The growth of antimonides by MOVPE

Prog. Crystal Growth and Charact. Vol. 35, Nos. 2-4. pp. 207-241, 1997 © 1998 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0960-8974/98 $19.00 + 0.00

Pergamon

PII: S 0 9 6 0 - 8 9 7 4 ( 9 8 ) 0 0 0 0 4 - 7

T H E G R O W T H OF A N T I M O N I D E S BY M O V P E A. Aardvark, N. J. Mason and P. J. Walker Clarendon Laboratory, Physics Department, University of Oxford, OXl 3PU, U.K.

ABSTRACT There are three main reasons for the study of antimonides, they are the optical [mainly infrared], electrical [mainly InSb and the GaSb/InAs heterojunction] and structural [mainly ordering and spinodal decomposition] properties. These properties, together with the various techniques used to measure them, are discussed in the context of several difficulties from which the growth of antimonides suffer compared to the growth of nitrides, arsenides or phosphides. These difficulties include the vapour pressure of antimony over the growing surface, the lack of a stable group V hydride, the kinetically controlled nature of the growth and the lack of an insulating antimonide substrate. The effect of these difficulties on the growth of the binary materials, and hence, the various antimonide based devices such as lasers, LEDs, photodetectors, and Hall probes; will be discussed. 1

SCOPE OF REVIEW

This review paper will cover growth of the binary antimonides [AISb, GaSb, InSb] by MOVPE together with most of the important ternaries [e.g. A1GaSb, GaAsSb, InAsSb, InGaSb, GaPSb, InPSb and A1AsSb]. Some of the quaternaries will be discussed, where they are of importance for their optical, electrical or structural properties, or where they form part of a device. There will not be room to discuss other, related growth techniques that use alkyls or hydrides such as metaiorganic molecular beam epitaxy [MOMBE], gas source molecular beam epitaxy [GSMBE], chemical beam epitaxy [CBE], vacuum chemical epitaxy [VCE] or metalorganic magnetron sputtering [MOMS]. Neither is it a review of antimonide materials p e r se and there will not be room to discuss many specific device parameters, however, there have been two recent reviews 1,2 on GaSb materials properties and antimonide based devices to which the reader is referred for more information. Not all of the 300+ papers on the growth of antimonides by MOVPE have been included in the bibliography for reasons of space, but they are all accessible as references from the papers that are included. 2

NOMENCLATURE

We have attempted to adopt a systematic, if idiosyncratic, approach to the nomenclature of both the materials discussed and the alkyls used to grow them. In particular we have avoided the use of subscripts such as AlxGa~.xSb when dealing with general aspects of the alloy and only included them when a specific alloy content or contents are being discussed.

We have ordered the elements within the sublattices AllnGa &

AsPSb. For the alkyls we have used the usual TM for trimethyl and TE for triethyl. The element is given its full symbol, e.g. TMA1 not TMA [to distinguish it from trimethylamine, TMA] and when tris or tertiary are part of the abbreviation we have used lower case e.g. t B A s . 207

A. Aardvark e t al.

208

HISTORICAL ASPECTS

Fig. 1 shows the number of publications on MOVPE growth of antimonides plotted over the last twenty years and it can be seen that there has been a steady increase in publications in this area. The growth of GaAsSb was briefly included in the first report of MOVPE by Manasevit 3 in 1969 [this is omitted from the figure for reasons of clarity] a mixture of stibine and arsine being used as the group V sources. It was noted that TMSb could perhaps be used instead of stibine and ten years later, the same author made a more thorough study of GaSb 4 specifically using TMSb and TMGa [or TEGa] as the source materials.

1996 1995 1994 1993 1992 1991 1990

1989 1988: >-

1987 1986 1985 1984 1983 1982 1981 1980 1979 0

10 20 30 Number of publications on antimonides grown by MOVPE

Fig. 1.

40

Number of antimonide MOVPE publications per year for the last 16 years.

The following year FukuiS, 6 made a thorough study of the growth of InAsSb including the first report of an antimonide superlattice [InAs/InAsPSb] in which the interfacial layer was found to be 6nm thick by X-ray diffraction [XRD], a considerable achievement for such early work. The same year problems with carbon incorporation in AISb were first reported 7 and a thorough study of' GaAsSb and GaSb made 8,9 where the issue of control of the V/III ratio was examined in detail. A light emitting diode [LED] structure was reported in 1984 l0 and was based on the lnGaAsSb/GaAsP superlattice with emission at around 1 ~m.

The first

photodetectors in 1988 were based on InGaAsSb 11,12 and operated at 1.55 ~m. The following year the first long wavelength photovoltaic infrared detectors were fabricated from the InAsSb alloy system 13. In 1991, the first laser structure, operating at 3.06 I.tm, 14 was fabricated from heterojunction system.

the in InGaAsSb/InPSb double

Also in I991 the first studies were made on new antimony precursors trivinyl

antimony 15 and triallyl antimony t6 in an attempt to solve sonae of the problems concerning pyrolysis mentioned below. Finally, in 1996, the first MOVPE antimonide based device to go into industrial production was the magneto Hall sensor based on InSb 17,18.

The Growth of Antimonides by MOVPE

4

209

REASONS FOR STUDYING ANTIMONIDES

There are three main reasons for the study of antimonides and they are the optical [mainly infrared], electrical [mainly InSb and the GaSbflnAs heterojunction] and structural [mainly ordering and spinodal decomposition] properties. These properties, together with the various techniques used to measure them, are discussed in the next section•

4_4j_.

Ootical device oroverties.

The antimonides have the smallest bandgaps [and hence longest

wavelengths] of any of the III-V family of semiconductors, ranging from gallium antimonide j9 [GaSb] [1.6btm] to indium thallium antimonide2° [InT1Sb] [>11 btm]. Thus optoelectronic devices fabricated from these materials can cover much of the infra-red wavelength range. Hence they are of interest as potential replacements for more established materials such as lead selenide [PbSe] or mercury cadmium telluride [HgCdTe]. The first optoelectronic devices were photodetectors l l,21-30 but recently emitters [both LEDs t 0,3135 and lasers 14,32,34-39] have been successfully demonstrated. The relationship between bandgap and lattice parameter for some of the binary antimonides and other III-Vs is shown in fig.2.

1.8 1.6

~Sb GaAs InP

1.4

1.2 ~. 1.0 • GaSb

1~ 0.6 InAs

0.4

II.

0.0

InSb •

"•""-..•.•..

