Appl Phys A (2010) 99: 305–310
DOI 10.1007/s00339-009-5532-4
The effect of cesium metal clusters on the optical properties
of cesium iodide thin films
Kuldeep Kumar · P. Arun · Chhaya Ravi Kant ·
N.C. Mehra · Vincent Mathew
Received: 13 July 2009 / Accepted: 14 December 2009 / Published online: 22 December 2009
© Springer-Verlag 2009
Abstract Cesium metal clusters strongly affect the optical
properties of cesium iodide thin films. The metal clusters are
formed during film formation by thermal evaporation. The
cesium cluster of 30–40 nm in the matrix of cesium iodide
insulating thin films results in Surface Plasmon Resonance
(SPR). The peak position of these SPR peaks showed a red
shift. This was shown to be due to changes in the dielectric
constant of CsI resulting from the strains in the films caused
by the metal clusters themselves.
1 Introduction
Recent years have seen renewed interest in Alkali Halides
(AH) thin films due to their potential use as a photo-cathode
in particle detectors using the Ring Imaging Cherenkov
Technique [1–4]. Of all the alkali halides, cesium iodide
holds the maximum promise because of its high Quantum
K. Kumar · P. Arun ()
Department of Physics & Electronics, S.G.T.B. Khalsa College,
University of Delhi, Delhi 110007, India
e-mail: arunp92@physics.du.ac.in
Fax: +91-011-27666220
C.R. Kant
Department of Applied Sciences, Indira Gandhi Institute of
Technology, Guru Gobind Singh Indraprastha University,
Delhi 110006, India
N.C. Mehra
University Science & Instrumentation Center, University of Delhi,
Delhi 110007, India
V. Mathew
Postgraduate and Research Department of Physics, St. Thomas
College, Palai, Kerala 686574, India
Efficiency (QE) [5]. Studies on cesium iodide films have
shown that their stability depends on the substrate on which
they are grown [6], the rate at which the films are grown [7]
and the method of deposition [8]. Even doped cesium iodide
composites have been studied for applications in the detec-
tors [9–11]. Of the methods used for cesium iodide film de-
position, thermal evaporation has been reported as the best.
Even with such potential applications, detailed characteri-
zation and accumulation of data on CsI films for different
thickness is absent in the literature. With this in view, we
have studied the optical properties of thermally evaporated
thin films of cesium iodide for a thickness of 400–900 nm.
2 Experimental
Transparent thin films of cesium iodide were obtained by
thermal evaporation of pellets made using powder of ce-
sium iodide obtained from Central Drugs House Pvt Ltd,
Mumbai. The starting material was of 99.98% purity. Films
were grown at vacuum better than 1.4 × 10−5 Torr on mi-
croscopic glass substrates maintained at room temperature
and a deposition rate of 1.5 nm/sec. Heating of the tungsten
boat was done by passing a current of 15 Amps. One of the
problems with AH and so also with cesium iodide is their
reactivity with water. They react with humid air on exposure
even at room temperature [6, 7]. Hence the films were stored
in desiccators and only were taken out for characterization
studies.
X-ray Diffraction studies were done with Philips PW
3020 diffractometer while the surface morphology was ex-
amined using a JEOL (JSM)-840 Scanning Electron Micro-
scope (SEM). The optical studies of our samples were done
using Shimadzu’s UV 2501-PC UV–visible spectroscope.
306 K. Kumar et al.

Fig. 1 Scanning Electron

Microscope (SEM) (a and c)
and Atomic Force Microscope
(AFM) (b and d) images
showing the surface
morphology of thin films of CsI.
The film thickness of samples
shown in micrographs (a and b)
is ∼690 nm, while those in
micrographs (c and d) are
thicker and have thickness of
∼880 nm

3 Results and discussion

3.1 Structural and morphological studies

Interesting information can be inferred by just examining the

surface morphology of our samples with both the Scanning
Electron Microscope (SEM) and Atomic Force Microscope
(AFM). The SEM micro-graphs of our films show large
white grains present on a black background. The micro-
graphs are similar to those reported by Senesi et al. [7] and
suggest some aging effects in the films. The grain size of the
films were determined from the SEM micrographs, using
the reference scale given by the electron microscope. The
value reported here are average sizes of 10 to 15 grains se- Fig. 2 Chemical composition of the two distinctly visible phases of
lected randomly in the field of view of the micrograph. This our films were determined by EDX. The spectra (a) suggests the white
method gives the size of the grains lying on the surface. The grains of Fig. 1(a and c) have chemical composition of CsI while (b)
shows that the dark contrast region of Fig. 1(a) is metallic cesium
grain size and density depends on the film thickness. In the
thinner films the white grain density is poor with a large in-
termediate dark region (Fig. 1a). However, with increasing have determined the chemical composition of the two dis-
film thickness, the grain size and density increased to such tinct regions using Energy Dispersive X-ray Analysis, EDX
an extent that the whole film is covered with these white (Fig. 2). Comparison of the spectral peaks and lack of iodine
grains (Fig. 1c). peaks in the dark region established the fact that the white
The dark background also shows some morphological grains are of cesium iodide (CsI), while the dark region is
features suggesting material is present in this region. We films of cesium metal. Also, notice the existence of silicon
The effect of cesium metal clusters on the optical properties of cesium iodide thin films
and oxygen peaks contributed from the substrate; it has in-
creased (proportion of these peak intensities in Fig. 2b) sug-
gesting the dark background is thinner than regions where
the white grains exist. Senesi et al. [7] did not report lack
of iodine in the dark background. We believe they might
have missed this since the films in their study were very
thin (∼300 nm). Hence, the amount of cesium present would
have been too small to give a strong enough signal in EDX.
