the
sample ion mixed at 585 C with 1 X 10 Ar + cm - at 190 keV, the
implantation time is 15 min, and the top spectrum is for the sample with
an implantation time of 80 min. In Fig. 6(b) the bottom spectrum is for
the as-grown sample, the middle spectrum is for the sample implanted at
room temperature with 1 x lOL5Ar+ cm * ions at 190 keV followed by
annealing in forming gas at 585 C for 15 min, and the top spectrum is for
the sample implanted with the same conditions but annealed for 80 min at
585 C.

Ea=0.24ev

~,ol)
1

lb)

ing was significantly larger for samplesannealedfor 80 min

at 585 C than for those annealedfor only 15 min.
1

C. Post-implant

1000,;

FIG. 5. Ion mixing rate vs l/T (a) for AlGaAs/GaAs samples implanted
with Si + (180 keV) or Ar+ (190 keV) ions. The mixing rate is proportional to KD [see Q. (2)]. Within experimental uncertainties, the mixing
rates were the same for both ions. The solid symbols represent the net
mixing rate, i.e., subtracting the rate below T, from that above T, (b)
For InGaAs/InP samples implanted with Ar + (190 keV) ions.

dle spectra in Fig. 6(a) that changing the dose rate by a

factor of more than 5 (i.e., increasing the implantation
time of 15 min to 80 min for a given doseof Ar of 1 x lOI
cm -) did not affect the degree of disordering. The
amount of ion mixing dependsonly on the ion dose and
apparently not on the dose rate; this independence of mixing on doserate has been reported for metal/S systems.29
This observationimplies that there is an equivalenceof ion
dosewith annealingtime in a normal diffusion process.On
the other hand, the IA processdependson the annealing
time, as shown in Fig. 6(b) where the degreeof disorder2606

J. Appl. Phys., Vol. 71, No. 6, 15 March 1992

annealing

Figure 7 shows the x-ray rocking curves of an

Alo.,GacSAs (100 A)/GaAs (100 A) sample with 16 periods before and after ion implantation followed by a proximity anneal at 850 C for 2 h in an ambient of flowing
forming gas.The as-grownsample shows the characteristic
satellite peaks of the superlattice structure (spectrum a).
Annealing this sampleat 850 C for 2 h doesnot causeany
changein the XRC, suggestingannealingunder theseconditions does not causedisordering. A portion of this sample was then implanted with Ar + ions at 77 K to a doseof
3 X 1014cm -2 with an energy of 190 keV, followed by a
proximity annealat 850C for 2 h. The XRC (spectrum b)
obtained on this sample indicates the absenceof any satellite peaks,suggestingsignificant or complete compositional
disordering due to this IA processingstep. In addition, we
found that samples implanted at temperatures ranging
from 77 to 473 K (200 C) followed by annealingat 850 C
showed very similar XRCs, indicating a similar degreeof
disordering in these samples.However, increasing the implantation temperature to above 573 K (300 C) tends to
reduce the degreeof disordering after annealing. This can
be seenfrom the XRC in Fig. 7 (spectrum c) for a sample
implanted at 425 C followed by annealing at 850 C. The
characteristic satellite peaksare still present although with
Xia ei a/.

