Thin Solid Films 339 (1999) 284±289

Formation of ultra-thin ceramic TiO2 ®lms by the Langmuir±Blodgett

technique ± a two-dimensional sol-gel process at the air±water interface
Monika Oswald a, c, Volker Hessel b, Ralf Riedel a,*
a
Fachgebiet Disperse Feststoffe, Fachbereich Materialwissenschaft, Technische UniversitaÈt Darmstadt, Petersenstrasse 23, D-64287 Darmstadt, Germany
b
Institut fuÈr Mikrotechnik Mainz GmbH (IMM), D-55071 Mainz, Germany
c
Fraunhofer-Institut fuÈr Silicatforschung (ISC), Neunerplatz 2, D-97082 WuÈrzburg, Germany
Received 17 April 1998; accepted 31 July 1998

Abstract
Different molecular titanium alkoxides were investigated as precursors for the synthesis of thin to ultra-thin TiO2 ceramic ®lms. The ®lms
were prepared by the Langmuir±Blodgett technique. Therefore, the precursor was dissolved in CHCl3 and subsequently spread on water,
aqueous acetic acid and aqueous acetylacetone as the subphase. Hydrolysis of the titanium alkoxides, namely Ti(OR)42x(OR 0 )x with x ˆ 0
(R ˆ n-C4 H9 or n-C9H19) and x ˆ 2 (R ˆ n-C4 H9 and R 0 ˆ 2; 4 pentanedionate) and [(RO)2Ti-O-]n with R ˆ n-C4 H9 was performed at the
air±water interface. This reaction can be considered as a two-dimensional sol-gel-process. The surface-pressure±area (p ±A) isotherms as
well as the in¯uence of the molecular structure of the precursor on the morphology of the resulting condensation products (gels) are
discussed. Pyrolysis of the transferred gels under oxygen atmosphere up to 7008C gives the desired TiO2-layers. q 1999 Elsevier Science
S.A. All rights reserved.
Keywords: TiO2®lms; Langmuir±Blodgett technique; Sol-gel process; Air±water interface

1. Introduction PbS, Au or Pt [6,7]. Especially, TiO2 ®lms are used as anti-

re¯ectants and as semiconducting layers within photovoltaic
The Langmuir±Blodgett (LB) technique for the prepara- cells and can also be applied in the form of PZT and BaTiO3
tion of organic ultra-thin ®lms is a traditional object of as piezoelectric and ferroelectric ®lms [8±11]. The synthesis
research, since these ®lms ®nd a wide ®eld of application of TiO2 thin ®lms by the LB technique has been ®rst
due to their well-ordered structure. They can be used for described by Moriguchi et al. [12]. This procedure starts
example as sensors in piezo- and pyroelectric devices and as with the hydrolysis of titanium-n-butoxide tetramer spread
gas separating membranes [1,2]. A potential disadvantage on a water surface, followed by condensation forming a gel
of organic ®lms formed by the LB method is their low ®lm or gel particles. The resulting gels can be transferred
thermal, chemical and mechanical resistance. However, onto substrates and densi®ed to ceramic ®lms comprised of
new developments are enlarging the scope of materials titania by a subsequent heat treatment (pyrolysis). Various
available by the introduction of inorganic materials. Films substrates can be used since temperatures far below 10008C
comprised of titanium dioxide or silver particles can be can be applied to cleave the remaining organic groups and to
processed by simple chemical means. By use of a ®lm form the ®nal ceramic. Aqueous acetic acid or aqueous
balance a particle ®lm can be formed with controllable acetylacetone instead of water have been used as a subphase
interparticle distances and can also be transferred onto since they tend to form complex compounds with Ti-alkox-
substrates [3±5]. The range of technological applications ides. This complexation can be utilized to control the hydro-
of ultra-thin ®lms can be widened up by extension of this lysis of the precursor at the air±subphase-interface [12].
method to wet chemistry: it could allow the formation of In this study, a variety of Ti-alkoxides shown in Scheme 1
high temperature and corrosion resistant, semiconducting are comparatively discussed as precursor molecules suitable
and high temperature superconducting ultra-thin ®lms for the formation of titania-based thin ceramic ®lms by the
comprised of ceramics and other materials like CdSe, LB technique. In particular, the two-dimensional sol-gel
process at the air±water interface has been studied namely
* Corresponding author. Fax: 1 49-61-5116-6346;
with titanium-n-butoxide monomer (TNB), titanium-n-
e-mail: dg9b@[Link].