It appears that as the film is being deposited, chemi-
cal dissociation takes place followed by iodine sublimat-
ing from the film surface. Hence, the samples are multi-
phased films of CsI and Cs. However, as the film thickness
increases, disassociation is discouraged and we successfully
obtain uniform films of CsI. The whole surface is tightly
packed with white large grains of CsI if the grown films have
a thickness greater than 780 nm.
Figure 1(b) and (d) shows some of the sample’s surfaces
as seen using the AFM. As compared to SEM, AFM shows
a larger grain density, which is uniformly distributed on the
surface for the same sample. Grains are even seen in the
SEM’s dark background regions. The disparity between the
two images is basically due to the difference in image for-
mation of the two methods. The dark contrast region of ce-
sium showed no distinct morphology in SEM due to poor
formation of secondary electrons. However, Van der Waals
interaction makes the granularity of this region visible in
AFM. On the other hand it is not possible to resolve which
grains are of cesium metal and which are of cesium iodide.
The cesium metal grains, however, seem to be smaller than
the cesium iodide grains, since the average grain size as
determined from AFM images is smaller than that deter-
mined from SEM. The inset of Fig. 3 shows the variation
Fig. 3 Variation of average grain size (grains of both phases, cesium
metal and cesium iodide) with film thickness. The inset shows the re-
lation of grain size of cesium iodide (determined from SEM) with av-
erage grain size (determined from AFM), using which the variation
of cesium iodide grain size with film thickness was found to follow
3.527T − 1416, where T is the film thickness in nm
307
of grains size as determined from AFM images with corre-
sponding size determined from SEM micro-graphs. The lin-
earity shows a correlation between the cesium iodide grain
size and the average grain size (considering both cesium and
cesium iodide grains). Hence, we can infer the grain size of
CsI from the AFM images. Figure 3 shows that variation of
the average grain size (as determined from AFM) increased
linearly for increasing film thickness. Using the equation of
a least square fit line of the two figures, we have an equation
describing the variation of CsI grain size with film thickness:
CsI = 3.527T − 1416 (1)
where ‘T ’, is the film thickness in nm.
X-Ray diffraction studies showed that the films of CsI
grown at room temperature were polycrystalline in nature
without exception. The existence of cesium in elemental
state in the films whose thicknesses lie below 780 nm is also
evident from the X-ray diffractograms of our samples shown
in Fig. 4. They show a prominent broad peak at 27.5o that
on close examination can be deconvoluted into two peaks
(Fig. 4). The first deconvoluted peak matches the peak po-
sition listed in ASTM Card No. 42-1245 of pure cesium
(2θ = 27.4).
X-ray diffractograms also show two other peaks of vary-
ing prominence, marked as (211) and (220) in Fig. 4. These
peaks match the peak positions listed for cesium iodide in
ASTM No. 06-0311. Thus, as our morphology studies sug-
gested, our film have two phases, namely cesium metal that
exists in tetragonal phase (a = 3.3645 Å and c = 12.552 Å)
and CsI in cubic phase (a = 4.568 Å). The second of the de-
convoluted peaks can be ascribed to the (110) peak of CsI.
