Applied Surface Science 138–139 Ž1999.

617–621

Pulsed laser deposition of lithium niobate: a parametric study

a,)
D. Ghica , C. Ghica b, M. Gartner c , V. Nelea d , C. Martin e, A. Cavaleru a ,
I.N. Mihailescu e
a
National Institute of Optoelectronics, PO Box MG-5, 76900 Bucharest, Romania
b
IPCMS-GSI, 23 rue du Loess, F-67037, Strasbourg, France
c
Institute of Physical Chemistry of the Romanian Academy, 202 Spl.Independentei, 77208, Bucharest, Romania
d
ENSAIS, 24 Bld. de la Victoire, F-67084 Strasbourg, France
e
National Institute of Laser, Plasma and Radiation Physics, PO Box MG-54, 76900 Bucharest, Romania

Abstract

We report the deposition of high optical quality LiNbO 3 thin films on SiŽ111. substrates by pulsed laser ablation using a
KrF) excimer laser Ž l s 248 nm, t s 20 ns. source. Experiments have been conducted in oxygen at 5–20 Pa. SiŽ111.
collectors were uniformly heated at 500–7008C. Some of the as-deposited collectors were submitted to an in-situ thermal
treatment in oxygen Ž10 3 –10 4 Pa. at the same temperature. The deposited thin films were characterised by grazing incidence
X-ray diffraction ŽGIXRD., transmission electron microscopy ŽTEM. and spectroscopic ellipsometry ŽSE.. Our LiNbO 3 thin
films, achieved at relatively low temperature Ž5508C., are the first textured and high optical quality pulsed laser deposited
films on Si. q 1999 Elsevier Science B.V. All rights reserved.

PACS: 81.15.Fg; 77.84.Dy

Keywords: Pulsed laser deposition; LiNbO 3 thin films

1. Introduction fabrication of LiNbO 3 thin films, by various experi-

Lithium niobate ŽLiNbO 3 . is an intensively stud-
ied material, due to its very attractive optical, elec-
trooptical, acoustooptical and piezoelectric properties
w1x. For the purpose of commercial applications, it is
of great importance to grow epitaxial or at least
textured LiNbO 3 thin films on Si based substrates, in
view of integrating complex hybrid systems. During
last years, a lot of work has been devoted to the
)
Corresponding author. Tel.: q40-1-420-10-01; Fax: q40-1-
420-10-01; E-mail: ghica@alpha2.infim.ro
mental techniques: molecular beam epitaxy w2x, liq-
uid phase epitaxy w3x, rf sputtering w4x and particu-
larly by pulsed laser deposition ŽPLD. w5–10x. Since
the successful growth of high Tc superconductors by
PLD, this technique has become a universally ac-
cepted solution to obtain high quality stoichiometric
multicomponent thin films w11x.
Epitaxial LiNbO 3 layers have already been
achieved on sapphire substrates w5–7x. Films de-
posited on Si substrates were rather polycrystalline
w8x or amorphous w9,10x. In all these attempts, much
care was paid to prevent the growth of a Li deficient