0040-6090/99/$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.
PII: S00 40-6090(98)0122 8-0
 M. Oswald et al. / Thin Solid Films 339 (1999) 284±289 285

Scheme 1. Molecular structures of the investigated Ti-alkoxide amphiphiles TNB, TNN, TDB and PBT.

nonoxide (TNN), titanium-di-n-butoxide(bis-2,4-pentane- 18 MW/cm), 0.01 M aqueous acetic acid (Fluka) or 0.01
dionate) (TDB) and poly(di-n-butyltitanate) (PBT). M aqueous acetylacetone (Fluka). After 30 min the
compression of the gel was performed with a barrier
speed of 1.5 cm/min. The transfer was performed at a
2. Experimental details surface pressure of 15 mN/m, lift speed was 7 mm/min.
After upward transfer, the substrate remained for 180 s in
For the isothermal DSC measurements, 11±13 mg of each air, followed by downward transfer with a pause of 20 s in
Ti-alkoxide given in Scheme 1 were exposed in air at 258C water. Pyrolysis of the hydrolyzed and transferred Ti-alkox-
for 15 h in a Netzsch DSC 200. p ±A isotherms were ides was conducted in a tube furnace (Nabertherm HT 16/
measured using a Langmuir ®lm balance FW 2 (Lauda). 18) under O2 atmosphere with a heating rate of 5 K/min up
The precursor solutions were prepared by dissolution of to 300, 500 and 7008C. After an isothermal hold of 30 min at
100 mg Ti-alkoxide in 10 ml of chloroform. This led to the ®nal temperature, the samples were allowed to cool
concentrations of 0.03 mol/l for TNB (Aldrich), 0.015 down to room temperature with a rate of 2.5 K/min.
mol/l for TNN (ABCR), 0.025 mol/l for TDB (ABCR) AFM measurements were carried out using a SFM-BD2
and 0.05 mol/l for PBT (ABCR). The solutions were spread (Park Scienti®c Instruments). The UV-vis spectroscopy was
at 158C on the subphase by using a microlitre syringe performed on a spectrometer U-3000 (Hitachi). With
(Hamilton). The subphase was puri®ed water (Millipore, increasing layer number n, the UV-vis absorption edge
shifts to higher wavelengths, indicating a particle growth.
For the FTIR measurements a Magna-IRe spectrometer
(Nicolet) was used. X-ray diffraction studies were carried
out with a Philips PW 1050/25 diffractometer with Cu Ka
radiation.

3. Results and discussion

Only few data concerning the hydrolysis kinetics of tran-

sition metal alkoxides are available so far. According to
Livage et al. [13], a hydrolysis rate constant of about K H ˆ
1023 mol/s for Ti(OR)4 compounds at pH ˆ 7 can be
Fig. 1. Isothermal differential scanning calorimetry (DSC) measurements
of TNB and TNN. Accordingly, TNN is more reactive towards hydrolysis roughly assumed. To estimate the relative hydrolysis reac-
than TNB. A strong endothermic reaction is found for TNN after 140 min tivity of the Ti-alkoxides given in Scheme 1, isothermal
exposure in air at 258C while that for TNB is analyzed after 8 h. DSC-measurements of the pure TiO2 precursors were
286 M. Oswald et al. / Thin Solid Films 339 (1999) 284±289

