Spectrochimica Acta Part B 63 (2008) 1117–1121

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Spectrochimica Acta Part B

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s a b

Characterization of nano-composite oxide ceramics and monitoring of oxide thin film

growth by laser-induced breakdown spectroscopy☆
J.D. Pedarnig a,b,⁎, J. Heitz a,b, T. Stehrer a,b, B. Praher a,b, R. Viskup a,b, K. Siraj b, A. Moser b, A. Vlad b,
M.A. Bodea b, D. Bäuerle b, N. Hari Babu c, D.A. Cardwell c
a
Christian Doppler Laboratory for Laser-Assisted Diagnostics, Johannes Kepler University Linz, A-4040 Linz, Austria
b
Institute of Applied Physics, Johannes Kepler University Linz, A-4040 Linz, Austria
c
Department of Engineering and IRC in Superconductivity, University of Cambridge, Trumpington Street, Cambridge, CB2 1PZ, UK

a r t i c l e i n f o a b s t r a c t

Article history: Multi-component oxide ceramics and epitaxial oxide thin films are analyzed by laser-induced breakdown
Received 21 November 2007 spectroscopy (LIBS). Furthermore, pulsed-laser deposition (PLD) of thin films is investigated by long-term
Accepted 27 June 2008 monitoring of the optical plasma emission. Both nano-composite high-temperature superconductors (HTS)
Available online 13 July 2008
consisting of YBa2Cu3O7 − δ bulk and Y2Ba4MCuOx (M-2411, M = Ag, Nb) nano-particles, and semiconducting
ZnO doped with Aluminum and Lithium are ablated by nano-second laser pulses. The plasma emission is
PACS:
52.25.Os Emission, absorption, and scattering
recorded using grating spectrometers with intensified gated detectors. The LIBS signals of nano-particles
of electromagnetic radiation correlate with the nominal content of the M-2411 phase (0–15 mol%) and reveal a strong signal of Ytterbium
52.50.Jm Plasma production and heating by impurity (3–35 ppm). In situ monitoring of the PLD process shows element signals that are stable for more
laser beams than 10,000 laser pulses for both HTS and ZnO ceramics. The relative concentration of elements in thin films
62.23.Pq Composites (nanosystems embedded and ceramics as determined by LIBS is almost the same.
in a larger structure) © 2008 Elsevier B.V. All rights reserved.
81.15.Fg Laser deposition

Keywords:
Laser induced breakdown spectroscopy
Nano-composite materials
Process control
Pulsed-laser deposition
High-temperature superconductors
Thin films
YBa2Cu3O7
ZnO

1. Introduction the spectrum employing calibration curves or internal standards

Laser induced breakdown spectroscopy (LIBS) is a powerful
method for fast and accurate composition analysis of many classes of
solid, liquid and gaseous materials. In LIBS, a short and intense laser
pulse is focused on the material under investigation and the optical
emission of the laser-induced plasma is spectroscopically analyzed.
The element distribution in the analyte material can be derived from
☆ This paper was presented at the Euro Mediterranean Symposium on Laser Induced
Breakdown Spectroscopy (EMSLIBS 2007) held in Paris (France), 11-13 September 2007,
and is published in the Special Issue of Spectrochimica Acta Part B, dedicated to that
conference.
⁎ Corresponding author. Christian Doppler Laboratory for Laser-Assisted Diagnostics,
Johannes Kepler University Linz, A-4040 Linz, Austria. Tel.: +43 732 2468 9246; fax: +43
732 2468 9242.
E-mail address: Johannes.Pedarnig@jku.at (J.D. Pedarnig).
[1,2].
Oxide materials reveal a wealth of functionality including high-
temperature superconductivity (e.g., YBa2Cu3O7), piezoelectricity (e.g.,
Zn1 − xLixO, GaPO4), colossal magneto-resistivity (e.g., La,SrMnO3), inter-
face conductivity (LaAlO3 / SrTiO3), semiconductivity (e.g., Zn1 − xMnxO)
and ferroelectricity (e.g., PbZrxTi1 − xO3, BaTiO3) [3]. Functional oxides are
multi-element materials that contain two or more different elements in
the unit cell and have complex structure–property phase diagrams. The
synthesis of such materials as bulk and thin films requires precise
control of the fabrication process. Pulsed-laser deposition (PLD) is an
outstanding technology to produce stoichiometric layers of such
materials [4]. Detection of the optical plasma emission enables to
investigate the ablation and deposition process in situ. The combination
of LIBS and PLD has been demonstrated in principle for various classes of
materials such as superconductors [5–7], piezoelectrics and ferro-
electrics [8–10], semiconductors [11], molecules and polymers [12,13]

0584-8547/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2008.06.012
1118 J.D. Pedarnig et al. / Spectrochimica Acta Part B 63 (2008) 1117–1121

and others [14–16]. For PLD process control, however, spectroscopic

monitoring over the total time of film deposition is required.
In this paper, we report on the element analysis of functional oxide
ceramics, the long-term monitoring of plasma emission in PLD of oxide
layers and on the element distribution in epitaxial thin films and
ceramics by means of LIBS method.

