Applied Surface Science 250 (2005) 252–267

www.elsevier.com/locate/apsusc

Surface structure and composition of flat titanium thin films

as a function of film thickness and evaporation rate
Kaiyong Cai a, Michael Müller a, Jörg Bossert a,
Annett Rechtenbach b, Klaus D. Jandt a,*
a
Institute of Materials Science and Technology, Friedrich-Schiller-Universität Jena, Löbdergraben 32, Jena 07743, Germany
b
Department for Materials Technology, University of Applied Sciences Jena, Carl-Zeiss-Promenade 2, Jena 07745, Germany
Received 28 September 2004; received in revised form 5 January 2005; accepted 6 January 2005
Available online 16 February 2005

Abstract

To correlate flat titanium film surface properties with deposition parameters, titanium flat thin films were systematically
deposited on glass substrates with various thicknesses and evaporation rates by electron-beam evaporation. The chemical
compositions, crystal structure, surface topographies as well as wettability were investigated by using X-ray photoelectron
spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM) and water contact angle measurement,
respectively. The films consisted mainly of TiO2. Small percentages of Ti2O3 and metallic Ti were also found at the film
surface using high-resolution XPS analysis. Quantitative XPS showed little differences regarding elemental compositions
among different groups of films. The films were obtained by varying the deposition rate and the film thickness, respectively.
XRD data showed consistent reflection patterns of the different titanium samples deposited using different film thicknesses.
Without exception measurements of all samples exhibited contact angles of 808
58. Quantitative AFM characterization
demonstrated good correlation tendency between surface roughness and film thickness or evaporation rate, respectively. It is
important to notice that titanium films with different sizes of grains on their surfaces but having the same chemistry and film bulk
structure can be obtained in a controllable way. By increasing the film thickness and evaporation rate, the surface roughness
increased. The surface morphology and grain size growth displayed a corresponding trend. Therefore, the control of these
parameters allows us to prepare titanium films with desired surface properties in a controllable and reproducible way for further
biological investigations of these materials.
# 2005 Elsevier B.V. All rights reserved.

PACS: 81.15; 68.35.B; 61.16.C; 79.60

Keywords: Titanium thin film; Surface characterization; XPS; AFM; XRD; Contact angle; Nanostructure

1. Introduction
* Corresponding author. Tel.: +49 3641 947730;
fax: +49 3641 947732. Titanium is a successful biocompatible material.
E-mail address: k.jandt@uni-jena.de (K.D. Jandt). It has been extensively used in dental, orthopedic

0169-4332/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2005.01.013
 K. Cai et al. / Applied Surface Science 250 (2005) 252–267
and cardiovascular fields for manufacturing bone-
anchoring devices, such as dental implants or hip-joint
replacement devices as well as heart-valves and
cardiac pacemakers [1,2]. For example, commercially
pure titanium (cp Ti) has been successfully used in
dental prosthetic applications [3,4]. Its bulk and surface
properties have advantages compared with other metals
used in implants: in particular, a relatively low modulus
of elasticity, a high strength and fatigue-resistance,
excellent resistance to corrosion and superior biological
performance.
Although titanium implants have been successfully
used in clinical applications, the mechanism of how
adsorbed proteins and host tissue interact with the
titanium surface on a micro/nano scale still needs to be
further investigated. With the advent of atomic force
microscopy (AFM), direct observation of individual
protein molecules with nanometer resolution has been
achieved [5–9] on biomaterials. Due to the size of a
single protein molecule of a few 10 nm, AFM can only
be performed to image proteins on relatively smooth
surfaces in order to resolve the molecular protein
conformation. To this end, relatively flat model
surfaces are required for these investigations. Flat
titanium films can be prepared via several techniques,
such as sputtering [10–12], chemical vapor deposition
[13], template stripping [8] as well as anodic growth
method [14]. In this study, the flat titanium thin films
were prepared by the electron-beam evaporation
method.
The biological performance of implants strongly
depends on the first interaction occurring when
implant surfaces come into contact with a biological
environment [15]. Surface modification is a usual
way to control such interaction by modifying the
surface properties, such as the chemistry, surface
charge and the topography of the material surface.
Flat titanium films are good substrates to create
a nanostructure to investigate the effects of topo-
graphy on protein adsorption at the nanometre
scale. Galli et al. [16,17] created nanostructural
titanium surfaces with sizes comparable to protein
dimensions by local anodic oxidation using atomic
force microscopy without changing its chemical
composition, and then investigated protein adsorption
behaviours.
It is well known that surface physical properties have
great influence on the protein adsorption behaviour
253
including the adsorbed amount and conformation
[18–20]. Therefore, it is important to investigate the
chemical compositions and structures of the titanium
thin films. XPS was performed in this study to
determine the surface chemical composition, the
oxidation state of titanium in its oxide layers and the
elemental distribution as functions of depth. AFM
can be used to measure large areas ranging from
approximately 1 nm  1 nm to 250 mm  250 mm
simultaneously quantifying and statistically analysing
topographic features ranging in height from 0.1 nm to
10 mm [21].
The aim of the present study is to investigate the
surface properties (chemical composition, surface
topography as well as microstructure) as functions of
film thickness and evaporation rate. The aim is to
develop a correlation between the surface properties
and the parameters of the film deposition. This will be
useful for investigations of the potential correlation of
the surface properties and the biological reactions
(protein adsorption and cell growth) in the near future.
The production and characterization of the flat Ti
films will be of future importance in the preparation of
self-assembled monolayers using titanium rather than
gold substrates.
2. Materials and methods
2.1. Sample preparation
Titanium was purchased from Mateck-Material-
Technologie & Kristalle GmbH, Germany, with purity
of 99.99%. BOROFLOAT1 B33 glass slides were
purchased from Jena 4 H Engineering GmbH, Jena,
Germany. Titanium thin films were evaporated on
freshly cleaned glass slides by electron-beam eva-
porator (Univex 350, Leybold, Germany) with various
evaporation rates and film thicknesses (see Table 1) at
a vacuum of 8  106 mbar. Film thickness was
monitored by a quartz balance installed inside the
evaporation chamber, which was adjusted to an
accuracy of
5 nm. The evaporation rate was kept
constant and controlled by a deposition monitor with an
error range of 0.01 nm/s. The glass was cleaned with a
seven steps procedure. Briefly, glass substrates were
immersed in 1% (v/v) Blanchipon (Hans Rosemann,
Berlin) solution for 5 min; rinsed three times with
254 K. Cai et al. / Applied Surface Science 250 (2005) 252–267

