Vacuum/volume 41/numbers 4-6/pages 1038 to 1042/1990

Printed in Great Britain

0042-207X/9053.00 + .00
1990 Pergamon Press plc

Phase sequence of silicide f o r m a t i o n at

m e t a l - s i l i c o n interfaces
R Pretorius,

I o n - S o l i d Interaction Division, Van de Graaff Group, National Accelerator Centre, Faure 7131,

South Africa

There is considerable interest in the solid state interaction between metals and silicon to form silicides, as
these compounds are widely used in silicon devices as interconnects and contacts. In this study an effective
heat of formation rule is formulated for predicting the sequence in which silicide phases form in metal-silicon
binary systems. In the presence of very small amounts of Au at the S i - C o interface, CoSi2 is the first phase
to form instead of C02Si. This reversal of phase sequence is explained using the effective heat of formation
rule. This concept is also used to evaluate the influence of oxygen impurities on nickel silicide formation.

1. Introduction

Solid phase interaction between thin metal films and silicon,

has been widely studied because of the importance of silicides
as interconnects and contacts (Schottky and Ohmic) in silicon
devices 1-3. The first silicide compound phase grows, until all
the metal or silicon is consumed, thereafter other silicide phases
richer in the remaining element form during further heating.
Thin nickel films for instance will react with thick silicon to first
form Ni2Si at about 280C, followed by the formation of NiSi
and NiSi 2 at higher temperatures. In the case of chromium the
chromium reacts with silicon to form CrSi 2 as can be seen from
the Rutherford backscattering measurements given in Figure 1.
Heating of the sample for longer times at higher temperatures
does not lead to the formation of any other compound phases,
although the C r - S i binary phase diagram shows the existence
of Cr3Si, CrsSi3, CrSi and CrSi 2.
There has been considerable interest in formulating rules for
predicting the first silicide phase which forms, as well as the
sequence of subsequent phases 4-6. These rules rely heavily on
phase diagram information such as the lowest eutectic, stability
(as manifested by melting point and congruency) and on diffusion species, but do not directly use thermodynamic data.
Pretorius 7 has, however, shown that by formulating an effective
heat of formation concept, theormodynamic data can be used
to predict first compound phase formation and subsequent
phase sequence. In this work this concept is expanded and it is
shown how the effect of oxygen on Ni silicide formation and
gold on Co silicide formation can be explained in terms of the
effective heat of formation model.

entropy. For solid state interactions AS ~ 0 and AG is thus

approximated by the change in enthalpy AH, during the reaction ~'9. If we now look at the heats of formation for the
different compound silicide phases which can form in the C r - S i
binary system, we see that CrsSi 3 has the most negative value,
namely - 7 8 . 4 kcal g - l m o l - i (see Table 1). This is not the
phase which forms first as it has been well established that
CrSi 2 is the first phase (see Figure 1 and ref 1, 11 and 12). It is
however clear that the main reason why CrsSi 3 has the most
negative AH is because it has the most bonds per molecule.
This can be corrected for, by expressing AH in terms of kcal
g - l a t - l , but even then it can be seen from Table l that CrsSi 3
has the most negative heat of formation. It is thus clear that the
concentrations of the reactant species also have to be taken into
consideration by evoking the concept of AH', the effective heat
of formation 7.
Consider for example the interaction between Cr and Si to form
the compound phase Cr a Si. Let us also assume a situation during
solid state interaction where the effective concentration of silicon
is 70 at% and Cr is 30 at%. We therefore have for Cr3Si that;
Heat of formation = - 3 3 . 2 kcal g - l m o l - I
( -- 8.3 kcal g - l a t - l )
Compound formed = Cro.7sSi0.25 (Cr3Si)
Available concentration = Cro.3oSio.70
Therefore the limiting element is Cr.

