11

X-Ray Analysis on Ceramic Materials

Deposited by Sputtering and Reactive
Sputtering for Sensing Applications
Rossana Gazia1, Angelica Chiodoni1, Edvige Celasco2,
Stefano Bianco1 and Pietro Mandracci2
1Center
2Materials

for Space Human Robotics@PoliTo, Istituto Italiano di Tecnologia

Science and Chemical Engineering Department, Politecnico di Torino
Italy

1. Introduction
Piezoelectric materials have been extensively studied and employed over the last decades
with the aim of developing new sensors and actuators to be applied in a wide range of
industrial fields. The continuous increase of miniaturization requirements led also to an
increasing interest in the synthesis of piezoelectric materials in the form of thin films.
As an example, the growth of wireless mobile telecommunication systems favored the
expansion of the design and fabrication of high-frequency oscillators and filters (Huang et
al., 2005). Within this context, conventional surface acoustic wave (SAW) filters were
gradually replaced by film bulk acoustic resonator (FBAR) devices. Their advantage in
comparison with SAW devices resides in a higher quality factor (Lee et al., 2003) and lower
fabrication costs (Huang et al., 2005). These kinds of devices are based on piezoelectric
materials. Thus, an improvement in such material properties can have a strong impact in
communication performances.
A similar situation exists in the field of sensing. The increase of the sensitivity in
piezoelectric sensors is one of the main targets which could be achieved by improving
material characteristics.
Therefore, the interest in this class of materials is not decreasing with time. On the contrary
the enhancement of the piezoelectric material performances, together with the synthesis of
new lead-free piezoelectric materials and the integration of ceramic materials with flexible
substrates (Akiyama et al., 2006; Wright et al., 2011), is one of the latest research goals.
Most piezoelectric materials are metal oxide and few metal nitride crystalline solids and can
be single crystals or polycrystalline materials. In both cases, piezoelectric materials are
anisotropic and the determination of the response of the material to an external mechanical
stress induced along a certain direction on its surface must be performed along different
crystallographic axes. Quantitative information about how the material responds to external
stresses is given by the piezoelectric constants.
Thus, the efficiency of the piezoelectric response can strongly vary with the crystal
orientation of the material, and this occurs for bulk materials and thin films (Du et al., 1999;
Yue et al., 2003).

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The dependence of the piezoelectric response with the crystallographic orientation makes
the control of the crystal properties during the growth of thin films one of the critical points
in material synthesis.
Nevertheless, also material stoichiometry control is a relevant element for the enhancement
of the piezoelectric efficiency because either the presence of impurities or the lack in some of
the compound constituent elements can introduce a distortion in the crystal unit cell, which
may be detrimental for the piezoelectric response (Hammer et al., 1998; Ramam &
Chandramouli, 2011).
In many deposition techniques the control of film stoichiometry can be a difficult task,
especially for high vacuum techniques, where the presence of residual gases in the vacuum
chamber can affect the final quality of the thin films.
Among them, the sputtering technique is widely used in the synthesis of piezoelectric thin
films. Two approaches can be used in the growth of such materials. In the simplest, the
source of material (target) is a ceramic material with the same stoichiometry as that of the
desired thin film. The other approach requires the presence in the vacuum chamber of a gas
able to react with the material removed from the surface of the target and form a compound
while the deposition is being carried out. The main difference between the two methods is
that, with the latter, a control of stoichiometry can be achieved. On the other hand, the
insertion of reactive gases leads to a decrease of the sputtering rate and to target
contamination. In particular, target contamination can be avoided by changing the
parameters during the deposition process but, as a drawback, an increase in process
complexity is introduced.
The use of characterization techniques able to give detailed information about crystal
structure and chemical composition is therefore necessary in order to assess the quality of
the piezoelectric thin films. Among the numerous techniques available, X-Ray Diffraction
(XRD), Energy-Dispersive X-ray spectroscopy (EDX or EDS) and X-ray Photoelectron
Spectroscopy (XPS) analyses can be considered exhaustive enough for the determination of
such information.
Each of these characterization techniques helps in determining those film properties which
are at the basis of the correct operation of the materials as piezoelectrics.
Film orientation, as previously asserted, is probably the most important characteristic
regarding materials with piezoelectric properties and XRD analysis is, therefore, one of the
fundamental characterization techniques to be employed for providing such information.
However, materials such as ceramics tend to grow in a polycrystalline form and the
evaluation of the actual orientation of the crystals can be puzzling whenever impurities and
contaminations are present in the films. As an example, some peaks present in XRD spectra
related to films grown by sputtering, which is a technique that can likely produce films in a
crystalline form without the need of post-annealing processes, can be attributed to some
crystalline phase formed by the main compound with the residual oxygen still present into
the vacuum chamber at the time that the deposition is carried out. Thus, the cross-check
with information supplied by compositional analysis is of fundamental importance, in order
to better interpret data from XRD analysis.
In particular, EDX can help in the first qualitative evaluation of the species present in the
films, while XPS can give detailed information about the nature of the bonds occurring
between atoms in the films and also semiquantitative information. Thus, if the orientation of
the film does not correspond to what expected, compositional analysis can provide an
explanation for that, indicating whether the problem resides in the fact that the preferred

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orientation of the film is different from the desired one, or in the presence of impurities in
the film or in a deviation from the right stoichiometry introducing stresses in the thin film.
Aim of this work is to compare the quality of films of aluminum nitride and zinc oxide,
which are piezoelectric materials, grown by sputtering and reactive sputtering in order to
understand how the different approaches adopted during the deposition processes affect the
film quality.

2. Sputtering growth of ceramic materials

Sputtering technique is one of the most common PVD methods used for the growth of thin
films. This technique is based on the removal of atoms from the surface of a target material
by using inert gas ions such as Ar ions. The atoms so obtained are able to head towards a
substrate, where they can nucleate and grow as thin film. A typical sputtering system
consists of an ultra-high vacuum chamber containing a target material and a substrate
holder, opportunely polarized. The system is equipped with mass flow controllers, valves
and gas inlets in order to create a controlled atmosphere in the vacuum chamber, which is of
fundamental importance for the creation of a stable plasma. Gas plasma is generated by the
voltage applied between the cathode represented by the target material and the substrate. A
bias voltage could be applied when required. The ionized gas atoms or molecules present in
the plasma are accelerated towards the target and are able to sputter away from its surface
some atoms that afterwards are deposited on the substrate surface. There, through
nucleation and coalescence processes, the atoms create a first layer of material, which is
followed by the formation of additional layers, as the deposition process is carried out.
During the target bombardment, secondary electrons are also emitted, allowing the plasma
to be maintained (Kelly & Arnell 2000).
The target is usually composed of a metallic material or other alloys and compounds with
high conductivity as well as the substrates. In fact if an insulating material is used, the DC
polarization applied between target (cathode) and substrate (anode) in a sputtering system
induces a charge accumulation able to slowly reduce the ions acceleration towards the
target, with the creation of an electric field in opposition to that generated by the DC
polarization. For this reason it turns out to be necessary to modify the set up for the
deposition of insulating materials. The application of a high frequency voltage can
overcome the problem of charge accumulation, and this solution is found in RF sputtering
systems. The typical voltage frequency for a standard RF sputtering system is 13.56 MHz.
Such solution allows for the deposition of oxides, nitrides and other insulating materials on
both metallic and insulating substrates.
The sputtering rate associated to each material depends on numerous parameters, including
the sputtering efficiency of the gas which is strictly related to the mass of the gas atoms. For
this reason gases with heavy atoms are preferred and argon is the most common gas used in
sputtering processes. However, when compounds are to be obtained by sputtering, reactive
gases are used, such as oxygen or nitrogen. Because of the role played by these gases during
a thin film deposition, they are named sputtering gases.
In a sputtering process the gas is inserted in the vacuum chamber only after a very low
pressure (of the order of 10-5 Pa) has been reached. At these pressure levels, most of the
contaminant species that could alter the film final composition are not present anymore,
with some exceptions, and in principle the sole gas participating to the growth process is the
one deliberately inserted in the vacuum chamber. In order to achieve low pressure values

