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The evaporation of InP under Knudsen (equilibrium) and Langmuir (free) evaporation

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1974 J. Phys. D: Appl. Phys. 7 2436

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J. Phys. D: Appl. Phys., Vol. 7, 1974. Printed in Great Britain. 01974

The evaporation of InP under Knudsen (equilibrium) and

Langmuir (free) evaporation conditions

R F C Farrow
Royal Radar Establishment, St Andrews Road, Great Malvern, Worcs, WR14 3PS

Received 12 July 1974, in final form 16 August 1974

Abstract. The evaporation of InP under Knudsen and Langmuir conditions has been
investigated mass-spectrometrically using a modulated molecular beam technique com-
bined with phase-sensitive detection and signal averaging to separate evaporating species
from background species in the vacuum system. PZwas found to be the dominant species
over InP under Knudsen conditions but significant evaporation fluxes of In and P4
were also detected. The P4 flux was attributed to PzfPz association on the oven walls.
A congruent evaporation point under these conditions was predicted at 629 2 5 K.
Under Langmuir evaporation conditions the only evaporating species detected were
In and Pz. Up to 638k 5 K the (100) surface evaporated congruently but above this
temperature there was a disproportionate loss of PZfrom the surface. The equilibrium
vapour pressures of In, PZ and P4 over InP and of In over pure In are presented and
enthalpies for the reactions InP(s)+ In(s)++Pz (g); 2Pz (g)+ P4 (g); In (s)+ In (g)
calculated.

1. Introduction

A detailed knowledge of both the Knudsen (equilibrium) evaporation and Langmuir

(free) evaporation behaviour of InP is necessary for an understanding of the kinetics of
epitaxial growth of InP films from beam sources (Farrow 1974a). It is also of basic
importance in understanding the thermodynamics of the In +P system.
The Knudsen evaporation of InP has been studied previously by Drowart and Gold-
finger (1958) and Panish and Arthur (1970), but no studies of the Langmuir evaporation
of InP have been reported. Both of these groups of authors examined the Knudsen
effusion flux of InP mass-spectrometrically but the techniques which they employed for
discriminating the Knudsen eRusion flux of phosphorus species from background phos-
phorous species in the vacuum system have recently been criticized by Foxon et aZ(l974).
These latter authors showed that when the evaporation flux from a III-V compound is
detected mass-spectrometrically, fast association reactions between adsorbed group V
dimers on the walls of the vacuum system (or surfaces in the mass spectrometer ion
source region) can lead to group V tetramers in the vapour phase. These tetramers can
easily be mistaken for a direct evaporation flux of tetramers from the III-V compound
unless modulated molecular beam techniques combined with signal-averaging or fast
Fourier transform spectroscopy are employed. The beam detection techniques of Panish
and Arthur (1970)-using a beam shutter with a cooled shield around the spectrometer-
and of Drowart and Goldfinger (1958)-with line-of-sight evaporation from oven to

2436
 The evaporation of InP 2437

spectrometer and no shutter-were shown by Foxon et aZ(l973, 1974) to lead to con-

siderable overestimates of the equilibrium pressure of As4 when used to detect the Knud-
sen evaporation flux from GaAs. In addition, it is doubtful whether mass discrimination
effects in the quadrupole mass spectrometer were adequately taken into account by
Panish and Arthur (1970) in determining the vapour pressure of species over InP. 'For
these reasons we have re-investigated the Knudsen evaporation of InP and studied the
Langmuir evaporation of InP using, in both cases, a modulated beam technique com-
bined with signal averaging to separate the direct evaporation flux from background
species. The evaporation of pure In has also been studied with this technique. Further-
more, mass discrimination effects in the quadrupole mass spectrometer have been taken
into account in the way described by Foxon et aZ(1974).
We report the equilibrium vapour pressures of In, PZand P4 over InP and of In over
pure In and have calculated enthalpies for the following reactions :
InP(s) -,In(s) ++Pz(g) (1)

using Second and Third Law methods (Horton 1966) where in the case of reaction (1)
accurate high-temperature heat-capacity data (Pankratz 1965) for InP has been used for
the first time.

