Optics Communications 333 (2014) 109114

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Optics Communications
journal homepage: www.elsevier.com/locate/optcom

Excited state dynamics of nanocrystalline VO2 with white light

continuum time resolved spectroscopy
Ula Krm a, H. Gul Yaglioglu a,n, Betl Kkz a, R. Mustafa Oksuzoglu b,
Mustafa Yldrm b, A. Murat Yac b, Sami Pekdemir b, Ayhan Elmali a
a
b

Department of Engineering Physics, Faculty of Engineering, Ankara University, 06100 Ankara, Turkey
Department of Materials Science and Engineering, Faculty of Engineering, Anadolu University, 26470 Eskiehir, Turkey

art ic l e i nf o

a b s t r a c t

Article history:
Received 1 November 2013
Received in revised form
22 July 2014
Accepted 23 July 2014
Available online 7 August 2014

In an attempt to use ultrafast pump probe spectroscopy technique with white light continuum to reveal
wavelength dependent dynamics of VO2, bandgap needs to be opened. Therefore, nanostructured
amorphous and crystalline VO2 thin lms were prepared with pulsed DC magnetron reactive sputtering.
The mean diameters of grains were measured as 227 0.1 nm and 44 7 0.1 nm for amorphous and
crystalline VO2 thin lms, respectively. Temperature dependent resistance measurements show that
nanocrystalline VO2 thin lm exhibit metal insulator phase transition. The lms exhibited dual band
gaps (2.3 eV, o 0.6 eV for amorphous lms and 1.3 eV, 1.8 eV for crystalline lm). Increased band gaps
made it possible to perform time resolved transmission and reection experiments with white light
continuum at uences above and below photo induced phase transition threshold. Although transmission chance due to photo induced phase transition of VO2 in the literature usually takes places at infrared
region of the spectrum, transmission chance was observed in visible as low as 630 nm in broadband
probe spectra. It was observed that measured time scales depend on not only pump uence but also
probe wavelength. Experiments gave the evidence of the long-lived lower energy non-equilibrium state
related to the photo induced phase.
& 2014 Elsevier B.V. All rights reserved.

Keywords:
Vanadium oxide
Ultrafast dynamics
Phase transition
White light continuum probe

1. Introduction
Vanadium dioxide (VO2) is one of the technologically signicant materials due to its ultrafast insulator to metal phase transition (MIT) property. VO2 is an insulator semiconductor at room
temperature. First order insulator to metal phase transition can be
induced either thermally, at 68 1C critical temperature or by laser
excitation [15]. Ultrafast light induced phase transition property
makes VO2 lms good candidates for optical applications such as
actuators, optical switches, thermochromic windows, and diffractive elements [611].
Although MIT of VO2 was discovered long ago [1], recent
progress in ultrafast time resolved techniques attracted attention
on light induced phase transition phenomena. Phase transition
dynamics of VO2 were investigated with time resolved optical [3],
terahertz [12], X-ray spectroscopic [13], and crystallographic [4,5]
measurements. These measurements revealed that due to ultrafast
photoexcitation of monoclinic VO2 insulator, ultrafast transition

Corresponding author. Tel.: 90 312 2033507; fax: 90 312 2127343.

E-mail address: yoglu@eng.ankara.edu.tr (H.G. Yaglioglu).

http://dx.doi.org/10.1016/j.optcom.2014.07.064
0030-4018/& 2014 Elsevier B.V. All rights reserved.

takes place in not only atomic structural arrangement but also

in electronic properties. These experiments were not able to conclude
whether changing the symmetry of unit cell or creating instantaneous
holes cause MIT. Time resolved spectroscopy experiment [14] with
15 fs resolution revealed that MIT cannot be explained by only
considering excitation of carriers across the semiconducting band
gap. Photo injection of holes into the valance band of insulator VO2
triggers nonthermal rearrangement in atomic and electronic structures. Therefore, MIT can be explained by structurally mediated
transition where transitional phonons connect the two crystallographic phases [15]. On the other hand, recent study on ultrafast time
resolved THz spectroscopy of nanogranular VO2 revealed that both the
transition phonons and electronic excitations are necessary to drive
the ultrafast phase change throughout the lm [16].
Ultrafast time resolved broadband spectroscopy is a powerful
tool to investigate the nature of the dynamics in complex materials [1719] and to study the photoinduced phase transition
dynamics [20] by tting the broadband change in reectivity data
to the time dependent parametization of static dielectric function
[21]. Since there are several broad spectral features overlapping
for VO2, it is difcult to analyze data to obtain whole dielectric
function of the material [22]. However, qualitative assessment of

