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surface science
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ELSEVIER

Surface Science 301 (1994) 203-213

Characterization of thin titanium oxide adhesion layers on gold:

resistivity, morphology, and composition
K.W. Vogt, P.A. Kohl *, W.B. Carter,
Georgia Institute of Technology, Atlanta,
(Received

22 March

1993; accepted

R.A. Bell, L.A. Bottomley

GA 30332-0100,

for publication

10 August

USA
1993)

Abstract
Group
1B metal films (copper, silver and gold) are attractive for metallizations
in multichip modules (MCM) and
integrated
circuits because
they have high electrical
conductivities.
Unfortunately,
Group 1B metals require
additional bonding layers for adhesion to insulators (i.e. silicon dioxide or polymers). In this work, thin electrically
insulating films of titanium oxide on titanium have been investigated
as adhesion layers between gold and a wide
variety of insulators. The adhesion layer does not alter the dielectric properties
of the insulator surrounding
the
metal because it is thin. The morphology, composition,
and resistivity of the titanium oxide films were studied with
angle resolved X-ray photoelectron
spectroscopy
(XPS), scanning tunneling
microscopy
(STM), and electrical
resistance
measurements.
The results show that sputter-depfsited
titanium
films grow by an island growth
(Volmer-Weber)
mechanism. The islands coalesce after lo-20 A of titanium deposition. Following deposition, the
titanium films were oxidized by exposure to air at relatively low temperatures
(T < 1OOC). Very thin titanium films
(3 A) oxidized completely. When thin titanium films (lo-20 A> were oxidized, a layered film formed with a sub-oxide
(TiO) core and a titanium dioxide surface layer. When thicker films (> 20 A> were oxidized, a layered film was also
produced with a titanium core and titanium oxide surface layer.

1. Introduction
The high conductivity
of Group 1B metal films
(copper, gold and silver) is appealing
for use in
metallizations
for microelectronics
interconnections. In addition, the inertness of gold makes it
attractive for high reliability applications.
Transition metal films are commonly used as adhesion
layers for metals which do not easily form stable
oxides. The adhesion
properties
of transition

* Corresponding

author.

0039-6028/94/$07.00
0 1994 Elsevier
SSDI 0039-6028(93)E0490-L

Science

metals,
particularly
Groups
IVA-VIIIA,
have
been correlated
to the heat of formation
of the
oxide [ll. Group 1B metals (copper, silver, and
gold) do not form oxides adequate for adhesion.
Recently,
a thin film of titanium
oxide on
titanium
(< 100 A> has been investigated
as an
adhesion layer between gold and silicon dioxide
or polymers [2,3]. The titanium oxide is deposited
on the metallization
to provide an adhesive film
for the subsequent
deposition
of an insulator. In
addition to being electrically
insulating,
titanium
oxide films do not alter the dielectric properties
of the insulator on, or under the metal because
they are thin. The titanium-gold
metallurgy also

B.V. All rights reserved

204

K.W Vogtrlal.
/Swfacr Sciencr 301 flYY4)
203-213

makes titanium
a desirable
adhesive
material.
Although titanium-gold
interdiffusion
is fast, titanium out-diffuses
along grain boundaries
and
quickly oxidizes at the surface of the gold. The
surface oxidation
causes continued
outdiffusion
and a chemical potential
sink [4]. Thus, stable
titanium oxides can be formed on the surface of
gold. This behavior is unlike some transition
metals on gold which diffuse into the gold and significantly reduce its electrical conductivity
111. In this
study, thin titanium adhesion layers were characterized to understand
the nature of growth and
adhesion mechanism
of the films to gold.
Titanium films have been deposited by several
techniques
including
chemical vapor deposition
[5], evaporation
[6], and sputtering
[7]. In this
study, the properties
of thin titanium
films deposited with DC magnetron
sputtering have been
analyzed by electrical
resistance
measurements,
XPS, and STM. These techniques
will help characterize
the resistivity,
composition,
and morphology of the thin titanium films.

oxidation
in air at room temperature
for two
weeks, the composition
of the films was measured
with sputter-profile
XPS, and the morphology
was evaluated with angle resolved XPS and STM.
A Surface Science Laboratories,
Inc. SSX-100
X-ray photoelectron
spectrometer
with an Al Ka
X-ray source (1486.6 eV> was used for angle
resolved
and sputter-profile
XPS studies. The
base pressure was lower than 1 x lo- Torr. Argon ion sputtering
was used to etch away the
surface during profiling. The Kratos Mini-Beam
II ion gun was operated
at 4 keV in an argon
pressure of 3.7 x lo- Torr.
STM images were obtained with a Digital Instruments,
Inc. Nanoscope
II scanning tunneling
microscope. The STM tips were prepared by mechanically
shearing
platinum/
iridium wire. Images were obtained in the constant current mode
at a tunneling
current of 0.5- 1.0 nA, and the
tunnel junction bias was between f 50 and k 250
mV. Most images were acquired at scanning rates
between 2 and 3 Hz. The images were flattened
prior to analysis.