Table 1
Quantitative XPS surface composition of the titanium films prepared using different deposition parameters (n = 4, mean
S.D.)
Group Evaporation rate (nm/s) Thickness (nm) Composition
Ti (at.%) O (at.%) C (at.%)
1 0.05 100 35.0
1.2 51.9
2.3 13.1
1.9
2 0.1 100 35.8
2.2 49.4
2.4 14.8
2.3
3 0.5 100 33.3
1.7 50.4
2.8 16.4
2.9
4 0.05 200 30.4
0.6 52.5
2.5 17.1
2.8
5 0.1 200 33.0
1.1 53.6
2.2 13.4
1.5
6 0.5 200 32.0
1.1 54.1
3.0 14.0
2.4
7 0.05 500 31.1
1.7 50.2
2.5 18.7
2.9
8 0.1 500 30.6
0.8 51.7
1.7 17.7
2.1
9 0.5 500 31.9
1.2 54.8
3.0 13.3
3.2

distilled water; then the samples were transferred to 5%
(v/v) Optical II (Mineralöle Albert, Jena) and washed
3 min in an ultrasonic bath. Subsequently, the samples
were immersed into high purity ethanol and distilled
water for 10 min, respectively; followed by immersing
samples in 35–36% (v/v) HNO3 for another 30 s; then
these cleaned samples were intensively washed with
double distilled water and stored until use. Glass
substrates were dried with nitrogen immediately before
being mounted for film deposition.
2.2. XPS
For chemical composition analysis, specimens
were characterized using XPS (Quantum 2000, PHI
Co., Chanhassen, MN, USA) with a focused mono-
chromatic Al Ka source (1486.6 eV) for excitation
and a 100-mm diameter beam. The electron take-off
angle was 458 and the analyser was operated in the
constant energy mode for all measurements. XPS
survey spectra over a binding energy range of 0–
1000 eV were acquired using analyzer pass energy of
58.7 eV and 23.5 eV for high-resolution elemental
scan. Argon ion sputtering was performed during
XPS to estimate the thickness and structure of the
surface layers. The vacuum pressure was around
7.5  108 mbar during spectral acquisition. Spectra
were peak fitted after background subtraction by
assuming a Gauss/Lorentz (90–70/10–30) peak shape
except for the asymmetric metallic Ti peak. Data
analysis was carried out with Multipak software
provided by the manufacturer. The hydrocarbon peak
maximum in the C 1s spectra was set as 284.8 eV to
reference the binding energy scales for the samples.
Intensity ratios were converted into atomic concen-
tration ratios by using the sensitivity factors proposed
by the manufacturer. For quantitative chemical
composition analysis, four samples in each group
were acquired and the survey scans were performed in
two different areas on each sample.
2.3. XRD
A Siemens D5000 (Brucker AXS GmbH, Karls-
ruhe, Germany) diffractometer was employed to
determine the structures of titanium films in this
study. The diffractometer was operated in the u–2u
arrangement, where u is the angle between the incident
X-ray and sample surface normal and the diffraction
angle; 2u, is the angle between the incoming X-ray
beam and the diffracted beam. XRD measurements
were carried out with a detector scan mode using Cu
Ka radiation. The incident angle was 18 and the
effective penetration depth of the X-ray beam was
approximately 430 nm. Large-angle range survey
spectra with 2u value ranging from 228 to 858 were
recorded with step of 0.0158 and a step time of
10 s/point. Diffrac-AT software was used to process
the results and subsequently compare them to the
Powder Diffraction FileTM release 2002 (PDF-2)
database.
2.4. Contact angle
The contact angle with respect to double-distilled
water was measured with a DSA 10 drop shape
analysis system (Krüss GmbH, Hamburg, Germany).
The images were recorded by a camera, and then
 K. Cai et al. / Applied Surface Science 250 (2005) 252–267
analyzed using the software supplied by the manu-
facturer. Four samples were measured in each group.
Three different points were measured for each sample.
Every drop was deposited to the sample surface and
after 15, an image of the drop was captured and then
analyzed. All measurements were performed at
ambient temperature.
2.5. AFM
The AFM characterization was performed using a
Dimension 3100 AFM (Digital Instruments, Veeco,
CA) in tapping mode at ambient temperature. The
topographic and phase images were recorded simul-
taneously with a standard silicon tip on a cantilever
beam. The spring constant of the cantilever was
between 20 and 100 N/m and the length was 125 mm.
Root mean square (RMS) surface roughness value was
determined on an area of 50 mm  50 mm per sample.
RMS data were used for quantitative analysis.
Roughness parameters RMS were calculated using
the roughness analysis software provided by the
manufacturer of the instrument.
3. Results and discussion
3.1. XPS characterization
XPS is a sensitive surface analysis technique,
which is capable of providing both qualitative and
quantitative information about the presence of
different elements at the surface. Table 1 lists the
surface chemical compositions of the titanium films
deposited with different evaporation rates and film
thicknesses. In addition to the expected titanium and
oxygen, which were present in the titanium dioxide,
carbon was also observed on all samples. The presence
of carbon originated from surface contamination since
the samples were exposed to air after e-beam
processing. Small differences in chemical composi-
tion on Ti, O or C were observed among different
groups. This indicates that deposition parameters in
this study have relatively little influence on the
chemical composition of these films.
The original high-resolution XPS-spectrum of the
Ti 2p peak (Fig. 1a) shows three peaks. After peak-
fitting treatment, the dominant doublet peaks in the
255
spectrum were attributed to TiO2, corresponding with
Ti 2p3/2 at a binding energy (BE) of 458.0 eV and Ti
2p1/2 at BE of 463.6 eV, being a typical value for TiO2
[22–24]. The binding energy difference of 5.6 eV
between these two peaks for TiO2 correlated well with
previous studies (DBE from 5.5 eV to 5.8 eV) [24,25–
27]. The lowest energy peak was assigned to metallic
Ti with an observed BE for the Ti 2p3/2 of 453.1 eV. In
addition, Ti3+ (Ti 2p3/2 at BE of 456.3 eV) from
substoichiometric oxide, Ti2O3, was present, as also
reported in previous XPS studies [25,27,28].
The O 1s peak (Fig. 1b) shows three components:
the first, at 531.0 eV, was attributed to the titanium
oxide; the second peak at 532.3 eV was fitted and
assigned to hydroxide and hydroxyl species; the third
oxygen peak at BE of 533.2 eV was associated with
surface contamination, usually water and carbonates
[22,24,25].
XPS survey spectrum demonstrates the carbon
contamination on the titanium surface, which is
typical for adventitious, unavoidable hydrocarbon
contamination, adsorbing spontaneously from ambi-
ent air onto the surface [29–31]. From the high-
resolution spectrum of C 1s (Fig. 1c), three peaks were
fitted and assigned as follows: the main carbon peak at
284.8 eV was assigned to hydrocarbon species (C–H);
the other two fitted peaks attributed to C–O (i.e.
alcohol) species at 286.1 eVand C O (i.e. carbonates)
species at 288.5 eV, respectively.
Argon ion etching XPS depth profiles perpendi-
cular to the sample surfaces show a carbon
contamination overlayer on the surface. This carbon
contaminant was removed after the first several
etching cycles (Fig. 2). About 45 at.% oxygen was
present on the film surface, which came from the
native oxide layer on the titanium film. The oxygen
concentration decreased dramatically after the initial
etching cycles. At greater depth of about 8–10 nm,
titanium and oxygen concentrations remained almost
constant at about 95 at.% and 5 at.%, respectively,
until the silicon substrate interface was reached. As for
the remaining oxygen (approximately 5 at.%) inside
the titanium film, there were three factors that might
contribute to this. The first was the environmental
oxygen presenting in the chamber used for titanium
sample preparation. Titanium is highly reactive with
oxygen. During titanium deposition, titanium atoms
evaporated from the titanium source may have reacted
256 K. Cai et al. / Applied Surface Science 250 (2005) 252–267