2. Experimental details

Measurements were carried out in a stainless steel ultra-high-vacuum system pumped

with a 120 litre s-1 triode ion pump. A schematic diagram of the experimental arrange-
ment within the system is shown in figure 1. Two Knudsen effusion ovens were used, one
containing In the other InP. The ovens were of high-purity (total impurity level < 1e4 ppm)

Ptwtotransistor
r e f e " signal
InP wen

a
T
Lpnp

1
';
S

- I
I -

-- 1 -
I

lnaven
I
1
Postoncf InP crystcl
for Longmuir studies
\
eeam+ Mass spectromhter ion source

Figure 1. Schematic diagram of experimental arrangement. Cross-hatched areas denote

cooling to liquid nitrogen temperature.
 R F C Farrow
graphite, and each was contained inside an alumina heater jacket wound with tungsten
heater wire. An outer alumina sleeve was fitted over the heater wire and several turns
of thin (0.0125 mm) crinkled tantalum foil loosely wrapped around the sleeve provided
efficient radiation shielding. The temperature of each oven was monitored using a
chromel/alumel thermocouple junction, spot-welded to a tantalum radiation collector
disc and suspended inside a black-body cavity in the back of the graphite oven. This
arrangement minimized heat losses due to conduction and radiation from the junction
region and calculations show that the measured temperatures should be correct in
absolute terms to t- 3 "C. The oven temperature was maintained constant to within
f 1 "C by adjusting the power input to the tungsten heater. The ovens were contained
inside a liquid-nitrogen-cooled shield with a 3.5 mm thick copper cryopanel which served
both to collimate the molecular beams from the ovens and to reduce the background
pressure in the vacuum system by cryopumping condensible species. The total back-
ground pressure in the vacuum system with both ovens operating was in the 10-9-10-8 Torr
(1.33 x 10-7- 1-33x 10-6 P) range and consisted mainly of HZand CO. A beam shutter
S could be used to switch the beams on or off. The beams were modulated by a six-
blade rotary chopper and detected by a quadrupole mass spectrometer. After passing
through the spectrometer ion source region the beams were condensed on a liquid-
nitrogen cooled surface surrounding the mass spectrometer. The modulated beam signals
were recovered by phase sensitive detection and signal averaging techniques. This
method of beam detection ensured that the direct-beam flux was discriminated from
background species (Foxon et a2 1974).
In the Langmuir evaporation studies the evaporation flux from the single-crystal
specimen was modulated and detected in the same way as the Knudsen effusion flux.
The background pressure in the vacuum system during these studies was in the
10-10-3 x 10-9 Torr (1.33 x 10-8-3.99 x 10-7 P) range. The specimen was in the form
of a rectangular cross section bar 40 x 8 x 2 mm3 with the 40 x 8 mm2 faces parallel
(within k2") to the (100) plane. It was held in platinum-covered tantalum clips in the
position shown in figure 1, and its temperature controlled to 5 1 "C by direct resistance
heating. The temperature was monitored by a chromel/alumel thermocouple with the
junction at the centre of an 8 mm long x 0.25 mm diameter hole drilled through the
centre of the specimen.
For the Knudsen evaporation studies polycrystalline InP from MCP Electronics
Ltd with a total impurity content of < 1016 cm-3 was used. The In used in these studies
was Johnson Matthey Puratronic Grade A1 (total impurity level < 1 ppm). The InP
specimen for the Langmuir studies of InP was n-type, Sn-doped toflD-nA- 3 x 1017Cm-3.
Both (100) faces of the specimen were polished using a 2 % bromine in methanol solution.
Immediately prior to loading, the specimen was washed in a vapour degreaser containing
high-purity isopropyl alcohol.