2. Experimental
3. Angle-resolved
Titanium
and gold films were deposited
sequentially
by DC magnetron
sputtering.
The
sputtering
targets
were 99.99% titanium
and
99.99% gold, and the base pressure was 2 X 10ph
Torr. The temperature
during the deposition was
below 50C and the d?position
rate for both gold
and titanium was 60 A/min.
Three sets of samples were prepared.
Electrical conductivity
measurements
were made by
sputtering
titanium
between two closely spaced
gold strips on a silicon dioxide substrate.
The
electrodes were 3.5 cm long, 3 mm thick, and had
40 mm lines and spaces. The resistance
of the
titanium
film between the electrodes
was measured as a function of post-processing
conditions.
For composition
and morphology
studies, 3, 10,
and 75 A titanium films were investigated.
Identical titanium films were prepared
on both evaporated gold and sputtered
gold osubstrates. The
evaporated
gold film was 2500 A thick and deposited on mica, and the sputtered gold film was
1500 A thick and deposited
on silicon. After

XPS morphology

model

During the deposition of titanium, film growth

can occur by several mechanisms
[8]. During
Frank-Van
der Merwe (layer-by-layer)
growth,
one monolayer of coverage is completed before a
second begins. The second possible growth mechanism is Stranski-Krastanov
(layer-plus-islanding) growth. After the substrate surface is completely covered by the first monolayer,
subsequent deposition
of material forms islands. The
third method is Volmer-Weber
(island) growth,
where islands nucleate,
grow, and coalesce as
deposition continues.
In this work, angle resolved XPS and STM
have been used to characterize
and distinguish
between
the film growth mechanisms.
A layerby-layer model for angle resolved XPS was first
discussed by Henke [9] and further developed by
Fadley [lo]. The XPS intensity
from a semi-infinite substrate covered with an overlayer material was measured as a function of photoelectron
take-off angle, 0. The intensity of the XPS signal

K. W. Vogt et al. /Surface

from the substrate (Isubstrate),was attenuated

ponentially by the overlayer.

ex-

I substrate

(1)

l;bstrateeXP(

t/hsubstrate

sin

e>.

Science 301 (1994) 203-213

The intensity from a semi-infinite, atomically

clean surface of the substrate material was
the thickness of the overlayer film was t,
h:bstrate~
the attenuation length for the photoelectrons
from the substrate material as they travel through
the overlayer was Asubstrate,and the photoelectron
take-off angle measured from the plane of the
sample was 0.
The XPS intensity of the overlayer material
(loverlayer)was simultaneously measured. The photoelectrons originating from the overlayer film
are also attenuated exponentially with depth.
I OVerlayer
= Z:.erlayer[I - exp( - t/*oerlayer sin e)] .
(2)

The intensity from a semi-infinite, atomically

clean surface of the overlayer material was
I,,er,ayer,and the attenuation length of the photoelectron from the overlayer as it travels through
the overlayer film was Aoverlayrr.
A single parameter, R(O), is obtained for the
layer-by-layer model after dividing eq. (2) by eq.
(1).

205

the observed
intensity
from the substrate
(Isubstrate) has contributions from the overcoated
and bare portions of the substrate. The XPS
intensity from the overcoated substrate, eq. (4),
was attenuated by islands with uniform height, h,
whereas, the signal from the bare surface was not
attenuated by the overcoat layer.
I substrate= Zsmubstrate
I(1-

Y1
+Yexr4-h/bubstrate
sinQl .