Fig. 1. Typical high-resolution XPS-spectra of titanium sample binding state: (a) Ti 2P; (b) O 1s; and (c) C 1s (film thickness: 100 nm;
evaporation rate: 0.1 nm/s).

with oxygen atoms in the chamber and titanium–
oxygen compounds may have been captured within
the titanium films. Since the vacuum was around
8  106 mbar, it is not surprising to find some oxygen
in the chamber. The second factor was the margin error
associated with XPS quantitative analysis, which is
about
5–10% of the measured value [32]. The third
factor might be related to the well-known ‘‘knock-on’’
effect [33] of ion etching, pushing the surface oxygen
atoms deeper into the film at the initial sputtering stage.
Simultaneously with the reduction in titanium con-
centration, the oxygen level rose and a silicon signal
appeared in the spectrum when the titanium–glass
substrate interface reached. It was important to note
that the carbon concentration dropped dramatically
from ca. 11 at.% down to zero at the initial etching
cycles.
3.2. XRD
Fig. 3 shows the XRD patterns of titanium films
deposited at a fixed evaporation rate of 0.5 nm/s, but
with different film thicknesses of 100 nm, 200 nm and
500 nm, respectively. It displayed the (0 0 2), (1 0 2)
and (1 0 3) reflection peak around 2u = 388, 538, and
70.68, respectively, which were characteristic peaks of
a-titanium [31,32]. The crystal structure of titanium is
hexagonal with a0 = 0.295 nm and c0 = 0.4686 nm
 K. Cai et al. / Applied Surface Science 250 (2005) 252–267
Fig. 2. XPS depth profile of titanium sample surface (film thickness:
100 nm; evaporation rate: 0.1 nm/s).
Fig. 3. XRD patterns of the titanium films (fixed evaporation
rate = 0.5 nm/s) as a function of film thicknesses: (a) 500 nm; (b)
200 nm; and (c) 100 nm.
257
[34]. The (1 0 3) peak is the typical reflection in
hexagonal a-titanium. No evidence for TiO2, a
common titanium oxide on the surface of titanium
was found in the XRD data. The native TiO2 layer is
typically about 5 nm [27], which was too thin to yield
sufficient signals detectable by XRD technique used in
this study.
The distinct XRD peaks mentioned above were
only found on samples with a film thickness of 200 nm
and 500 nm, respectively. A small peak contributed to
(0 0 2) and no peak attributed to (1 0 2) reflections
were observed on the titanium film with a thickness of
100 nm. The main reason is that the titanium sample
with a film thickness of 100 nm did not yield sufficient
XRD signals to identify these peaks. However, (1 0 3)
reflection pattern was clearly identified in all titanium
films with different film thicknesses. Different relative
change behaviours of reflection patterns [(0 0 2),
(1 0 2) and (1 0 3)] indicated the texture existed in
titanium films presented in this study.
3.3. Contact angle measurement
Fig. 4 shows the contact angle data determined
using double-distilled water of titanium films prepared
with various film thicknesses and evaporation rates.
Within the margin of error there was no difference
of contact angle except for the titanium sample,
which was deposited with parameters of 500 nm film
thickness and evaporation rate of 0.5 nm/s. It had the
Fig. 4. The contact angles of titanium films prepared using different
evaporation rates and film thicknesses (n = 4, mean
S.D.).
258 K. Cai et al. / Applied Surface Science 250 (2005) 252–267
lowest contact angle (77.38
2.48) among all
titanium samples.
Contact angle measurements are important to
characterize the wetting proprieties of biomedical
materials. Previous studies [35,36] revealed that the
hydrophilic and/or hydrophobic properties, which
were determined by contact angle measurements, of
biomaterials are probably closely related to protein
adsorption behaviour of the biomaterials. The contact
angle of a material was determined by the surface
chemistry (elements and functional groups) and
surface roughness of the material surface [37,38]. It
has been reported that totally hydrophobic materials
can be converted to hydrophilic ones just by rough-
ening their surface morphologies [39]. In the present
study, XPS characterization was performed on the
titanium films deposited with different parameters
(film thickness and evaporation rate). Within the
margin of error of the XPS measurements, the samples
showed small differences in the chemical composition
of the film surfaces. Differences in contact angle, if
any, may therefore originate from differences in
surface roughness of the sample.
The wetting behaviour of a surface is mainly
determined by intrinsic factors of its surface chemistry
and extrinsic factors of surface roughness. The
hydrophobicity and wetting behaviour of a liquid on
a solid surface depends on the balance of forces at the
contact line arsing from the three interfacial tensions,
gSL, gSV and gLV, occurring at the solid–liquid, solid–
vapor, and liquid–vapor interfaces, respectively.
The relationship of the forces, respectively, surface/
interfacial tensions at the three phase points can be
described by Young’s equation:
g SV  g SL
cos use ¼ (1)
g LV
where use is the equilibrium contact angle. Another
view of balance forces is to consider the interfacial
tensions as surface energies per unit area of the inter-
face. In this approach, the effect of increasing the area
covered by contact line by a small amount, DA, is to
replace the solid–vapor interface by a solid–liquid
interface, thus changing the surface free energy by
(gSL  gSV)DA. In addition, the movement of the
liquid creates additional liquid surface area of
DA cos u, resulting in a surface free energy increase
of gLV DA cos u [40]. If the surface free energy is to be
at a minimum, then the overall change of surface free
energy must vanish and this gives Young’s law for the
equilibrium contact angle (Eq. (1)). Roughness of
surface modifies this argument because the rough
surface has a larger area f DA than horizontal projec-
tion of the area [39], where f is the roughness factor
and is greater than 1. Where perfect smoothness is an
acceptable assumption, as at liquid–liquid or liquid–
gas interfaces, actual surface and geometric surface
are identical, but at the surface of any real solid the
actual surface will be greater than the geometric sur-
face because of surface roughness. The surface ratio
here will be termed the ‘‘roughness factor’’, and