2. Experimental

The materials investigated by LIBS are high-temperature super-

conducting (HTS) ceramics, epitaxial HTS thin films and doped II–VI
semiconductor ceramics. The HTS ceramics have a nano-composite
structure consisting of YBa2Cu3O7 − δ (Y-123) as host material and
Y2Ba4MCuOx (M-2411, M = Ag, Nb) nano-particles that are embedded
as secondary phase in the superconductive matrix. The M-2411 nano-
particles have diameters of less than 50 nm. The amount of secondary
phase in the composite ceramics was varied from 0 to 15 mol%. The
particles act as effective pinning centers for the magnetic flux lines and
thereby strongly increase the critical current densities of the HTS
materials [17,18]. For preparation of the M-2411 / Y-123 composites,
commercially available Y-123 (Nexans Superconductors, 99.9%) was
used as host material. The M-2411 material was prepared by solid state
reaction from Y2O3 (99.9%), BaCO3 (99.9%), CuO (99.8%) and M–O (99.9%).
The main impurity in Y2O3 are other rare-earth oxides (b0.1%). Epitaxial
HTS thin films were grown by PLD method on (001) MgO substrates [19].
The films were deposited from Nb-2411 (15 mol%) / Y-123 ceramic
targets and had a thickness of 400 nm. The Al-doped ZnO and Li-doped
ZnO ceramics were prepared by solid state reaction using commercial
powders of ZnO (99.5%), Li2O (99.5%) and Al2O3 (99.5%) as starting
materials. The composition of materials was (Al2O3)0.008 (ZnO)0.992 and
Zn0.88 Li0.12 O before sintering. The Al:ZnO ceramic contained relatively
large Al2O3 grains (diameter ~10 µm) as the sintering temperature
(1200 °C) was much below the Al2O3 melting point (2045 °C).
LIBS measurements of the oxide ceramics and epitaxial thin films
were performed in air by focusing the pulsed Nd:YAG laser radiation
(wavelength λ = 1064 nm, pulse length τL ≈ 6 ns, pulse repetition
frequency υr = 20 Hz) onto the sample surface (spot diameter ~ 1 mm,
laser fluence Φ ~ 12 J/cm2). The focal length of the lens was 12 cm and
the focal point was approximately 5 mm below the sample surface.
Fig. 2. LIBS spectra of YBa2Cu3O7 − δ (Y-123) ceramics containing Y2Ba4CuAgOx (Ag-2411)
The optical plasma emission was collected by means of a quartz fiber and Y2Ba4CuNbOx (Nb-2411) nano-particles as secondary phase. The content of M-2411
that was coupled to an Echelle spectrometer. The fiber had a core phase (M = Ag, Nb) in the ceramic ranged from 0 to 15 mol%. Spectra recorded in air reveal
diameter of ~ 50 µm and a numerical aperture NA = 0.22 (acceptance various atomic and ionic lines of the nominal element components [Cu I (Y), Y II (▼), Y I
angle θmax = arcsin(NA) ≈ 12.5°) and it was placed at a distance of ~ 7 cm (▿), Ba II (a), Ag I (●), Nb I (■)] and lines of an element impurity [Yb II (▲), Yb I (Δ)].