(4)

The fraction of the surface covered by the film

was y, and the uncovered fraction was (1 - Y>.
Likewise, the XPS intensity from the overlayer
1 has an exponential attenuation with
(Zoverlayer
thickness because the photoelectrons
originate
from different depths in the overlayer film, as
shown by eq. (5).
ZOVerlayer
= Y Z:erlayer[ 1 - exp( -VLerlayer

e)].

sin

(5)

The analogous quantity to eq. (3) (R(B), layerby-layer model) for the island growth model is
given by eq. (6) which was obtained by dividing
eq. (4) by eq. (5).
Zoverlayer/Zoave*layer
R(B) = Z_

I oerlayer/Z&_rlayer
R(O) = Z

substrate/zs:bstrate

substrdzs%strate

= 1 - ew( -t/Aoverlayersin0)
exp(-t/hsubstrate

sin

e,

(3)

[@

Y[

1 -

Y)

ew(
+

-Woverlayer
exp(

sin

-h/Asubstrate

e)]
sin

e>I

(6)

A model for the Volmer-Weber

(island)
growth mechanism has also been developed [ll].
The film has been approximated as a patched
overlayer of the overcoat material. In this model,

have been measured as a function

of the photoelectron take-off angle (substrate =

Table 1
Measured

of titanium

resistance

(R) and calculated

Oxidized

resistivitv

(4) as a function

The
and

four

quantities,

zsubstrate,

z;bstrate~

zoverlayer~

Gerlayer7

thickness

and amount

of oxidation

at 95C

0 min
R(n)

5 min
p (fi.crn)

R (a)

10 min
p (R.cm)

R (0)

p(n.crn)

lO.&Ti

1.70 x 10

14900

> 9.99 x 10s

> 87 400

> 9.99 x lox

> 87 400

20 .& Ti

160000

28

1.30 x 108

29 600

> 9.99 x 10

> 175 000

30 A Ti

10

0.0026

51.6

0.0144

100

0.0260

K. W. Vogt et al. /Surface

206

gold, overlayer = titanium)

and fitted to the two
models discussed
above. Non-linear
regression
analysis was used to analyze the fit of eq. (3) and

Ti *P

s/2

(a)

ii(t4)
v

Tit?

$0)

Science 301 (1994) 203-213

eq. (6) to the R(0) versus 0 data. The overlayer

thickness (t) or island height (h) and fractional
coverage (y) were estimated from the deposition
process and were confirmed from the regression
analysis. Further
discussion
concerning
the assumptions
in the angle resolved XPS models is
included in the Appendix.

4. Results and discussion

4.1. Resistance / resistivity measurements

30 seconds

469

4th

463
Biidiig

460
Energy kv)

457

454

M
Ti(+4)
+

469

451

The electrical resistance

between two 3.5 cm
long electrodes with 40 mm spacing and titanium
overcoat thicknesses
of 10, 20, and 30 w were
measured
after heat treatment
in air at 95C
(4.5% relative humidity measured
at 20C) for 0,
5, and 10 min. The maximum DC resistance
of
the meter was 1 GR. The resistivity of the titanium films was calculated, R = pL/A, where R is
the measured
resistance
(a), p is the resistivity

I
466

I
463
Biidiig

Fig. 1. Titanium
etching.

I
I
457
460
Fnergy kV)

2p XPS spectra

Tit+2
+

Ti(O)
$

I
454

for (A) the 3 i\ titanium

4 51

film (B) the 75 I% film, and (C) the 10 A film as a function

of argon

K.W. Vogtetal./Surface
Science301
(1994)
203-213

(0. cm), L is the distance between the anodes

(cm), and A is the cross-sectional area (thickness
times electrode length) of the film (cm2). As the
film thickness increased from 10 to 30 A, the
resistivity significantly decreased, as shown in
Table 1. Second, the resistivity of each film increased with air exposure time at 95C. With a 10
min exposuie to air at 95C the resistance of the
10 and 20 A thick films was greater than 1 GR,
the meters limit. For the 10 A film, a 5 min
exposure was sufficient to produce greater than a
gigaohm resistance.
These results show that oxidation of 10 and 20
A films for 10 min was sufficient to convert the
titanium conductive path to a non-conductive path
(i.e. titanium oxide). If the films were grown with
an island growth mechanism, oxidation of the
outer shell of the titanium islands would have
adequately
eliminated
any conductive paths,
whereas with a layer-by-layer growth mechanism,
the bulk of the film would have oxidized. Thicker
films (30 A> are either not completely oxidized, or
the voids between the islands are filled with metal
causing an increase in the conductivity.
4.2. Sputter-profile X-ray photoelectron
spectroscopy
The Ti2p XPS spectra for 3, 10, and 75 A
titanium overcoats on gold were obtained as a
function of argon ion sputter@g time, as shown in
Fig. 1 for the 3 and 75 A titanium on gold
samples. The peak positions have been referenced to the adventitious C 1s peak at 284.6 eV.
In addition to the carbon reference, the binding
energy for gold was measured, and its position
was unchanged. The spectra can be interpreted in
terms of three doublets associated with Ti (zero
valence state), TiO (+ 2 oxidation state), and
TiO, (+ 4 oxidation state) [12]. The peaks in each
doublet correspond to photoemission from the
titanium 2p,,, and titanium 2~i,~ energy levels.
The three 2p1,* p eaks are located between 461
and 467 eV, and the three 2p3,2 peaks are located between 453 and 461 eV. The titanium
2P 3,2 peaks are commonly used for the identification of the titanium oxidation states because of
their high photoemission intensity [13]. The bind-