designed by f [41]:
actual surface
f ¼ roughness factor ¼ (2)
geometric surface
While the surface roughness alters the surface free
energy at the solid interface, it does not change the
liquid–vapor contribution.
The overall effect of topography is to result in an
equilibrium contact angle on a rough surface, ure , given
by Wenzel’s equation [41]:
cos ure ¼ f cos se (3)
Wenzel’s equation can be used to predict the influence
of roughness on the contact angle. If the contact angle
on a smooth surface is lower than 908, roughness
(rougher surface) will reduce the observed contact
angle, but if it is higher than 908, roughness will
further increase the observed contact angle. The flat
titanium thin films presented contact angles around
808 in the present study, lower than 908. Thus, it was
not surprising to find that the roughest titanium film
(confirmed by AFM measurement) was having the
lowest contact angle of 77.38
2.48. However, since
the surface roughness difference among various tita-
nium films was not so much, much difference could
not be expected among different groups.
However, the data showed that high film thickness
and high evaporation rate had little influence on the
contact angles of titanium films. The contact angle
values in the present study (around 808) were higher
than those of previous studies [42–44]. The major
reason for this was the larger surface roughness of
samples used in those studies. Since the differences in
contact angles between the samples in this study were
 K. Cai et al. / Applied Surface Science 250 (2005) 252–267
relatively small, major differences in surface rough-
ness between the samples were not expected. To
confirm this, AFM measurements of the titanium
samples were carried out.
3.4. AFM characterization
While XPS allows an overview of surface
chemistry as well as element distribution along depth
of titanium films prepared with different parameters
(film thickness and evaporation rate) on a comparable
big area, AFM has its strength on a microscopic view
of titanium surface on a qualitative and quantitative
basis. Surface morphology, morphological evolution
and grain growth behaviours of titanium films were
resolved in the present study.
The surface morphologies of bare glass substrate
and the titanium thin films had been investigated in
this study with AFM. Fig. 5 presents bare glass
substrate and a representative group of titanium film
surface morphologies as a function of evaporation rate
with the fixed film thickness of 200 nm. The studied
surfaces are equal to 1 mm  1 mm in area.
Bare glass substrate displayed quite smooth
surface morphology with little defects compared with
those of titanium films. Its RMS roughness was
0.8 nm
0.2 nm in a 50 mm  50 mm measuring area.
Samples deposited with the lowest evaporation rate of
0.05 nm/s (Fig. 5a), showed small spherical grains with
an average diameter of 29.3 nm
2.9 nm (n = 50),
more or less coalescent and easily distinguishable,
forming a relatively smooth surface. At a higher
evaporation rate of 0.1 nm/s, the increased diameter
(38.4 nm
4.3 nm; n = 50) of spherical grains lead to a
slightly rougher surface morphology (Fig. 6b). Increas-
ing the evaporation rate to 0.5 nm/s (Fig. 5c), the strong
coalescence of neighbouring grains resulted in larger
grains with an average diameter of 64.1 nm
7.3 nm
(n = 50) and rough surface morphology. The RMS
surface roughness measured over 50 mm  50 mm
area correspondingly increased from 2.2 nm
0.2 nm
nm (0.05 nm/s), to 2.6 nm
0.2 nm (0.1 nm/s) and
4.9 nm
0.2 nm (0.5 nm/s). This indicated that the
evaporation rate had a distinct effect on the surface
morphology.
Fig. 6 shows the evolution of surface morphology
accompanying line profiles of titanium films as a
function of film thicknesses and evaporation rates. In
259
the present study, the effects of film thickness and
evaporation rate on surface roughness were investi-
gated in a matrix (3  3) mode, i.e. using three
different film thicknesses and three various evapora-
tion rates. All surfaces exhibited grain features.
Fig. 6a–c, d–f and g–i showed the influence of film
thickness in each group on film surface morphology at
fixed evaporation rates of 0.05 nm/s, 0.1 nm/s and
0.5 nm/s, respectively. The morphology was relatively
uniform for films with 100 nm film thickness as shown
in Fig. 6a, d and g compared to films with thicknesses
of 200 nm and 500 nm (where some larger grains can
be seen) in each group. The results suggested that
surface morphology evolutions of these films were
dependent on their film thickness. This finding is in
agreement with the results from a previous study [32].
With increasing film thickness, some small voids were
present and enlarge.
As shown in Fig. 6, the line profiles of titanium
films displayed a trend: with increasing film thickness
and/or evaporation rate, the surface became rougher.
The line profiles of titanium films provided information
about the surface roughness along the lines at the
section. To obtain more information about the mean
grain size, particle analysis was performed in this study.
Fig. 7 shows mean grain sizes (n = 4, at least 50
measurements were performed) of titanium film
surfaces prepared with various film thicknesses and
evaporation rates. The grains varied in a broad range
from 16 nm to 108 nm depending on their deposition
parameters. It is interesting to note that in the present
study titanium films with different sizes of grains at
their surfaces but having the same chemistry and film
bulk structure can be obtained in a controllable way.
With increasing film thickness and evaporation rate,
the mean diameters of grains increased (see Fig. 7). It
was well known that both surface chemistry [45–47]
and surface topography [48–50] would affect protein
adsorption and cell adhesion behaviours. Since most
topographical variations were accompanied with
chemical heterogeneities [51], dividing topographical
from chemical effects was quite difficult in most cases.
The titanium films in the present study may be
regarded as a potentially important model surface for
such kinds of investigations, especially on a nano-
scopic scale. Galli et al. [16] demonstrated that
proteins could ‘‘sense’’ the topography of surfaces at
the nanometer scale.
260 K. Cai et al. / Applied Surface Science 250 (2005) 252–267