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two kinds of vacuum pumps are required: one for the rough vacuum and one for the high
vacuum. Typically, a rotary pump and a turbomolecular pump are employed for reaching
high vacuum regime in a sputtering system. Rotary pumps usually allow to reach pressures
of about 10-1 Pa while, with turbomolecular pumps, pressures down to 10-5 Pa can be
achieved.
When the gas is inserted in the vacuum chamber at the desired flow, and the gas pressure is
set to the value fixed for the deposition process, the plasma can be generated between the
two electrodes present in the system. The target material is actually one of the two
electrodes (the cathode). To provide a compensation for the local temperature increase
caused by the energy transfer from the incident ions to the target surface, and during the
high temperature processes, the cathode is usually equipped with a cooling system. The
substrate is placed at the anode. This is the simplest sputtering system configuration, the socalled diode sputtering (Wasa et al., 2004a) and can be used with both DC and RF power
supply. In order to increase the sputtering efficiency, a system of magnets with an
appropriate configuration can be adopted. This system is intended to create a magnetic field
parallel to the target surface that, affecting the trajectory of the secondary electrons, is able
to confine them in proximity of the target surface, increasing the probability of collision
between electrons and gas atoms and consequently of their ionization (Kelly & Arnell 2000).
This region of denser plasma increases the sputtering rate of the target material. This
modified system is called magnetron sputtering (Wasa et al., 2004b).
2.1 Sputtering growth of ceramic materials in reactive mode
The reactive sputtering technique is similar to the classic sputtering technique in all aspects,
with one exception, that is the type of gas inserted in the vacuum system. In section 2, argon
is indicated as the gas usually employed in a sputtering deposition process. However, for
reasons that will be explained later in this section, it is necessary sometimes to be able to
vary the stoichiometry of a compound to be grown in the form of thin film. In such cases,
what is called a reactive gas must be inserted in addition or in substitution of the
sputtering inert gas. If the latter condition occurs, the gas is at the same time named
sputtering and reactive gas.
At the base pressure reached with conventional vacuum systems, almost all those species
that could alter the desired stoichiometry of a thin film are absent. However, in real systems
there is always some residual unwanted gases that participate in the reaction between the
target material and the reactive gas (Sproul et al., 2005). As previously asserted, the most
commonly used reactive gases are oxygen and nitrogen, the former being used in oxide
depositions, the latter in nitrides formation. In both cases, the target is usually a metallic
material that reacts with the ionized gas atoms or molecules, generated by plasma, after its
transition into vapor phase. The reason for using this approach is that it allows the control of
the stoichiometry of the films formed on the substrate material. Although targets made of
stoichiometric compounds are commercially available, sometimes it is required to adjust the
stoichiometry of the films in order to gradually change their properties. By regulating the
gas flow in the chamber or the concentration of the reactive gas in a mixture of sputtering
and reactive gases, it is possible to regulate also the percentage of gas atoms or molecules
bound to the metal ions.
The most important drawback in such a process is the phenomenon of the so-called target
poisoning. It basically consists of the contamination of the target surface with the compound

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223

formed by the reaction between gas molecules and target atoms (Sproul et al., 2005), while
in solid phase. When the target surface is totally covered by this compound, the target is
poisoned (Sproul et al., 2005). Many works (Berg & Nyberg, 2005; Maniv & Westwood, 1980;
Safi, 2000; Sproul et al., 2005; Waite & Shah, 2007) reported on the dependence on the
reactive gas flow of both the target poisoning effect and the sputtering rate of the target
material. Sputtering rates from compound targets are lower than that of pure metallic
targets mainly because the sputtering yield of metal atoms from a compound on the target
surface is lower than that from a pure metallic target. The ideal working point in terms of
gas flow should be in between the elemental region (i.e., where the target is not
contaminated at all), and the condition of target poisoning, but this region is not very stable
and even weak variations of the growth conditions can lead to target poisoning (Sproul et
al., 2005). Thus, it is very often necessary to work at low deposition rate and not having a
full control of the stoichiometry of the thin films. The phenomenon of target poisoning
described above occurs only when cathodes having uniform plasma density at their surface
are used. In the case of magnetron cathodes, the formation of a compound at the target
surface is position-dependent due to the low spatial homogenity of the magnetic field, and
there is the possibility of the contemporary presence of three states across the surface:
metallic, oxidized and partially oxidized (Safi, 2000). Many solutions for the process
stabilization have been proposed, based on the variation of different parameters, such as
pump speed or gas flow inserted into the vacuum chamber (Safi, 2000; Sproul et al., 2005).

3. Growth of piezoelectric ceramic materials on silicon substrates

The sputtering system used for depositing the films herein described and analyzed includes
a stainless steel cylindrical reactor containing a magnetron sputtering source, capable of
carrying a target of 10 cm in diameter. The source is fixed at the upper part of the reactor,
facing downwards, whilst the silicon substrates are placed at the bottom part of the reactor,
facing upwards, at a distance of 80 mm from the sputtering target. The system is pumped
both by a turbomolecular pump and a mechanical pump in sequence (nominal pumping
speeds 350 l/s and 15 m3/h respectively). The gases employed during the growth processes
are injected into the reactor by means of mass flow controllers and the plasma discharge is
lit by applying a radio frequency voltage at a frequency of 13.56 MHz between the target
and the grounded substrate holder. The plasma impedance is then tuned by a matching
network to reduce reflected power down to negligible values.
Before each deposition process the silicon substrates were cleaned in an ultrasonic bath with
acetone (10 min) and ethanol (10 min) and dried under direct nitrogen flow. The substrates
were then placed inside the vacuum chamber, which was evacuated down to a pressure of
about 10-5 Pa.
3.1 Growth of ZnO thin films
Zinc oxide thin films were grown on [100]-oriented silicon substrates at room temperature,
i.e., no intentional heating was applied to the substrates. Two different targets were used for
the deposition processes: a Zn target (Goodfellow, purity 99.99+%) and a ZnO target
(Goodfellow, purity 99.99%). The films were deposited according to three different
approaches exploiting the two targets and different gas mixtures. In particular the films
were grown by:

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sputtering the Zn target in a mixture of Ar and O2

sputtering the ZnO target in Ar atmosphere
sputtering the ZnO target in a mixture of Ar and O2
Two of the three approaches involve the reactive sputtering mode, while the other method
avoids the use of a reactive gas, and the only source of oxygen should be the target itself.
The complete sets of process parameters are reported in Table 1.

Sample
Name

Base
Ar
O2
Deposition
Pressure Power
Thickness
pressure
flow
flow
time
Target
(Pa)
(sccm) (sccm)
(Pa)
(W)
(min)
(nm)

ZnO_MR

Zn

5.3E-05

39

0.67

100

60

220

ZnO_CN

ZnO

1.6E-05

40

0.67

100

120

210

ZnO_CR

ZnO

2.9E-05

40

0.67

100

120

200

Table 1. Deposition conditions for the growth of ZnO thin films

The name of each sample reports the name of the material and two letters representing the
nature of the target (Metallic, Ceramic) and the sputtering mode (Reactive, Non-reactive).
The deposition time was chosen on the basis of a previous optimization work performed on
the conditions of depositions of each class of films.
3.2 Growth of AlN thin films
Aluminum nitride thin films were grown on [100]-oriented silicon substrates at room
temperature. Two different targets were used for the deposition processes: an Al target
(Goodfellow, purity 99.999%) and an AlN target (Goodfellow, purity 99.5%). As for ZnO
films, AlN films were deposited according to three different approaches involving the two
targets and different gas mixtures. In particular the films were grown by:
sputtering the Al target in N2 atmosphere
sputtering the AlN target in Ar atmosphere
sputtering the AlN target in a mixture of Ar and N2
The complete sets of process parameters are reported in Table 2.
Sample
Name

Deposition
Base
Ar
N2
Pressure Power
Thickness
flow
time
pressure
flow
Target
(Pa)
(sccm) (sccm)
(Pa)
(W)
(min)
(nm)

AlN_MR

Al

4.0E-05

40

0.35

100

180

210

AlN_CN

AlN

1.6E-05

40

0.67

100

120

60

AlN_CR

AlN

2.9E-05

40

0.67

100

120

55

Table 2. Deposition conditions for the growth of AlN thin films

For the names of the samples, the same criterion exposed in section 3.1 was applied. As well
as in the case of ZnO thin films, the sputtering time and the gas pressure used for the
growth of sample AlN_MR were chosen on the basis of the characterization results obtained
from previous depositions of AlN films.

