ELSEVIER Thin Solid Films 268 (1995) 13-17

Li2B407 thin films prepared by the pyrosol process

A. El Bouchikhi a, P. Papet b, A. Haidoux b, E. Philippot b
aLaboratoire de I’Etat Solide, Far&e des Sciences de Kinitra, KLnitra, Morocco
h Luboratoire de Physicochimie des Matkiaux Solides. cc 003. UniversitP de Montpellier II, F-34095 Montpellier cidex S, France

Received 27 July 1994; accepted 6 June 1995

Abstract

Thin films of lithium tetraborate (Li2B407) were obtained by the pyrosol process based on the pyrolysis on a heated substrate of an aerosol
produced by the ultrasonic spraying of a solution. The films exhibited some preferential crystalline orientations. The effect of various parameters
such as the concentration of precursors in methyl alcohol, and the nature and temperature of the substrate were studied to control the
morphology and the preferential orientation of the thin film.

Keywords: Deposition process; Methanol; Pyrolysis

1. Introduction
Due to its high electromechanical coupling constants and
its crystal orientations for which the temperature coefficients
of frequency and time delay are zero [l-6], lithium tetra-
borate (Li2B,0,) seems to be a suitable material for fabri-
cating bulk and surface acoustic wave devices. The crystal
structure of Li*B,O, was studied by Krogh-Moe [7] who
found the crystals belong to the space group 14,cd with the
unit-cell dimensions a = 9.47 A, c = 10.26 A. The basic unit
of the network is a group consisting of two boron atoms
tetrahedrally coordinated by oxygen and two boron atoms
triangularly coordinated by oxygen [ 71. The preparation of
Li2B407 thin films by the sol-gel method 18,9], radio fre-
quency sputter deposition and vapour deposition under low
gas pressure have been described [ lo].
Concerning the sol-gel growth, this low-temperature fab-
rication process has been carried out by Yamashita et al. [ 81,
who used the classical sol-gel method to prepare the thin
films. Substrates such as silicon glasses, oriented Si single
crystal plates and oriented sapphire single crystal plates were
dipped into the coating solution and withdrawn at fixed
speeds in a dry nitrogen atmosphere. Coating solutions were
prepared by dissolving the required amounts of lithium meth-
oxide and boron tri-n-butoxide in methanol, and adding water
and acid to the solution. The results of Yamashita et al. [ 83
show that Li,B40, films with a highly-oriented (122) plane
on Si ( 100) substrates are obtained after heat treating to 800
“C when a sufficient amount of water and acetic acid are
incorporated in the starting solution. By using r.f. sputtering,
it was found this method was not suitable at high r.f. power
for the Li2B407 film fabrication because of the material
decomposition. Under low r.f. power (less than 300 W) the
growth of Li*B,O, thin films is possible.
With the vapour deposition technique (a 50 Pa Argon
overpressure is required in order to avoid decomposition of
Li2B,0, above its melting point in vacuum), c-axis oriented
films were produced on Si ( 100) substrates heated to 480 “C
during film deposition.
In this paper, we report the preparation of oriented LiZB407
films on Si( 111) and SiOZ quartz substrates by the pyrosol
process.
2. Experimental
The deposition process used to perform experiments was
based on the pyrolysis of an aerosol containing the dissolved
alcoxide precursors. The generation of aerosol is realized by
a piezoceramic disc electrically excited which generates an
aerosol with droplets small enough to ensure vapour depo-
sition [ 1 I]. The spray set-up is shown schematically in
Fig. 1. The substrate is heated in a furnace and dry air is used
as the carrier gas for the sprayed solution. As the droplets
approach the substrate, the solvent vaporizes then the solid
sublimes and the vapour diffuses to the substrate. This chem-
ical vapour deposition process is complex because more than
one compound is used and the chemical reaction process
which gives rise to Li,B,O, thin films after pyrolysis and

Elsevier Science S.A.

