SPECTROSCOPIC CHARACTERIZATION OF NANOCRYSTALLINE

VICe OXIDES FOR NOVEL COUNTER ELECTRODES

Z. CRNJAK OREL I and A. TURKOVIC';2

lNational Institute o/Chemistry, Hajdrihova 19, P.O Box 3430, SI-IOOl,
Ljubljana, Slovenia;
2Rudjer Boskovic Institute, P.O. Box 118, Bijenicka 54, HR-l0002 Zagreb,
Croatia

1. Introduction

The preparation of vanadium oxide and new mixed vanadium cerium (VICe) oxides thin
films as intercalation compound for lithium ions started from aqueous inorganic
precursors. Thin films of pure V and mixed (VICe) oxides at 78,55,38 and 32 at% of
V were obtained via sol-gel process by dip-coated method which is a well known
synthetic route for preparation of various oxide and mixed oxides materials. These
films were prepared for counter electrode in electrochromic devices. All films were
investigated by cyclic voltammetry CV, UV-VIS technique, FT-IR and Raman
spectroscopy, atomic force microscopy (AFM), grazing-incidence X-ray reflectivity
(GIXR), and grazing-incidence small-angle X-ray scattering (GISAXS) and grazing-
incidence wide angle diffractiop. (GIWAXD). Improved electrochemical properties and
cycling behaviour of vanadium oxide films were obtained after the addition of Ce02.
The intercalation of Li+ ions in VICe films was followed by FT-IR spectroscopy in
combinations with CV measurements. The transmittance did not change significantly
after cycling. The fundamental absorption edge shifts after the intercalation of Lt ions.
The best intercalation properties and cycling durability were obtained for films prepared
at 55 and 38 at% ofV. The amorphous grains between 50-100 nm were observed on the
films surface at 55 at% of V, with AFM. No grain structure was observed at 38 at% of
V but after the cycling increase the surface roughness and grain with grains size of 100
nm were observed. Layered structure in all VICe oxides was revealed by GIXR
method. The average grain radius <R>, obtained by GISAXS, was correlated within
layer thickness. Porosity of samples was obtained by GISAXS. The structure of VICe
oxides was studied using IR and Raman spectroscopies.
Novel nanophase materials require new methods of characterisation. GISAXS,
GIXR and GIWAXD, performed at synchrotron ELETTRA, are such advanced
methods in use. In this paper, GISAXS method is supported by all above mentioned
optical and electrical methods of measurements.
Observed sample which consists of nanometer grains, or have variations in
electron density, will scatter incident electromagnetic wave at small angles. For x-
rays, scattered intensity is measured as a function of scattering angle e. Such

T Tsakalakos et al. (eds.) pgs. 441 - 447

Nanostructures: Synthesis, Functional Properties and Applications;
© 2003 Kluwer Academic Publishers.
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experimental method is called SAXS (small-angle x-ray scattering). Wave vector is
given by equation (1).

q = ~[Sin ~] (1)

where A. is wave vector of probe.

For crystalline materials, peaks of scattered intensity occur at such scattering angles,
that wave vector obeys relation:

q = 2lr , _BRAGGS scattering/diffraction (2)

I .
I = distance between atomic planes

For nanocrystalline grains, which have well defined long range atomic ordering,
nanometer grains are randomly oriented each to other, and Bragg's peaks will be
known as well known peaks of polycrystalline material with significant broadening
of diffraction lines.

2. Experimental

VICe mixed oxides on glass substrate were prepared by sol-gel dip-coating

procedure [1,2]. Data that we obtain from scattering curve depend about the
geometry of experimental set-up. Standard way of measurements is with
perpendicular transmission ofx-rays through the sample.
a) incoming beam at right angle - transmittance occurs if beam· income at right
angle to the surface of the sample. Incoming rays pass through the layer and
substrate and scatter at the other side of sample. Substrate has to be as thin as
possible and not too strong absorbant of x-rays and the path through the layer
depends about the thickness of the layer.
Next relation represents outcoming intensity I, of roentgen ray which passes
through material of thickness d:

I = Ie-I'd
o
(3)
where are;
Jl = linear coefficient of absorption
d = thickness of material
10 = intensity of incoming beam
a) incoming beam at small grazing-incidence angle Beam incoming to sample is
closing a small angle with its surface. With the change of beamS incident angle, we
choose part of sample that is irradiated and scatters the irradiation. We control the
penetration depth of x-rays by changing the incidence angle and substrate
background is relatively small. Our samples of VICe oxides were measured in