0.2

516

518

610 L ce

~2 (A)

614

616

Fig 2 Latticeparameterand bandgapdata for variousantimonidcsand other III-V materials

4.2

Onfical assessment The principal technique used in the optical assessment of the layers is

photolumincsccnee. This gives general information 4°about the purity of the sample as impurities which are donors and acceptors can sometimes be icl~ntified by thor optical transitions. The wavelength of emission

210

A. Aardvark ot al.

gives information about the band edge transitions 41, and hence composition in alloys; whilst the sharpness of the peak gives information about crystal quality in bulk materials 42 and interface abrupmess in structures 43 with quantum wells. Raman scattering has also been used to investigate ternary alloys. The lattice dynamics of III-V ternary alloys can show either "one-mode" where the optical frequency varies across the alloy range from one binary value to another, or "two-mode" where two sets of optical phonons are observed and sometimes a mixture of the two types are seen. Raman has also been used to investigate the degree of spinodal decomposition within the miscibility gap 44 and interface modes 4s at the interface between GaSb and InAs in superlattices. Spinodal decomposition has also been investigated by absorption for the InPSb and GaPSb systems 46,47.

4.___33

,g~ir,,~A~91Led31~. There are few specifically electrical devices which have been fabricated from

the antimonides and those that have tend to be of academic rather than industrial interest. The exception to this is the magnetic field sensor based on heteroepitaxial InSb on a GaAs substrate and as such this merits its own section below. GaSb/InAs is a crossed gap type II system with the conduction band of InAs lying below the valence band of GaSb. Furthermore, the bandgap, defined in terms of the energy difference between the electron confinement energy in lnAs and the hole confinement in GaSb, is found to switch from being positive [semiconductor like] to negative semimetal like] when the InAs layer thickness exceeds 85 /~. As such this GaAsSb/InAs system has been widely studied. Hot electron transistors 48-54 and some tunnelling devices 55-60 both of which involve carrier transport perpendicular to the heterojunction between GaSb and InAs. Much work has been published on the parallel transport measurements in superlattice structures such as [GaSb/InAs] which can be grown with equal numbers of electrons and holes and are considered an ideal candidate for studying such intrinsic systems 6j-63. There are two reports of a bipolar transistor based on the GaAsSb/InP system64, 65. A table of antimonide based devices thbricated from MOVPE grown material is given at the end of the review, together with a table of the papers dealing with the physics of such devices and structures.

4._44

Electrical assessment.

Basic electrical assessment is one of the most important techniques for

assessing crystal quality for all III-V materials and the antimonides are no exception. Van der Pauw [clover leaf] and Hall samples are routinely measured at room temperature and 77K to give an indication of crystal quality. The mobility will give an indication of the structural integrity and the carrier concentration the degree of purity of the crystal. Sometimes the assessment is very simple and the electrical, optical and structural techniques concur, e.g. for GaSb 66 but in other materials, e.g. InSb 67 the presence of a dislocated heterointerface and a surface inversion layer make for a complicated scenario that is difficult to interpret simply. Simple IV and CV measurements are more difficult for undoped GaSb because the work function of the surface does not allow a Schottky barrier to be formed and for the same reason the electrochemical profiler [Polaron] does not give accurate cartier concentrations when used with undoped GaSb.

The Growth of Antimonides by MOVPE 4.___fi5 Structural properties

21 1

Many of the ternary antimonides have been studied for structural reasons

because they exhibit interesting material properties such as growth within the miscibility gap or ordering.

4,5.1 Sninodal decomaosition In a quaternary system such as InAsPSb, growth by equilibrium techniques [such as LPE] is limited by the presence of miscibility gaps, the position of which must be accurately determined within the phase diagram for the material in question. Any attempt to grow within a miscibility gap can result in spinodal decomposition, where it is energetically more favourable for the quaternary material to grow in phases of more stable binary or ternary compounds, driven by thermodynamic needs. MOVPE, is not a near equilibrium technique and can grow such quaternary systems throughout the composition range, even within a miscibility gap, because of the kinetic limitations on the speed with which the arriving atoms can rearrange themselves on the surface during growth 68. However, careful controls of growth parameters such as temperature, V/III ratio and growth rate are important in order to achieve highquality material across the composition range. Further details will be given in the relevant ternary and quaternary sections below.

4.5.2

Ordering. This phenomenon was first observed 69 in MOVPE antimonides in 1986 and since then in

nearly all alloy systems. There is an excellent review available70 but briefly for a ternary III-V compound A B C the lattice arrangement would normally be expected to be based on the zinc-blend structure with the A-C bonds forming a random [or disordered] arrangement. In an ordered structure the A-C bonds form a regular pattern with formation of a superlattice having a periodicity that is usually double that of the normal lattice. Often the superlattice structure is classified by the face centred cubic [fcc] metal superlattice structure which has the same arrangement of ordered atoms as present on the ordered fcc sublattice of the zincblende III-V ternary alloy e.g. CuPt-type with ordering along <111> directions or CuAu with ordering along <100> and <110> directions. For instance Fig. 3. shows the [110] projection of the ordered InAs05Sbo.5which has 50 percent arsenic/antimony on the group V sub-lattice shows areas of material [domains] with a regular arrangement of the group V atoms forming effectively a InAs/InSb superlattice with periodicity in the <11 l>direction. The phenomenon is not just of interest to material scientists but also to device engineers as the bandgap of an antimonide alloy system and hence emission energy33,71 has been shown to be strongly affected by the degree of ordering present. Again these ordered phase domains will be discussed in more detail in relation to particular ternary material.

212

A. Aardvark et al.

(1il) /" / /

/

[110] projection

yy,yyy •

Sb

o In o As

/

,YYY

"r"

Fig. 3. [11o] projectionof an orderedInAs05Sb,5crystalstructureshowingthe 111 planes as dashedlines

4.8

Material assessment The initial structural assessment is often simply carried out by looking at the

morphology via an optical microscope with a polarising attachment. The higher magnification available from a scanning electron microscope [SEM] allows greater detail to be obtained and subtler morphological differences to be observed7,72"83. SEM has the added advantage of two attachments; electron probe microanalysis [EPMA] and energy dispersive x-ray analysis [EDX] which can give information about the elemental composition in alloys. These two techniques have been especially usefu14,75,82,s4,85 when investigating the phase separation of ternary or quaternary systems which are susceptible to spinodal decomposition.