Table 1. Standard heats of formation for the chromium silicide

phases l
2. Effective heat of formation model

The driving force for a process to take place, is given by the

change in the Gibbs free energy:
AG

= AH

TAS

where AH is the change in enthalpy (or heat of formation)

during the reaction at temperature T and AS is the change in
1038

Phase

AH
(kcal g - i mol-t)

AH
(kcal g - i at-Z)

Cr3Si
CrsSi 3
CrSi
CrSi2

- 33.2
-78.4
- 19.0
-28.8

- 8.3
-9.8
-9.5
-9.6

R Pretorius:

Phase sequence of silicide formation

t,O00

A general definition of the effective heat of formation (AH'),

can therefore be given as;

Cr
1000

<10@

3000

available concentration limiting element

A H ' = AH x compound concentration limiting element'

2Mev

VIRGIN

where AH = Heat of formation in kcal g - 1 a t - 1.

By using this equation the effective heat of formation of any
compound can be calculated as a function of the concentrations
of its reacting components, thereby linking thermodynamics
and kinetics, For the above case of Cr3Si formation the effective heat of formation is - 3.32 kcal g - [ a t - [.

2000

100(

3000

L;

1200k 6001

>-

Walser and Ben~ 13 postulated that during preparation of silicon-metal thin film couples by evaporation or sputtering the
interface consists essentially of a metallic glass with a concentration near the lowest-temperature eutectic in the binary system. Also, it can be expected that when such a structure is
heated, intermixing at the interface would take place at concentrations similar to that of the lowest eutectic. It is thus reasonable that for prediction of first phase silicide formation the
effective heat of formation of the different compounds which
could possibly form, should be compared at the lowest eutectic
composition of the particular binary system. It should also be
noted that the non-congruent silicide phases are relatively
unstable and are usually 'skipped' during silicide formation1.4. 14.

500~C-8min

o
z_

3. Effective heat of formation rule for first phase formation

Cr
"

,~

oc
LLI 2000
I--"

" "

L)
co

Si

-,c 1000

1k,

3oook
300(3 S

"

500"C-20 rain
2000

~")t,,...

1000

(1)

C.r

..

0,~

o.B

1.2

1.6

2.0

ENERGY (MeV)
Figure 1. Rutherford backscattering spectra (E, = 2.0 MeV, 0 = 165),
showing the solid state interaction between a thin chromium film and
single crystal silicon to form CrSi2, which is the first and only phase to
form, even after extended periods of heating at higher temperatures.
The ratio of the Cr to Si signal heights as well as electron and X-ray
diffraction measurements are used for phase identification.

If a total of 100 atoms in the C r - S i system are available for

interaction to form Cr3Si we see that because Cr atoms are
limiting, only 10 Cr3Si molecules can form. In the process all 30
Cr atoms react, while only 10 Si atoms are used up, the other
60 Si atoms not contributing to the total heat released by the
system given by;
3O
Total heat released = AH x - - = 332 kcal,
3
where AH is the heat of formation for Cr3Si expressed in kcal
g - 1 m o l - 1. It is thus clear that the heat released depends on the
available concentration of the limiting element and the concentration of the limiting element in the compound to be formed.

We have calculated the effective heats of formation (AH') of

all the known chromium silicide phases as a function of concentration. This effective heat of formation diagram is given together with the C r - S i phase diagram in Figure 2. It is clear that
all the phases the most negative AH" and thus the release of the
most energy from the system occurs when the concentration of
Cr and Si matches that of the composition of a particular
compound. At the lowest temperature eutectic composition
(85 at% Si) it can be seen that CrSi2 has the most negative
AH'. The effective heat of formation rule therefore predicts that
CrSi 2 will be the first phase to form in the C r - S i binary system,
which is in agreement with experimental observations1' 11, 12. A
rule for first phase formation can thus be formulated which
states;
'The first silicide compound to form during metal-silicon
interaction is the congruent phase with the most negative
effective heat of formation (AH') at the concentration of the
lowest temperature eutectic of the binary system.'
To test this rule, the values of AH' have been calculated in
Table 2, for the Cr, Co and Ni silicide phases at the lowest
melting eutectic composition. In Table 3 predicted first phases
are compared with experimentally determined first phases for
all those silicides with known heats of formation and for which
phase diagrams exist for which the lowest eutectic compositions
may be obtained. The agreement between predicted and experimentally observed first phases is excellent, except for Mn and
Ni. It should however be remembered that the uncertainty in
heats of formation is at least 10%, It should also be noted (see
Table 3) that ZrSi 2 is a non-congruent phase and phase diagrams show that probably all the zirconium silicide phases are
non-congruent. If no congruent phases exist the system has
no choice and is expected to form the non-congruent phase