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U. Krm et al. / Optics Communications 333 (2014) 109114

the data still gives valuable information about photoinduced phase

transition. If the optical band gap of VO2 is opened, ultrafast pump
probe spectroscopy with white light continuum would reveal
wavelength dependent dynamics within the band gap of VO2. It
is known that the response of VO2 as well as the band gap can be
tailored by forming nanocrystals. For example, a new cubic crystal
structure for VO2 nanorods with a large optical band gap (2.7 eV)
has been reported recently [23]. In another recent study, optical
properties of nanostructured VOx thin lms were altered by
post annealing in oxygen [24]. They have observed altered band
gap due to occupied states resulting from vanadium oxide with
low oxygen content. Therefore, we prepared nanostructured VO2
lms followed by post annealing and investigated the ultrafast
dynamics with pump probe spectroscopy experiment with white
light continuum. We discuss here the experimental observation of
time resolved dynamics of nanocrystalline VO2 in a broad spectral
range within the white light continuum spectra.

chosen as 400 nm. Pulse duration inside pump probe experimental set up was measured as 100 fs via cross correlation of pump
and probe pulses. Although the response of reection and transmission pump probe experiments are connected, transmission
mode may show wavelength dependent excited state absorption
features more clearly. Therefore, pump probe measurements
were performed in reection and in transmission modes where
reected and transmitted probe beams were monitored with ber
optic spectrometer, respectively. According to our sign convention
positive sign of pump probe data (R/R) corresponds to decrease
in reection whereas negative sign corresponds to increase in
reection due to the effect of the pump beam in the reection
mode. In transmission mode, positive sign of pump probe data
(T/T) corresponds to nonlinear absorption (NA) whereas negative
sign of T/T corresponds to saturable absorption (SA).

2. Experiment

GIXD patterns of as-deposited and annealed lm indicate that

as deposited lms have amorphous structure and annealed lms
show VO2 crystal structure. Fig. 1a and b shows representative
AFM images of as deposited and annealed lm, respectively. Fig. 1a
reveals that as deposited lm has randomly distributed isolated
particles with the grain size distribution varying from 107 0.1 to
3070.3 nm (mean diameter of grains is 227 0.1 nm). As shown in
Fig. 1b, the post annealing induces an increment in the mean
diameter of the grains and the distribution ranges from 10 70.1 to
7070.3 nm (mean diameter of grains is 44 70.1 nm). As a result
of the structural analyses one can say that post annealing under
vacuum not only increases the mean diameter of the nano-grains
and their distribution of nanostructured VO2 amorphous lm, but
also causes nanocrystalline VO2 lm to be formed.
It is known that the thickness of the lm, presence of
impurities and defects on the crystal structure as well as the
particle size play important role on the transition temperature.
Therefore, MIT transition temperature gives information about the
characteristics of the sample. Recently, transition temperature of
VO2 lm was measured as 64 1C [26]. It was reduced signicantly
with W doping. Transition temperature of V1  xWxO2 lm (for x
2.5) was measured about 32 1C. It is known that MIT temperature
of pure VO2 is 68 1C. Temperature dependent resistance measurements performed on as deposited lms did not show any MIT
phase transition. However, annealed sample exhibit MIT (Fig. 2) at
about 62 1C on heating. Although transition temperature measurement of nanocrystalline VO2 sample is smaller than that of pure
VO2, it is not very far from that value. Therefore, one could say that

Thin lm samples were deposited using the pulsed DC reactive

unbalanced magnetron sputtering technique. The deposition rate
was calibrated using the X-ray reectivity technique and the
thickness of the lm was adjusted by the deposition time. The
lm with 150 nm thickness was deposited onto 30  30 mm2
quartz substrate with an Ar:O2 gas ow ratio of 2:0.6 at 5 mTorr
constant deposition pressure, without substrate heating. Details of
the pulsed DC reactive process are given elsewhere [25]. Postannealing was performed at 400 1C (measured on the substrate
surface) for 1 h under vacuum. Structures of investigated samples
were determined by the Grazing incidence X-ray diffraction
(GIXD) technique (GIXD, Bruker D8 Advance). The surface morphology and grain size were characterized using the Atomic
Force Microscopy (VeecoMultimod 5-AFM with the analyze software Nanoscope 5). Temperature dependent resistance measurements were performed on annealed and as deposited lms
between 20 1C and 110 1C. The absorption spectra of the VO2 lms
(Fig. 4a) were taken using a UVvisible absorption spectrophotometer (Shimadzu UV-1800) versus an uncoated glass substrate as
reference.
Wavelength dependent pump probe measurements were performed by using Ti:Sapphire laser amplier-optical parametric
amplier system (Spectra Physics, Spitre Pro XP, TOPAS) with
44 fs pulse duration and 1 kHz repetition rate. Commercial pump
probe experimental setup with white light continuum probe beam
(Spectra Physics, Helios) was used. The pump wavelength was

3. Results and discussion

Fig. 1. AFM images of (a) as-deposited and (b) post-annealed lm taken in tapping mode in 1  1 mm2 areas.