pressure increased, the opposite was found for non-de®ned

forms which showed a decrease of the area values and the
collapse pressure. The most stable TNB derived ®lm was
formed with an aqueous subphase containing acetylacetone
yielding highest values for area and surface pressure. In
addition, TNN, TDB and PBT solutions were spread on
water as a subphase and the phase behaviour was deter-
mined. The resulting isotherms in comparison to that of
TNB with an aqueous subphase containing acetylacetone
are shown in Fig. 2. The precursor molecules TNN and
TNB(acac) needed approximately the same area per mole-
cule, as well as PBT and TDB. The highest collapse pressure
was reached with TNB(acac) which demonstrates that
complexation stabilizes the ®lms due to the preferred forma-
Fig. 2. p ±A isotherms of the precursor amphiphiles spread at 158C on water tion of two-dimensional gel structures.
and 0.01 M acetylacetone, respectively. TNB(acac) and TNN show nearly The theoretical value for the molecular area of TiO2 has
the same value of area as well as TDB and PBT. The collapse pressure been estimated to be 30 A Ê 2 by use of a space ®lling model
varies in a rather wide range. assuming complete hydrolysis of the alkoxy groups of the
precursor. This value has never been attained in the experi-
performed in air at 258C. One surprising result derived from ments (Fig. 2). Therefore, a three-dimensional rather than a
these studies is that TNN exhibits the highest reactivity two-dimensional growth of the TiO2 gel has to be consid-
towards hydrolysis (Fig. 1). The compounds TDB and ered.
PBT show a moderate reactivity while the hydrolysis of To get information about reversibility of the phase beha-
TNB is analyzed to be the slowest reaction. This was not viour, hysteresis curves (p ±A isotherms) of TNB(acac) and
expected, since TNN containing C9 carbon chains is steri- TNN have been measured (Fig. 3). It is known from the
cally more hindered than TNB with C4 carbon units. This literature that TiO2 particles derived from titaniumtetraiso-
®nding indicates that TNN will preferentially form a three- propyloxide tetramer exhibit an irreversible behaviour that
dimensional particulate gel structure whereas TNB is becomes reversible after eight compression±expansion
expected to generate a two-dimensional layer like gel cycles [3]. The same behaviour was found for Fe3O4 parti-
network. cles, which gave reversibility after eleven cycles [14]. The
To study the phase behaviour, a TNB solution in chloro- layers of TNB(acac) revealed a hysteresis but the differ-
form was spread on (i) water, (ii) 0.01 M aqueous acetic acid ences between values of area reached at the beginning of
and (iii) 0.01 M aqueous acetylacetone (acac) as subphases the compression and at the end of expansion became closer
and the surface-pressure±area (p ±A) isotherms were with each series. The Ti-alkoxide TNN behaves in the same
measured. As mentioned above, the complexation of the way but the difference of area values between compression
Ti-alkoxides by acetic acid and acetylacetone retards their and expansion is much smaller than that found for TNB(a-
hydrolysis reaction and leads, therefore, to a two-dimen- cac) and, thus, reversibility is nearly reached after three
sional form of the corresponding gel. By formation of cycles (Fig. 3).
such laminar particles the values of area and the collapse On the basis of the results obtained from the ®lm balance
measurements, gels synthesized from TNB(acac) and from
TNN were used to study their transfer onto substrates. For
TNB(acac) the transfer on mica was not successful, whereas
the gel could be transferred onto hydrophilic silicon ((100)
oriented) and hydrophilic SiO2 glass. The transfer mechan-
isms have been analyzed to be z-type. Samples with 1, 7, 8,
17, 18 and 27 layers were prepared. After drying the trans-
ferred layers were pyrolyzed at 7008C in O2. The ®lms were
examined by AFM, UV-vis and FTIR spectroscopy as well
as by X-ray diffraction. AFM images of a TNB derived gel
on SiO2 glass were recorded before and after pyrolysis. The
transferred gel forms micron-sized agglomerates on the
substrate (Fig. 4a) which grow with every additional layer.
Fig. 3. The hysteresis curves of TNN on water as the subphase narrow with
The size of the agglomerates transferred on silicon is smal-
increasing number of cycles. Reversibility is nearly reached after three
cycles. Experimental conditions: concentration of TNN, 0.015 mol/l; ler compared to that on SiO2 glass. The surface covering is
temperature, 15 8C; maximum pressure, 40 mN/m; compression speed, not complete for both substrates. With increasing heat treat-
1.5 cm/min; holding time, 2 min; expansion speed, 1.5 cm/min. ment the gel gradually transforms to TiO2 and the agglom-
 M. Oswald et al. / Thin Solid Films 339 (1999) 284±289 287