SSDlOO40-6090(95)06760-4
14 A.E. Bouchikhi et al. /Thin Solid Films 268 (I 995) 13-17
Fig. 1, Schematic diagram of the pyrosol apparatus.
oxidation of the starting compound is not very well under-
stood at this time.
In our experiments the spraying solution consisted of a
mixture of precursors, lithium methoxide or lithium acetyla-
cetonate (LiAA) and boron tri-n-butoxide, in a solvent
(water, methyl or ethyl alcohol). We used a different con-
centration of starting compounds in the concentration range
of 0.01-0.05 mol 1-l for lithium methoxide or lithium ace-
tylacetonate, with a constant ratio [Li] / [B] =OS. The dif-
ferent solutions were sprayed onto heated Si ( 111) or SiOZ
quartz substrates at a rate of 90 ml hh ‘. The average working
parameters for producing a stable spray and steady-state flow
are: a generator frequency - 800 kHz, a power of generator
u 90 W and a flow rate of the carrier gas N 180-200 1 h- ‘.
The morphology of the thin films was observed by scan-
ning electron microscopy (SEM) and the crystallographic
orientations were determined with an X ray diffractometer.
3. Results and discussion
3.1. Effects of the nature of precursors/solvents
With lithium methoxide and boron tri-n-butoxide as pre-
cursors and ethanol as a solvent, no clear solution was
obtained because of the low solubility of boron alkoxide.
However, when water was used as the solvent with the same
precursors, clear and stable solutions were obtained. A series
of experiments were performed with these solutions at vari-
ous substrate temperatures (up to 620 “C) . Unfortunately, no
thin film deposition was observed even after changing the
experimental conditions, such as precursor/solvent concen-
tration ratio, flow rate of carrier gas, etc. Finely divided solid
products were found in the cold part of the pyrosol apparatus.
Upon heating this fine powder at 600 “C X-ray diffraction
patterns exhibited the same pattern as the Li2B407 powder,
indicating that some chemical reactions have taken place in
the vapour phase. Owing to the natural convection above the
heated substrate, however, no thin film nor solid product
deposition onto the substrate were observed. By using lithium
acetylacetonate and boron tri-n-butoxide in methanol in con-
centrations of l.lO-* to 5.10-’ mol l-‘, we obtained crys-
tallized thin films in the substrate temperature range 450-620
“C.
This can be due to the reactivity of these chemical species
which probably form by a hydrolysis/polycondensation
process some polymeric species containing lithium and boron
atoms. These volatile compounds were thermally decom-
posed as the droplets of the spray approach the heated sub-
strate and the resultant gaseous species diffused to the
substrate giving rise to the thin film. By using water as the
solvent, hydrolysis of the precursors is the main chemical
reaction giving rise to soluble compounds which were not
highly volatile and formed very small precipitates before
reaching the substrate as the solvent evaporated.
3.2. Effects of the precursor concentration
In order to examine the precursor concentration effects on
the preferential crystal growth of Li2B407 films formed onto
Si ( 111) substrate, a series of experiments with various pre-
cursor concentrations were performed.
For a LiAA concentration in methanol lower than 0.01
mol 1-l , thin films deposited by spray pyrolysis onto a silicon
( 111) substrate heated at different temperatures in the tem-
perature range 400-600 “C were amorphous. However when
the LiAA concentration was higher than 0.01 mol l- ’ some
crystalline thin films can be deposited depending on the sub-
strate temperature which has to be increased for the lowest
concentration, As can be seen from Fig. 2, which shows X-
ray diffraction patterns of the deposits onto silicon ( 111)
substrates, the crystallized films exhibit a preferred orienta-
tion along the [ 0011 direction for a substrate temperature up
to 500 “C and along the [OOl] and [ 0101 directions as soon
as the temperature is increased. Table 1 gives the relative
intensity of (004) and (040) X-ray peaks versus the substrate
temperature for a LiAA concentration of 0.03 mol l- ‘. These
experimental results suggest the orientation along the [ 0101
IV ZU 30 40 50 60
20 (degrees)
Fig. 2. X-ray diffraction patterns (Cu Kcr) of Li,B,O, thin films onto
Si( 111) substrate at various temperatures. [LiAA] =0.03 mol I-‘.
 A.E. Bouchikhi et al. /Thin Solid Films 268 (1995) 13-17 15

Table 1
Experimental X-ray diffraction data for LiZB407 thin films corresponding to various substrate temperatures on a Si( 111)substrate

d hkl I ASTM I.,, ([LiAA] =0.03 mol I-‘)

400 “C 450 “C 500 “C 580 “C 620 “C

2.51 (004) 6 Amorphous 1000 1000 1000 1000

2.36 (040) 6 0 700 900

Table 2
Experimental X-ray diffraction data for LiZB407 thin films corresponding at various precursors concentration onto a Si( I 11) substrate held at T= 580 “C

d hkl 1ASTM I_,, (T=580 “C)

0.05 mol I-’ 0.03 mol I- ’ 0.02 mol I - ’ 0.01 mall-’