In order to examine issues of ordering and spinodal decomposition accurately a transmission electron technique is usually used. Often the simple electron diffraction pattern gives enough information 42,86-88. Further structural information, especially of interface abruptness or the extent of dislocations can be obtained by transmission electron microscopy [TEM]23,66,TI,s9-1°5 or X-ray diffiaetion [XRD]. Recently atomic force microscopy [afro] has proved a useful tool for the analysis of the sm'faee of the grown layer89,100,106-t08. This technique can-resolve atomic steps and help determine whether the mode of growth is 2-D [layer by layer] or 3-D [island growth] and this has important applications for the antimonides where the growth is often not lattice matched.

The Growth of Antimonides by MOVPE 5

213

DIFFICULTIES AND DIFFERENCES

The growth of antimonides by MOVPE is quite different from that for nitrides, arsenides or phosphides for four major reasons:- the vapour pressure of antimony over the growing surface, the lack of a stable group V hydride, the kinetically controlled nature of the growth and the lack of an insulating antimonide substrate.

5.1

Vapour pressure.

The first difference is that the vapour pressure of the elemental antimony is very

low compared to that for nitrides, arsenides or phosphides. This leads to the need for precise control of the V/Ill ratio to near unity at the growing surface 19. If conditions of excess group V are used, as is normal in MOVPE, then excess antimony is precipitated at the growth front and perturbs the crystal growth. This is a particular problem during the initial stages of a growth run when the substrate oxide is desorbed. In the case of InP or GaAs, the substrate is heated up to a specific temperature where it is known that the oxide is removed. In order to protect the surface from loss of the more volatile group V element [P or As] an overpressure of phosphine [PH3] or arsine [ASH3]

is maintained throughout this process [the atomic

hydrogen from the hydride used may also be important in reducing the oxide] and no excess arsenic or phosphorus remains on the surface. Antimonide substrates need the protection of Sb in the vapour but this has to be accurately controlled to avoid growth of antimony during b',,keout. Fig. 4a shows the surface of a GaSb substrate when too much antimony has been used to protect the surface during bakeout. Quite large crystals of antimony can build up on the GaSh surface when a TMSb mole fraction of l x l 0 4 is used [this is a typical mole fraction used during growth of GaSb]. Fig 4b shows the effect of insufficient antimony during bakeout and here the lack of sufficient antimony to protect the surface has led to gallium droplets forming on the surface. A specular GaSb surface can be obtained when it is protected by TMSb at a mole fraction of lxlO s.

=

i........ Fig. 4 showimgfl~eeject ~ |l~ ~tO I~ttCh8 ~ O m y ~ d ~] not ~

m~m~y C~Zq~r~M~~

!,! O~a ~

~te.

214

A. Aardvark e t al.

As well as leading to problems with substrate deoxidation, the vapour pressure of antimony leads to problems during the growth of all the antimonides and requires very close control of the V/III ratio. This aspect is explained further in the section on GaSb below.

5.2

Groun V source

The second difference is that the group V hydride [stibine, SbH3] has been used

infrequently and unsuccessfully in the MOVPE of antimonides. It is much more unstable than ammonia [NH3], phosphine and arsine, and does not store and transport successfully109 or reproducibly. Thus alkyl antimony compounds [e.g. trimethylantimony [TMSb] or triethylantimony [TESb]) are used as group V sources. This leads to major problems of carbon incorporation when growing A1Sb from trimethylaluminium [TMAI] and [TMSb] equivalent to those seen when trying to grow AlAs from TMA1 and TMAs.

5.3

Growth kinetics Fig. 5. shows the degree of alkyl pyrolysis for four common precursors, [TMIn100,

tBAs, TMGa t°° & TMSbl°°]. The data were obtained by measuring the UV absorption at 200 nm in the exhaust line of the reactor [as the temperature in cell increases, more alkyi is pyrolysed and the UV signal decreases].

I

~--

lO0(r

tBAs

90 c 80 r0 O~ 0 Q.

E 0 0

70 60 50 40

\a\

30 2O 10 0 1O0

I

I

200

300

,

400

I

I

500

600

,

I

700

Temperature/C

Fig.5. The percentagedecorapositionof variousalkylsversussusceptortempers;ture,measuredby UV adsorption

The data shows the virtually indistinguishable decomposition temperatures of TMGa and TMSb.

The

absolute values are higher than those seen in mass spectrometric studies l] 0,In using a packed tube because of the longer residence time in the hot zone in the latter experiments, however the relative difference between the alkyls is very close to that observed elsewhere. Under growlh conditions typical for GaAs all the alkyls are pyrolysed [>600°C] and the growth is in the "mass transport limited regime" [ i.e. the growth rate is controlled almost uniquely by the concentration of TMGa]. The: same is true of the role of TMIn in the

The Growth of Antimonides by MOVPE

215

growth of InP. However, under growth conditions typical for the antimonides [<550°C] the situation is more complicated. Because the TMGa is incompletely pyrolysed at typical antimonide growth temperatures the growth rate of GaSb is not controlled solely by the mass transport of the gallium species through the boundary layer but also by the degree of pyrolysis of TMGa, this is the "kinetically controlled regime" not normally observed in GaAs growth because of the poor crystal quality achieved for GaAs at such low temperatures. The two regimes are more clearly demonstrated by plotting the natural logarithm of the growth rate against reciprocal temperature.

The data shown in Fig. 6. were obtained by growing an InAs/GaSb

superlattice and varying the temperature of each period and measuring the growth rate at each temperature. Temperature (°C)

600 580 560 540 0.36788

'

'

520

'

500

480

460

'

'

'

440

0.13534

GaSb i InAs

c-

E

~

0.04979 i I

.~

0.01832

~

0.00674

e -~

I

slope =

0.0O248

I!

Fitted P-..Nd~Uata

Ea

-23 4 6 = - E a t l 0 0 0 R

= 8 314x 1000x23 4 6 Jo~es/rnoJ

= 1g~ k.Jln~ol

9.11882E-4 1.15

, 1.20

1.25

t 1.30

,

I 1.35

, 1.40

1000FF (K) Fig. 6. Kinetics aspects of growth of InAs and GaSb

The square points show the growth rate of the GaSb, it can be clearly seen that the growth rate is dependent on the temperature and that below 520 °C it is possible to fit the data to obtain the slope and hence the activation energy. The value obtained for this [195 kJ/mol] is close to that for the growth of GaAs in the kinetically controlled region 112. Above 520 °C the data points are turning more horizontal indicating that the growth is entering the "mass transport limited regime". For the circles [indicating the InAs growth rate] the growth is fully in the "transport limited regime" because as can be seen from fig. 5. both the tBAs and the TMIn should be fully pyrolysed in the temperature range 460-560 °C. Indeed the InAs data seem to indicate that above 520 °C the growth is entering the "high-temperature limited regime" where the increasing depletion of species from the growing surface with increasing temperature is causing a reduction of the growth rate [this is also seen in the growth of GaAs, but at higher temperatures (>800 °C)].