U. Krm et al. / Optics Communications 333 (2014) 109114

although our sample mostly contains nanocrystalline VO2, nanoVOx with lower oxygen content may also exist in the lm.
The absorption spectra of the VO2 lms (Fig. 3a) shows that
depending on the oxygen supply at the deposition or annealing
process, vanadium may be in V0 (metallic), V2 , V3 , or V5 forms
[27]. Absorption spectrum of as-deposited sample is a typical
spectrum of V0 (metallic) state. On the other hand, shoulder around
320 nm shows that the annealed sample contains more VO2 as
observed in the literature [27]. Optical band gaps of the lms were
evaluated from the plot of (h)1/2 vs h shown in Fig. 3b. Both lms
show dual optical band gaps. Optical band gaps of as deposited lm
were calculated as Eas-dpt1 2.3 eV and Eas-dpt2 o0.6 eV. It is known
that band structure of a single crystal VO2 shows 0.6 eV and 2.3 eV
band gaps [28] corresponding V3dV3d intra band transition and
O2pV3d inter band transitions, respectively. In VO2, the vanadium
atoms are in 4 valance state, and therefore a single electron
resides in the d orbitals [28]. Since as-deposited sample is amorphous with nano-scale grains as shown in Fig. 1a, some oxygen
deciency can be expected due to imperfections and grain boundary
effects, and some V4 ions might be present in the lm as
interstitial ions. Accordingly, obtaining smaller band gap (Eas-dpt2
o0.6 eV) may be attributed to the localized states between V3dV3d
bands. On the other hand, two optical band gaps were calculated as
Eannealed1 1.3 eV and Eannealed2 1.8 eV for the annealed lm. Luo
et al. also measured two optical band gaps as 1.3 eV and 1.9 eV for
annealed vanadium oxide lms [29]. They concluded that larger
optical band gap is due to VO2 and the smaller band gap is due to
existence of occupied states bellow Fermi level resulting from the

Fig. 2. Temperature dependent resistance measurements of annealed sample.

111

existence of vanadium oxides with lower oxygen content in the

nano-VOx lms. Although absorption spectra show that our sample
may contain nano-VOx with lower oxygen content, transition
temperature measurements (Fig. 2) reveal that our lm mostly
contains nanocrystalline VO2. Achieved higher band gap values
made it possible to use time resolved pump and probe spectroscopy
experiments with white light continuum to investigate ultrafast
dynamics of the prepared lms.
Fig. 4a and b shows time resolved reection measurements at
4 mJ/cm2 pump energy and 100 fs pulse duration for both amorphous and crystalline lms. Fig. 4c shows normalized reection
versus wavelength graph at zero and 3.1 ms delay times for both
amorphous and crystalline forms of the sample. It is seen from
Fig. 4a that there is no signature of MIT on the amorphous lm.
Besides, the lifetimes of the dynamics on the amorphous lm
(about 150 fs at 550 nm and about 5 ps at 680 nm) are considerably shorter than that of crystalline lm (longer than 1 ns for both
wavelengths). On the other hand, there are two distinct features at
longer and shorter wavelengths on the transient reectivity signal
for crystalline lm (Fig. 4b and c). It shows increased normalized
reection above 610 and decreased reection bellow that region.
Similar observation was seen very recently [30] at 525 nm and
800 nm probe wavelengths when excited with pump uence
bellow Fth 7 mJ/cm2 (photoinduced phase transition uence
threshold). It was explained that while dynamics at longer
wavelengths is related with transitions between the d|| bands
and thus are strongly affected by changes in the number of free
carriers around the Fermi level, dynamics at shorter wavelengths
is related with the transitions between the O2p to V3d states
which is less affected by the phase transition. In an attempt to see
these transitions clearly, time resolved transmission experiments
with white light continuum at various pump uences were
conducted for nanocrystallineVO2 lm.
Fig. 5ac shows normalized transmission data versus wavelength graphs at various delay times at 0.8 mJ/cm2, 4 mJ/cm2, and
8 mJ/cm2 input uences, respectively. Time evolution of the
normalized transmission data for these uences at 460 nm,
570 nm, and 690 nm wavelengths are also given in Fig. 6ac,
respectively. Data with 0.8 mJ/cm2 input uence (Fig. 5a) shows
NA signal throughout the white light spectra with very long
lifetime. NA signal is bigger around 460 nm wavelength range.
Data with 4 mJ/cm2 input uence (Fig. 5b) shows NA signal similar
to 0.8 mJ/cm2 pumping data at zero delay. A gap with smaller NA
signal centered around 570 nm region appears within 100 fs time
delay and it saturates (SA signal) after 500 fs (Fig. 5b and Fig. 6b).