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4. X-Ray analysis on ceramic thin films

PVD techniques usually allow the growth of thin films having the same stoichiometry of the
source of material used during the deposition process. However, in the case of growth of
compound thin films, the conditions in which the growth processes occur can cause either
lacks of some of the elements making part of the compound, or contamination with other
undesired elements. In other words, a key role is played by the deposition conditions in the
growth process of a thin film with the correct stoichiometry.
The concentration of elements, and the way they are bound to each other, affects also the
physical properties of materials. For this reason, chemical composition analysis is of
fundamental importance since it helps to optimize those process parameters which directly
influence the chemical composition of materials in order to obtain high-quality thin films,
with optimum properties.
Energy Dispersive X-ray spectroscopy is a powerful technique for the investigation of the
chemical species present in a material. It is based on the analysis of the energy and intensity
distribution of the x-ray signal generated by the interaction of an electron beam with a
specimen (Goldstein et al., 2003a). EDX is an optional tool installed on electron microscopes.
In such a set up an electron beam is directed towards the sample to be analyzed. The
electrons with a certain kinetic energy can interact with the nucleus or with the electrons of
a specific atom. The Coulombic interaction with the positive nucleus causes a deceleration
that is responsible for an energy loss, the so called bremsstrahlung radiation (Goldstein et
al., 2003b). Since the electrons may lose any amount of energy between zero and the initial
energy, the detection of this emitted radiation gives rise to a continuous electromagnetic
spectrum that constitutes the background of the collected spectrum (Goldstein et al., 2003a).
When the primary electrons interact with the electrons of the atom, ionization phenomena
occur, usually involving K shell electrons. Since the atom in this excited state tends to reach
the minimum of energy, the electrons from L or M shells can occupy the vacancy left from
the K shell electron. The transition between L and K or M and K shells cause an emission of
X-ray radiation designated as K and K, respectively (Goldstein et al., 2003c). The energy
difference between L, M and K levels are well defined for each element, so the emission of
K and K X-rays identifies the elements present in the analyzed sample. The detection of
this transition levels should in principle give a line in the continuous electromagnetic
spectrum. However, the typical peak width of an EDX spectrum is about 70 times wider
than the natural line width (Goldstein et al., 2003d). The spatial resolution of this technique
is strictly related to the region of the sample interacting with the electron beam that is the Xray generation volume. In fact, this volume depends on the material density and on the
critical ionization energy, i.e., the energy that the primary electron beam should have in
order to ionize atoms of the specimen (Goldstein et al., 2003e).
Both the depth and the lateral distribution of the X-ray production is relevant because in
depth it determines the amount of photoelectric absorption of X-rays from the material
atoms, and laterally it determines the spatial resolution of the X-ray microanalysis.
However, the photoelectric absorption phenomenon is not significant in micron-sized
samples so this side effect can be ignored (Goldstein et al., 2003e).
A fundamental aspect of this technique is the X-ray detection. It is usually performed using
solid state detectors, especially lithium-drifted silicon detectors. The detection range is
comprised between 0,2 and 30 KeV (Goldstein et al., 2003f). EDS analysis on ZnO and AlN

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thin films were performed with an Oxford INCA Energy 450 installed on a Field Emission
Scanning Electron Microscope SUPRA 40 (ZEISS).
X-ray Photoelectron Spectroscopy is an advanced technique for the study of the surface
composition of a wide range of materials, stated that they have to be vacuum-compatible.
The sampling depth, defined as the depth from which 95% of all photoelectrons are
scattered by the time they reach the surface, ranges between 5 and 10 nm below the surface.
The phenomenon at the basis of this technique is the photoelectron emission that involves
energy exchanges between a source of x-rays and a specimen, according to the following
equation (Briggs, 1983):

EK h EB

(1)

2 dhkl sin

(2)

where EK is the measured electron kinetic energy, hthe energy of the exciting radiation, EB
the binding energy of the electron in the specimen, and the work function, the latter
having a specific value depending on the material and on the spectrometer (Briggs, 1983a).
As stated above, the exciting radiation is derived from an X-ray source. The material
responsible for the emission of X-rays must be chosen taking into account two aspects: the
X-ray line width cannot exceed a certain value that otherwise would strongly limit the
resolution of the measurement, and the energy associated to the X-ray must be high enough
to allow the ejection of a sufficient range of core electrons for unambiguous analysis (Briggs,
1983b). Usually K radiation from aluminum or magnesium is employed to excite the
material atoms. Photoelectron energy is measured by an appropriate analyzer. Many types
of analyzers have been proposed over the last decades, although the simplest and most
common ones are the cylindrical mirror analyzer (CMA) and the concentric hemispherical
analyzer (CHA) (Briggs, 1983c). The energy associated to the photoemitted electrons
precisely identifies a material. Since this energy varies with respect to the shell the electron
is ejected from, each peak in the spectrum will correspond to the energy associated to the
electrons ejected from all those levels that require an excitation energy lower than that of the
incident X-rays. If the specimen is a compound material, each peak will represent the energy
associated to the photoelectrons from all the elements present in that compound. However,
peaks corresponding to the same element undergo what is called a chemical shift if the
boundary conditions of the element change, i.e., the energy associated to photoelectrons
ejected from an atom of an element changes with the molecular environment, with the
oxidation state, or with its lattice site (Briggs, 1983d). Chemical shifts allow to understand
how atoms are bound within compounds and alloys. Aluminum nitride and zinc oxide thin
films were characterized with XPS technique in order to determine their exact chemical
composition. The instrument used for XPS analysis was a PHI 5000 VersaProbe Scanning
ESCA microprobe - Physical Electronics, equipped with an ion gun used in these
experiments for cleaning the surface before each measurement, in order to remove any
impurity from the analyzed area. A dual beam charge neutralization method was employed
during the measurements, in order to reduce the charging effect on the samples. This charge
neutralization method consists in a combination of low energy argon ions and electrons.
X-Ray Diffraction technique is employed for the analysis of the crystallographic properties
of materials. The diffraction method is based on the following equation:

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the well known Bragg law, where is the x-ray wavelength which irradiates the sample to
be analyzed, dhkl is the lattice spacing of a specific (hkl) family planes of the crystalline
material, and is the diffraction angle of the X-ray beam with respect to the direction
parallel to the (hkl) plane. For a given (hkl) family, characterized by a precise value of dhkl,
the conditions on and are then very stringent. According to this equation, in a crystal it is
possible to observe diffracted beams only along fixed directions, determined by the
constructive interference between diffracted beams at the different crystal planes. Each
single atom is actually able to scatter an incident beam of X-rays along every direction, but a
periodic arrangement of atoms cancels, with a destructive interference phenomenon, all
those beams scattered along the directions not satisfying equation (2). The analysis of
materials with unknown values of lattice spacing is carried out by varying either the
incidence angle or the wavelength of the X-ray beam. Depending on which of the two
parameters is varied, the diffraction methods are named as follows (Cullity, 1956a):
Laue method, where is varied and fixed;
Rotating-crystal method, used for monocrystals only, where is fixed and the crystal
rotates;
Powder method, where is fixed and is varied.
The latter has been used for the characterization of all the samples described in the next
chapters, although thin films were not reduced in powder.
The instrument used to perform XRD measurements is called diffractometer, and it consists
of a monochromatic X-ray source and an X-ray detector (commonly named counter), both
placed on the circumference of a circle having its centre on the specimen. The specimen is
held by an appropriate holder, placed on a table which can rotate about its axis, which is
also the axis about which X-ray source and detector are able to rotate. X-rays are sent to the
specimen where they are diffracted to form a convergent beam focused on a slit placed just
before the X-ray detector.
A filter is also placed in the diffracted beam path in order to suppress K radiation. The
counter position can be read on a graduated scale of the goniometer and it corresponds to
2. Moreover the table where the specimen holder is fixed and the counter are mechanically
coupled in a way that a rotation of the specimen of x degrees corresponds to a rotation of the
counter of 2x degrees (Cullity, 1956b). The values of the parameter correspond to the
angular positions where peaks of diffracted X-ray intensity are registered. After the whole
set of values for is determined, lattice spacings dhkl corresponding to different crystal
planes can be calculated. Lattice spacing, however, is not the only parameter that can be
obtained from an XRD measurement. The evaluation of the crystals size (t) is strictly related
to the structural properties of materials, (Cullity, 1956c) and can be calculated as follows:
t

0.9
B cos B

(3)

where is the X-ray wavelength, B is the peak width in radians, measured at the half the
maximum intensity, and B is the angle satisfying equation (2). Equation (3) is known as the
Scherrer formula (Cullity, 1956d). Because of its formulation, equation (3) does not take into
account the role of strain in the material.
The instrument used for the characterization of AlN and ZnO films was a Panalytical XPert
MRD PRO diffractometer, equipped with a Cu K radiation source (= 1.54056 ).