to the plasma plume. The spectrometer was equipped with an

intensified CCD camera. Time gated spectra were recorded in the

Fig. 1. Schematic setup for pulsed-laser ablation of solid target materials, in situ LIBS
analysis of plasma plume and for deposition of thin films. For LIBS measurements, the
optical plasma emission is collected at a view port of the chamber using a quartz fiber.
Dashed lines indicate the acceptance cone of the quartz fiber used for light collection
(cone angle 2 × θmax ≈ 25°). LIBS measurements in air were performed without chamber
and with the laser beam oriented perpendicular to the target surface.
range of 200–850 nm with a spectral resolution λ / Δλ ≥ 10,000
employing a delay time of ΔtD = 1 µs and a gate width of ΔtG = 5 µs. For
LIBS measurements performed during thin film deposition the
ceramic targets were ablated by UV-excimer laser pulses (λ = 248
nm, τL ≈ 20 ns, υr = 10 Hz, Φ = 2–3 J/cm2) in an oxygen gas background
(p(O2) ≤0.7 mbar). Here, the focal length of the lens was 20 cm and the
focal point was slightly above the target surface to achieve uniform
fluence in the spot [4]. The optical plasma emission was recorded by
placing the quartz fiber close to an optical window of the PLD chamber
(Fig. 1). The distance of the fiber to the plume kernel was ~ 15 cm. The
diameter of the relevant area of detection as calculated from the fiber
acceptance angle was comparable to the length of the visible plasma
plume (~5 cm). Up to ten spectra per second were measured in situ
using either an Echelle spectrometer or a portable grating spectro-
meter. For data analysis the observed atomic and ionic emission lines
were identified [20] and Gaussian profiles were fitted to selected lines
using a multi-peak fitting routine. The optical emission signals were
calculated by integrating the fitted peaks over the relevant spectral
range and by subtracting the integrated background intensity. The
optical signals were normalized (e.g., signal from Ag normalized to the
 J.D. Pedarnig et al. / Spectrochimica Acta Part B 63 (2008) 1117–1121 1119

signal from Y) and the signal ratio was correlated to the chemical
composition of the materials investigated. For all materials the
ablation rate was WA ~ 100 nm / laser pulse.

3. Results and discussion

Fig. 2 shows the LIBS spectra of different nano-composite Y-123

based oxide ceramics. Various samples of Ag-2411 / Y-123 (Fig. 2a) and
of Nb-2411 / Y-123 (Fig. 2b) containing 0 to 15 mol% of Ag-2411 and Nb-
2411 nano-particles, respectively, were investigated. For each ceramic
sample 120 single-shot spectra (20 shots per site, 6 different sites)
were collected and averaged. The optical emission of the laser-induced
plasma contains atomic and ionic lines of Cu, Y, Ba, Ag, Nb, and Yb. The
most intense lines are marked by different symbols in the figure. The
spectral patterns are due to the elements nominally contained in the
target material and ytterbium as impurity element. Heavy rare-earth
impurities such as Yb and Dy were observed in Y-123 already earlier
[21]. The signal intensities of Cu I (Y), Y II (▼), Y I (▿), and Ba II (a) are
about the same for all samples investigated. The signals of Ag I (●), Nb I
(■), Yb II (▲), and Yb I (Δ) reveal intensities that depend on the sample
composition. The variation of Ag, Nb, and Yb optical signals with M-
2411 content in the nano-composite ceramics is shown in Fig. 3. The
signals were calculated by integrating the optical intensities for Ag I
(λ = 328.07 nm), Nb I (λ = 405.89 nm), Y I (λ = 410.24 nm), and Yb I
(λ = 398.80 nm) over relevant spectral ranges. The normalized signals
for metals M, Ag I / Y I (■) and Nb I / Y I (●), strongly increase with
increasing M-2411 content (Fig. 3a). The concentration of metal M in a
ceramic containing 1 mol% of M-2411 is ~ 1510 ppm. The limit of
Fig. 4. In situ monitoring of plasma emission in pulsed-laser deposition of thin films.
detection (LOD) is estimated by confidence band method [22]. This Ceramic targets are ablated in low pressure oxygen background (b 1 mbar) and LIBS
limit is defined as the analyte concentration that generates an analyte spectra are recorded continuously during film deposition. (a) Temporal evolution of LIBS
signal (calibration curve) which is comparable to the minimum signals from nano-composite Y-123 based high-temperature superconductors [Ba II / Y II
detectable signal. The minimum signal is the value of the upper (□), Nb I / Y I (▿), Yb I / Y I (Δ)]. (b) LIBS signals from differently doped ZnO
semiconductors [Li I / Zn I (○), Al I / Zn I (w)].