This peak is shifted from the 2θ = 27.59° position listed in
the ASTM card. A shift in the peak position when compared
to its position for single crystal of the sample indicates that
the crystal is in a stressed state. A displacement of the X-ray
peak to the right as compared to the peak position of single
crystal indicates a decrease in d-spacing, implying compres-
sive stress acting on the film, and vice versa the increase in
d-spacing is indicative of tensile stress. The term “residual
stress” (or simply stress) emphasizes the fact that the stress
remains after all external forces are removed. These stresses
acting in the film can cause important effects on the prop-
erties of the material. Hence, we shall try to understand the
role of stress on our samples. The stress in the film is calcu-
lated after evaluating the strain using the relation
d dobs − dASTM
= (2)
d dobs
where dobs is the d-spacing measured for the thin film and
dAST M is the corresponding peak’s d-spacing of the single
crystal as reported in the ASTM Card. The stress then can
be determined by multiplying the average strain d/d by
308
Fig. 4 Some X-Ray
diffractograms of CsI films. The
X-ray diffractograms are
identical in nature with Cs metal
peaks and CsI peaks
Fig. 5 variation in strain acting perpendicular to the planes of cesium
iodide crystals with increasing film thickness. Strain acting perpendic-
ular to parallel planes (110) and (220) decreases with increasing film
thickness. However, it shows an increasing trend in the direction per-
pendicular to (211) plane
the elastic constant of material. We have characterized our
films with respect to strain, since it is fundamental in nature.
Cesium iodide’s peak showed shifts indicating that the
samples are in a state of stress. The stress in our samples
essentially arises from the thin film state they are in. This
is evident from the variation in strain acting on CsI with
film thickness. The parallel planes of (hh0) show decreas-
ing tensile stress with increasing film thickness for films
whose thicknesses lie between 550 to 780 nm. The (211)
plane shows a slow increase in tensile stress with film thick-
ness. The variation is so small that for all practical purposes
with respect to the stress on (hh0) plane we can consider that
there is no variation in stress on the (211) plane with vary-
ing film thickness. Interestingly, samples of thickness lower
than 550 nm showed compressive stress. However, the data
points of these samples did not fall on the linear trend ex-
hibited in Fig. 5. Hence, we believe that while film thick-
K. Kumar et al.
Fig. 6 The variation in strain acting on CsI is seen to be influenced
by the strain acting on the Cs dispersed in the film. The correlation of
0.9645 shows the strong linear relation between the two
ness maybe a contributing factor, the stress acting on CsI is
influenced by some other factors.
The Cs (101) peak is also displaced from its ASTM
position of 27.4°, indicative of strain. Evaluation of this
shows that compressive stress acts on cesium polycrystalline
grains. The tensile and compressive stress acting on CsI
shows a dependency on the stress acting on cesium grains
(Fig. 6). As stated earlier, the compressive stress acting on
CsI did not show any correlation with film thickness. This
suggests that the stress acting on the cesium iodide unit cell
is essentially due to the deforming stress acting on the ce-
sium unit cell, or in other words, the mismatch in lattice
structure between the two manifests as stress. Cesium in the
elemental state exists in the tetragonal state, and one would
expect the stress applied on the CsI unit cell would deform
its cubic structure to a tetragonal structure. As can be under-
stood from Fig. 7, the tensile stress acting along the diagonal
(perpendicular to 110 plane) would result in an expansion of
the unit cell in the ‘x’ and ‘y’ direction. This would result in
a compressive force acting along the ‘z’ direction. In other
words, the stress would result in an increase in lattice con-
stant ‘a’ and decrease in lattice constant ‘c’.
The effect of cesium metal clusters on the optical properties of cesium iodide thin films
Fig. 7 The tensile stress acting
on the (110) plane leads to an
expansion of the unit cell in the
‘x’ and ‘y’ axis that results in a
compressive force acting on the
‘z’ axis
Fig. 8 variation in lattice constants of CsI as a function of the strain
acting perpendicular to the plane of (110). The cubic structured crys-
tal (lattice constant 4.5679 Å, shown by a dashed line) deforms and
becomes tetragonal with ‘a’ increasing and ‘c’ decreasing with strain
increasing (≥0.002)
To test this we have estimated the value of lattice con-
stants maintaining the Miller indices. The average value of
lattice constant ‘a’ was evaluated using the new inter-planar
distances (d) for the (hh0) planes. Using this, the lattice con-
stant ‘c’ was calculated using the inter-planar distances for
the (211) plane. Figure 8 shows the variation of lattice con-
stants with the stress acting perpendicular to the (110) plane.
As can be seen, the lattice deformation only becomes evi-
dent for large stress (strain ≥0.002). Thus, both small com-
pressive and tensile stress show lattice constants approxi-
mately equal to that of the undeformed cubic unit cell. How-
ever, with increasing tensile stress (or decreasing film thick-
ness, Fig. 5), there is an increase in the lattice size in the ‘x’
and ‘y’ axis. As suggested above, this in turn leads to a com-
pressive force in the ‘z’ direction resulting in the decrease in
lattice constant ‘c’. This proves that the mismatch in crys-
tal structures of cesium and cesium iodide results in stresses
that tend to modify the cubic unit cell of CsI to tetragonal
cells.