3. Mass spectrometer calibration

The sensitivity of the quadrupole mass spectrometer for In was determined by measuring
the mass spectrometer In+ signal due to a flux of In from the In Knudsen oven as a
function of oven temperature. The absolute value of the In flux at a known distance
from the In oven orifice and hence the equilibrium vapour pressure of In was determined
at a particular oven temperature (1 186.8 K) by measuring the In condensation rate on a
piece of A1 foil placed in the In beam. Weight gain measurements of the A1 foil sample
 The evaporation of InP 2439

indicated a mean equilibrium vapour pressure of 0.88 f 0.05 atm at the calibration point,
assuming a condensation coefficient of unity for In on the room temperature ( 293 K)
A1 foil sample. It was confirmed from separate In beam scattering experiments that the
condensation coefficient of In on the A1 foil (and on the In deposit) at 293 K was > 0.999.
The vapour pressure of In as a function of temperature was then calculated from the
mass spectrometer signal (ion current) I(In+) using the relation
p(In) = a(In) TZ(In+) (4)
where T i s the oven temperature and .(In), the mass spectrometer constant, was calcula-
ted from the measured In vapour pressure and mass spectrometer signal at the calibration
point. The good agreement between the slope of the line of In p (In) against 1jT for the
present data and for the most accurate previously published data (see table 1) indicates
that the present oven temperature measurements are probably correct to within ri: 3 "C
as expected.

Table 1. Equilibrium vapour pressure parameters A , B derived from least-squares fit

of the equation In p = - 104A/T+B ( p in atm, T in K ) to measured vapour pressures
over InP and In
(a) InP

Species: In PZ P4
~~ - -~ _-_ __~_________
A (present data): 2.902 & 0.08 3405 f0,045 4.654 k 0,080
__ - - -

A (Panish and Arthur 1970): 2,45510.07 3.372k0.095 4,296k0.16

-_ ~~~ . - - - - - - ~ _ _ _ _ _ -
B (present data): 12.843f0.96 26.50210.53 34.159+0 94
B(PanishandArthur 1970): 8.978f0.83 23.310+ 1.1 31*181&1*9

A (present data) : 2.850f 0.02

- -
A (Macur et a1 1966): 2.909 k 0.07
- - -- -

A (Panish and Arthur 1970): 2.455 i0.07

-_ ~ _ _ -- -

B (present data): 12.327f0.22

. _

B (Macur et a1 1966): 13.314f 0.58

B (Panish and Arthur 1970): 8.978 f0.83

The sensitivity of the mass spectrometer for PZand P4 vapour species was calculated
from that for In in the following way. The mass spectrometer signal for a Knudsen
effusion flux of molecules or atoms of species i into the mass spectrometer ion source
from an oven of orifice area a (including conductance factor) at a distance d from the
centre of the spectrometer ion source is given by

where c is a constant depending only on the geometry and operating parameters of the
mass spectrometer, p (i) is the equilibrium vapour pressure of species i, m(i) is the mass
2440 R I; C Farrow

of the molecular or atomic species, u(i) is the ionization cross section of species i, e(i) is
the efficiency of extraction of ions of species i from the ion source,f(i) is the transmission
of the quadrupole mass filter for ions of species i, and g ( i ) is the gain of the electron
multiplier for ions of species i.
The relative values of u(i) for P2, In and Pq were taken to be 1 : 1 : 2, respectively
(Otvos and Stevenson 1956). The relative values of e(i) for these species were estimated
by measuring the dependence of the I(P2+) fI(In+) and I(Pz+) :I(P4+) signal ratios on
extraction voltage (ie ion energy) keeping all other ion source potentials at their normal
operating values. Both of these ratios decreased monotonically with increasing extraction
voltage, reaching plateau values above 30 V. This plateau was assumed to represent the
same maximum extraction efficiency for all species and the relative values of e(i) calculated
by back correction to the normal operating ion energy (9 eV). The relative values of
f ( i ) for Pz, In and P4 were determined in the way described by Foxon et aZ(1974). The
relative values of g(i) were calculated assuming that g(i)cc (m(i))-1/2(Beynon 1960). The
overall mass spectrometer sensitivity factors (a(i))with all the above effects taken into
account were therefore given by
a(PZ)/a(In) = 1/3*35, a(P4)/a(In)= 1/1.925. (7)
Small but significant additive corrections to the I(Pz+) and I(P4+) values were made
to take into account dissociative ionization of P2+ to PI+ and P4f to P3+ (see $4.1 and