Fig. 5. AFM images of the glass substrate and titanium films (thickness = 200 nm) deposited with different evaporation rates: (a) substrate; (b)
0.05 nm/s; (c) 0.1 nm/s; and (d) 0.5 nm/s.

Fig. 8 shows quantitative AFM data of titanium
film RMS surface roughness measured in 50 mm 
50 mm areas as functions of evaporation rate and film
thickness, respectively. In three groups with different
fixed evaporation rates (Fig. 8a), a similar effect
of film thickness on film surface roughness in
each group was observed: with increasing film
thickness surface roughness increased. It showed
good correlation with the variations of grain sizes for
titanium films as shown Fig. 7. This result reflected
that the grain size variations caused the surface
roughness change on titanium films prepared with
 K. Cai et al. / Applied Surface Science 250 (2005) 252–267 261

Fig. 6. AFM images (1 mm  1 mm) and accompanying line profiles of titanium films deposited with different evaporation rates and film
thicknesses (z-axis range: 30 nm). (a) Evaporation rate: 0.05 nm/s; film thickness: 100 nm; (b) evaporation rate: 0.05 nm/s; film thickness:
200 nm; (c) evaporation rate: 0.05 nm/s; film thickness: 500 nm; (d) evaporation rate: 0.1 nm/s; film thickness: 100 nm; (e) evaporation rate:
0.1 nm/s; film thickness: 200 nm; (f) evaporation rate: 0.1 nm/s; film thickness: 500 nm; (g) evaporation rate: 0.5 nm/s; film thickness: 100 nm;
(h) evaporation rate: 0.5 nm/s; film thickness: 200 nm; (i) evaporation rate: 0.5 nm/s; film thickness: 500 nm.
262 K. Cai et al. / Applied Surface Science 250 (2005) 252–267