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4.1 X-Ray analysis on ZnO thin films

ZnO was extensively studied over the last decades with the aim of producing high-quality
thin films for the fabrication of SAW and FBAR devices (Ferblantier et al., 2005; Huang et al.,
2005; Lee et al., 2003). These kinds of devices exploit the piezoelectric properties of their
active layers. Materials exhibiting high piezoelectric coupling factor are usually highly
oriented along one axis. For ZnO the c-axis orientation presents the highest piezoelectric
coefficient and for this reason many works, more or less recent (Muthukumar et al., 2001;
Sundaram et al., 1997; Yan et al., 2007), focused their attention on the XRD analysis and
electrical characterization of the piezoelectric layers, often neglecting the analysis of the film
composition. The lack of one of the elements in the film can be detrimental in the final
response of the material when used in the fabrication of piezoelectric devices. For this
reason it is crucial to grow highly oriented and highly stoichiometric materials for
optimizing their piezoelectric properties. Moreover, techniques such as sputtering require
very long optimization processes in order to satisfy the two requirements.
The combination of the results obtained from the X-ray analyses performed on the films
described in this work will show how important is to combine the information collected by
different techniques in order to precisely evaluate and improve the material properties.
4.1.1 EDS analysis on ZnO thin films
A first evaluation of the composition of the ZnO thin films grown by the three different
approaches described in section 3.1 was assessed by EDS analysis. The system for the
microanalysis was first calibrated with a Co sample, used as reference material to check the
performance of the instrument. The spectra reported in Figure 1 refer to the whole area of
the FESEM images shown below. All the spectra were collected by using the same
conditions (electron energy, magnification, integration time).
The spectra were analyzed in standardless mode and the related semiquantitative
information about the elements and their concentration is reported in Table 3. Four elements
were detected. The Si peak is related to the substrate contribution, the C peak is related to
organic impurities on the surface of the sample. The Zn peak is obviously related to zinc
oxide, while the oxygen peak is partially related to this oxide.

Element

CK
OK
Si K
Zn K
Atomic
Atomic
Atomic
Atomic
concentration concentration concentration concentration
(%)
(%)
(%)
(%)

ZnO_MR

6.79

31.28

45.97

15.97

ZnO_CN

5.90

31.35

46.72

16.03

ZnO_CR

5.31

30.00

49.96

14.73

Table 3. Atomic percentages of the elements detected by EDS analysis on the ZnO thin films
The excess of oxygen with respect to the desired stoichiometry of the films can be attributed
to the fact that silicon is bound to oxygen, creating an oxide phase at the interface between
the substrate and the film. However, since the oxygen peak area is the result of the
contributions of the oxygen in the zinc oxide film and the oxygen present in the native
silicon oxide layer present at the substrate surface, it is not possible to precisely determine

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the amount of oxygen actually bound to zinc in the compound. With the exception of
carbon, usually present on the surface of materials exposed to air, no element different from
the expected ones was detected with EDS analysis. A more precise evaluation of the film
composition must be supplied with the help of other techniques.

Fig. 1. EDX spectra and FESEM images of ZnO thin films grown from metal target (a, d),
ceramic target in Ar atmosphere (b, e) and ceramic target in a mixture of Ar and O2 (c, f).
4.1.2 XPS analysis on ZnO thin films
The XPS technique can give precise information about the composition of the first atomic
layers of a material. This capability is of fundamental importance when dealing with
applications where the study and control of surface properties is crucial. In the present case,
instead, the desired information is not related to the actual surface composition: the
piezoelectric constants of the materials are not related to the surface composition but to the
crystallographic orientation of grains with the right stoichiometry. The exposure of the
samples to air promotes the contamination of the surfaces (as shown from the EDX spectra
reported above). As a result, the elements present on the sample surface are not the same
that constitute the overall material layer. For this reason, in order to obtain information
about the composition of the whole film, the removal of surface contamination before the
acquisition of each XPS spectrum is mandatory and is usually performed by sputtering the
surface with argon ions. The contamination of surfaces (adventitious carbon) due to
exposure to air mainly generates C-C and C-H bonds. Carbon peak C1s is commonly used
as a reference for the compensation of the XPS spectrum shift caused by the charge
accumulation effect due to the charged particles reaching the sample surface during the
analysis. However after the removal of all the surface contaminations the carbon peak is not
detectable anymore since no source of this element is present during the film growth
process. On the basis of these considerations, XPS spectra were acquired before and after the
surface cleaning. With a high resolution acquisition before the surface cleaning the C1s peak
position was precisely determined. The second high resolution acquisition determined the

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position of the peaks related to each constituent element in the film. The difference between
the energy the C1s peak is centered at and the energy the carbon peak from database is
centered at (fixed at 284.6 eV) gives the shift to be applied to all the acquired peaks in the
XPS spectrum. This procedure was applied to all the samples herein described. For the
determination of the exact peak positions all the peaks were fitted with a GaussianLorentzian function. The concentration of the elements in the film was calculated by the
MultiPak v.9.0 software according to the following equations:
Oxygen concentration (%)

Zinc concentration (%)

AO SFO
100
AO SFO AZn SFZn

(4)

(5)

AZn SFZn
100
AO SFO AZn SFZn

where AO and AZn are the areas of the O1s and Zn2p3/2 peaks, respectively, and SFO and
SFZn are the sensitivity factors for oxygen and zinc, respectively. Figure 2 shows the O1s and
Zn2p3/2 peaks acquired with the post-cleaning high-resolution analysis on the ZnO_MR
sample.

Fig. 2. O1s and Zn2p3/2 XPS peaks acquired after surface cleaning on ZnO_MR sample. The
dotted red line represents the peak fitting the O1s peak.

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The O1s peak is centered at 529.9 eV, the typical position of the oxygen peak in Zn-O bonds
(Haber et al., 1976). The calculated concentrations are reported in Table 4. The excess of Zn
with respect to oxygen reveals that the film contains also Zn-Zn bonds. In order to evaluate
the percentage of such bonds, the zinc peak should be fitted with two appropriate curves.
The areas of the fitting curves centered at the typical binding energies of Zn in the Zn-Zn
and Zn-O bonds represent the percentages of the metallic phase and the oxide phase.
Unfortunately these binding energies are 1021.5 eV and 1021.7 eV, respectively (Klein &
Hercules, 1983), and are too close to univocally fit the Zn2p3/2 peak. However, for the
absence of any other contaminant in the film, it is reasonable to assert that the overall Zn
excess constitutes a metallic zinc phase in the film.
Figure 3 reports the high resolution peaks of ZnO_CN sample. Again it is not possible to
precisely determine the metallic phase percentage by fitting the peaks revealed during the
analysis. However, again in this case, the amount of impurities can be neglected. The carbon
concentration is very low indeed (Table 4) and there is no evidence that a consistent portion
of it could be bound to oxygen atoms. The peaks fitting the O1s peak and centered at 529.7
eV, 531.6 eV and 532.3 eV can be in fact identified with the binding energies of O-Zn bonds
(Chen et al., 2000), O-H bonds and oxygen bound in the H2O molecule, respectively (Avalle
et al., 1992). The latter is present in particular because of the possible presence of humidity
inside the vacuum chamber which is not equipped with a load-lock chamber and requires to
be opened every time a substrate has to be loaded for a new process.

Fig. 3. O1s and Zn2p3/2 XPS peaks acquired after surface cleaning on ZnO_CN sample. The
dotted red lines represent the peaks fitting the O1s peak.