207

ing energy of the titanium 2p,,, peak for the 3 A

titanium overcoat sample occurred at 458 eV
after 0, 10, 20, and 30 s of sputter etching, as
shown in Fig. la. This binding energy corresponds to Ti4+ (i.e. TiO,). This indicates that
within the sensitivity of XPS, the 3 A film was
TiO,.
Fig. lb shows the XPS spectra for the 75 A Ti
film at 0, 200, and 1100 s of sputter etching. The
oxidation state of titanium on the surface was
primarily Ti4+, just like the 3 A film. After 200 s
of sputter etching, the Ti2p,,,
peak shifted to
454 eV, corresponding to Ti. The peak at 461 eV
corresponds to the TiO 2~,,~ signal. After 1100 s
of sputter etching, only a small quantity of tita@urn remained on the gold surface. Thus, the 75
A film was a layered structure with an oxide
surface and a metal core. Since a sub-oxide was
not observed after a significant amount of sputter
etching, it was concluded that sputter etching did
not reduce titanium oxide or oxidize titanium to
form a sub-oxide (Ti2+l.
Fig. lc shows that the oxidation state of the
surface of the 10 A titanium film (prior to sputter
etching) was also primarily Ti4+ (TiO,), analogous to the 3 A film. However, unlike the 3 A
film, the observed oxidation state after 45, 90 and
135 s of sputter etching was found to change from
Ti4+ to Ti2 (the binding energy of the Ti2p,,,
peak shifted from to 458 to 456 eV). Elemental
titanium (binding energy at 454 eV) was not observed. Thus, assuming sputter etching does not
produce titanium sub-oxide, the 10 A titanium
film was a layered structure with a TiO, surface
and a sub-oxide core (TiO or possibly Ti,O,).
Previous studies have found similar results for
room temperature Fxidation. Evans [14] has suggested that 6-12 A of oxide form on titanium
metal within the first few seconds of oxidation,
followed by a slow oxide growth which ceases
after 70 days. Others have shown that oxide
growth on titanium is a logarithmic function of
temperature below 300C [15,16]. The oxidation
quickly becomes diffusion limited at low temperatures because of the inward movement of oxygen
to the oxide-metal interface [15,17,18]. Kofstad
[15] has shown that the oxide film which formed
on titanium has a sub-oxide (TiO and Ti,O,)

20X

K.K

Vogt et al. /Surface

Scimce 301 11994) 203-213

4.3. Angle resolued X-ray photoelectron

spectroscopy

at the interface between the titanium metal and

the surface TiO,. Similar results were found by
Aouadi et al. for the oxidation of tungsten films
[191. In this case, WO, was found between a
tungsten metal substrate and a WO, surface oxide.

In this section, the angle-resolved XPS data

will be presented and compared to the theoretical
predictions discussed earlier. The titanium 2p

2.5 -

\
I

(al
\

23

\
L

- -_+_-__- _ ,___ -- 10

20

--

30

40

50

60

70

60

90

photoeiectron takeoff angle tdeam)

*---

.---t

_-

10

lb)

--

20

30

pi

40

-_-

50

_.__.~+---d

60

70

Bo

90

photoelectron takeoff angle (degrees)

31

\
l

\
.

11

'.
'.
,_

1+
0

I
l-y.____
0

_-..
10

20

30

40

.
_-.

60

*.
-_.