2606

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disordering in the super-latticestructure.2627These results are consistent with the concept of the Fermi-level
effect discussedpreviously. For the IM process,compositional disordering occurs primarily during ion irradiation
at elevatedtemperatures.The sampleis not under equilibrium, and the Fermi level has no significant meaning. It
follows then that the disordering mechanismbasedon the
Fermi level effect for the IA processmay not apply to the
IM process.X-ray measurementswere used to monitor the
ion mixing rate of an AlesGae5As/GaAs sampleirradiated
by either Si + ions ( 180 keV) or Ar + ions ( 190 keV) at
different temperatures to a dose of 5 X 1Ol4cm - 2. The
slight difference in energy ( 180 keV vs 190 keV) of the
incoming ions is to compensatefor the projected range due
to the atomic mass differencebetweenSi and Ar. It can be
seen from Fig. 5(a) that within the scattering of experimental data, the ion mixing rate is the samefor Si as well
as for Ar, over the temperature range from -585 C to
room temperature. These results indicate that electrically
active ions, such as Si in AlGaAs/GaAs, do not enhance
disordering as it is observedfor the IA process. Similar
results have also beenobservedfor the Si/Ge system.*The
disordering mechanismunder ion mixing conditions is es0
-0.4
-0.2
0.0
0
sentially due to the thermal migration of defects (likely to
Angle (Degre??
be vacancies) whose population is apparently not affected
by the presenceof electrically active ions, other than that
due to collisional processesduring ion irradiation at eleFICI.7. X-rayrockingCUIWS
(200reflection)for Al,,ZGa,,SAs/GaAsvated temperatures.
samplewith 16periods:(a) as-grown,
(b) afterion implantation
with
Ar + ionsat 77K to a doseof 3X lOI cm- with anenergy
of 190 keV
andannealed
at 850C for 2 h, and(c) afterimplantation
at 425C and E. Insulating ions
annealed
at 850C.
From the experimentalresults shown in Fig. 5(a), it is
clear that electrically active ions are not required to induce
disordering by ion mixing. This fact presents one of the
reduced intensities, suggestingincomplete disordering in
major
advantagesof ion mixing since the electrical conducthe sample. It should be pointed out that the critical temtivity
of
the disorderedregion can remain unaffected.Mixperature, To of the Q curve for this system is between200
ing
ions
such
as 4oAr+ are also readily availablecompared
and 300 C [seeFig. 5 (a)]. It appearsthen that implantato
28Si+
ions.
On the other hand, when a change of the
tion at temperaturesbelow T, followed by high-temperaelectrical
property
is called for, properly chosen ions can
ture annealingsleads to a similar degreeof disordering in
be
used
to
cause
simultaneous
compositional disordering
the sample,whereasimplantation at temperaturesabove T,
and
modification
of
electrical
properties.
In photonic de(i.e., in the thermally activated regime) followed by a post
annealing at higher temperatures reduces the disordering vice fabrication, it is often necessaryto isolate neighboring
devices electrically to reduce crosstalk. Oxygen has been
efIiciency. These results suggestthat defects generatedby
reported to form donor states in InP and InGaAs.53 For
implantation at temperaturesbelow T, are frozen in and
become active in causing disordering during the post-an- this reason,oxygen ions were chosenin this study to mix a
p-type InGaAs/InP superlatticestructure to achievesimulnealing process.Defects generatedby implantation at temtaneous compositional disordering and the formation of
peraturesabove T, are active in causingdisordering during
the implantation period and becomeexhaustedin numbers high resistivity material.
Figure 8 showsthe x-ray rocking curvesfor an InGaAs
after implantation. Fewer defects are, therefore, available
(20
rf)/InP (80 A) sample with 50 periods before and
for causing further disordering during the post-anneal.
after
ion mixing at 5 15 C with 1 X 1013cm - oxygen ions
Since simple defectssuch as interstitials are mobile even at
at
180
keV. It can be seen that all satellite peaks disaplow temperatures,the frozen-in defectsthat becomeactive
pearedafter mixing, suggestingcompletedisordering of the
during post-implantation annealing are thought to be vastructure. It should be noted that the ion dose neededto
cancies.
disorder the InGaAs/InP system is very small compared
to that for the AlGaAs/GaAs system. Generally speaking,
D. Electrically active ions
about 100 times higher dose is required to disorder the
For the IA process,it is often observedthat electrically
AlGaAs/GaAs system. Figure 9(a) shows the photolumiactive ions (i.e., shallow dopants), such as Si in AlGaAs/
nescence(PL) data at 10 K from the as-grownsampleand
GaAs, enhance the rate and the range of compositional Fig. 9(b) shows the PL data for the ion-mixed sample at
2607
J. Appl. Phys., Vol. 71, No. 6, 15 March 1992
Xia et a/.
2607.
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5.
Y
5
,x
E
Lii
9
x
.G6
ii
_c
-Ig

-1.5

-1.0

-0.5
Angie

0.0
0.5
(Degree)

1.0

1.5

FIG. 8. X-ray rocking curves for InGaAs (20 &/InP

(80 A) sample
with 50 periods before (a) and after (b) ion mixing at 515 % with
IX lOI 0 + cm- ions at 180 keV.