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However the total area of the two peaks related to the binding energy of oxygen bound to
hydrogen atoms is less than the 7% of the total O1s peak area. This means that the 93% of
oxygen atoms are bound to zinc. The Zn excess produces a metallic phase in the film as for
ZnO_MR sample. Although the target used for the growth of sample ZnO_CN is
stoichiometric, the film presents a lack of oxygen which needs to be compensated.
In the case of ZnO_CR sample, grown in a mixture of Ar and O2, there was still an excess of
zinc (see Table 4). However the concentration of oxygen in the gas mixture was very low (1
sccm over a total flow of 41 sccm) and probably the amount of gas required to obtain the
right stoichiometry should be higher. High resolution peaks for ZnO_CR sample are
reported in Figure 4. Zinc peak was not fitted because of the impossibility to exactly
determine the position of the two peaks representing the binding energies associated to ZnO and Zn-Zn bonds. The O1s peak was fitted with two curves, one centered at 529.7 eV (OZn bonds), and the other centered at 531.7 eV (O-H bonds), very close to those chosen for
fitting the O1s peak in the XPS spectrum of ZnO_CN sample. The amount of contamination
due to the humidity present in the chamber is basically the same as that of ZnO_CN. It is
identified by the small peak on the right-bottom part of the O1s peak shown in Figure 4,
with a peak area of about the 4% of the total O1s peak area.

Fig. 4. O1s and Zn2p3/2 XPS peaks acquired after surface cleaning on ZnO_CR sample. The
dotted red lines represent the peaks fitting the O1s peak.

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C atomic
concentration

O atomic
concentration

Zn atomic
concentration

(%)

(%)

(%)

ZnO_MR

40.9

59.1

ZnO_CN

0.7

44.0

55.3

ZnO_CR

43.9

56.1

Sample
name

Table 4. Atomic concentrations obtained by fitting the O1s and Zn2p3/2 peaks from the XPS
spectra of ZnO thin films
4.1.3 XRD analysis on ZnO thin films
XRD analysis on ZnO thin films was carried out in order to assess the crystallographic
orientation of the material since from this information it is possible to predict how efficient
the material will be in terms of piezoelectric response. XRD spectra acquired on ZnO are
shown in Figure 5 and the peak positions are reported in Table 5. The peak positions were
determined by fitting the spectra with Pseudovoigt curves.

Fig. 5. XRD patterns of ZnO thin films

Two main peaks were identified in the XRD patterns of all the three samples, one related to
the [002] orientation and one to the [103] orientation of ZnO. Peaks detected in the ZnO_MR

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sample are the most shifted with respect to the database peak positions (JCPDS, 1998a).
These data are in agreement with the fact that the metallic phase in this film was the largest
in comparison with the other samples. The presence of a high amount of metallic phase
might have induced a tensile stress in the zinc oxide unit cells with the effect of producing a
shift towards lower angle values. To this end it is worth to notice that no peak related to any
zinc crystallographic orientation was detected. Thus we can consider the metallic zinc as an
impurity instead of a single phase.
For what concerns the peak relative intensities, the [002] peak intensity of sample ZnO_CR
is about 10 times higher than the [103] peak intensity, meaning that during the growth from
ceramic target the presence of oxygen favors the growth of crystals along the [002]
orientation.
The ratio between the intensities of the two peaks in sample ZnO_CN was in fact lower
(about 8). The sample grown from the metal target (ZnO_MR) showed the lowest intensity
ratio (about 3).
It can be concluded that, on the basis of the whole set of results, ZnO_CR sample could in
principle perform better than the other samples in terms of piezoelectric properties.

Peak position (2)

Sample name

Database (JCPDS, 1998a)

ZnO [002]

ZnO [103]

(degrees)

(degrees)

34.3790.001 62.7770.001

ZnO_MR

33.860.02

62.170.02

ZnO_CN

34.030.02

62.330.02

ZnO_CR

34.030.02

62.220.02

Table 5. Position of the peaks detected during XRD analysis performed on ZnO thin film
4.2 X-Ray analysis on AlN thin films
Aluminum nitride is a semiconductor of the III-V semiconductor group, with an
hexagonal wurtzite crystalline structure (Penza et al., 1995; Xu et al., 2001), lattice
constants of a = 0.3110 nm e c =0.4980 nm (Xu et al., 2001), and is characterized by a broad
direct energy gap (6.2 eV) (Cheng et al., 2003; Hirata et al., 2007; Penza et al., 1995),
chemical stability (Cheng et al., 2003; Penza et al., 1995), high thermal conductivity (3.2
W/mK) (Cheng et al., 2003), low thermal expansion coefficient (4.5 ppm/C) (Ruffner et
al., 1999), high breakdown voltage (Hirata et al., 2007; Xu et al., 2001), high acoustic speed
(Cheng et al., 2003; Xu et al., 2001), high refractive index (n = 2.1) (Penza et al., 1995), high
electrical resistivity (1011-1014 cm) (Ruffner et al., 1999) and, above all, good piezoelectric
response (Cheng et al., 2003; Hirata et al., 2007; Penza et al., 1995; Ruffner et al., 1999; Xu
et al., 2001) (piezoelectric coefficient of 5.4 pm/V) (Ruffner et al., 1999). Piezoelectric
behaviour of AlN strongly depends on its crystallographic orientation (Cheng et al., 2003)
and, in particular, films grown in the [002] orientation are preferred as the highest

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piezoelectric stress constant is associated to this orientation (Cheng et al., 2003).

Piezoelectricity in AlN has been demonstrated only when in the form of a thin film
(Gautschi, 2002). Analysis performed by many research groups on reactive-sputtered AlN
films (Cheng et al., 2003; Penza et al., 1995; Xu et al., 2001) revealed the strong dependence
of film crystal orientation on growth parameters, such as target-substrate distance, power
applied to the target, substrate temperature, process pressure, and gas relative
concentration when a mixture of Ar and N2 was employed for the depositions of AlN. An
interesting advantage of growing AlN by reactive sputtering is the possibility to obtain
polycrystalline films at low substrate temperatures (from room temperature up to 200 C
(Penza et al., 1995; Xu et al., 2001).
As for ZnO, AlN thin films were characterized by EDS, XPS and XRD techniques, in order to
assess the film quality and to find out relationships between film properties and growth
conditions.
4.2.1 EDS analysis on AlN thin films
EDX spectra and FESEM images obtained from the analysis of AlN thin films, deposited
with the three different approaches described in section 3.2, are shown in Figure 6. The
results from microanalysis are reported in Table 6.

Fig. 6. EDX spectra and FESEM images of AlN thin films grown from metal target (a, d),
ceramic target in Ar atmosphere (b, e) and ceramic target in a mixture of Ar and N2 (c, f).
The information acquired with this kind of analysis is of fundamental importance for the
interpretation of the results obtained from the other analysis performed on the AlN samples.
It can be observed indeed that the nitrogen peak was not detected in any of the films
deposited from ceramic target, while it is present in the spectrum of the sample grown from
a metallic aluminum target in nitrogen atmosphere. Also in this case the data acquired with
the EDS technique are not enough to assert that AlN_CN and AlN_CR samples do not

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contain nitrogen. A relevant issue for the energy-dispersive X-Ray spectroscopy technique is
that release of volatile elements (such as nitrogen) can occur during the analysis (Bohne et
al., 2004). Thus, in samples characterized by low nitrogen concentration the detection of the
nitrogen peak can be difficult.
In the case of the two samples grown from ceramic target only aluminum and oxygen were
detected (as well as the silicon peak from the substrate and carbon traces as impurities).
For what concerns the film grown from a metal target, nitrogen and oxygen peaks are strong
enough to be clearly distinguished. Oxygen peak detected on the sample comprises the
contribution of the signals generated by the oxygen contained in the film and by the oxygen
contained in the layer of native oxide present on the silicon substrate, and it is not possible
to estimate which is the percentage of each contribution for the two layers (Bohne et al.,
2004). In consideration of the limit of this characterization further analysis are required in
order to better evaluate the composition of each film.
NK
Element

CK

OK

Al K

Si K

Atomic
Atomic
Atomic
Atomic
Atomic
concentration concentration concentration concentration concentration
(%)