Fig. 6. (Continued ).

different parameters (film thickness and evaporation when the evaporation rate was increased in each
rate). Fig. 8b shows the influence of the evaporation group.
rate on surface roughness when the film thickness Upon coalescence of the surface nuclei to form a
is fixed. It showed an increased surface roughness continuous film, the nucleation process of film
 K. Cai et al. / Applied Surface Science 250 (2005) 252–267 263

Fig. 6. (Continued ).

deposition is complete, and the step for development the ratio of the substrate temperature Ts to the melting
of bulk film structure starts. The film structure depends point of the film Tm, Th = Ts/Tm (in K), known as
among other factors on the amount of thermal motion ‘‘homogeneous’’ or ‘‘reduced’’ temperature (Th).
taking place during film formation, which scales with Three so-called structural zones (Z1, Z2 and Z3)
264 K. Cai et al. / Applied Surface Science 250 (2005) 252–267

Fig. 7. Mean grain sizes of titanium films prepared using different

evaporation rates and film thicknesses.

plus a transition zone were identified in the

evaporative deposition study that included both metals
and ceramics [52], and those zones have been
observed in a wide variety of film materials deposited
by all of the vapor-phase processes. In the first zone
(Z1), which is occurring at Ts/Tm < 0.3, the grain
growth is controlled by the low atom mobility and the
grain size increases with the growth temperature. The
second zone (Z2), which occurs at Ts/Tm > 0.3,
displays crystallites formed by higher surface mobi-
lity. The crystallite size increases with increasing
growth temperature. A transition to Z3 occurs in
certain instances at Ts/Tm > 0.5, which is high enough
Fig. 8. The relationship between surface roughness and (a) film
for considerable bulk annealing of the film to take
thickness; (b) evaporation rate of samples used in this study (n = 4,
place during deposition. Z3 is characterized by more mean
S.D.).
isotropic or equiaxial structure, and again, the grain
size increases with growth temperature. The zone ZT (evaporation rate is 0.5 nm/s) increased from 100 nm
is found between Z1 and Z2 where small grains are not to 200 nm and 500 nm, some small voids were present
well defined which is usually associated with energy- and enlarge. Their RMS surface roughnesses corre-
enhanced processes. It is clear that the temperature is spondingly increased from 3.5
0.3 nm, to 4.9