515 C! with oxygen. The PL spectrum of the as-grown

superlatticedisplays two well-resolvedpeakswhich are attributed to transitions originating from quantum well regions varying by one monolayer. An effective band gap

-0.4

-0.2
Angle

0.0
0.2
(Degree)

0.4

FIG. 10. X-ray rocking curves for an AlGaAs/GaAs sample with 16

periods. The bottom spectrum is for the as-grown sample. Tme middle
spectrum is for the sample ion mixed with 585 C with 1 X 10 Ar cm -
at 190 keV. The top spectrum is for the sample ion mixed at 585 C! with
1 X lOI Ne + cm - at 120 keV. The energies of the ions were adjusted for
approximately the same range.

blue-shit of 106 meV corresponding to the mixed

InGaAsP alloy is obtained from ion mixing. Linewidth
broadeningand integrated PL intensity reduction does occur due to the damageinduced by the implantation process.However, due to the low implantation dose and elevated implantation temperature, a PL signal is readily
obtained which is not the case for room-temperature implants at moderate dose.
F. Ion mass dependence

1100

1200

Wavelength (nm)
FIG. 9. Low-temperature (-10 K) photoluminescence (PL) spectra for
a 50-period 20-A InGaAs/SO-A InP SL structure before (a) and after (b)
ion mixing at 515C with 1X1013 O+ cm-ions
at 180 keV.
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J. Appl. Phys., Vol. 71, No. 6, 15 March 1992

The comparative study of impurity induced disordering has showns4that the Si-implanted sample has higher
mixing efficiency than that of the Ge-implanted sample,
although Ge has a higher atomic massthan that of Si. The
mixing efficiency in metal/% systems has been found to
depend on the mass of the mixing ions.? A similar effect
was also observedin ion mixing of semiconductor layered
structures. Figure 10 shows the x-ray rocking curves obtained from an AlGaAs/GaAs superlattice mixed with Ne
ions (Z = 10) and with Ar ions (Z = 18). It can be seen
that the degreeof disordering was much more significant
for the Ar ion-mixed sample than for the Ne ion-mixed
sample.Ion mixing is more efficient with heavier ions. It is
sometimesnecessaryto use ions with a light mass due to
range consideration. The mixing efficiency for light ions
can be improved by increasing the mixing temperature.
For a given superlattice system, two degreesof freedom
Xia et al.

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(i.e., temperature and ions) are usually available to achieve

the optimal disordering scheme.
G. Device applications

As discussed earlier, high-temperature processing is

undesirable for device fabrication. To demonstrate ion
mixing as a potentially viable device fabrication technique,
we have made planar buried rib waveguides by ion
mixing.@ The waveguides, operating at 1.5~pm wavelength, were fabricated using I~I~~~G~.~~As(20 A)/InP
(80 A) superlattice (50 periods) structures grown by
MOCVD. A metallization schemeof W ( 1500A)/Hf ( 100
&/Au (3200 A> was used as self-aligned ion masks (5
,um in width) for 180-keV 0 + ions. Ion mixing was performed at 515 C at a dose of 1 x 1013cm -. The InGaAs/
InP superlattice was found to be compositionally disordered by x-ray rocking curves, optical absorbance
measurements, and PL measurements. Waveguide effects
are routinely observed at 1.5~pm wavelength with propagation losses in the 1.5-dB/500+m range, which corresponds to an absorption rate of about 7/cm. This result is
reasonableconsidering the fact that the absorption edge is
fairly close to the operating wavelength. More work is now
in progress to improve the waveguide performance and to
fabricate other photonic devices such as modulators and
lasers using ion mixing.
IV. SUMMARY

The ion mixing behavior of semiconductor superlattice

structures has been investigated. We found that: ( 1) the
ion mixing behavior of these systems shows a thermally
activated regime as well as an athermal regime, similar to
that observed for metal-semiconductor systems, (2) ion
mixing in the thermally activated regime can lead to efficient compositional disordering without resorting to hightemperature post-annealings, (3) the IM has a dose dependence of #.5, whereas the IA process has a dose
dependenceof #.3. IM is, therefore, a more efficient processin utilizing the ions, and (4) electrically active ions do
not lead to enhancement of ion mixing rates, contrary to
that observed for the IA process. More readily available
ions, such as Ar ions, can be used for ion mixing.
Most of the results reported here were obtained on the
AlGaAs/GaAs system. However, the general conclusions
also apply to the InGaAs/InP system and perhaps even to
the Ge/Si system. Ion mixing appears to be potentially
useful for optoelectronics applications, especially in planarization of devices and self-aligned technology. In order
for the opto-electronic community to accept ion mixing as
a processing technique, it is important to eliminate or to
reduce defectsgeneratedby ion irradiation to an acceptable
level. This is now the challenge and much more work is
needed to address this issue.
ACKNOWLEDGMENTS

The financial support of the Department of Energy

(grant No. FG03-84ER45156, Jerry Smith) is greatly appreciated. The work at Oak Ridge was supported by the

Division of Materials Sciences,U.S. Department of Energy

under contract No. AC05-84-OR21400 with Martin Marietta Energy Systems,Inc. P.K.L.Y. also acknowledgesthe
support of DARPA.
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