1039

R Pretorius: Phase sequence of silicide formation

-lz.c

'-~

-8.1

-2.1

F
20

20001

t.0

t_J

80

60

100

t~

16
I
g.

Lowest
eutectic
(at% Si)

Predicted
phase

Observedt
phase

AH'
(kcal/g- t a t - i)

Co
Cr
Fe
Mn

23
85
34
22

C o 2 Si

Mo
Nb
Ni

97
96
46

Pd
Pt
Ta
Ti
V
W
Zr

16
23
99
86
97
99
91

Co 2 Si
CrSi 2
FeSi
MnSi
MnsSi 3
MoSi2
NbSi2
Ni2Si
NiSi
Pd 2Si
Pt 2Si
TaSi 2
TiSi 2
VSi 2

- 6.4
-4.3
- 6.5
- 3.2
-3.5
-0.8
- 0.9
-9.2
- 9.8
- 3.3
- 4.8
-0.2
-4.5
-0.9
- 0.2
-3.4

WSi 2

ZrSi2(NC )

CrSi 2
FeSi
MnSi
-MoSi 2
NbSi2
Ni2Si
-Pd 2Si
Pt 2Si
TaSi 2
TiSi 2
VSi 2
WSi 2
ZrSi2(NC )

*Heats of formation from refs 9 and 10.

t F r o m ref 1.

1/+00t

"

85/a

I I

il
II

1200
F
IO00L
0

System
,o.,

//

-6.C
-t+.O

Table 3. Prediction of first phase silicide formation by using the

effective heat of formation (AH') rule*

,":

Cr

I
20

1335"E

i
/.,0

i
60

I
80

4. Phase sequence

100
Si

Atomic % Si

Figure 2. Effective heats o f formation (AH') diagrams and the phase

diagram for the C r - S i binary system.

with the m o s t negative effective h e a t o f f o r m a t i o n w h i c h is

ZrSi2. T h e q u e s t i o n o f c o n g r u e n c y a n d n o n - c o n g r u e n c y is
by n o m e a n s clear, b u t generally it s e e m s t h a t t h e d e g r e e o f
n o n - c o n g r u e n c y ( i n d i c a t e d by the t e m p e r a t u r e difference
b e t w e e n the liquidus curve a n d the eutectic p h a s e ) is i n d i c a t i v e
o f instability 5.

T o illustrate h o w the effective h e a t o f f o r m a t i o n ( A H ' ) c o n c e p t

m a y be used to p r e d i c t p h a s e s e q u e n c e we a g a i n c o n s i d e r the
C r - S i b i n a r y system; the A H ' d i a g r a m o f w h i c h is given in
F i g u r e 2. A s has been d i s c u s s e d in S e c t i o n 3, CrSi 2 is p r e d i c t e d
to be the first p h a s e to f o r m . F o r the case o f a thin C r film o n
a thick silicon s u b s t r a t e ( C r < Si) all the C r will be c o n s u m e d
to f o r m CrSi2 a n d b e c a u s e the effective c o n c e n t r a t i o n o f Si at
t h e S i - C r S i 2 interface will m o v e to values g r e a t e r t h a n the
c o m p o s i t i o n o f CrSi2, n o f u r t h e r p h a s e s will f o r m as n o n e exist
in this c o n c e n t r a t i o n region. I f h o w e v e r , the s i t u a t i o n is c o n s i d ered w h e r e there is m o r e c h r o m i u m available t h a n Si ( C r > Si),
CrSi2 will again be t h e first p h a s e to f o r m a c c o r d i n g to the
effective h e a t o f f o r m a t i o n rule a n d will c o n t i n u e to f o r m until
all the silicon is c o n s u m e d . T h e effective c o n c e n t r a t i o n s o f the