?
__.r

60

__

70

__

60

xl

photoelectron takeoff angle (degrees)

Fig. 2. The intensity ratio, R(B), as a function of the photoelectron

Ti/Au/Si
film, (c) 3 A Ti/Au/mica
film, and Cd) 10 I% Ti/Au/mica

take-off
film.

angle

for the (a) 3 i

Ti/Au/Si

film, (bt 10 A

K.W. Vogt et al./Surface

10

20

30

209

Science 301 (1994) 203-213

40

50

60

70

80

90

photoelectron take-off angle (degw1

Fig. 2 (continued).

and gold 4f XPS spectra were measured as a

function of photoelectron take-off angle (the angle between the plane of the sample and the
entrance to the analyzer). In this case, the overlayer film is titanium (oxide) and the substrate is
gold. Th,e measurements were made for 0, 3, 10,
and 75 A titanium films on evaporated and sputtered gold zubstrates. The thick sputtered gold
film (1500 A) was deposited on silicon and the
thick evaporated gold film (2500 A> was deposited on mica. Analysis of films on sputtered
gold/silicon substrates are useful for study of
microelectronics applications. Evaporated gold on
mica substrates form atomically flat surfaces and
are suited for characterization of adsorbates [201.
No photoelectrons were observed from either the
silicon or mica beneath the gold. The intensities
(Zi) of the titanium 2p and gold 4f XPS spectra
were determined by numerically integrating the
area of each photoemission peak using a linear
background function. The intensity ratios, R(8),
were calculated and plotted versu: the photoelectron take-off angle for 3 and 10 A titanium films
for both sputtered gold (sput. Au) substrates (figs.
2a and 2b) and for evaporated gold (evap. Au)
substrates (figs. 2c and 2d). The measured value
for thick titanium, ZTi, was obtained from the 75
A titanium sample and the value for ZiU was
obtained from the clean gold films.
The intensity ratio (R(0)) for the 3 A Ti/sput.
Au sample, Fig. 2a, decreases slightly with increasing take-off angle. The intensity ratio for the

10 A Ti/sput. Au, Fig. 2b, behaves similarly, but

the intensity of the XPS signal from the overcoat
layer is greater. At smaller angles, the patio, Z?(8),
again increases. Similarly for the 3 A Ti/evap.
Au data in Fig. 2c, R(B) is near 3 for small
take-off angles and 1 fcr larger take-off angles.
Lastly, R(8) for the 10 A Ti/evap. Au starts near
5 for small angles and decreases to about 2 for
large angles.
The layer-by-layer model, eq. (3), and the island model, eq. (61, were used to fit the data and
are also included in figs. 2a-2d. The adjustable
parameters for the models were layer thickness
0) for the layer-by-layer model and island height
(h) and fractional coverage (y) for the island
model. The electron inelastic mean free paths (A)
were calculated using the methods of Tokutaka et
al. [21], Seah and Dench [22], and Penn [23].
Average vatues of A,, = 22 A, hTi = 21 A, and
Ario, = 27 A were used in both models. These
values are similar to those previously reported for
gold and titanium [10,12,21,24,251.
The two models are easily distinguished at low
take-off angles, when the XPS analysis depth is
approximately equal to the film thickness. At low
angles, the exposed substrate in the island model
allows a significant gold signal to be observed,
whereas the layer-by-layer model does not. The
calculated values of R(8) for the two models are
plotted in Fig. 2. The islanding model very closely
fits the data when overcoat thicknesses of 10, 42,
12, and 20 A were used for figs. 2a-2d, respec-

210

K. W. Vogt et al. /Surface

tively. A possible source of the small deviations

from the islanding
model can be attributed
to
shading/ roughness effects ignored in the derivation of the models (see Appendix). At small takeoff angles (0 < lo), some shading effects may
have occurred making Zsuhstratesmaller (and R(B)
larger) than predicted.
At large take-off angles
(0 > SO>, the rough substrate
accented
ICwerlayer
resulting in a larger R(B) than predicted,
especially for the sputtered Au/silicon
substrate which
has a rougher surface than evaporated
Au/mica.
The island height (h) and fractional coverage (y)
yere 28 A and 47% forothe 3 A Ti/sput.
eu, 46
A and 94% for, the 10 A Ti/sput.
AU& 18 A and
74% for th: 3 A Ti/evap.
Au, and 30 A and 82%
for the 10 A Ti/evap.
Au. The values of overcoat