Fig. 3. (a) Linear optical absorption spectra versus wavelength (b) Inset shows the graphs of (h)1/2 versus photon energy of lms.

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U. Krm et al. / Optics Communications 333 (2014) 109114

Fig. 4. Normalized reection versus wavelengths at 4 mJ/cm2 pump energy for (a) amorphous,(b) crystalline lms at various delay times and (c) for both lms at zero and
3.1 ns delay times.

While SA signal turns to NA again, NA signals around 460 nm and

690 nm region start increasing after 1 ns (Fig. 6a and c, respectively). Although the gap with smaller NA signal centered around
570 nm region still appear at 8 mJ/cm2 pumping which is above Fth
(Fig. 5c and Fig. 6b), it does not turn to saturation. We believe that
absorption signal turning into a saturation signal within 500 fs
time delay around 570 nm region has not been observed experimentally. This signal can be explained as followed:
Normalized transmission data can be evaluated qualitatively.
Pump pulse excite the system to an intermediate state. With
sufcient optical pumping, relaxation from the intermediate state
to the long lived lower energy non-equilibrium state related to the
photoinduced phase [21,31] takes place. From the photoinduced
state the system nally relaxes to one of the equilibrium states. This
nal process occurs usually via heat transfer and therefore has ps
timescale. SA signal seen around 570 nm on the normalized transmission data at 4 mJ/cm2 input uence may be related with the
saturation of this long lived non-equilibrium photoinduced state.
Since photoinduced phase transition takes place at uences above
Fth we do not see saturation signal at 570 nm at 8 mJ/cm2 pumping
uence. On the other hand, nonlinear absorption signal seen at
460 nm (Fig. 6a) which is related with the transitions between the
O2p to V3d states [21] has a very short (a few hundred fs) and
long components. The long component signal increases over time.
As seen from Fig. 6a the time evolution of this signal does not
change with input uence which is due to the fact that transitions
between the O2p to V3d states are less affected by the phase

transition. However, time evolution of the normalized absorption

signal seen at 690 nm changes from low pumping (FoFth) to the
higher one (F4Fth). That is because, longer wavelength signals are
related with transitions between the d|| bands and thus are strongly
affected by changes in the number of free carriers around the Fermi
level [21].
It is known that transmission chance due to photo induced
phase transition is more pronounced above 900 nm [32]. One of
the important results of these experiments is that photo induced
phase transition can be seen at wavelength as low as 630 nm
(Fig. 4b and c) in our sample. We believe that oxygen content as
well as nano crystalline structure may play important role on the
wavelength of photo induced phase transition. More experimental
evidences are needed to clarify this issue. Shifting the photo
induced phase transition wavelength to visible rage is important
for switching applications requiring visible light.

4. Conclusion
In conclusion, we have prepared nanostructured amorphous
VO2 thin lm by using pulsed DC magnetron reactive sputtering.
Post annealing under vacuum produced nanocrystalline VO2 thin
lm. Evaluation of band gap revealed that nanostructured crystalline VO2 lm has increased and dual band gaps around 1.3 eV and
1.8 eV. Due to increased band gap we were able to use pump probe

U. Krm et al. / Optics Communications 333 (2014) 109114

113

Fig. 5. Normalized transmission versus wavelength graphs of crystalline lm at various delay times for (a) 0.8 mJ/cm2, (b) 4 mJ/cm2, and (c) 8 mJ/cm2 input uences.

Fig. 6. Time evolution of the normalized transmission graphs of crystalline lm for (a) 460 nm, (b) 570 nm, and (c) 690 nm wavelengths.

spectroscopy technique with white light continuum for VO2 thin

lms. Although transmission chance due to photo induced phase
transition of VO2 in the literature usually takes places at infrared
region of the spectrum, broad band time resolved probe spectra in
this work revealed that transmission chance could be observed as
low as 630 nm wavelength. Besides, it was shown that time
scales are not only pump uence dependent, but also wavelength
dependent. These results may be important for applications
requiring visible light such as switching. In addition to those,
time resolved transmission experiments showed saturation of
absorption signal region around 570 nm and nonlinear absorption

at shorter and longer wavelengths at 4 mJ/cm2 pump uence. This

observed saturation signal was attributed to the long lived lower
energy non-equilibrium state related to the photoinduced phase.

Acknowledgments
This work is supported by the Scientic and Technological
Research Council of Turkey (TUBITAK, Project No: TBAG-111T351).

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U. Krm et al. / Optics Communications 333 (2014) 109114

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