0169-4332r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 4 3 3 2 Ž 9 8 . 0 0 4 6 3 - 2
618 D. Ghica et al.r Applied Surface Science 138–139 (1999) 617–621
Fig. 1. GIXRD spectra Ž l s1.789 A ˚ . of LiNbO3 rSi: Ža. poly-
crystalline thin film in the case of sample 1; LiNb 3 O 8 phase is
also present, Žb. texturing tendency showed by sample 2, Žc. Ž104.
textured thin film in the case of sample 3.
phase ŽLiNb 3 O 8 . along with the desired LiNbO 3
phase. For this purpose, several solutions were pro-
posed: in Refs. w5,9x Li-enriched sintered targets
were used, while in Ref. w8x depositions were per-
formed in an O 2 and Ar gas mixture. Also, in Ref.
w10x a new configuration in the deposition chamber
was used, in which the substrate did not face the
target, but it was oriented in the opposite direction.
On the other hand, in Refs. w6,7x single phase high
quality LiNbO 3 films were obtained by using classi-
cal conditions: single-crystal LiNbO 3 target, O 2 at-
mosphere and usual PLD configuration. Thus, it is
obvious that conditions for producing epitaxial and
stoichiometric LiNbO 3 thin films are not yet well
established, and certainly, a lot of work is still to be
done on this subject.
In this paper, we report the deposition of high
optical quality LiNbO 3 stoichiometric thin films on
SiŽ111. substrates by PLD. We emphasise our efforts
to prevent the possible growth of Li deficient phases,
as LiNb 3 O 8 .
2. Experimental
A KrF) excimer laser Ž l s 248 nm, t s 20 ns,
repetition rate of 2 Hz. source was used to ablate the
single-crystal LiNbO 3 target. The laser beam was
focused on the target to obtain fluences of 4–8
Jrcm2 at 458 incidence angle. The target was
mounted on a rotating holder in order to ensure a
constant angular distribution of the ejected matter
from the target during deposition. The heated SiŽ111.
substrates were placed parallel to the target at a
distance of 3 cm, in a vacuum chamber evacuated
down to a residual pressure of 10y3 Pa. LiNbO 3
films were deposited in a flowing oxygen atmo-
sphere Ž0.3 sccm. at a pressure in the 5–20 Pa range.
The deposition temperature was set in the 500–7008C
range. Some of the as-deposited collectors were sub-
mitted to an in-situ thermal treatment in oxygen
Ž10 3 –10 4 Pa. at the same temperature for 1–2 h.
The temperature was slowly varied for all the sam-
ples Ž48Crmin., both prior and after deposition, in
Table 1
Deposition parameters and the corresponding samples codification
Sample Fluence Deposition O 2 Annealing O 2 Temperature
ŽJrcm2 . pressure ŽPa. pressure ŽPa. Ž8C.
1 4 20 – 700
2 6 5 10 3 Ž1 h. 550
3 8 5 10 4 Ž2 h. 550
 D. Ghica et al.r Applied Surface Science 138–139 (1999) 617–621 619

order to avoid stresses due to the mismatch of ther-
mal expansion coefficient between LiNbO 3 and Si.
The deposited thin films were characterised by
grazing incidence X-ray diffraction ŽGIXRD., trans-
mission electron microscopy ŽTEM. and spectro-
scopic ellipsometry ŽSE.. GIXRD spectra of the
deposited films were recorded with a Siemens Krys-
talloflex D 5000 diffractometer using the Co K a
radiation Ž l s 1.789 A˚ .. TEM studies have been
performed on a Topcon 002B electron microscope
operating at 200 kV accelerating voltage. Samples
for TEM observation have been mechanically thinned
by the tripod technique. SE analyses have been made
on a null UV–VIS ellipsometer in PCSA ŽPolarizer-
Compensator-Sample-Analyzer. configuration at 708
incidence angle. The accuracy of the polarizer, ana-
lyzer and compensator readings is 0.018.
3. Results and discussions
Fig. 1 shows GIXRD spectra for LiNbO 3 thin
films obtained in various experimental conditions.

Fig. 2. Plane-view TEM images and the corresponding SAED patterns of LiNbO 3 thin films in sample 2 Ža. and sample 3 Žb..
620 D. Ghica et al.r Applied Surface Science 138–139 (1999) 617–621

Fig. 3. Cross-section TEM image of sample 3 showing a columnar growth mode.