(%)

(%)

(%)

(%)

AlN_MR

38.76

9.72

24.11

27.40

AlN_CN

2.17

16.32

3.91

77.60

AlN_CR

2.50

16.83

4.20

76.47

Table 6. Atomic percentages of the elements detected by EDS analysis on the AlN thin films
4.2.2 XPS analysis on AlN thin films
AlN samples were treated with the same surface cleaning process as ZnO samples (see
section 4.1.2). XPS spectra acquired on sample AlN_MR confirmed the presence of nitrogen
found by means of the EDS analysis. The peaks of the elements present in the film are
shown in Figure 7, while the values of elemental concentration obtained for all the AlN
samples are reported in Table 7. If qualitative information is basically the same for the two
techniques, with the exception of the presence of the silicon peak that is not found in the
XPS spectrum for the intrinsic properties of such a technique, quantitative information are
different. By comparing the values reported in Table 6 and Table 7 it is evident that the
concentrations of each element are strongly different. For what concerns the oxygen
concentration, which results to be much higher from the XPS analysis than from EDS
analysis, it has to be noticed that the surface of the material can contain a higher amount of
this element if compared with bulk because of the capability of the surface to be oxidized. In
principle, the oxygen concentration calculated from EDX spectra could be more accurate
when considering the whole film volume composition. On the other hand the surface
cleaning process performed just before the XPS analysis should have prevented from the
analysis of the very first layers of the sample which could have undergone a higher
oxidation with respect to deeper layers. For this reason information from the XPS analysis
are expected to be more reliable.

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Fig. 7. O1s, Al2p and N1s XPS peaks acquired after surface cleaning on AlN_MR sample.
The dotted red lines represent the peaks fitting the O1s peak.
The curves used for fitting the peaks, reported in Figure 7, represent a possible way to fit
the XPS peaks found in the sample in order to understand how the atoms are bound in the
film. The peaks used to fit the spectrum are those reported in literature, corresponding to
Al-O and Al-N bonds. However, by using this method, the resulting percentage of Al-O
bonds is too low (about 8%) if considering the oxygen concentration in the film (26.7 %).
For this reason it is possible to assume that the film contains an AlOxNy phase which
cannot be exactly estimated because a small variation of the position of each peak used for
the fit of the main Al peak determines a high variation in the relative percentages of the
different bonds.
The results obtained from the XPS analysis performed on AlN thin films deposited from a
ceramic target confirm what already shown by EDS analysis: nitrogen was not detected in
the films. XPS spectra for AlN_CN and AlN_CR are shown in Figure 8 and Figure 9. In spite
of the absence of nitrogen in the films, a deeper investigation on the spectra can lead to
interesting information. There is, in fact, a slight difference in the two spectra.
Although an accurate estimation of the concentration is not allowed because of the low and
noisy signal obtained in the spectral region corresponding to the nitrogen peak position, a
faint peak can be distinguished in Figure 9 at binding energies around 397.5 eV, the typical
binding energy at which the N1s peak is centered when nitrogen is bound to aluminum
(Manova et al., 1998).

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The collection of the nitrogen peak in sample AlN_CR allows to assert that the presence of
nitrogen gas during the sputtering process is necessary in order to include nitrogen in the
film. Nonetheless the amount of gas used during the growth process was too low, and that
is the reason why only noise was acquired in the spectral region of the N1s peak.

C atomic
concentration

N atomic
concentration

O atomic
concentration

Al atomic
concentration

(%)

(%)

(%)

(%)

AlN_MR

34.2

26.7

39

AlN_CN

0.03

66.91

33.06

AlN_CR

0.28

0.35

65.73

33.63

Sample name

Table 7. Atomic concentrations obtained by fitting the C1s, N1s, O1s and Al2p peaks from
the XPS spectra of AlN thin films

Fig. 8. O1s, Al2p and N1s XPS peaks acquired after surface cleaning on AlN_CN sample

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Fig. 9. O1s, Al2p and N1s XPS peaks acquired after surface cleaning on AlN_CR sample
4.2.3 XRD analysis on AlN thin films
Without the support of the EDS and XPS analyses on the AlN thin films grown from metal
and ceramic targets, the interpretation of the XRD patterns would be more complicated. It is
not usual in sputtering processes to obtain materials not maintaining a stoichiometry similar
to that of the material source. However, for some classes of compounds, such as nitrides,
this phenomenon is more frequent because one of the constituting elements is volatile and is
less reactive than oxygen. In vacuum chambers used for the growth of both oxides and
nitrides the chances of introducing contaminations in the films are numerous because of the
residual oxygen trapped at the chamber walls. Moreover the residual humidity in the
chamber containing oxygen is also responsible for the presence of oxide phases in the thin
films. With such a low amount of nitrogen in the chamber, the compensation for the loss of
nitrogen during the film growth cannot be achieved.
XRD patterns for all the analyzed samples are shown in Figure 10, while the peak positions
are reported in Table 8. On the basis of the results discussed above, it was obvious that any
peak acquired by XRD analysis of AlN_CN and AlN_CR samples should be identified as a
peak corresponding to crystalline alumina phase and not to AlN crystalline phases. The
chances that the 0.3 % of nitrogen found by fitting the XPS peak might form a crystalline
phase with aluminum that could be detected by XRD are in fact very low. For this reason, all
the diffraction peaks of the samples deposited from ceramic target were compared with the
database peaks of Al2O3. The only detectable peak (with the exception of the peaks

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Fig. 10. XRD patterns of AlN thin films

Peak position (2)
Sample name
Database (JCPDS,
1998b)
AlN_MR

AlN [002]

Al2O3 [122]

(degrees)

(degrees)

35.9810.001 34.7340.001
36.150.02

AlN_CN

34.570.02

AlN_CR

34.620.02

Table 8. Position of the peaks detected during XRD analysis performed on AlN thin film
produced by the sample holder) and present in the spectra of both films, was attributed to
the [122] orientation of crystalline alumina.
For sample Al_MR instead, a peak corresponding to the [002] orientation of crystalline AlN
was detected. In the view of obtaining films with good piezoelectric properties this is a good
result since the highest piezoelectric coefficient for AlN is found to be along the c-axis
orientation. There is certainly a problem of oxygen contamination that has to be solved in
order to minimize the amorphous AlOxNy phase and increase the quality of the material but
it is strictly related to technological issues.
The correct interpretation of XRD patterns was possible only on the basis of the results
obtained from EDS and XPS analysis. If considering only the growth conditions of the films,

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the attribution of the sole detected peak to an alumina phase could not be so obvious. The
assignment of the detected peak to an aluminium oxide nitride compound, for example,
would have been straightforward. From the database, in fact, it is possible to find a peak
corresponding to the [103] orientation of such a compound centered at 34.357 (JCPDS,
1998c), very close to the position of the peaks detected in the AlN_CN and AlN_CR samples.
On the basis of the sole experimental set up the material could be logically thought as a
nitride. The misinterpretation of the XRD results was avoided just because of the availability
of additional data related to the film composition.

5. Conclusions
Aluminum nitride and zinc oxide thin films were grown by the RF magnetron sputtering
technique. Three methods were used for depositing each of the two materials, involving the
use of different material sources and gas mixtures. Both materials are piezoelectric and this
property is guaranteed and maximized when the material has certain characteristics. The
analysis based on X-ray spectroscopy of all the samples was aimed at the comparison of the
quality of films grown with the different methods and to select the most effective. In
addition, the characterization results were used to underline the differences in the
technological processes used for the growth of different classes of materials (oxides and
nitrides). In particular, the growth of nitrides is characterized by issues due to the nature of
the material itself, especially for what concerns nitrogen which is a volatile element and is
characterized by a higher ionization energy than oxygen, that make it less reactive, lowering
the possibilities to include such element in the films.
With reference to the growth of zinc oxide thin films, the approach that guaranteed a good
stoichiometry and at the same time favored the growth along the c-axis was that
characterized by the use of a ceramic target in the presence of a gas mixture containing Ar
and O2. Although a slight excess of zinc with respect to the right stoichiometry was
detected, the film was mainly [002]-oriented. The future optimization of the parameters will
be aimed at the growth of fully [002]-oriented ZnO thin films in order to maximize the
piezoelectric coefficient of the material.
An aluminum nitride thin film was successfully grown only by reactive sputtering in
nitrogen atmosphere. The growth from ceramic target led instead to the growth of
aluminum oxide as confirmed by the X-ray spectroscopy analysis performed on the
samples. The amount of nitrogen required for its inclusion in the film is higher than that
used for the growth of the oxide samples. In spite of the not fully positive results related to
the presence of nitrogen in the films, these experiments were useful for assessing the great
importance of the combination of results coming from different analysis. The correct
interpretation of XRD patterns of samples grown from ceramic target was possible only
because of the presence of EDS and XPS data.