Pt

! !
150 Kxl 50
Moss numbcr(mJ

Figure 2. Mass spectrum of species detected by phase sensitive detection from InP
Knudsen effusion oven at T=926 K. Beam modulation frequency, 120.8 Hz;electron
energy, 70 eV; filament emission current, 1 mA.

figure 2) at the 70 eV electron energy used in the present measurements. For this pur-
pose, estimates of the relative mass spectrometer sensitivity to PI+ and P3f were made
in the way described above except that the ionization cross sections of PI and P3 were
not involved in these calculations. The equilibrium vapour pressures of PZ and P4
were then calculated from equations analogous to equation (4).
 The evaporation of InP 244 1

4. Results

4.1. Knudsen evaporation studies

The Knudsen evaporation of InP was studied, using the modulated molecular beam
technique described in $2yin the oven temperature range 818-930 K. PI+,P2+,Pa+, P4+
and In+ signals, modulated at the beam-chopping frequency were detected over the
entire temperature range and modulation frequency range (DC to 400 Hz) of the measure-
ments. Figure 2 shows the mass spectrum of the species detected by phase-sensitive
detection from the InP oven at 926 K and at a beam modulation frequency of 120.8 Hz.
The relative ratios of peak heights of these species and their temperature dependence was
independent of InP oven orifice area over the range (7.85 x 10-3-0.196 cmz) studied and
also of the amount of excess liquid In in the InP cell. This confirmed that the system was
genuinely close to equilibrium. No time dependence of the signal levels of these species
could be detected when the oven was held at constant temperature. Detailed examination
(Foxon et al 1974) of the position and shape of the signals of each species in the time
domain using a signal averager showed that the only molecules in the direct effusion
flux from the oven were Pz, In and P4 and that the PI+and P3+ signals could be attri-
buted to dissociative ionization of PZand P4 molecules respectively.
The equilibrium vapour pressures of Pa,In and P4 over InP were calculated using the
methods described in $3 and are plotted in figure 3 on a logarithmic scale as a function of
104/T. The equilibrium vapour pressure of In over pure In was also determined and the
data are included in figure 3. The vapour pressure data of In, PZ and P4 over InP and of
In over pure In are also summarized, respectively, in tables 2 and 3. The measured

I i
Pz
\ *+
\
lo-'
2442 R F C Farrow
Table 2. Equilibrium vapour pressures p(In), p (Pz), p (P4)over InP and enthalpies
+
A H 0 2 9 8 for the reactions InP(s) --t In(s) +Pz(g); 2Pz(g) -+ P4(g)

InP -+ In++Pz 2Pz --t P4

3rd Law 3rd Law
AH0z98 - AH"z9s
T ( K ) p On) (atm) p (Pz)(atm) p (P4) (atm) (kcal mole-9 (ked mo1e-l)
816 1 . 3 5 0 ~1O-IO
818 2.108 x 10-8 1.188 x 10-10 57.93
820 1.584 1.668 37.57
824 2.992
827 2.024
828 2.183
828 2391
830 2.274 2.992
832 4.365
833 4.273
833 4.753
834 3.164 4.488 4.008 37.64 58.56
834 4.937 37.57 58.24
840 3.673 6.381
835 5.355
835 5.604
838 6.162
838 5,806
842 6.967
846 9,902
850 1.188 x 10-9
855 7.449 1.473 x 10-8 1.357 37.58 58.04
855 6.436 1.669 37.49 57.61
863 9.192 2.079 2.383 37.60 58.36
864 2.229 3.235 37.55 58.71
864 2.628 3.269 37-43 58.16
865 3.079
868 1 . 3 0 2 ~10-9
868 1,303 3.794
877 1.590 5.039 6.633 37.42 57.99
881 4.652
886 2.414 7.530 9.095 37.47 57.71
886 8.141 9.446 37.41 57.50
891 2.798 9.201 1.036~10-8 37.52 57.55
891 1.520 37.44 58.23
897 2.522 1.324x 10-7 2,174 37.37 57.96
900 1,313
900 1.363
901 1.395