Table 2. Standard heats o f formation for various Cr, Co and Ni silicide phases, and the effective heat of formation A H ' given in the last column
as calculated for the lowest-melting eutectic composition for the metal-silicon binary system*
Phase

Composition

Lowest eutectic = Cro.~5Sio.s5

Cr 3Si
( Cro.75 Sio.25)
Cr 5Si 3
(Cro.63 5io.37)
CrSi
(Cro.soSio.5o)
CrSi z

(Cr0.33 5i0.67 )

AH
(kcal g - ' m o l - ')

AH
(kcal g - ~a t - 1)

Limiting
element

AH"
(kcal g - ~a t - ')

- 33.2
- 78.4
- 19.0
-28.8

- 8.3
- 9.8
-9.5
-9.6

Cr
Cr
Cr
Cr

- 1.7
- 2.4
-2.9
-4.3

- - 27.6
--24.0
- - 24.6

- 9.2
- 12.0
-- 8.2

Si
Si
Si

- 6.4
-5.5
- 2.8

- - 72.1

-- 10.3
- 11.4
- 11.1
-- 10.7
-- 7.5

Ni
Ni
Ni
Si
Si

-- 7.8
-9.2
-9.9
- 9.8
- 5.2

Lowest eutectic = C00.77Si0.23

C o 2 Si

(C00.67 5io.33 )

CoSi

(Coo.5oSio.5o)

CoSi 2

(C00.33 Si0.67 )

Lowest eutectic = Nio.s4 Sio.46

Ni 5Si 2
(Nio.Tt Sio.29)
Ni2Si
(Nio.67 Sio.33)
Ni3Si 2
(Nio.6oSio.4o)
NiSi
(Nio.5o Sio.5o)
NiSi 2
(Ni0.33 5i0.67)
*To convert kcal to kJ multiply by 4.187.
1 040

-34.1
-55.5
-- 21.4
- 22.5

R Pretorius: Phase sequence of silicide formation

reactants at the Cr-CrSi2 interface will now move to the left of

the effective heat of formation diagram (see Figure 2) until an
effective concentration of about 42% Cr and 58% Si is reached
where CrSi formation should lead to the most negative AH'.
This phase does, however, not form as it is non-congruent and
is 'skipped', CrsSi 3 formation taking place instead. After complete transformation of CrSi2 to CrsSi 3 the effective concentration at the Cr-CrsSi 3 interface moves to the left until Cr3Si
formation becomes the most likely phase to form. When all the
CrsSi 3 is converted to Cr3Si no further reaction will take place
as no other phases exist, which are more metal rich. The above
predictions of phase sequence for Si > Cr and Cr > Si agrees
with experimental observation t4. An effective heat of formation
rule for phase sequence can now be formulated.

-14.0

--

towest
eutectic/~

\'

":~ -t,.0

'After first phase silicide formation, the next phase formed at

the interface between the compound and remaining element
(Si or metal) is the next congruent phase richer in the
unreacted element, which has the most negative effective heat
of formation.'
For an isolated binary system which has an atomic ratio of
I : 1, CrSi will be forced to form even though it is a non-congruent phase, because the effective heat of formation diagram
shows that this is the phase which will lead to the lowest total
free energy. This has been confirmed experimentally~4 by evaporating thin Cr and Si films onto an inert substrate with the
thickness chosen so as to give an atomic ratio of one.
The effective heat of formation diagram for the C o - S i
system (see Figure 3) shows that unlike the C r - S i system a
more metal rich phase namely Co2Si is expected to form first,
because the lowest melting eutectic is on the metal rich side of
the diagram. In the case of thin Co films (Co < Si), CoSi will be
the second phase to form whereafter CoSi 2 will be the final
phase. This prediction of phase sequence agrees with the experimental observations 1. The effective heat of formation rule can
also be used to predict phase formations when a thin metal film
is deposited onto a silicide. Measurements show that for thin
Co films evaporated onto thick CoSi2, Co2Si is the first phase
to form ~5. When all the Co has reacted the Co2Si reacts with
the CoSi 2 to form CoSi giving a Si-CoSi2-CoSi structure. At
this stage CoSi is converted to CoSi 2, the extra silicon being
supplied from the substrate. These observations can also be
explained by the effective heat of formation rule using the same
reasoning as above.