Science 301 (1994) 203-213

thickness,
island height and fractional
coverage
are high, but in semi-quantitative
agreement with
the quantity of titanium deposited, within experimental error. They are viewed as semi-quantitative because the model assumes a specific shape
which only approximates
the natural
variation.
When titanium
is oxidized to titanium
dioxide,
the volume of the film approximately
doubles and
the density decreases,
assuming
that the TiOz
formed is similar to bulk anatase. The deposition
rate of titanium was estimated to be 1 A/s based
on 500-5000 s depositions;
however, the actual
deposition
rate in the first seconds of sputtering
could not be measured.
Also, the error in the
deposition
time was + 1 s due to the sample
rotation
and shutter mechanisms.
However, the

Fig. 3. STM images of (A) clean gold/silicon

10 A titanium on gold/mica.

substrate,

(B) 10 A titanium

on gold/silicon,

(C) clean gold/mica

substrate,

and (D)

K. W. Vogi et al. /Surface Science 301 (I 994) 203-213

211

fact that all the approximations are high suggests

that this error is not important. The inelastic
mean free paths were also approximations which
may have been overestimated. This would result
in elevated predictions for island height. In any
case, the large ;esistivities observed for thicknesses below 30 A are due to incomplete titanium
coverage.

oxidation) of 10 A of titanium, 50-100 A diameter, and 20-30 A tall islands were easily identified, as shown in Fig. 3D. The valleys between
the islands appear to reach to (or nearly to) the
gold substrate. The height of the titanium islands
correspond well to the numerical values used in
the R(B) island growth model above.

4.4. Scanning tunneling microscopy (STM)

5. Summary

STM imaging of the Ti/Au samples was performed to investigate the fractional coverage and
size of the titanium/ titanium oxide islands. Images of the sputtered gold on silicon and evaporated gold on mica samples (with and without
titanium overcoats) were obtained. Fig. 3A, is a
1000 x 1000 nm STM image of clean, sputtered
gold on silicon. The surface was covered with
50-100 nm diameter hillocks. The three-dimensional data were analyzed statistically in order to
estimate the surface roughness. The height of the
islands was normally distributed with a mean of
3.4 nm and a variance of 2.1 nm.
A STM image of 10 A Ti/sput. Au is shown in
Fig. 3B. Compared to Fig. 3A, the surface no
longer has uniform mounds; instead, it is rough
with islands of material on the surface. The
heights of the islands are normally distributed
with a mean of 4.9 nm and a variance of 6.0 nm.
Thus, the titanium formed with an island-like
morphology. The mean height and distribution of
the surface topography significantly increased
over the values for the substrate. If the titanium
film had formed in a uniform, conformal layerby-layer fashion, the mean height and distribution
would not have changed.
Although the titanium/sput.
Au/silicon samples compare with adhesion layer films in microelectronics, atomic resolution images are complicated by the roughness of the gold on silicon.
Images of atomically flat, evaporated gold on
mica were taken to more closely examine the
morphology of the titanium deposition. Previously, this substrate has been used to obtain
atomic scale images of thin adsorbate films [22,27].
Fig. 3C shows atomically flat gold plateaus on
mica with a 3 A step. After deposition (and

The electrical resistance, XPS, and STM results all support the island growth formation of
titanium on gold, as illustrated in Fig. 4. This
model can be used to understand how the thin
titanium films function as adhesion layers on
gold. The titanium nucleates aad grows in islands, as evidenced by the 3 A titanium film,
which sparsely covers the surface with TiO, islands. The monolayer of titanium directly on the

Titanium
Deposition
3 A (0.1 mg/cm 3

114

nnn
Titanium
Deposition
IO A (0.5 mg/cm?

Titanium
Deposition
20-30 A (091.4 mg/cm

11

Titanium
Deposition
> 30 A (>1.4 mgkm2)

Fig. 4. Composition and morphology summary for the thin

titanium adhesion layers.