(3rd Law) mean: 37.50 f0.1

AH"ag8 - 58.04 f0.3
AH0z9s(2ndLaw): 3747 i0.5 - 59'72 f 1.8

vapour pressures could be well represented by an equation of the form

l n p = -104A/T+B (8)
over the temperature range of the data, and the values of the parameters A and B derived
from a least-squares fit of equation (8) to the data are summarized in table 1. The pre-
viously published InP vapour pressure data (Panish and Arthur 1970) and the In vapour
pressure data of Macur et a1 (1966) are also included in this table for the purposes of
 The evaporation of InP 2443

Table 3. Equilibrium vapour pressures p (In) over pure In and enthalpies Aff298' for
the reaction In@) In(g)
--f

3rd Law 3rd Law

hH"298 AH"m
T ( K ) P (In) (atm) (kcal mole-1) T ( K ) P (In) (atm) (kcal mole-I)
806 0.993 x 1O-IO 57.18 888 2.617 x 10-9 58.05
818 1.451 58.28 888 2.567 58.08
818 1.437 58.29 895 3.687 57.90
821 1.919 58.05 895 3.392 58.05
823 2.105 58.04 898 3.602 58.09
826 2.386 58.07 901 3.891 58.12
848 6.597 57.84 905 4.882 58.00
858 8,593 58.07 908 5.458 58.01
858 8.786 58.03 910 5.567 58.07
860 1.005 x 10-9 57.89 918 6.781 58.23
867 1.251 58.00 918 7.666 58.01
870 1,306 58.08 922 8.294 58.07
875 1,698 57.96 924 9.155 58.06
876 1.555 58.17 924 9,159 58.04
876 1.898 57-87 925 8.442 58.22
876 1.947 57.82 925 9,208 58.08
880 1.908 58.06 939 1,520x 10-6 58.14
887 2.569 58.02 943 1.655 58.07
888 2.812 57.92 943 1.690 58.06
888 2,668 58.02 943 1.708 58.05

(3rd Law) mean: 58.03 k 0.05

AH"298 (2nd Law): 58.3 k 1.2

comparison. It can be seen from this table that the slopes of the In, PZ and P4 vapour
pressure lines from the present data are all systematically greater than the corresponding
values of Panish and Arthur. Since, in addition, the slope of the In over In vapour
pressure line from the present data is in excellent agreement with the data of Macur
et a1 (1966) (whose temperature measurements are probably accurate to f 3 "C) it is
likely that the oven temperature measurements of Panish and Arthur were systematically
low, possibly as a result of heat losses by radiation and conduction from the thermocouple
junction region.
Several significant features are evident from the present data. Firstly, in common with
Panish and Arthur (1970), no systematic difference could be detected between the vapour
pressures of In over InP and In over In (see figure 3 and table 1). Secondly, unlike the
cases of GaAs and GaP (Foxon et a1 1974) the use of the modulated molecular beam
technique with phase sensitive detection and signal averaging revealed that the group V
tetramer (P4) vapour pressure previously detected with unmodulated beam techniques
could be genuinely attributed to an equilibrium vapour pressure of this species in the
oven. Thirdly, over the temperature range of the present work P2 was the dominant
species over InP. Furthermore, the present data indicate a congruent evaporation temp-
+
erature, at which p (In) =2p (Pz) 4p (P4), of 629.3 K. The data are considered further
in $6.