These pyrolysis characteristics for the TMGa, TMIn and TMSb have important implications for the growth of GaSb, InSb and InGaSb. The fact that both the TMGa and TMSb pyrolyse at about the same rate means that the V/III ratio at the growth surface is very close to that at the gas inlet, thus preventing any excess

216

A. Aardvark et al.

antimony being deposited. Fortunately for GaSb growth this merely demands that the growth is undertaken at one temperature or, if a temperature ramp is needed, that the growth rate at various temperatures is calibrated, when using trimethyl precursors.

The growth of InSb is even more complicated as it melts at 525 cc and the optimum growth tempera~tre is 450 °C with the maximum about 500 °C. At 500 °C the TMSb is hardly pyrolysed at all whereas the TMIn is adequately pyrolysed.

This leads to two problems: a small change in growth temperature over the

susceptor can lead to a large change in V/III ratio [which needs to be very close to 1:1 see above] and the process is very wasteful with 99% of the TMSb being unreacted and wasted.

When growing temaries such as InGaSb the ratio of the elements on the group II! sub-lattice is very closely influenced by the growth temperature because of the disparity in the pyrolysis of the TMIn and TMGa. Thus any increase in growth temperature will lead to a decrease in indium content and an increase in growth rate, because of the increase in the contribution from the gallium as the degree of TMGa pyrolysis increases.

Whilst nothing can be done about the antimony vapour pressure the other difficulties mentioned above have led to a large effort to find more suitable precursors for antimonide MOVPE. These new precursors have been designed to have lower pyrolysis temperatures and ideally an active hydrogen or some mechanism of reducing carbon incorporation into the growing layer.

5.4

Substrates

The final difference between the growth of antimonides and that of arsenides and

phosphides is that the latter are usually grown on insulating GaAs or InP substrates if their electrical properties are to be investigated by Hall transport measurements. Unfortunately, none of the binary and few of the ternary antimonides are lattice matched to GaAs or InP. Attempts have been made to use doped [cadmium or germanium] or co-doped [tellurium and cadmium] InSb or GaSb to generate high resistivity crystals but these are not readily available commercially because a large partition coefficient of the dopant in the crystal leads to large inhomogeneity of the dopant concentration113. This makes manufacture expensive and irreproducible as only a small part of the boule will have the desired properties.

There are other

problems of InSb:Cd type-conversion which will be dealt with bel,ow in the section on InSb. Instead, most work has concentrated on growing on GaAs substrates and investigating the role of the buffer layer [usually low-temperature as for the growth of GaAs on silicon substrates] in reducing dislocations and improving electrical or optical properties. Another problem with antimonide substrates is that they are very difficult to etch successfully when preparing for growth 114. Recently both InSb and GaSb substrates have recently become commercially available as "Epiready" 50 mm wafers and improvements in this aspect of epitaxy have resulted in concomitant improvement in device yield and pertbrmance.

The Growth of Antimonidos by MOVPE

217

Much of the work published on the growth of antimonide layers has been dedicated to solving or at least understanding the above problems. They will be further examined in the context of each of the binary materials discussed below. 6

MATERIALS

6.1

Aluminium antimonide As well as the usual problems of oxygen incorporation from the ambient, the gas stream or precursors, that beset the growth of AlAs and AlP, A1Sb has the additional problem of carbon incorporation. In the arsenides and phosphides, carbon can be reduced by increasing the group V hydride over pressure to ensure an adequate supply of atomic hydrogen to assist in the removal of methyl species from the growth surface.

The equivalent experiment has been attempted 115 by generating stibine

electrochemically in situ but because a large excess of stibine merely resulted in the deposition of an excess antimony phase this was not a success. Hence most of the work on AISb has concentrated on finding alternative aluminium precursors rather than alternative antimony precursors.

Table 1 lists some of these

studies together with the outcome in terms of carbon and oxygen incorporation. The most promising

Table 1. Precursor combina~ons and their effect on carbon and oxygen incorporation in AISb

Alumininm precursor TMA1

Antimony Comments on carbon and oxygen incorporation etc. Precursor TMSb Very high carbon incorporation, A14C3 phase identified by EDX TiBA1 & TMA1 TMSb A14C 3 phase only present when using TMAI TMA1 TMSb Very high carbon incorporation, identified in SIMS, and electrically insulating, poor quality layers in TEM TMA1 TMSb Good morphology, carbon not measured TEA1 TESb Good quality AISb as determined by XRD, Raman and PL of InAs/AISb and GaSb/AISb superlattices Less than lx 10t9carbon measured by SIMS TESb TMA-A1H3 4x10 TMp-type carrier concentration, 5X1019 oxygen by SIMS TMSb TtBAI probably from TMSb, TESb gives lower carbon but adduct TESb formed with TtBAI.

References 7 83 97 116 55,117,118 119 120

precursors appear to be those with isobutyl [triisobutyl aluminium [TiBAI]] or tertiary butyl (tritertiarybutyl aluminium [TtBAI]) groups attached to the aluminium. This is reasonable because such organic radicals are considered to be "good leaving groups" and can easily leave the aluminium without an A1-C bond remaining, the same argument can hold for the alane (trimethylamine alane [TMA-AIH3]) compound as this has no A1-C bonds. The triethyl groups appear to give good structural and optical results but as yet, there are no electrical measurements reported. Unfortunately the batch-to-batch reproducibility of precursors like TtBAI and TMAA1H3 are not as good as for TMAI [and perhaps TEA1] simply because the alkyl manufacturers are unable to justify significant resources being used for small batches of metalorganics that do not have a big market

218

A. Aardvat'k et al.

share. Even with relatively common precursors like TMSb and TESb batch to batch contamination with oxygen 121 containing species seems to vary widely, probably because until the recent upsurge in interest in A1Sb and associated alloys, it has not been a problem in need of a ,;olution, as InSb and GaSb based materials seem impervious to small amounts of oxygen. It may be that in the long term TEA1 will prove to be a more reproducible route to high quality A1Sb. As can be seen from Table 1, it has only recently been possiblO 20 to grow A1Sb which is electrically active and this is a major step forward, this paper is one of only two listed in Table 1,119,120 to have reported success in doping A1Sb and as those reports are more related to the doping of ternary cladding layers they will be dealt with below.