212

K. W. Vogt et al. /Surface

gold may be in the Ti2+ oxidation state. As the

growth proceeds, as in the case of the 10 A
titanium film, the individual islands grow closer
together. When-oxidized, the islands have a TiO
core (andgossibly Til and are covered with TiO,.
After 20 A of Ti deposition, the islands coalesce.
The core of the titanium is not completely oxidized, and the films resistivity doecreases. After
deposition and oxidization of 30 A of titanium, a
layered film forms with a titanium base and oxide
surface layer. The oxide growth is limited, most
likely by the diffusion of oxygen throughothe
oxide layer. The XPS depth profile of a 75 A Ti
film demonstrates that the film is layered with a
titanium core and a oxide surface layer.
These results suggest how the adhesion layer
functions. The metal core layer bonds to the gold
substrate. Even though only thin layers are used,
the adhesive layer in the monolayer closest to the
gold is adequate for bonding. Because the layers
are very thin, the electrical effects of TiO, are
negligible on the properties of the metals and
insulators. Although thin layers of an adhesive
material are adequate for adhesion, the ability of
titanium to diffuse out of gold and form a potential-sink oxide is essential. In contrast to this
behavior, very thin films of metals and metaloxides which prefer to reside within the substrate
(for example at grain boundaries) would not be
expected to serve well as long-term adhesion layers. Lastly, the titanium oxide and titanium metal
strongly adhere to each other because the titanium oxide is grown at low temperature [261.
Titanium oxide grown at high temperatures is
susceptible to cracking, flaking and oxide/ metal
separation.

6. Conclusion
On gold substrates (sputtered and evaporated
gold films), sputter-deposited titanium films grow
by an island growth (Volmer-Weber) meochanism.
The islands grow together after lo-20 A of titanium deposition. After oxidation of the titanium
films in air at low temperatures (T < lOoC>, very
thin titanium films (3 A> oxidize completely. For
thin titanium films (10 A>, a layered island-like

Science 301 (1994) 203-213

film forms where the islands have a suboxide core

and titanium dioxide surface layer. For thicker
titanium films (> 20 A), oxidation produces a
layered film with a titanium core layer and titanium oxide surface layer.

Appendix:

assumptions

in the layer growth model

Several assumptions were made in the derivation of these models. Their validity and effects on
results are discussed below:
(1) The surface of the substrate was smooth
and roughness effects were neglected. Baird et al.
[27] studied the effects of large scale roughness
(on the order of lo4 A>. In general, they found
that rough substrate surfaces accent the substrate
signal at low take-off angles and accent the overlayer signal at large take-off angles. However, the
effects of small scale roughness (on the order of
50 A> were not observed, even though some effects were expected based on the theoretical
derivations of Fadley [lo] and Wagner and Brummer [28]. Ebel and Wernisch [29] also studied the
effect of roughness using grooved surfaces and
found that the roughness depth can be at least
ten times the mean free path of the incident
X-rays before shading effects occur. Thirdly,
Fadley [l 11 and Kim and Hummel 1301have studied gold films and suggested that they can be
considered as flat films.
(2) X-ray diffraction of the incident beam was
neglected. This is a good assumption for amorphous and polycrystalline materials.
(3) The incident X-ray flux was uniform. Any
non-uniform X-ray flux was determined experimentally by measuring Z~~~_,aver
and Zghstrate.Thus
the effect of any non-uniform flux cancels.
(4) Refraction and reflection of X-rays at the
surface were neglected. This assumption is valid
for incident angles greater than the critical angles
determined by Fadley [ll]. Typically, this angle is
2 for gold surfaces.
(5) The electrons were attenuated exponentially along their path length. This is a fair assumption in the XPS kinetic energy range. Recently, several researchers have found deviations

K. UC Vogt et al. /Surface

where the attenuation length is not only a function of the material but is also a function of
elastic scattering [31,32,331.
(6) Because the X-ray attenuation
lengths
(1000-10000 A> were much greater than electron
attenuation lengths (10-100 A>, X-ray attenuation was neglected.
(7) The electron path length was independent
of the depth of origin and angle of escape. Thus,
the path length was only a function of electron
energy and the material in which it was traveling.
(8) Electron refraction and reflection at the
surface were negligible. Fadley [ill has shown
that these effects occur mostly for take-off angles
less than lo. Also, the effect was minimized by
taking the ratio (loverlayer/l~erlayer)/ (Lbstrate/
Isubstrate I .
(9) The effects of elastic electron scattering on
angular distributions was neglected. Nefedov et
al. [34] investigated the effects of elastic scattering and only found small changes in the take-off
angle and mean free path, hi.
(10) The effect of diffraction of the emitted
electrons was neglected. The approximation is
valid for amorphous and polycrystalline samples.
(11) The attenuation
effect of adventitious
carbon was neglected. Baird et al. [27] found that
this assumption was a valid first approximation
when the ratio of the substrate and overlayer
intensities was used. Yabe and Yamashina [35]
experimentally determined the attenuation effect
of surface carbon contamination on the XPS signal and found that it was less than 2.5%.

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