the main determinant of film structure. 0.2 nm and 6.7
0.2 nm, which were consistent with
In the present study, titanium films were deposited the previous research results from Messier and Yehoda
at room temperature (around 22 8C). The melting [54]. The temperature was not kept constant during
point for titanium is 1660 8C. Thus, the ratio of Ts/Tm film deposition in this study. It changed little in the
(0.153) was so low that surface diffusion was chamber during the e-beam evaporation process.
negligible, belonging to Z1 structure [53]. Z1 consists However, according to the zone model mentioned
of columns typically tens of nm in diameter separated above, slight temperature changes, even several ten
by voids of a few nm across. These characteristics can centigrades, will not lead to transition from one zone
be seen in Fig. 6i in this study. In Z1 growth, voids are to another. Since in the present study the homogeneous
a key feature to considerably increase the rate of temperature (Th) was only 0.153, no change in zone
roughening. As shown in Fig. 7, when film thickness transition is expected. It also means slight temperature
 K. Cai et al. / Applied Surface Science 250 (2005) 252–267
changes will not result in changes of titanium film
structure and topography.
A Z1 structure generally consists of columns
having poor crystallinity (many defects) or is
amorphous. In thicker films, there are some wider
voids between the columns expected [53]. Our result,
as shown in Fig. 6i clearly demonstrated the void
formation (see arrows) as a function of film thickness.
The cones terminate in domes at the surface, and the
size of the domes increases with film thickness [53].
Concerning the observation regarding grain size
growth as function of film thickness (Fig. 7), our
results also presented a strong analogy with the zone
model as mentioned above. A previous study revealed
the microstructure of titanium films via transmission
electron microscopy (TEM). Those titanium films
were prepared using the electron-beam evaporation
method at ambient temperature, which was the same
condition as the present study. TEM results showed a
columnar structure within the titanium films [55].
It is well known that most metal adatoms are highly
mobile at room temperature. The immobility of the
surfaces results from the fact that the detachment of
metal surface atoms from steps and kinks is kinetically
hindered at these temperatures [56]. It is well known
that when the depositing titanium atoms reach the
substrate surface, two destabilizing factors, namely
statistical roughening and self-shadowing are always
at work. These two factors will affect the micro-
structure and morphology development of the films.
Statistical roughening arises from the statistical
fluctuation in the vapor arrival flux. A model has
been developed to describe this phenomenon [53],
which demonstrated that the roughness would be
increased as the film thickness increases. Wang and
Zhang [55] confirmed that surface roughness of films
increased with layer thickness. The results of the
present study were consistent with those findings as
shown in Fig. 7a.
Self-shadowing is the second factor that destabi-
lizes surface smoothness during film deposition, and it
is the cause of the characteristic voided columnar
structure. It has been suggested [53] that depositing
atoms generally can not perch on top of each other, but
rather settle sideways into the nearest ‘‘cradle’’
position in which they establish relaxed bond lengths
to their nearest neighbours. This is known as ‘‘ballistic
aggregation’’, leading to a rough surface with well-
265
known columnar growth structure [55]. When the
depositing atoms obliquely reaching the substrate
surface, self-shadowing increases and results in an
increased formation of Z1 structure. As an example in
this study, one group with fixed 500 nm film thickness
but with various evaporation rates was chosen to
investigate how evaporation rate affected its film
topography. With the lowest evaporation rate of
0.05 nm/s (Fig. 6g), the coalescence of free titanium
atoms is not so strong on the surface, forming a
smoother surface with a homogenous sphere structure.
An increased evaporation rate leads to higher vapor
pressure, thus a higher concentration of titanium
atoms. In this case, the nucleation and fast grain
growth dominated the surface diffusion of titanium
atoms, excessive grain growth then occurred, resulting
in the development of a coarse grain sized morphology
(Fig. 6i). Thus, a higher surface roughness could be
expected.
4. Conclusions
Flat thin titanium films were prepared by electron-
beam evaporation on a borofloat glass substrate. The
surface properties (chemical composition, surface
roughness and hydrophobicity/hydrophilicity) as
functions of film thickness and evaporation rate were
investigated.
Qualitative and quantitative XPS characterizations
were performed on titanium films deposited by
different parameters. Depth profile XPS displayed
the distribution trend for Ti, O as well as C along the
film layer. Carbon contaminant was found only
located on the top layer of titanium films. Quantitative
XPS data showed that there was no difference of their
chemical composition within error range of XPS
measurements among groups with different deposition
parameters.
XRD results showed that there was no difference in
crystal structure among different titanium films except
for the 100 nm film. The intensity difference among
different samples results from the XRD signals from
various titanium films with different film thickness.
Contact angle data showed that there were little
differences among samples deposited with different
parameters. Since there were small differences in the
chemical composition, any differences in the contact
266 K. Cai et al. / Applied Surface Science 250 (2005) 252–267
angle should relate to variance in their surface
roughness.
AFM images showed the relationship between