309
4 Optical studies
The existence of metal clusters embedded or dispersed in an
insulating background in our films whose thicknesses were
less than 780 nm is evident from their UV–visible absorp-
tion spectra. Such samples give peaks (generally broad) in
the visible region of the spectra. The increased absorption
corresponds to the resonant frequency of the “surface plas-
mons”. The Surface Plasmon Resonance (SPR) effect arises
due to the collective oscillations of free electrons in metal.
This essentially entails the localized excitation of electrons
and is observed in metal nanoparticles whose dimensions are
far smaller than the incident wavelength of light. The local-
ization of the electron excitation is achieved in nanoparticles
when they are isolated from each other either by dielectrics
or voids. In turn the resonant wavelength of SPR depends
on the nanoparticles size, shape and its dielectric constant
along with that of its surrounding. The inset of Fig. 9 shows
the peaks of SPR in two of our samples which confirms our
EDX analysis and proves the existence of two phases (ce-
sium metal in cesium iodide).
The UV–visible spectra of our films also show the sig-
nature of a thickness dependence. Only the samples whose
thickness is less than 780 nm show SPR peaks in the visible
region of the spectrum. The peak position and Full-Width at
Half-Maxima (FWHM) of the SPR are indicative of the ce-
sium cluster size. Assuming the nanocrystals to have spher-
ical shape, the nanocrystal size/diameter is estimated using
hvF
D = (3)
2πE1/2
where h is Planck’s constant, E1/2 is the full-width at half-
maximum of the absorption peak and vF is the Fermi ve-
locity of electrons. Liang-Fu Lou [12] gives the value of the
Fermi velocity to be around 1 × 108 m/s. Using this formula
we calculated the cesium grain size for different samples.
The values are listed in Table 1.
The grain size of cesium polycrystalline grains were also
calculated from the Full-Width at Half-Maximum (FWHM)
of the deconvoluted X-ray diffraction peaks using the Scher-
rer relation [13],
0.9λ
D= (4)
B cos θ
where D is the grain size (in Å), B is the FWHM of the
particular peak, θ (in radians) is the Bragg angle and λ
(∼1.5405 Å) is the wavelength of the X-rays. Table 1 com-
pares the grain sizes of cesium metal cluster obtained from
SPR and XRD results. The results from XRD would have
more error since it would depend on the accuracy of the de-
convolution of the peaks. The results indicate that the metal
nanoparticles are 30–40 nm in size.
310
Table 1 Table compares the grain size of cesium clusters as obtained
from deconvoluted X-ray peaks, SPR peaks and the surrounding CsI
grains (from (1))
Thickness (nm) SPR (nm) XRD (nm) CsI (from (1))
584.4 37.8 29.75 645
612.8 39.9 34.7 745
692.4 30.8 68.0 1026
724.5 29.1 39.1 1140
Fig. 9 The absorbance spectra (inset) shows classical SPR peaks due
to metal cesium clusters scattered in the films. The SPR’s peak posi-
tion decreases linearly with increasing grain size (the grain sizes were
determined using SPR peaks)
Figure 9 shows the correlation of the Cs cluster size with
peak position. The graph shows a red shift in SPR peak posi-
tion with decreasing grain size. Link [14] and Liu [15] have
shown that the SPR peaks of metal nanoparticles show a red
shift when they are embedded in a host with higher per-
mittivity. A careful examination of Fig. 9 with inferences
of this manuscript shows that the less strained films with
near-cubic structure have metal nanoparticles of ∼30 nm di-
ameter. However, the strained samples with tetragonal lat-
tice have metal nanoparticles of ∼40 nm diameter with their
SPR peaks at ∼300 nm. This implies that the lattice defor-
mities may lead to a lowering of the dielectric constant of
the cesium iodide host. A search of the literature does not
give any experimental confirmation to this idea. However,
Shukla et al. [16] theoretically show that an increasing lat-
tice constant of cubic CsI would result in a decreased dielec-
tric constant. These results, hence, could be useful to further
theoretical investigations to understand the dependency of
the crystal structure on the dielectric constant and in turn
K. Kumar et al.
the optical properties of cesium iodide in the nanoparticle
state.
5 Conclusions
The manuscript discusses the morphological and optical
properties of cesium iodide thin films. Results show the for-
mation of nanocrystalline films of CsI which have increasing
cesium metal nanoclusters presence for lower thicknesses.
These nanoclusters of cesium not only influence the opti-
cal properties directly, but also indirectly, by influencing the
host dielectric constant. These experimental results give in-
sight into the optical properties of CsI and its dependence on
its lattice constant.
Acknowledgements The help in completing the spectroscopic and
diffraction analysis by Mr. Dinesh Rishi (USIC), Mr. Padmakshan and
Mr. Rohtash (Department of Geology, Delhi University) is gratefully
acknowledged. Author K.K. wishes to acknowledge the financial as-
sistance from U.G.C.(India) in terms of Minor Project 6-1(222)/2008
(MRP/NRCB).
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