6. References
Akiyama, M., Morofuji, Y., Kamohara, T., Nishikubo, K., Tsubai, M., Fukuda, O. & Ueno, N.
(2006). Flexible piezoelectric pressure sensors using oriented aluminum nitride thin
films prepared on polyethylene terephthalate films. Journal of Applied Physics, Vol.
100, No. 11, pp. 114318
Avalle, L., Santos, E., Leiva, E. & Macagno, V. A. (1992). Characterization of TiO2 films
modified by platinum doping. Thin Solid Films, Vol. 219, No. 1-2, pp. 7-17, ISSN
0040-6090

www.intechopen.com

242

X-Ray Spectroscopy

Berg, S. & Nyberg, T. (2005). Fundamental understanding and modeling of reactive

sputtering processes. Thin Solid Films, Vol. 476, No. 2, pp. 215-230, ISSN 0040-6090
Bohne, W., Rhrich, J., Schpke, A., Selle, B., Sieber, I., Fuhs, W., del Prado, ., San Andrs,
E., Mrtil, I. & Gonzlez-Daz, G. (2004). Compositional analysis of thin SiOxNy:H
films by heavy-ion ERDA, standard RBS, EDX and AES: a comparison. Nuclear
Instruments and Methods in Physics Research Section B: Beam Interactions with Materials
and Atoms, Vol. 217, No. 2, pp. 237-245, ISSN 0168-583X
Briggs, D. & Seah, M. P. (1983a). Practical Surface Analysis: Auger and X-ray photoelectron
spectroscopy., Briggs, D. & Seah, M. P., pp. 112, John Wiley & Sons, Chichester
Briggs, D. & Seah, M. P. (1983b). Practical Surface Analysis: Auger and X-ray photoelectron
spectroscopy., Briggs, D. & Seah, M. P., pp. 51, John Wiley & Sons, Chichester
Briggs, D. & Seah, M. P. (1983c). Practical Surface Analysis: Auger and X-ray photoelectron
spectroscopy., Briggs, D. & Seah, M. P., pp. 69, John Wiley & Sons, Chichester
Briggs, D. & Seah, M. P. (1983d). Practical Surface Analysis: Auger and X-ray photoelectron
spectroscopy., Briggs, D. & Seah, M. P., pp. 120, John Wiley & Sons, Chichester
Chen, M., Wang, X., Yu, Y. H., Pei, Z. L., Bai, X. D., Sun, C., Huang, R. F. & Wen, L. S. (2000). Xray photoelectron spectroscopy and auger electron spectroscopy studies of Al-doped
ZnO films. Applied Surface Science, Vol. 158, No. 1-2, pp. 134-140, ISSN 0169-4332
Cheng, H., Sun, Y., Zhang, J. X., Zhang, Y. B., Yuan, S. & Hing, P. (2003). AlN films
deposited under various nitrogen concentrations by RF reactive sputtering. Journal
of Crystal Growth, Vol. 254, No. 1-2, pp. 46-54, ISSN 0022-0248
Cullity, B. D. (1956a). Elements of x-ray diffraction, Cullity, B. D., pp. 92, Addison-Wesley
Publishing Company, Reading, Massachusetts, USA
Cullity, B. D. (1956b). Elements of x-ray diffraction, Cullity, B. D., pp. 189-190, AddisonWesley Publishing Company, Reading, Massachusetts, USA
Cullity, B. D. (1956c). Elements of x-ray diffraction, Cullity, B. D., pp. 281, Addison-Wesley
Publishing Company, Reading, Massachusetts, USA
Cullity, B. D. (1956d). Elements of x-ray diffraction, Cullity, B. D., pp. 102, Addison-Wesley
Publishing Company, Reading, Massachusetts, USA
Du, X.-h., Wang, Q.-M., Belegundu, U., Bhalla, A. & Uchino, K. (1999). Crystal orientation
dependence of piezoelectric properties of single crystal barium titanate. Materials
Letters, Vol. 40, No. 3, pp. 109-113, ISSN 0167-577X
Ferblantier, G., Mailly, F., Al Asmar, R., Foucaran, A. & Pascal-Delannoy, F. (2005).
Deposition of zinc oxide thin films for application in bulk acoustic wave resonator.
Sensors and Actuators A: Physical, Vol. 122, No. 2, pp. 184-188, ISSN 0924-4247
Gautschi, G. (2002). Piezoelectric Sensorics (1st edition), Springer-Verlag Berlin Heidelberg
New York, ISBN 978-3-540-42259-4, Germany.
Goldstein, J., Newbury, D.E., Joy, D.C., Lyman, C.E., Echlin, P., Lifshin, E., Sawyer, L.C. &
Michael, J.R. (2003a). Scanning Electron Microscopy and X-ray Microanalysis,
Goldstein, J., pp. 297, Springer Science + Business Media, ISBN 0306472929, New
York, USA
Goldstein, J., Newbury, D.E., Joy, D.C., Lyman, C.E., Echlin, P., Lifshin, E., Sawyer, L.C. &
Michael, J.R. (2003b). Scanning Electron Microscopy and X-ray Microanalysis,
Goldstein, J., pp. 271, Springer Science + Business Media, ISBN 0306472929, New
York, USA

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Goldstein, J., Newbury, D.E., Joy, D.C., Lyman, C.E., Echlin, P., Lifshin, E., Sawyer, L.C. &
Michael, J.R. (2003c). Scanning Electron Microscopy and X-ray Microanalysis,
Goldstein, J., pp. 275, Springer Science + Business Media, ISBN 0306472929, New
York, USA
Goldstein, J., Newbury, D.E., Joy, D.C., Lyman, C.E., Echlin, P., Lifshin, E., Sawyer, L.C. &
Michael, J.R. (2003d). Scanning Electron Microscopy and X-ray Microanalysis,
Goldstein, J., pp. 282, Springer Science + Business Media, ISBN 0306472929, New
York, USA
Goldstein, J., Newbury, D.E., Joy, D.C., Lyman, C.E., Echlin, P., Lifshin, E., Sawyer, L.C. &
Michael, J.R. (2003e). Scanning Electron Microscopy and X-ray Microanalysis,
Goldstein, J., pp. 286-288, Springer Science + Business Media, ISBN 0306472929,
New York, USA
Goldstein, J., Newbury, D.E., Joy, D.C., Lyman, C.E., Echlin, P., Lifshin, E., Sawyer, L.C. &
Michael, J.R. (2003f). Scanning Electron Microscopy and X-ray Microanalysis,
Goldstein, J., pp. 349, Springer Science + Business Media, ISBN 0306472929, New
York, USA
Haber, J., Stoch, J. & Ungier, L. (1976). X-ray photoelectron spectra of oxygen in oxides of
Co, Ni, Fe and Zn. Journal of Electron Spectroscopy and Related Phenomena, Vol. 9, No.
5, pp. 459-467, ISSN 0368-2048
Hammer, M., Monty, C., Endriss, A. & Hoffmann, M. J. (1998). Correlation between Surface
Texture and Chemical Composition in Undoped, Hard, and Soft Piezoelectric PZT
Ceramics. Journal of the American Ceramic Society, Vol. 81, No. 3, pp. 721-724, ISSN
1551-2916
Hirata, S., Okamoto, K., Inoue, S., Kim, T. W., Ohta, J., Fujioka, H. & Oshima, M. (2007).
Epitaxial growth of AlN films on single-crystalline Ta substrates. Journal of Solid
State Chemistry, Vol. 180, No. 8, pp. 2335-2339, ISSN 0022-4596
Huang, C.-L., Tay, K.-W. & Wu, L. (2005). Fabrication and performance analysis of film bulk
acoustic wave resonators. Materials Letters, Vol. 59, No. 8-9, pp. 1012-1016, ISSN
0167-577X
Joint Committee on Powder Diffraction Standards (JCPDS) databaseInternational Center
for Diffraction Data (1998a) PCPDFWIN v.2.01. The JCPDS card number of ZnO is
89-1397
Joint Committee on Powder Diffraction Standards (JCPDS) databaseInternational Center
for Diffraction Data (1998b) PCPDFWIN v.2.01. The JCPDS card number of AlN is
89-3446 and JCPDS card number of Al2O3 is 88-0107
Joint Committee on Powder Diffraction Standards (JCPDS) databaseInternational Center
for Diffraction Data (1998c) PCPDFWIN v.2.01. The JCPDS card number of
aluminum oxide nitride is 48-1581
Kelly, P. J. & Arnell, R. D. (2000). Magnetron sputtering: a review of recent developments
and applications. Vacuum, Vol. 56, No. 3, pp. 159-172, ISSN 0042-207X
Klein, J. C. & Hercules, D. M. (1983). Surface characterization of model Urushibara catalysts.
Journal of Catalysis, Vol. 82, No. 2, pp. 424-441, ISSN 0021-9517
Lee, J. B., Kim, H. J., Kim, S. G., Hwang, C. S., Hong, S.-H., Shin, Y. H. & Lee, N. H. (2003).
Deposition of ZnO thin films by magnetron sputtering for a film bulk acoustic
resonator. Thin Solid Films, Vol. 435, No. 1-2, pp. 179-185, ISSN 0040-6090