Indium antimonide.

The most important property of interesl in the study of InSb is its electrical

characteristics. To this end the majority of InSb related papers published use the Hall mobility and carrier concentration [either room temperature or 77K or both] as their primary judge of quality. The lack of a reliable and reproducible source of InSb:Cd insulating substrates means that many reports rely on insulating GaAs substrates which leads to major problems 122 with the 14% mismatch when growing layers for electrical assessment on GaAs substrates. In addition there are problems of precursor pyrolysis. Typical MBE growth temperatures for InSb are around 400-450°C, at these temperatures TMSb is cracked only to a few percent whereas TMIn is significantly decomposed.

Thus, with small temperature variations across the growth

surface, large differences of V/III ratio can occur making it very difficult to control the growth morphology. To this end, a number of new antimony precursors have been investigated, primarily with the aim of reducing the pyrolysis temperature of the source.

For the first ten years of research into the growth of the antimonides by MOVPE, standard trimethyl or triethyl precursors were used.

The choice was usually

based on whether the materials were grown at

atmospheric pressure [where trimethyl precursors were favoured] or reduced pressure [where triethyl precursors were favoured]. In 1991 a series of new compounds began to be examined, their vapour pressure and 50% pyrolysis temperatures [Tso] were measured first usually in an "ersatz" reactor i.e. one where there is no epitaxial growth but where various carrier gases can be used to determine the mechanism of pyrolysis. Usually combinations of hydrogen [Hz] deuterium [D2] and helium [He] were used.

The results are

summarised in Table 2. When pyrolysis measurements have been made on "real" reactors [by measuring the output of an alkyl from the exhaust using UV absorption] slightly higher values for the pyrolysis temperatures Ts0 have been observed 1°° but the overall trend and indeed, the relative difference between various alkyls is very similar. It can be seen that a gradual reduction in T~o has been achieved. Some of the more promising precursors have subsequently been rejected because of long-term stability problems in the bubbler [TASb]23]. Others have suffered from batch-to-batch irreproducibility, in situ monochromatic UV monitoring of alkyls in the growth cell 1°6 led to the discovery that tBDMSb had a constantly dropping vapour pressure, this was subsequently traced to it being a mixture of the mono- and di-tcrtiary butyl compound, presumably because synthetically it is difficult to stop al one substitution in the synthesis t24.

The Growth of Antimonides by MOVPE

219

Table2 Precursorsused in the growth oflnSb Alkyl name

Acronym

Formula

Trimethylantimony Triethylantimony Trivinylantimony

TMSb TESb TVSb

(CH3)3Sb (CH3CH2)3Sb (CH2=CH)3Sb

Triallylantimony Neopentylstibine Triisopropylantimony Diisopropylantimony hydride Tertiarybutyldimethyl antimony Trisdimethylamino antimonide

TASb nPSb TiPSb DiPSbH

50% pyrolysis temperature [Tso] 450 °C 450 °C

VP/torr at 15 °C 65.7 2.1 8.5

(CH2=CHCH2)3Sb (CH3(CH2)4)SbH 2 ((CH3)2CH)3Sb ((CH3)2CH)zSbH

150 °C n/a 350 °C 200 o C

0.7 n/a 0.5 7.9

tBDMSb

[(CH3)3C](CH3)2Sb

300 °C

7.7

127

tDMASb

[(CH3)2N]3Sb

200 o C

0.75

42,128

Ref. 16

15

16 74,125 16 126

Others have too low a vapour pressure for realistic growth rates [TiPSb]. The most promising candidate was DiPSbH 129 because this had an Sb-H bond and could perhaps decrease any carbon contamination compared to all methyl precursors. Oddly, this gave higher rather than lower carbon levels in InSb 13°. At the moment the most promising low-temperature antimony source appears to be tDMASb although there has been some report of nitrogen contamination in the growth of GaSb TM so there may still be some unforeseen problems with the growth of InSb.

Many of the precursors listed in Table 2 have been used in the growth of InSb and various precursor combinations are listed in Table 3, together with their room- and low-temperature and Hall mobilities. These two figures taken together, give a good indication of the electrical and structural quality of the InSb. It is relatively easy to get high room-temperature mobilities, but much more difficult to achieve these at 77K, when the role of dislocations at the heterointerface becomes important. Thus, the table gives a simple way of assessing the efficacy of the new precursors, using a standard test. Most of the post growth assessment of such layers is electrical. The dislocations induced by the 14 percent mismatch when growing InSb on GaAs can make interpretation of the electrical results quite complicated. It is possible to get room temperature results which look quite promising but when the temperature is reduced to 77 K the mobility decreases by a large factor [see Table 3]. To get round this particular problem some groups have grown lnSb [normally ntype] on cadmium doped InSb substrates. These substrates are p-type and are considered isolated from the epitaxial layer, when making Hall measurements. However the substrates are difficult to manufacture reproducibly because the partition coefficient of the dopant leads to in_homogeneityacross the Czochralski or Bridgman boule. Also the dopant lattice location is not stable to temperatures seen during the growth of the epitaxial layer]0°and they can type-convert to n-type InSb within the substrate, leading to apparently high mobility measurements which are unrelated to the quality of the epitaxial layer. This is perhaps the

220

A. Aardvark e t a / .

explanation of the very high result t32 which has not been repeated in the literature. In addition, the surface accumulation layer can make interpretation of simple Hall measurements somewhat problematical unless care is taken with fitting the data with a two- or three- carrier fit67,133. As was mentioned above, the room temperature mobilities are a poor indicator of underlying structural integrity as, provided a reasonable thickness is grown [> 2~m] 134 quite respectable figures can be obtained.

In one study 135 there appears to

be no difference between growth with TMIn/TMSb and TMIn/TESb which seems surprising.