confidence band at zero concentration. The estimated LOD values are

Fig. 3. LIBS signals of Ag, Nb, and Yb depending on the M-2411 content in M-2411 / Y-123
nano-composite ceramics (M = Ag, Nb). (a) Signals of some main elements normalized to
yttrium, Ag I / Y I (■) and Nb I / Y I (●). (b) Signal of impurity normalized to metal M of the
secondary phase, Yb I / Ag I (▼) and Yb I / Nb I (▲).
2.6 mol% and 5.1 mol% for Ag-2411 and Nb-2411, respectively. The
normalized signals Yb I / Ag I (▼) and Yb I / Nb I (▲) do not significantly
depend on composition and show large scatter at small concentrations
(≤3 mol%, Fig. 3b). The results indicate that Yb is introduced to the
ceramics as impurity of the M-2411 phases. The Yb impurity level in
Y2O3 powder used for M-2411 material preparation is ≤0.1% and the
concentration of Yb in the composite material is ~25 ppm at 10 mol%
M-2411. Due to its relatively large signals at comparatively low
concentration Yb can serve as spectroscopic marker of the secondary
M-2411 phases.
We have employed LIBS also for process monitoring in thin film
deposition. The laser-induced plasma emission of HTS ceramics and
ZnO ceramics was recorded in situ during pulsed-laser deposition of
oxide films. Spatially averaged spectra were continuously recorded for
more than 10 min of deposition time (laser pulse repetition rate
10 Hz). The temporal monitoring of the plasma emission of nano-
composite Nb-2411 (15 mol%) / Y-123 ceramics and of Al-doped ZnO
and Li-doped ZnO ceramics is shown in Fig. 4. For HTS ceramics, the
normalized optical signals of Ba II / Y II (□) and Nb I / Y I (▿) and of the
impurity Yb I / Y I (Δ) show significant scatter between individual
measurements (Fig. 4a). The relative standard deviation (RSD) of
normalized optical signals is 8.2%, 14.6%, and 22.5% for Ba II / Y II, Yb I /
Y I, and Nb I / Y I, respectively. The time-averaged signals are stable as
is determined from linear fits to the data. The optical signals of both
types of ZnO ceramics, Li I [λ = 610.4 nm] / Zn I [λ = 636.2 nm] (○) and
Al I [λ = 669.6 nm] / Zn I [λ = 636.2 nm] (w), were recorded separately
and show similar scattering and average temporal stability (Fig. 4b).
The RSD is 14.9% and 7.9% for Li I / Zn I and Al I / Zn I, respectively. The
long-term stability of ablation enables to deposit compositionally
homogeneous layers of material from a single multi-component target
1120 J.D. Pedarnig et al. / Spectrochimica Acta Part B 63 (2008) 1117–1121

[4]. Furthermore, layers of composite material or stacks of different

layers, e.g., multi-layers consisting of highly insulating Li:ZnO and
highly conductive Al:ZnO thin films, can be deposited by alternating
ablation of different targets [23].
The HTS thin films deposited from Nb-2411 / Y-123 and Ag-2411 /
Y-123 ceramics reveal higher critical current densities as phase pure
Y-123 films depending on the M-2411 concentration [19]. For element
analysis, the HTS films were investigated by LIBS and the spectra of
films and of Nb-2411 (15 mol%) / Y-123 ceramics employed for film
deposition were compared (Fig. 5). The film spectrum shown is the
average of six single-shot spectra (only 3 shots per site to avoid
ablation of the underlying MgO substrate, 2 different sites). The
epitaxial thin film and the bulk ceramic produce very similar spectra
with intense emission lines for Cu I (Y), Y II (▼), Y I (▿), Ba II (a), Nb I
(■), Yb II (▲), and Yb I (Δ). The linear correlation coefficient R of the six
single-shot spectra from film and the averaged spectrum from bulk
ceramic is R = 0.883 ± 0.006. Spectra from phase pure Y-123 films and
ceramics were discussed qualitatively in earlier work [24].
The LIBS spectra of HTS thin films and ceramics were quantitatively Fig. 6. Emission intensity of atomic copper depending on excited state energy Ei
measured for Nb-2411 (15 mol%) / Y-123 ceramic (○) and epitaxial thin film (■). Lines
analyzed and plasma temperatures and signal strengths of the
are linear fits to the data in semi-logarithmic representation (Boltzmann plot).
different elements were derived for both materials. The optical
intensity Iij emitted due to transitions between states i and j in an
optically thin plasma in local thermodynamic equilibrium (LTE) is dependence (R = 0.977 for the ceramic, R = 0.962 for the film). This
described by Eq. (1) energy dependence indicates that the plasma is in effective LTE during
    the time of optical measurement (1–6 µs after the laser pulse). The
Iij λ 1 hcN fitted plasma temperatures are 9800 ± 1300 K and 11,000 ± 1100 K for
ln ¼− Ei þ ln ð1Þ
Aij gi kTe Z ðT Þ the film and the ceramic sample, respectively. The temperature values
for both materials are quite similar (0.9 ± 0.15 eV) and comparable to
with Aij the transition probability, gi the degeneracy factor of state i, Ei
earlier results obtained by nano-second laser ablation of pure Y-123
the energy of the upper level of transition, the Boltzmann constant k,
ceramics (1.0 to 0.5 eV during plume expansion [26], ~ 0.8 eV for delay
electron temperature Te, particle number density N, Planck constant
times N1 µs [27]). For ZnO ceramics an electron temperature of ~1.2 eV
h, speed of light c, and the partition function Z(T). The emission
was measured under similar experimental conditions [28]. More
intensity of atomic copper (wavelengths 333.78 nm, 427.51 nm,
accurate determination of plasma temperature and of temperature
465.11 nm, 510.55 nm, 515.32 nm, 521.82 nm, 578.21 nm) was
profiles would require spatiotemporally resolved spectroscopic
analyzed, the most intense lines (324.75 nm, 327.40 nm) revealed self-
measurements [1,2,26,27].
absorption and were not considered. Fig. 6 shows the Cu I optical
Fig. 7 shows element distributions of the Nb-2411 (15 mol%) / Y-123
emission at different energies Ei for films (■) and ceramics (○) as
ceramic and the epitaxial thin film. The distributions are derived from
calculated from the measured intensities Iij and the spectroscopic data
LIBS spectra without re-calibration due to the similar plasma
of Cu I [25]. The optical emission fits reasonably well to a linear energy
temperatures for film and ceramic. The optical signals are obtained
by averaging over several lines for each transition (Cu I, Y II, Nb I, Ba II,
Yb I, and Yb II) and normalization to the Y II intensities. The
distributions are strongly correlated (R = 0.997) and the normalized