We summarise in Table 1 the deposition parameters avoid the Li re-emission by the heated substrate, we
and the corresponding samples codification. We ob- reduced the substrate temperature of sample 2. As a
served that sample 1 corresponds to a polycrystalline result, the presence of LiNb 3 O 8 was not so reduced
LiNbO 3 film with no preferential crystallographic as expected, but the LiNbO 3 phase showed a prefer-
orientation ŽFig. 1a.. One can also observe the pres- ential growth orientation ŽFig. 1b.. The thermal treat-
ence of the undesired LiNb 3 O 8 phase. According to ment is responsible for the improvement of the crys-
previous experimental studies w7,10x, the presence of tallisation degree observed in sample 2. A further
a Li deficient LiNb 3 O 8 phase could be the conse- increasing of the laser fluence combined with a
quence of collisional processes in plasma and of longer thermal treatment Ž2 h. at a higher oxygen
surface phenomena occurring as a result of the sub-
strate heating. The nature and pressure of the buffer
gas influence the angular distribution of the atomic
species in the laser plasma, i.e., the lighter the
atomic species, the larger the scattering angle. In
order to reduce the scattering angle for the Li atoms,
we decreased the oxygen pressure during deposition
in the case of sample 2. The laser fluence was
increased for the same reason. The possible resulting
oxygen loss was compensated by an annealing treat-
ment. On the other hand, the substrate temperature
during deposition could influence the film stoichiom-
etry. It is well known that Li is a highly volatile
metal, for which films deposited at high temperature Fig. 4. Refractive indices of sample 3 ŽNo and Ne. compared to
are usually Li deficient. This is why, in order to the single-crystal bulk values ŽNo-bulk and Ne-bulk..
 D. Ghica et al.r Applied Surface Science 138–139 (1999) 617–621
pressure Ž10 4 Pa. resulted in the deposition of a
stoichiometric LiNbO 3 thin film with a higher degree
of crystallographic orientation ŽFig. 1c.. The lattice
parameters calculated by using the X-ray diffraction
pattern presented in Fig. 1a are a s 5.1205 A ˚ and
c s 13.8146 A,˚ which means D a s 0.58% and D c
s 0.36% variations from the corresponding stoichio-
metric bulk values.
TEM studies confirmed the GIXRD results con-
cerning the crystalline structure and texturing ten-
dencies of the thin films. Plane-view images evi-
dence a better film crystallisation in sample 3 com-
pared to sample 2, the mean crystalline grain size
increasing from 50 nm in sample 2 ŽFig. 2a. to 100
nm in sample 3 ŽFig. 2b.. The degree of crystallo-
graphic orientation is also higher in sample 3 than
sample 2, as demonstrated by the corresponding
electron diffraction patterns. The texturing tendency
is evident from the aspect of the diffraction rings,
some of which appearing as circle segments. Images
obtained on samples prepared in the cross-section
configuration present a columnar morphology for all
our thin films ŽFig. 3..
The modelling programme we used in our SE
investigations to fit the ellipsometrical spectra is
based on the multilayer and multicomponent Brugge-
man Effective Medium Approximation ŽEMA. w12x.
The best fit for sample 3 Žthe textured one. corre-
sponds to a 3027 A ˚ thick layer. This thickness is in
good accordance with the value obtained by the
examination of the cross-section TEM image of this
sample ŽFig. 3.. In Fig. 4, we compare the calculated
thin film No Žordinary. and Ne Žextraordinary. re-
fractive indices with the corresponding single-crystal
bulk values taken from Ref. w1x. To our knowledge,
this is the best agreement ever reported between the
bulk values and the values measured on PLD LiNbO 3
thin films over the whole visible spectrum. These
results point out that our thin films are stoichiomet-
621
ric, having in view that the refractive indices depend
on the LirNb ratio w1,4x.
4. Conclusions
We report the first textured LiNbO 3 thin films of
high optical quality obtained by PLD on Si sub-
strates. Our films, deposited at relatively low temper-
ature are stoichiometric and Ž104. textured. Refrac-
tive indices are very close to the bulk values all over
the visible spectral range. Experimental studies are
still in course in order to improve the crystallo-
graphic orientation of the LiNbO 3 thin films with
respect to the substrate.
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