2.57 (004) 6 1000 1000 500 0

2.36 (040) 6 0 700 1000 1000

Table 3 an anisotropic crystal growth along the c axis and/or b axis

influence of the nature of substrate on the crystal growth
as can be seen from Table 2. However for the deposited thin
‘f (“C)
film with a LiAA concentration of 0.01 mol l- ‘, the only
orientation it has been possible to find by X-ray diffraction
Substrate 450 “C 500 “C 580 “C measurement was along the [ 0101 direction and the resultant

Si(ll1) (004) (004) (004) (040)

AT( Quartz) (004) (004) (004)
AT/Au (040) (040) (040)

direction only appears for the highest temperature (typically

up to 580 “C) and for a given substrate temperature this
orientation is more suitable for the lowest concentration as
can be seen from Table 2 which carries the X-ray data show-
ing the shift of orientation from the [ 0011 direction to [ 0101
when the precursor concentration is decreased. The influence
of the nature of the substrate was examined using three kinds
of substrates, Si( 11 l), quartz and quartz with an Au thin
layer sputtered on, heated in the same temperature range
previously used and with a precursor concentration of 0.03
mol 1- ‘. Table 3 presents qualitatively the preferential ori-
entations we obtained in this series of experiments.

3.3. Morphology of the thin films

Fig. 3(a) shows the surface and Fig. 3(b) the cross-sec-
tional SEM photographs of films deposited onto a Si ( 111)
substrate heated at 580 “C and fabricated by spray pyrolysis
of a solution with 0.03 mol 1-l LiAA concentration in meth-
anol. With these experimental conditions the formation of a
deposit seems to be due to the crystal growth of a large
number of needle-shaped single crystals onto the surface of
the Si( 111) substrate and the resultant deposit does not
exhibit a dense microstructure.
The same morphological development of crystallites was
observed with a SiO, quartz substrate. The estimated thick- Fig. 3. Scanning electron micrographs of (a) the surface and (b) the cross-
ness of the deposit is 3-5 pm for a deposition time of 3 h. section of deposited LiZB407 thin films onto a Si( 111) substrate heated at
The morphological development of crystallites emphasizes T=580”C. [LiAA] =0.03 mol I-‘.
16 A. E. Bouchikhi et al. /Thin Solid Films 268 (I 995) 13-l 7
Fig .4. Scanning electron micrographs of (a) the surface and (b) the cross-section of deposited Li,B,O, thin films onto a Si( 111) ssubstrate heated at T= 580
“C. [LiAA] =O.Ol mol 1-l.
thin film presents a homogeneous microstructure (Fig. 41 a)
and 4(b) ) . When the two orientations coexist with an inten-
sity of X-ray peaks corresponding to the [OlO] and [OOl]
directions of the same order of magnitude, the two kinds of
film morphology will probably to be found, but owing to the
important anisotropic crystal growth of the needle-shaped
crystal it becomes very difficult to understand the relationship
between the crystallographic orientation of needle-shaped
crystals and the microstructure. Yampshita et al. [8] found
that on further heating to 800 “C preferential growth occurs
in the (122) plane for thin films deposited by sol-gel proc-
essing onto a Si ( 111) substrate, and the epitaxial growth of
Li2B407 gel films on substrates such as silicon single crystal
is considered to be possible, since the crystal growth proceeds
very slowly via tbe amorphous state. The ( 122) preferential
orientation was attributed to the relatively small number of
oxygen atoms in the ( 122) plane compared with the other
ones. This minimizes the lattice distortion energy between
the Li2B407 film and the Si substrate [ 81. By using the pyro-
sol method an extended single-crystal film formation on top
of a Si( 111) substrate cannot be synthesized with our exper-
imental conditions. Moreover in our experiments no ( 122)
preferential orientation was found and the c-axis oriented
Li2B407 films observed depend on precursor concentration,
nature and temperature of substrate. The (040) plane orien-
tation appears for the lowest precursor concentration and also
when the substrate is heated at high temperature. The precur-
sor concentration seems to drive the crystal growth with a
strong effect on the morphological development of crystal-
lites during film formation.
4. Conclusion
Li,B,O, thin films have been prepared on Si( 111) and
quartz substrates by the pyrosol process. Several precursors
 A.E. Bouchikhi et al. /Thin Solid Films 268 (I 995) 13-l 7
and solvents were tested and only a solution of LiAA and
boron tri-n-butoxide in methanol gives homogeneous and
oriented Li2B407 thin films. Anisotropic crystal growth was
found to be strongly influenced by the precursor concentra-
tion, the nature and the temperature of substrate. In summary,
the pyrosol process used to synthesize Li,B40, thin films
presents some advantages over the other processes because
it is not a costly apparatus, the deposition rate is faster than
sputtering one and it is a low-temperature fabrication process.
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