Fig. 4. AFM pictures of a TiO2 gel synthesized from TNB(acac) and transferred onto SiO2 glass, non-pyrolized (left, 18 layers, 50 £ 50mm 2) and pyrolyzed
®lm (right, 18 layers, 7008C, 50 £ 50mm 2). The values of surface roughness for the non-pyrolyzed gel are ptv peak to valley† ˆ 296 nm and
rms root mean square† ˆ 15 nm, for the pyrolyzed TiO2 layers ptv ˆ 183 nm and rms ˆ 7 nm. Therefore, the roughness and also the thickness of the coating
decrease by pyrolysis induced volume reduction.

erate size declines to submicron values (Fig. 4b). It is found after pyrolysis. Values of surface roughness for both the gel
that the obtained coating is more homogeneous and dense and the ceramic material are given in Fig. 4.
FTIR investigations in transmission mode of the non
pyrolyzed gel on silicon revealed the presence of organic
groups (vibrations originating from the precursor with
n (OH) at 3600±3200 cm 21, n (CHx) at 2960±2850 cm 21,
d (CHx) at 1470±1430 cm 21 and from unreacted acetylace-
tone with n (CvO) at 1705±1685 cm 21). Moreover, the
absorption band of the TiOZC bonding at 1125 cm 21 was
found by IR measurements in re¯ection mode [15]. Due to
limitations of the spectral range accessible the TiZO vibra-
tion band of rutile below 500 cm 21 could not be detected
[16]. UV-vis measurements of both non pyrolyzed and pyro-
lyzed gel on SiO2 glass showed that absorption increases
with increasing number of layers n (Fig. 5a). The absorption
edge of the TNB(acac)-gel ranges from 333 nm for a layer
number n ˆ 1 up to 350 nm for n ˆ 27 for the non-pyro-
lyzed gel. The absorption edge of the decomposed counter-
part is red shifted relative to that of the gel indicating a
growth of the individual particles of the agglomerates
induced by the annealing procedure (Fig. 5b).
A change to lower surface pressure during transfer led to
a deposition of a smaller amount of material. This has been
proven both by AFM measurements exhibiting the presence
of smaller aggregates as well as by UV-vis spectroscopy
indicating an enhanced transmission for samples prepared
at lower surface pressure.
Fig. 5. (a) UV-vis spectra of TNB(acac)-gel on SiO2 glass. Transmission The synthesized gel and the TiO2 layer derived therefrom
decreases with increasing number of transferred layers, i.e. more material is were found to be amorphous on SiO2 glass by X-ray diffrac-
deposited by additional transfer cycles. (b) Absorption edge of TNB(acac)- tion studies. In contrast, the ®lms on silicon revealed one
gel on SiO2 glass as a function of the number of layers for both non- re¯ection at 2u ˆ 32:808 corresponding to a d-value of
pyrolyzed and pyrolyzed gel. The absorption edge of both is blue shifted
0.273 nm which is attributed to brookite (200) [17]. The
relative to the values given in the literature. This effect is more pronounced
for the non-pyrolyzed gel compared to that of the pyrolyzed one. The red deviation from the theoretical value of 0.290 nm is
shift found after the thermally induced ceramisation is due to particle explained by the presence of some disorder. The other char-
growth and increased density. acteristic re¯ections of brookite with the d-spacing of 0.347
288 M. Oswald et al. / Thin Solid Films 339 (1999) 284±289