Table 3. Precursor combinations used in the growth of InSb together ~ith the electrical results

Indium

Antimony Mobility Precursor [290 K]/cm2fVs

Mobility [77K]/cm~/Vs

Epilayer thickness

Substrate

TEIn TMIn TMIn TMIn

TMSb TMSb TiPSb TMSb

4 ~tm 3 ~tm 1 ~tm 4 om

TMIn TMIn TMIn

TMSb TMSb TMSb

GaAs GaAs GaAs InSb:Cd GaAs GaAs GaAs GaAs

TMIn

TiPSb tBDMSb TESb TMSb

2,000 27,000 240 250,000 70,000 7,750 31500 900 3,000 22,000 78,000 67,500 n/a 2,000 2,000 2,000 n/a

2 ~tm 2 lam 5 I.tm 2 p.m 2.5 p.m

GaAs GaAs

142

68,990

5 p.m

InSb:Cd

143

Ref.

precursor

TMIn TMIn TMIn TMIn TMIn

TMSb TMSb TESb tBDMSb tDMASb

35,000 60,900 n/a n/a n/a 25,500 45,000 940 4,000 25,000

35,000 48,000 67,000 50,000 58,000 58,000 68,990

4 ~m 2 ktm 0.15 p.m 0.75 rtm 4.2 ktm 1.2 ~tm

136 93,137 109 132 77 81 134,138

InSb:Cd

139,140

GaAs GaAs

67

14l

135

The subsequent wide variation in the 77K figures shows just how crucial factors like initial nucleation, twostage buffer layers t37, V/III ratio and reactor geometry are. Like all III-V antimonides, the growth of InSb is constrained by the vapour pressure of the elemental antimony and close control of the V/Ill ratio near to unity is required. Sometimes there appears to be a very narrow window of V/III ratios for the growth of InSb, especially at the lower growth temperatures used with the new precursors 144. Given the discussion above about InSb:Cd substrates and the role of dislocations at 77K when using GaAs substrates, the most promising results seem to be those where the 77K measurements have been made on GaAs substrates and yet still have respectable values 81,93,144. Many of the results on GaAs substrates have been as a result of research on InSb magnetoresistive sensors, these are one of the few areas in which MOVPE grown antimonides have been developed for a large-scale industrial application. They are dealt with below.

The Growth of Antimonides by MOVPE

221

Ma~metoresistor sensor The issue over which sort of substrate to use is more straightforward when the InSb is being grown as part o f a magnetoresistive sensor 145. The growth has to be on GaAs substrates because the device is used as a magnetic field sensor in automotive control applications at elevated temperatures.

As

such the material must have high electron mobility at room temperature. Until recently they were made from bulk InSb wafers which have a phonon limited mobility of 78,000 cm2/Vs by developing a pre-growth coating of indium 142 a few seconds before growing the InSb it has been possible to get adequate room temperature mobilities and very high uniformity over 50 mm GaAs wafers. Other groups have grown such InSb for magnetoresistive sensors on production reactors 8J, J8

Long term progress on InSb growth

The work on InSb has generated a large number of alternative

precursors. Fig. 7. shows the number of publications associated with some of these precursors. It shows how the majority appear briefly in the literature for a couple of years and then disappear without trace as the original promise is replaced by various difficulties of low vapour pressure or poor pyrolysis characteristics. Alongside the new precursors are TMSb which shows [together with TESb to a lesser extent] a steady output of papers.

Nurr~er of papers

Ye£

publication Fig. 7. Publication year and number of papers for various antimony precursors.

It is salutary to note that production of the magnetoresistor device is undertaken using TMIn and TMSb as the precursors, again indicating perhaps, that batch-to-batch reproducibility in high volume alkyls is more important than better kinetics from newer precursors which perhaps solve problems that can be engineered out, in large-scale wafer process design.

222

A. A a r d v a r k et al.

Miscellaneous studies on InSb ~rowth An alternative method of increasing the pyrolysis of the TMSb is to use a two-zone heater with the front zone hot enough to crack the TMSb [450 C] with the back [where the CdTe substrate was located] varied in temperature to optimise the growth 75. No electrical data were given in the initial study but when it was repeated by others the electrical results were disappointing77. Usually InSb grown by MOVPE is n-type but occasionally there have been reports of unintentionally doped InSb being ptype146,147 though whether this is due to impurities is unclear. Hydrogen passivation of aeceptors in p-InSb has also been reported 148. InSb quantum wells have been grown in a GaSb matrix 149 with PL energies around 0.75 eV.

C.~t~d]l~lIilB~l~. Unlike A1Sb and InSb, GaSb is fairly simple to grow and the choice of whether to use trimethyl or triethyl precursors is usually decided by the pressure at which the reactor operates. Predominately the trimethyl precursors have been chosen and the triethyls restricted to studies involving the AISb related materials. GaSb 1,4,19,40,66,89,98,100,102,104,117,131,141,150-172is the most widely studied of the antimonides. The material quality has been mainly assessed by electrical and optical measurements the electrical measurements are again slightly complicated by the need to grow on a GaAs insulating substrate.

0.50 0.45 0.40 0.35 0.30

0.25 0.20 --

0.15

0.10 0.05

/

t

.°

.

•

0.00 i

I

i

1520

1500

I

1540

I

I

i

1560

1580

1600

I

1620

wavelength (nm)

Fig.8. Photolummescencespeca'a for GaSb grown under various V/III ratios Table 4. Electricalresults for GaSb layers shown in Fig. 8.

Sample #

TMSb flow

TMGa flow

475 478 479

20 18 15

10 13 13

input V/Ill ratio 0.75 1.06 1.28

Carrier cone. [290K]/em "3 2.3 x 1016 4.1 x 10 j6 5.7 x 101~

Mobility 1290K1/cmZNs 664 600 597

The Growth of Antimonides by MOVPE

223

Fig. 8 shows the 4K photoluminescence of GaSb grown under varying V/III ratio. The equivalent electrical results, together with the V/III ratio are given in Table 4. This ratio is based on the standard vapour pressure data, together with the assumption that both TMGa and TMSb are pyrolysed to the same extent at the growth temperature [560 °C]. As can be seen from fig. 5, this is a reasonable assumption so the input V/III ratio and that at the growing surface should be similar. At the lowest V/III ratio [#475] the main peak [1560 nm] (assigned as a bound exciton [BE4]) is at its strongest. Its strength decreases with an increasing V/III ratio which also leads to an increasing acceptor peak [1600 nm] within the material.

This acceptor has been

assigned to a complex antisite defect 40 and affects both the optical and electrical properties as can be seen from the associated mobilities and carrier concentration. There is a concomitant rise of carrier concentration and the acceptor peak at 1600 nm as the V/III ratio increases. If growth is attempted at lower V/Ill ratios a wet [excess Ga] surface is obtained. Thus, the optimum V/Ill ratio is close to 1:1 with only a small window of allowed values if good optical and electrical quality is to be obtained in the growth of GaSb. The initial nucleation of GaSb on GaAs has been shown to influence not only the dislocations at the heterointerface but also the optical and electrical properties of the structure or device 1°7,173.