-10.0
|

20

t,0

80

60

100

o
kJ

1600

I/I
t..J

I~0(
1310"[I 77.5 ?
i
1259[

120(

F--

1000

8O0

0
Co

20

40

6'0

,I

I
80

i
100

Si

Atomic % 5i
Figure 3. Effective heat of formation (AH') diagrams for the Co-Si

system. In this case unlike for Cr, the lowest eutectic is on the metal
rich side of the phase diagram, resulting in the prediction that Co2Si
will be the first phase to form according to the effective heat of
formation rule.

5. Effect of gold and o x y g e n on silicide formation

For thin Co-films deposited on thick silicon~, CoSi 2 formation

starts to take place at about 550C after formation of Co2Si
and CoSi. If, however, a very thin layer of Au (approx 2 nm)
is placed between the Si and Co, CoSi 2 is found to be the first
phase to form 16 at temperatures as low as 390C (see Figure 4).
This reversal of phase sequence can be explained using the
effective heat of formation diagram for the C o - S i system, given
in Figure 3. In the presence of Au, the effective concentration
of silicon increases dramatically to a value greater than 67 at%
Si, due to the very low A u - S i eutectic (375' C). In this concentration region CoSi 2 formation leads to the lowest free energy
for the system and is thus the first phase to form.
Although Ni2Si is known to be the first phase to form during
interaction between thin nickel films and single crystal silicon,
early experiments with amorphous silicon show that NiSi for-

t~
F-

ALPHA ENERGY{HeV}

Figure 4. Rutherford backscattering spectra (E~ = 2.0 MeV, 0 = 165)

showing silicide formation without (solid line) and with (points) Au.
The alpha particles scattered from gold have higher energies (hatched
area) and cause some overlapping with the Co signal. Au thicknesses as
small as 2 nm placed between the Si and Co, cause CoSi2 to be the first
phase to form instead of Co2Si, at temperatures below 400C (from ref
16).
1041

R Pretorius: Phase sequence of silicide formation

to form). The presence of oxygen in the amorphous silicon will

lead to the incorporation of oxygen in the Ni2Si during initial
silicide formation, thereby hindering Ni diffusion and decreasing the Ni flux and effective Ni concentration available for
silicide formation. Under such conditions NiSi can be expected
to form, as has been found experimentally17.

-12.C
--

-10.0

6. S u m m a r y

-6.0
":~ -~.C
-2.0
0

20

t~O

60

80

100

.N

1600 -

t~
Z

e~
I/.00

and conclusion

We have shown that by defining the concept of an effective heat

of formation (AH') the thermodynamics of solid state interaction in binary metal-silicon systems can be linked to the
concentrations of the interacting species and therefore to kinetics. By utilizing the concentrations of the lowest eutectic of
M - S i binary systems an effective heat of formation rule could
be formulated not only for first phase formation but also for
subsequent phase formation sequence. It has also been illustrated how the effective heat of formation rule can be used to
explain how the presence of impurities such as oxygen or small
amounts of Au can alter first phase formation during nickel
and cobalt silicide formation respectively.
References

,~ 1200
.=
i~ 1000

80C

600
Ni

20

t*0

60

80

100
5i

Atomic % Si
Figure 5. Effective heat of formation diagram for the Ni-Si system.
mation is the predominant first phase 17. It is known that during
the formation of amorphous silicon thin films by electron-beam
evaporation or sputtering, the films may contain a few atomic '
percent of oxgyen due to gettering in the vacuum. From the
N i - S i effective heat of formation diagram (Figure 5) and from
Table 3, it is clear that from a thermodynamic point of view
there is not much to choose between the formation of NizSi or
NiSi (Ni3Si2 is a non-congruent phase and is thus not expected

1042

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