Fig. 5. LIBS spectra of Nb-2411 / Y-123 ceramic and of epitaxial thin film deposited from Fig. 7. Distribution of elements in Nb-2411 (15 mol%) / Y-123 ceramic and thin film as
this ceramic. The Nb-2411 content of the ceramic was 15 mol% and the film thickness derived from LIBS measurements. The optical signals of Cu I b2N, Y II b5N, Nb I b2N, Ba II
was 400 nm. The spectra are recorded in air [Cu I (Y), Y II (▼), Y I (▿), Ba II (a), Nb I (■), b3N, Yb I b1N, and Yb II b2N are normalized to the Y II signal for both materials. Numbers
Yb II (▲), Yb I (Δ)]. in brackets indicate the number of spectral lines used for signal calculation.
 J.D. Pedarnig et al. / Spectrochimica Acta Part B 63 (2008) 1117–1121
element signals are about the same for both materials. The standard
deviation of signals is larger for the film than for the ceramic due to the
smaller number of available spectra used for averaging. From the long-
term stability of LIBS signals during PLD and the same element
concentrations for films and ceramics the stoichiometric transfer of
metal elements in the pulsed-laser ablation and deposition process is
concluded. The stoichiometric transfer is a prerequisite for epitaxial re-
crystallization of Y-123 matrix and Nb-2411 nano-particles in the
composite thin films [19]. For materials containing volatile species (e.g.
PbZrxTi1 − xO3) the PLD process is usually non-stoichiometric and
enriched targets (e.g. excess of Pb) can be used to compensate for the
loss of such species. Stoichiometric ablation enables the quantitative
analysis of multi-component materials by LIBS and other related
techniques.
4. Conclusions
In summary, we have reported on the element analysis of oxide
ceramics and thin films and on the in situ monitoring of thin film
deposition processes. The LIBS signals of nano-composite Y-123 based
ceramics scale with the amount of secondary phase nano-particles
mixed to the Y-123 host material (content N 3 mol%). Monitoring of
plasma emission in pulsed-laser deposition of Y-123 based and ZnO
based thin films yields spectroscopic signals that are stable for at least
6000 laser pulses employed for ablation. The nano-composite films
and the ceramics used for film deposition show same element
distributions as calculated from the LIBS spectra. The results indicate
that LIBS is a promising method for in-line control of complex
processes such as multi-component materials analysis and advanced
materials synthesis.
Acknowledgements
This work was financially supported by the Christian Doppler
Research Association (CD laboratory LAD), the Austrian Science Fund
(FWF project P18320) and the European Science Foundation (Research
networks THIOX and NES). K.S. acknowledges support by the Higher
Education Commission of Pakistan.
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