6.2

Grout) III ternaries

Aluminium gallium antimonide. This ternary has been the most difficult for growers 174,175,176,177,178 because of the problems mentioned above in the section on aluminium antimonide. Recently Wang et al have made some dramatic improvements in the growth of this ternary by using new precursors for the aluminium. Tritertiarybutyl aluminium was initially investigated as a possible precursor for metallization of low-carbon aluminium. In combination with triethyl antimony and trimethyl gallium it has produced the lowest carbon concentrations to date. Unfortunately the presence of oxygen in the layers is still an ongoing problem 120. However, whereas in the first reports for this material there were serious optical and structural problems97,116, it is now possible to grow it with good optical quality 117,172,175,179and, importantly for lasers, to dope it both p- and n-type37,12°.

Indium ~allium antimonide. This ternary has perhaps been the most studied 41,42,72,176-178,180-187of the group III ternaries. It changes from p- to n- type as the indium fraction is increased and good quality bulk layers can be grown up to an indium mole fraction of about 25-30%. Beyond that the morphology deteriorates sharply [which is the same for bulk InGaAs on GaAs]. With GaSb it forms strained multiquantum wells or strained layer superlattices similar to those in the InGaAs/GaAs system. 43,72,97,188-192. This InGaSb/GaSb system [as either single, double or multi quantum wells] involves a small level of strain and, as such, has been extensively studied43,1°1,188-2°4 both optically [using techniques such a photoluminescence, magneto photoluminescence, photoconductivity] and electrically. By growing on (111) substrates instead of the usual

224

A. Aardvark et aL

(100) additional piezo-electric effects have been reported and these include changes in wavelength of emission and doping level within the InGaSb well when compared to structures grown on (100).

Indium thallium antimonide. This material has been recently studied20,28,2°5"z08 as a possible infra-red detector material and cyclopentadienyl thallium was used as the precursor. There are theoretical predictions that suggest a limit to the solubility of thallium in InSb and indeed T1Sb does not have a ZnS-type structure but a CsCl-type structure. However alloys with low concentrations of thallium in InTlSb sufficient to achieve the 8 - 10 ~tm bandgap are believed to be stable ZnS-type structures.

6.3

Qroup V ternaries

Gallium arsenide antimonide. This was the first antimonide to be grown by MOVPE 3 and it has been studied both for its structural and optical properties 2°9. It is lattice matched to InP for GaAsxSb~_x when x is 0.53 and as such has formed part of a heterostructure bipolar transistor [HBT]64,65 the former reference concentrated on the useful doping properties of GaAsSb whilst the latter described the improved band offset between the haP and GaAsSb compared to that for InP and InGaAs. Both the CuAu-I ILl0] and the chalcopyrite [El ~] domains have been observed to be present in MOVPE GaAsSb 69,87. It is possible to grow metastable alloys provided the V/Ill ratio is less than unity82. New precursors such as tBAs [to replace arsine] have made the growth of GaAsSb somewhat simpler21°,211. GaAsSb has also been studied by Raman scatteringS4, 212 where the spinodal decomposition was found to start from the surface of the crystal when the material was annealed. The role of strain in the formation of high quality metastable GaAsSb has been investigated by growing on InP substrates [where it is lattice matched] and GaAs [where it is not] 213.

Indium arsenide antimonide. InAsSb has been usually grown with trimethyl alkyls and arsine as the starting materials88, 214-218 and sometimes the triethyl alkyls6,136 but recently newer precursors have been tested including tBDMSb al9 and tBAs 220. It has been less studied with regard to ordering but there are a few papers 33,86,88. Of these the latter is important because it deals with the effect of ordering on the band gap [and hence operating wavelength] of a device. InAs~_xSbxlattice matched on GaSb is lattice matched to GaSb for x = 9% and a photodiode operating at 4.2 p,m has been fabricated from such a system. Other photoconductors have been fabricated for longer wavelengths221 up to 14 pro. The Raman spectrum 216 of the alloy exhibits two modes for x <60% and single mode above 60%. The three-layer Hall effect model has been applied in an attempt to explain the transport properties of a bulk layer a22.

An n-n InAsSb/GaSb

heterojunction has been shown to have highly rectifying properties223when investigated by IV and CV.

The Growth of Antimonides by MOVPE

225

There have been three major attempts to include InAsSb into infrared active superlattices.

Initially

lnSb/InAsSb superlattices were attempted92,224 but despite a thorough study of possible buffer9],22s layers the active regions had microcracks running through them which prevented further work. A more successful approach was InAs/InAsSb35,226 the latter paper reporting a laser operating at 3.8 I.tm. A slightly different combination of InGaAs/InAsSb offering biaxial compression of the InAsSb32,86,95,227 has also been reported and formed the basis of lasers operating at 3.6/am. The physics of these superlattices, especially their band line up has been extensively studied 13,22"24,32,34,36,227"232.

Indium nhosnhide antimonide. This material has 233 the distinction of being grown by stibine in a conventional MOVPE reactor 233. As such the material was quite promising but the stibine was not easily synthesised in situ. It is more usually grown from the trimethyi precursors and phosphine46,94,234-238 and sometimes the triethyl 118,239. Some alloy decomposition has been observed via PL94. Very high quality InAs/InPSb superlattices have been grown as an Al-free alternative to InAs/A1Sb. An aluminium free laser 14 operating at 3.06 lain has been fabricated from InGaAsSb/InPSb.

Gallium ohosahide antimonide. GaP~_xSbx has been only studied by one g r o u p 47,235"238,240 and was grown from TMSb, TMGa and phosphine.

For x = 32% it is lattice matched to GaAs. It has a large, positive

enthalpy of mixing and for a number of years was assumed to be impossible to grow because of a miscibility gap at 530 °C extending from x = 1% to 99%. It has been studied by PL and absorption measurements to determine the band gap across the composition range. This alloy has shown weak LI~ ordering70 and has been investigated optically by Raman scattering238,240 over the whole composition range.

The optical

phonon modes [which are related to the vibrations within the lattice] show signs of alloy compositional fluctuations due to the onset of spinodal decomposition due to growth within the miscibility gap. The spinodal decomposition has also been studied by absorption47.

Aluminium arsenide antimonide. AIAsSb has been recently studied as a cladding layer for infrared lasers. By mixing the As/Sb on the group V lattice it is possible to avoid the serious carbon incorporation problems that beset AISb because arsine119 or tBms 241,24Zprovidesa source of atomic hydrogen to aid in removal of the methyl species from the alkyl aluminium compound. Like most of the group V ternaries, careful control of the V/Ill ratio is needed to get the expected incorporation of group V atoms into the lattice 243,244 Recently there have been reports showing it is possible to dope it both n- and p-type using tin and zinc respectively1 ]9. As a result of this a new laser has been fabricated 35based on A1AsSb/InAsSb.