www.intechopen.com

244

X-Ray Spectroscopy

Maniv, S. & Westwood, W. D. (1980). Oxidation of an aluminum magnetron sputtering target

in Ar/O2 mixtures. Journal of Applied Physics, Vol. 51, No. 1, pp. 718-725, ISSN 00218979
Manova, D., Dimitrova, V., Fukarek, W. & Karpuzov, D. (1998). Investigation of d.c.-reactive
magnetron-sputtered AlN thin films by electron microprobe analysis, X-ray
photoelectron spectroscopy and polarised infra-red reflection. Surface and Coatings
Technology, Vol. 106, No. 2-3, pp. 205-208, ISSN 0257-8972
Muthukumar, S., Gorla, C. R., Emanetoglu, N. W., Liang, S. & Lu, Y. (2001). Control of
morphology and orientation of ZnO thin films grown on SiO2/Si substrates. Journal
of Crystal Growth, Vol. 225, No. 2-4, pp. 197-201, ISSN 0022-0248
Penza, M., De Riccardis, M. F., Mirenghi, L., Tagliente, M. A. & Verona, E. (1995). Low
temperature growth of r.f. reactively planar magnetron-sputtered AlN films. Thin
Solid Films, Vol. 259, No. 2, pp. 154-162, ISSN 0040-6090
Ramam, K. & Chandramouli, K. (2011). Dielectric and piezoelectric properties of rare-earth
gadolinium modified lead lanthanum zirconium niobium titanate ceramics.
Ceramics International, Vol. 37, No. 3, pp. 979-984, ISSN 0272-8842
Ruffner, J. A., Clem, P. G., Tuttle, B. A., Dimos, D. & Gonzales, D. M. (1999). Effect of
substrate composition on the piezoelectric response of reactively sputtered AlN
thin films. Thin Solid Films, Vol. 354, No. 1-2, pp. 256-261, ISSN 0040-6090
Safi, I. (2000). Recent aspects concerning DC reactive magnetron sputtering of thin films: a
review. Surface and Coatings Technology, Vol. 127, No. 2-3, pp. 203-218, ISSN 0257-8972
Sproul, W. D., Christie, D. J. & Carter, D. C. (2005). Control of reactive sputtering processes.
Thin Solid Films, Vol. 491, No. 1-2, pp. 1-17, ISSN 0040-6090
Sundaram, K. B. & Khan, A. (1997). Characterization and optimization of zinc oxide films by r.f.
magnetron sputtering. Thin Solid Films, Vol. 295, No. 1-2, pp. 87-91, ISSN 0040-6090
Waite, M. M. & Shah, S. I. (2007). Target poisoning during reactive sputtering of silicon with
oxygen and nitrogen. Materials Science and Engineering: B, Vol. 140, No. 1-2, pp. 6468, ISSN 0921-5107
Wasa, K., Kitabatake, M. & Adachi, H. (2004a). Sputtering systems, in: Thin film materials
technology-sputtering of compound materials. K. Wasa, M. Kitabatake, H. Adachi, pp.
135, William Andrew Publishing, Norwick, NY/Springer-Verlag, ISBN 3-54021118-7, Heidelberg, Germany
Wasa, K., Kitabatake, M. & Adachi, H. (2004b). Sputtering systems, in: Thin film materials
technology-sputtering of compound materials. K. Wasa, M. Kitabatake, H. Adachi, pp.
139, William Andrew Publishing, Norwick, NY/Springer-Verlag, ISBN 3-54021118-7, Heidelberg, Germany
Wright, R. V., Hakemi, G. & Kirby, P. B. (2011). Integration of thin film bulk acoustic
resonators onto flexible liquid crystal polymer substrates. Microelectronic
Engineering, Vol. 88, No. 6, pp. 1006-1009, ISSN 0167-9317
Xu, X.-H., Wu, H.-S., Zhang, C.-J. & Jin, Z.-H. (2001). Morphological properties of AlN
piezoelectric thin films deposited by DC reactive magnetron sputtering. Thin Solid
Films, Vol. 388, No. 1-2, pp. 62-67, ISSN 0040-6090
Yan, Z., Zhou, X. Y., Pang, G. K. H., Zhang, T., Liu, W. L., Cheng, J. G., Song, Z. T., Feng, S.
L., Lai, L. H., Chen, J. Z. & Wang, Y. (2007). ZnO-based film bulk acoustic resonator
for high sensitivity biosensor applications. Applied Physics Letters, Vol. 90, No. 14,
pp. 143503
Yue, W. & Yi-jian, J. (2003). Crystal orientation dependence of piezoelectric properties in
LiNbO3 and LiTaO3. Optical Materials, Vol. 23, No. 1-2, pp. 403-408, ISSN 0925-3467

www.intechopen.com

X-Ray Spectroscopy

Edited by Dr. Shatendra K Sharma

ISBN 978-953-307-967-7
Hard cover, 280 pages
Publisher InTech

Published online 01, February, 2012

Published in print edition February, 2012

The x-ray is the only invention that became a regular diagnostic tool in hospitals within a week of its first
observation by Roentgen in 1895. Even today, x-rays are a great characterization tool at the hands of
scientists working in almost every field, such as medicine, physics, material science, space science, chemistry,
archeology, and metallurgy. With vast existing applications of x-rays, it is even more surprising that every day
people are finding new applications of x-rays or refining the existing techniques. This book consists of selected
chapters on the recent applications of x-ray spectroscopy that are of great interest to the scientists and
engineers working in the fields of material science, physics, chemistry, astrophysics, astrochemistry,
instrumentation, and techniques of x-ray based characterization. The chapters have been grouped into two
major sections based upon the techniques and applications. The book covers some basic principles of satellite
x-rays as characterization tools for chemical properties and the physics of detectors and x-ray spectrometer.
The techniques like EDXRF, WDXRF, EPMA, satellites, micro-beam analysis, particle induced XRF, and matrix
effects are discussed. The characterization of thin films and ceramic materials using x-rays is also covered.

How to reference

In order to correctly reference this scholarly work, feel free to copy and paste the following:
Rossana Gazia, Angelica Chiodoni, Edvige Celasco, Stefano Bianco and Pietro Mandracci (2012). X-Ray
Analysis on Ceramic Materials Deposited by Sputtering and Reactive Sputtering for Sensing Applications, XRay Spectroscopy, Dr. Shatendra K Sharma (Ed.), ISBN: 978-953-307-967-7, InTech, Available from:
http://www.intechopen.com/books/x-ray-spectroscopy/x-ray-analysis-on-ceramic-materials-deposited-bysputtering-and-reactive-sputtering-for-sensing-appl

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