surface morphology and deposition parameters.
Quantitative AFM analysis showed a linear relation
trend between surface roughness and evaporation rate.
As film thickness increased, the film roughness
increased although no strict linear correlation existed.
The grain growth within the film layer depended on
the film deposition conditions. The films consisted of
larger grains correlated with a higher RMS roughness.
Acknowledgements
We gratefully acknowledge the financial support
from the Thüringer Ministerium für Wissenschaft,
Forschung und Kunst (TMWFK) through the Projekt
‘‘Thüringer Schwerpunkt Grenzflächentechnologien’’
(B478-02001) and the partial financial support of the
BMBF for this work within the project ‘‘Innovations
und Gründerlabor für neue Werkstoffe (Biomateria-
lien) und Verfahren (IGWV) an der Friedrich-Schiller-
Universität Jena’’ Förderkennzeichen: 03GL0026.
References
[1] S.A. Brown, J.E. Lemons, Medical Applications of Titanium
and its alloys: The Material and Biological Issues, American
Society for Testing and Materials, Philadelphia, PA, 1996, pp.
3–18.
[2] M. Long, H.J. Rack, Biomaterials 19 (1998) 1621.
[3] C. Massaro, P. Rotolo, F. De Riccardis, Milella, A. Napoli, M.
Wieland, M. Textor, N.D. Spencer, D.M.E. Brunette, J. Mater.
Sci. Mater. Med. 13 (2002) 535.
[4] S. Poulin, E. Ndzbet, A. Debrie, O. Savadogo, E. Sacher, Appl.
Surf. Sci. 143 (1999) 238.
[5] P. Cacciafesta, A.D.L. Humphris, K.D. Jandt, M.J. Miles,
Langmuir 16 (2000) 8167.
[6] K.D. Jandt, Surf. Sci. 491 (2001) 303.
[7] N.B. Holland, R.E. Marchant, J. Biomed. Mater. Res. 51
(2000) 307.
[8] R.E. Marchant, M.D. Barb, J.R. Shainoff, S.J. Eppell, D.L.
Wilson, C.A. Siedlecki, Thromb Haemostasis 77 (1997) 1048.
[9] P. Cacciafesta, K.R. Hallem, A.C. Watkinson, G.C. Allen, M.J.
Miles, K.D. Jandt, Surf. Sci. 491 (2001) 405.
[10] K. Okimura, T. Nakamura, J. Vac. Sci. Technol. A 21 (2003)
988.
[11] L. Sirghi, Y. Hatanaka, Surf. Sci. 530 (2003) L323.
[12] D. Mardare, C. Baban, R. Gavrila, M. Modreanu, G.I. Rusu,
Surf. Sci. 507 (2002) 468.
[13] K.H. Ahn, Y.B. Park, D.W. Park, Surf. Coat. Tech. 171 (2003)
198.
[14] E. Vasilescu, P. Drob, M.V. Popa, M. Anghel, A.S. Lopez, I.M.
Rosca, Mater. Corros. 51 (2000) 413.
[15] D.G. Caster, B.D. Ratner, Surf. Sci. 500 (2002) 28.
[16] C. Galli, M.C. Coen, R. Hauert, V.L. Katanaev, P. Gröning, L.
Schlapbach, Coll. Surf. B 26 (2002) 255.
[17] C. Galli, M.C. Coen, R. Hauert, V.L. Katanaev, M.P. Wymann,
P. Gröning, L. Schlapbach, Surf. Sci. 474 (2001) L180.
[18] J.R. Capadona, D.M. Collard, A.J. Garcia, Langmuir 19 (2003)
1847.
[19] A. Krajewski, A. Piancastelli, R. Malavolti, Biomaterials 19
(1998) 637.
[20] F.A. Denis, P. Hanarp, D.S. Sutherland, J. Gold, C. Mustin,
P.G. Rouxhet, Y.F. Dufrene, Langmuir 18 (2002) 819.
[21] T.P. Niesen, M.R. De Guire, J. Bill, F. Aldinger, M. Ruhle,
A. Fischer, F.C. Jentoft, R. Schlogl, J. Mater. Res. 14 (1999)
2464.
[22] F. Pinzart, P. Ascarelli, E. Cappelli, R. Giorgi, Langmuir 18
(2002) 5457.
[23] J. Lausma, B. Kasemo, Appl. Surf. Sci. 44 (1990) 133.
[24] I. Bertoti, M. Mohai, J.L. Sullivan, S.O. Saied, Appl. Surf. Sci.
84 (1995) 357.
[25] C. Viornery, Y. Chevolot, D. Leonard, B.O. Aronsson, P.
Pechy, H.J. Mathieu, P. Descouts, M. Gratzel, Langmuir 18
(2002) 2582.
[26] F. Zhang, Z. Zheng, Y. Chen, X. Liu, A. Chen, Z. Jiang, J.
Biomed. Mater. Res. 42 (1998) 128.
[27] C. Sittig, M. Textor, N.D. Spencer, M. Wieland, P.H. Vallotton,
J. Mater. Sci. Mater. Med. 10 (1999) 35.
[28] M. Jobin, M. Taborelli, P. Descouts, J. Appl. Phys. 77 (1995)
5149.
[29] S.J. Xiao, M. Textor, N.D. Spencer, M. Wieland, B. Keller, H.
Sigrist, J. Mater. Sci. Mater. Med. 8 (1997) 867.
[30] M. Winkelmann, J. Gold, R. Hauert, B. Kasemo, N.D. Spencer,
D.M. Brunette, M. Textor, Biomaterials 24 (2003) 1133.
[31] H.K. Jang, S.W. Whangbo, H.B. Kim, J. Vac. Sci. Technol. A
18 (2002) 917.
[32] C.C. Ting, S.Y. Chen, D.M. Liu, J. Appl. Phys. 88 (2000)
4628.
[33] P. Cacciafesta, K.R. Hallam, C.A. Oyedepo, A.D.L. Humphris,
M.J. Miles, K.D. Jandt, Chem. Mater. 14 (2002) 777.
[34] W.B. Pearson, A Handbook of Lattice Spacings and Structures
of Metals and Alloys, Pergamon Press, London, UK, 1994.
[35] F.Q. Nie, Z.K. Xu, P. Ye, J. Wu, P. Seta, Polymer 45 (2004) 399.
[36] A. Azioune, M.M. Chehimi, B. Miksa, T. Basinska, S. Slom-
kowski, Langmuir 18 (2002) 1150.
[37] M.C.L. Martins, B.D. Ratner, M.A. Barbosa, J. Biomed. Mater.
Res. 67A (2003) 158.
[38] C.S. Zhao, X.D. Liu, M. Nomizu, N. Nishi, Biomaterials 24
(2003) 3747.
[39] J.F. Oliver, C. Huh, S.G. Mason, Coll. Surf. 1 (1980) 79.
[40] G. McHale, N.J. Shirtcliffe, S. Aqil, C.C. Perry, M.I. Newton,
Phys. Rev. Lett. 93 (2004) 036102.
[41] R.N. Wenzel, Ind. Eng. Chem. 28 (1936) 988.
 K. Cai et al. / Applied Surface Science 250 (2005) 252–267
[42] D.E. MacDonald, N. Deo, B. Markovic, M. Stranick, P.
Somasundaran, Biomaterials 23 (2002) 1269.
[43] Q. Liu, J. Ding, F.K. Mante, S.L. Wunder, G.R. Baran,
Biomaterials 23 (2002) 3103.
[44] D.E. MacDonald, B. Markovic, M. Allen, P. Somasundaran,
A.L. Boskey, J. Biomed. Mater. Res. 41 (1998) 120.
[45] G.B. Sigal, M. Mrksich, G.M. Whitesides, J. Am. Chem. Soc.
210 (1998) 3464.
[46] S. Kidoaki, T. Matsuda, Langmuir 15 (1999) 7639.
[47] K.B. MaClary, T. Ugarova, D.W. Grainger, J. Biomed. Mater.
Res. 50 (2000) 428.
[48] B.S. Wojciak, A. Curis, W. Monhagan, K. Macdonald, C.
Wilkinson, Cell Res. 223 (1996) 426.
267
[49] A. Higushi, S. Tamiya, T. Tsubomura, A. Katoh, C.S. Akaike,
M. Hara, J. Biomater. Sci. Polym. E 11 (2000) 149.
[50] Y.D. Dufrene, T.G. Marchat, P.G. Rouxhet, Langmuir 15
(1999) 2871.
[51] A. Curts, C. Wilkinson, Biomaterials 18 (1997) 1573.
[52] B.A. Movchan, A.V. Demchishin, Fiz. Metal. Metalloved 28
(1969) 653.
[53] D.L. Smith, Thin-Film Deposition: Principle and Practice,
McGraw-Hill, New York, 1995 , p. 159.
[54] R. Messier, J.E. Yehoda, J. Appl. Phys. 58 (1985) 3739.
[55] Y.L. Wang, K.Y. Zhang, Surf. Coat. Tech. 140 (2001) 155.
[56] G. Palasantzas, J.T.M. de Hosson, Physica C 330 (2000)
99.