226

~.~

A. Aardvark e t al.

Ouaternaries

Quaternaries are an important aspect of antimonide growth because the allow the growth of materials that are lattice-matched to common substrates like GaAs and InP whilst still allowing some degree of control of the band-gap [within the limits of the miscibility gap]. The growth and properties of the quaternaries can usually be deduced from their constituent ternaries and binaries. For reasons of space, they will be summarised in Table 5 which indicates the type of study undertaken or device fabricated from them.

Table 5. Variousquatenmryantimonidesand their associateddevice or property studied

Quaternary Device/Study AIGaAsSb

growth and PL 116,179 growth and Raman245, 246 cladding in 1.7 larn laser38 cladding in 2.1 ~tm laser39 doping] 2o

InGaAsSb

Photodiode [1.55 am] 11,12 Photodiode [2.0 ~tm] 29 Photodiode [2.25 p,m] 3o Photodiode [2.75 p.m] 247 Buffer layer study 186 Raman study248 Growth study 78-80 Laser [3.06 ~tm] 14 Laser [2.1 p,m] 39 Immiscibility studies85, 249 Led86,95

InGaPSb

Rarnan and growth studies246, 2s0,251

InAsPSb

Growth of superlattices 5,76 Spinodal decomposition99 Growth252

InAsSbBi

Growth and PL studies 253-256 257-260

The Growth of Antimonides by MOVPE

6.5

227

Doniw,.

The doping of the antimonides is more complicated 261 than that for the arsenides and phosphides. There are some similarities and some differences. The similarities are that group II metals are always p-type dopants in all antimonides e.g. Zn 29,119351,224,261, and Cd 24. Also the group VI elements Te and Se are always n-type e.g. Tel 1,18,24,37,65,12°,15°,163,167,184; Se 158,163,262,263 but there the similarity ends. Sulfur seems to behave oddly in GaSb, perhaps becoming a deep centre 15°. The group IV elements dope GaSb p-typO 87 and InSb ntype 263.

7

7..__[1

Phvsics and materials.

OTHER STUDIES

From the very beginning of antimonide growth the physics of the

heterostructures has formed a large part of the motivation for growth. Some of the physics is of an optical nature, some electrical. Again, for reasons of space, a Table 6 will show the major areas of interest.

Table 6. Physics and materials studies of various antimonide structures grown by MOVPE

Structure

Physics

Ref.

InAs/GaSb superlattice

Optical studies: for InAs thickness < 7 nm the superlattice has a bandgap related to the InAs thickness varying between 3 ~tm and 20 ~tm. Electrical studies: for InAs thickness > 7 nm with high mobility structures > 105 cm2/Vs. When grown on 111 orientation interesting piezoelectric properties have been established. Structural studies: the structural properties of these superlattices have been studied by Raman scattering, TEM and XRD The mismatch between the two components introduces controlled strain into the system and can alter the band overlap in a controlled and predictable way. Negative differential resistance has been demonstrated in a wide variety of antimonide/InAs structures. In the case of some of the InAs/GaSb structures, different resonances can be seen depending on the interface type [GaAs or InSb] Hot electron transistors have been demonstrated in the InAs/GaSb system

62,63,96,106,152,264-266

InAs/GaSb Superlattices InAs/InGaSb Superlattices

InAs/GaSb tunnel devices

InAs/GaSb hot electron transistors InGaSb/GaSb

This system has been studied optically in the 2 p.m region of the infrared and electrically, where some of the highest recorded hole mobilities have been measured [3x 104 cm2/Vs]

45,96,106,152,267-270

197,198,200-204

55-60,73,271

48-54,272

31,97,101,188-191,193-195,199

A. Aardvark e t al.

228

7.2

Devices

The various devices fabricated from MOVPE grown antimonides are summarised in the

table 6 below.

Table 7. Devices fabricated from MOVPE antimonide materials

Device

Reference

Tunnel diodes

55-60,273

Heterojunctions

274

Photoconductors

28,221

Photodetectors

I 1- 13,21.27,29,30, 92,173,184,214,224,275

Magnetoresistive sensors

17,18,142,145

Hot electron transistor

48-54,272

Light emitting diode

10,31.35

Heterojnnction bipolar transistor

64,65

Laser

14,32,34-39

Capacitors

276

8

CONCLUSIONS

The MOVPE growth of antimonides is an increasingly important area of research and it has presented new challenges compared to the growth of arsenides and phosphides. Many of the original problems have been solved and recent progress with new precursors means that for the first time, there is a real prospect of optical devices such as lasers being manufactured industrially.

Electrical devices such as the InSb based Hall

magneto sensors are already being manufactured. The market for both antimonide alkyls and substrates is expected to grow significantly in the next few years.

Many new markets are opening up for

thermophotovoltaic [TPV] devices for which the antimonides are ideally suited.

The future looks very

encouraging. 9

ACKNOWLEDGEMENTS

We would like to thank our colleagues at Oxford, and elsewhere, who have helped in the preparation of manuscript. We would also like to thank the referee for helpful advice, which improved the end result considerably. Any omissions and errors are our own and we would invite authors of papers on the MOVPE of antimonides to send us any corrections, or new papers, so that next time we do this it can be more up-todate and accurate. "In the writing of books there is no end..." Ecclesiastes

The Growth of Antimonides by MOVPE

229

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Aaron A a r d v a r k was educated in Algeria, and went on to study in France and England. He has been involved in the growth and characterisation of antimonides, at the Clarendon Laboratory, for the last ten years. He has authored over one hundred papers and two children.

Peter W a l k e r was educated at Bolton Grammar and took his first and second degrees at the University of Liverpool (1965-71). He taught chemistry at Henley Grammar School from 1971 to 1974 and then moved to the Clarendon Laboratory to work on the preparation and crystal growth from the melt of a variety of inorganic compounds. In 1985 he took charge of a new MOVPE facility for growth of low-dimensional antimonide structures. His first act was to appoint Dr. Mason.

Nigel Mason was educated at Hampton Grammar School and Studied for his first degree at the University of East Anglia. He left after a year having failed his first year exams. Studying by day release, at Kingston Polytechnic, he finally achieved HNC and then GRIC. After working as a leather chemist he took a PhD in Inorganic Chemistry at Sheffield. He then studied MOVPE under John Roberts and subsequently moved to the Clarendon Laboratory in 1985. He is hoping to take early retirement soon.