4 . 2 . Langmuir evaporation studies

The evaporation of the (100) InP surface under Langmuir conditions was studied using
the modulated molecular beam technique described in $2, in the specimen temperature
2444 R F C Farrow
range 600-690 K. In the initial heating of the crystal from room temperature, weakly
adsorbed species-eg HzO, CO, COZ, Nz and trace hydrocarbon species (the latter
probably arising from the final specimen wash)-were desorbed from the specimen sur-
face below 573 K. After the heating had been continued to 663 K,PI+,Pz+,P~+,P~+ and
In signals were detected at the beam modulation frequency. Signal averaging (Foxon et al
1974), however, revealed that the only molecules in the direct flux from the surface were
In and Pz. The In and PZ evaporation signals increased to stable plateau levels after
several minutes whilst the specimen was held at a constant temperature of 663 K. After
this initial transient behaviour, no time dependence of evaporation rates could be detec-
ted at any of the temperatures in the 600-690 K range over long (up to 4 h) periods
when the specimen was held at constant temperature. Furthermore, the evaporation
signals were perfectly reproducible when the specimen was cooled to room temperature
and recycled to 690 K.
T(K)
660 660 640 620
Kx)

Figure 4. Temperature dependence of I(In+), I(Pz+) signals and Z(Pz+)/I(In+) signal

ratio detected by phase-sensitive detection from InP (100) surface under Langmuir
evaporation conditions.

Figure 4 shows the modulated evaporation flux signals I(Pz+), I(In+) and the I(Pz+)/
I(In+) ratio plotted on a logarithmic scale as a function of lO4/T. The I(Pz+) and I(In+)
signals both increased with specimen temperature, but unlike the case of InP Knudsen
evaporation the temperature dependence of the signals did not follow a simple Arrhenius
behaviour over the entire temperature range of the data. In fact, the Langmuir evapora-
tion behaviour can be divided into two regions as is evident from the temperature depen-
dence of the I(P2+)/1(In+) ratio. Up to 638 t- 5 K this ratio was constant at N" 1.4 -+ 2,
but above this temperature the ratio increased exponentially. The mass spectrometer
sensitivity for PZmolecules was a factor of ~ " greater
3 than for In atoms (see $3), and
 The evaporation of I n P 2445

consequently within the limits of experimental errors and calibration errors the ratio of
evaporating fluxes from the surface was flux(Pz)/flux(In)z 0.5, which corresponds to
congruent evaporation of the (100) surface. Above 638 k 5 K there was a disproportionate
loss of phosphorus from the crystal surface.

5. Enthalpy of reaction calculations

The measured vapour pressures of In, PZ and P4 over InP are listed in table 2 and the
measured vapour pressures of In over pure In in table 3. The Third Law enthalpy
corrected to 298 K (AH0298) for reaction (1) was calculated from each experimental
value ofp(P2) at T(i) from the expression (Horton 1966)
AH0298 = T(i)(G(i) - R In K ) (9)
where S(i)=A [(-G(i)"+H02g8)/T(i)] is the change in free energy for reaction (1) and
K the equilibrium constant for this reaction. S(i) was calculated from the entropy and
enthalpy functions for PZ (JANAF 1965), In (Hultgren et a1 1963) and InP (Pankratz
1965). It was assumed in these calculations that K=(p(P~))l/z,since at the relatively
low temperatures ( > 400 K below the InP melting point) of the present data the activity
of In over the InP liquidus is essentially unity (Panish and Arthur 1970). The value of
~ ( P zused
) in the equation for K was taken as p(P2)+2p(P4), since, as pointed out in
$6, it is likely that the P4 pressure in the InP oven was not due to evaporation of P4 from
the InP but from association of PZ on the oven walls. The calculated values of AH0298
are summarized in table 2. The Third Law enthalpy, corrected to 298 K, for reaction
(2), was calculated using equation (9) with K=p(P4)/(p (Pz))~,where the free energy
functions for P2 and P4 were taken from JANAF (1965). The results are summarized in
table 2. The Third Law enthalpy, corrected to 298 K, for reaction (3) was calculated
using equation (9) with S(i) taken from the In free energy data of Hultgren et aZ(l963).
The results of these calculations are summarized in table 3.
Second Law values of AH0298 for reactions (l), (2) and (3) were calculated from the
expression