type. Fig. 7 shows AFM images of the gel layers obtained

on SiO2 glass and the corresponding TiO2 ®lms formed after
pyrolysis of the gel. The ®lm is composed of spherical
particles which are nearly closely packed and are uniform
in size. The ®nding of three-dimensional particles corre-
sponds to the DSC measurements indicating that TNN is
more reactive towards hydrolysis as compared to the beha-
viour of TNB. The diameter of the particles can be estimated
to be , 0.2 mm and , 0.1 mm for non-pyrolyzed and
pyrolyzed samples, respectively. This results in a volume
decrease of the TNN-derived gel by the applied heat treat-
ment as already found for that synthesized from TNB. The
covering is rather complete and the values of surface rough-
ness are given in the caption of Fig. 7. Compared with the
gel and the ceramic material obtained from TNB(acac) the
particle size is increased. UV-vis measurements also
Fig. 6. X-ray diffraction pattern of TNB(acac) on silicon as a function of
showed that the thickness of each transferred layer increases
the annealing temperature. The (200) X-ray re¯ection of brookite at 2u ˆ with increasing layer number n. In addition, the transmis-
32:818 increases and decreases in intensity with increasing temperature. sion for the TNB(acac)-gel is higher than that found for the
TNN-gel. Consequently, the latter is more dense and the
nm (intensity ˆ 100) and 0.138 nm (intensity ˆ 75) are not single layer is thicker than that of the TNB-derived ®lm.
visible which is discussed in terms of the formation of a As described in the literature, a correlation between the gel-
textured layer. The intensity of this re¯ection increased structure and the corresponding ceramic could be deter-
with increasing annealing temperature between 300 and mined. Accordingly, non speci®c aggregation results in
5008C and decreased after heating at 7008C as depicted in very porous ®lms while uniform particle formations give
Fig. 6. The phase transition from brookite to rutile as the 'thick' ®lms after heat treatment [20]. Films derived from
stable phase is usually found at 6508C, but seems to be TNB were found to exhibit such porous structures after
retarded by epitaxial growth [16]. On the contrary epitaxi- densi®cation, whereas that attained by TNN were character-
ally grown TiO2 ®lms on Si(100) under hydrothermal condi- ized to be 'thick'.
tions have been analyzed as anatase (112) [18], and ®lms
prepared by spin coating on Si(100) or rutile (110) are
comprised of the rutile structure [19]. 4. Conclusions
The TNN-derived gel with water as the subphase was
successfully transferred both on silicon and on SiO2 glass. In summary, the two-dimensional sol-gel-process at the
The transfer mechanisms have been determined to be z- air±water interface can be considered as a very promising
method for the formation of thin to ultra-thin ceramic ®lms.

Fig. 7. AFM pictures of the gel synthesized from TNN and subsequently transferred from water as the subphase onto SiO2 glass, non-pyrolyzed (left, seven
layers, 10 £ 10 mm 2) and pyrolyzed (right, seven layers, 7008C, 10 £ 10 mm 2). The particles are spherical and the size is reduced by the annealing procedure
from , 0.2 mm to , 0.1 mm. Compared to the transferred TNB(acac) gel the coating can be described to be a rather densely packed array of particles. Values
of surface roughness for the non-pyrolyzed gel are ptv ˆ 172 nm and rms ˆ 11 nm, for the pyrolyzed coating ptv ˆ 77 nm and rms ˆ 7 nm.
 M. Oswald et al. / Thin Solid Films 339 (1999) 284±289 289

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