where the equilibrium constants for the reactions were expressed as a function of temper-
ature using the least-squares-fitted vapour pressure equations summarized in table 1,
and AC, is the change in specific heat for the reaction (1) or (2) taken from the sources
given above for the enthalpy and entropy functions of Pz,In and P4. (T) was the
arithmetic mean of the temperatures of the vapour pressure measurements. The results
are summarized in tables 2 and 3.

6. Discussion

One of the most significant features which emerges from the InP Knudsen evaporation
studies described in $4.1is the existence of an equilibrium pressure of group V tetramers
in the InP oven. InP is the only III-V compound so far examined where such a tetramer
pressure has been positively identified (Foxon et a1 1974). In view of the absence of P4
in the Langmuir evaporation flux from InP and the absence of tetramers in both the
2446 R F C Farrow

Knudsen and Langmuir evaporation fluxes from other 111-V compounds it is likely that
+
the P4 pressure in the InP oven arises from PZ PZ association reactions on the walls
of the oven. The maximum InP oven temperature (930 K) in the present work is more
than 300 K lower than GaAs or GaP oven temperatures at which evaporation fluxes are
detectable from these compounds. Consequently, the X4+2Xz equilibrium probably
lies very far to the right at the GaAs and GaP oven temperatures.
The congruent evaporation point (629 i-5 K) for InP under equilibrium evaporation
conditions is at a considerably lower temperature than the corresponding points for
GaAs (898 f 5 K, Foxon et a1 1973) and GaP (945 f 5 K, Farrow 1974 unpublished).
This fact is representative of decreasing thermal stability through the series of 111-V
compounds Gap, GaAs, InP. The maximum temperature (638 2 5 K) of congruent
evaporation of the InP (100) surface under Langmuir evaporation conditions is also con-
siderably lower than the corresponding temperature (930 I: 10 K) for the (100) surface
of GaAs (Foxon et aZ1973) and the implications of this fact regarding the growth con-
ditions for InP films from beam sources have been discussed elsewhere (Farrow 1974a).
The much lower (by a factor of z lo4) free evaporation rate of InP compared with GaAs
near the respective maximum congruent evaporation temperatures probably accounts
for the fact that no time dependence of the InP free evaporation rate could be detected
(after the initial heating) in contrast with the case of GaAs (Foxon et aZl937). The rate of
thermal etching of the InP surface and consequent increase in effective surface area was
too slow to be detected over periods of only a few hours. The increase in In and PZ
evaporation rates at 663 K during the initial heating of the specimen may have been
due to desorption of OZ from the InP surface. Recent Auger electron spectroscopy
studies of InP (Kirk and Bayliss 1975) have suggested that submonolayer quantities of
adsorbed 0 2 stabilize the InP (100) surface.
The Second and Third Law enthalpies for reactions (l), (2) and (3) are compared with
previous determinations in table 4. In the cases of all three reactions the Second and
Third Law enthalpies from the present data are in good agreement. The standard

Table 4. Summary of enthalpy of reaction calculations

AHo2g8(kcalmole-l) AH0298(kcalmole-l) AH"29dkcal mole-l)

InP(s) + In(s)+&Pz(g) 2Pz(g) + P4(g) In@) + Idg)
Present data (3rd Law): 37.50i 0.1 - 58'04k 0.3 58.03k 0.05
Present data (2nd Law): 37.47k0.5 - 59.70i 1.8 58.30k 1.2
Panish and Arthur (1970)
(3rd Law): 35*60+0.5 - 53.80k 0.8 55.70 0.4
~ - ~~ ~ -~ _ ~ ~ _
Panish and Arthur (1970)
(2nd Law) 34.70 f0.5
________~__ - . __ ~ ~ .~ ~- ~ ~- ~ -
H0298from JANAF values -54'6+ 1.1
~ ~~

Macur et al(1966)
(3rd Law) 56.58 0.1
-~ - - -_ _ -~ _ _ _ - - ~- - _ __ - -
Macur et a1 (1966)
(2nd Law): 59.64k 1.5
_- - __ - __ - - ~

Value adopted by Macur

er aZ(l966): 57.51k 1.25
 The evaporation of InP 2447

deviations of the Third Law enthalpies, however, are considerably lower than the Second
Law values, as expected (Horton 1966). The Panish and Arthur values of AH0z98 for
reactions (l), (2) and (3) are significantly lower than the corresponding values from the
present work. This is probably due to the temperature and calibration errors in these
authors’ data discussed in 54.1 and $1 respectively. An additional contribution to the
discrepancy in the case of reaction (1) was the use by Panish and Arthur of the free energy
function for AlSb in their calculations instead of the free energy function for InP. The
fact that, in calculating AH3Z98 for reaction (l), Panish and Arthur did not correct the
measured p (Pz) values for the effect of PZ+ PZassociation in the oven had a much smaller
effect (< 1%) on the value of hH0298 than the other systematic errors in their data.
Since it is likely that no P4 is formed directly from evaporation of the InP, the reaction
InP(s) -+ In(s)++ P4 (8) may only occur indirectly via reactions (1) and (2). The value
of AH@298calculated for this reaction from the Third Law AH@298values for reactions
(1) and (2) quoted in table 2 is 22.99 -t 0.4 kcal mole-1, which is in good agreement with
the value 22.1 kcal mole-1 adopted by Panish and Arthur (1970).
The discrepancy between the value of AH0298 for reaction (2) calculated from the
JANAF data and the Third Law value from the present data can only be considered as
possibly significant in view of the large standard deviation of the former value. Although
the Third Law enthalpy for reaction (3) from the present data is significantly higher than
the Third Law value obtained by Macur et al, it is in agreement with the enthalpy value
adopted by Macur et a1 which represents the mean of all published values of AH@298,up
to 1966, including Macur et al’s value, weighted by the number of In vapour pressure
observations.
7. Conclusions
The evaporation of InP under Knudsen and Langmuir conditions has been investigated
mass-spectrometrically using a modulated molecular beam technique combined with
phase-sensitive detection and signal averaging to separate evaporating species from back-
ground species in the vacuum system. PZwas found to be the dominant species over
InP under Knudsen conditions, but significant evaporation fluxes of In and P4 were also
+
detected. The P4 flux was attributed to PZ PZ association on the oven walls. A con-
gruent evaporation point under these conditions was predicted at 625 k 5 K.
Under Langmuir evaporation conditions the only evaporating species detected were
In and Pz. Up to 638 & 5 K the (100) surface evaporated congruently but above this
temperature there was a disproportionate loss of PZ from the surface. In the specimen
temperature range (600-690 K) studied, no significant time dependence of evaporation
rates could be detected. This was attributed to the low ( 510-5 monolayer s-1) evapora-
tion rates of InP close to the maximum temperature of congruent evaporation.
The equilibrium vapour pressures of In, PZ and P4 over InP and of In over pure In
have been determined and enthalpies for the reactions InP(s) -+ In(s) ++Pz(g);
2Pz(g) -+ P4(g); In(s) -+ In(g) calculated. In determining the equilibrium vapour pres-
sures mass-discriminating effects in the mass spectrometer were taken into account. In
addition, in the calculations of the enthalpy for the reaction InP(s) -+ In(s)++P2(g)
accurate high temperature heat capacity data for InP have been used for the first time.

Acknowledgments
The author is indebted to G M Williams for his assistance in the measurements and
data processing and to Drs W Bardsley, D T J Hurle and J B Mullin for helpful
2448 R F C Farrow

discussions. The author also acknowledges with thanks the help of Dr W Bardsley in
initiating the present work. Copyright: Controller, HM Stationery Office.

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