OPEN Role of microstructures on the M1-M2

SUBJECT AREAS:
phase transition in epitaxial VO2 thin
PHASE TRANSITIONS
AND CRITICAL
PHENOMENA
films
STRUCTURAL PROPERTIES Yanda Ji1, Yin Zhang1, Min Gao1, Zhen Yuan2, Yudong Xia1, Changqing Jin2, Bowan Tao1,
Chonglin Chen3, Quanxi Jia4 & Yuan Lin1
Received
23 October 2013 1
State Key Laboratory of Electronic Thin films and Integrated Devices, University of Electronic Science and Technology of China,
Chengdu, Sichuan 610054, P. R. China, 2The Institute of Physics, Chinese Academy of Sciences, P.O. Box 603, Beijing 100190, P.
Accepted R. China, 3Department of Physics and Astronomy, University of Texas at San Antonio, San Antonio, Texas 78249, USA, 4Center for
14 April 2014 Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
Published
6 May 2014
Vanadium dioxide (VO2) with its unique sharp resistivity change at the metal-insulator transition (MIT) has
been extensively considered for the near-future terahertz/infrared devices and energy harvesting systems.
Controlling the epitaxial quality and microstructures of vanadium dioxide thin films and understanding the
Correspondence and metal-insulator transition behaviors are therefore critical to novel device development. The metal-insulator
requests for materials transition behaviors of the epitaxial vanadium dioxide thin films deposited on Al2O3 (0001) substrates were
systematically studied by characterizing the temperature dependency of both Raman spectrum and Fourier
should be addressed to
transform infrared spectroscopy. Our findings on the correlation between the nucleation dynamics of
Y.L. (linyuan@uestc. intermediate monoclinic (M2) phase with microstructures will open a new avenue for the design and
edu.cn) integration of advanced heterostructures with controllable multifunctionalities for sensing and imaging
system applications.

V
anadium dioxide (VO2) undergoes a metal-insulator transition (MIT) with the resistivity changing sharply
in 4–5 orders of magnitude just above the room temperature (341 K). Such unique characteristic can be
advantageously utilized in microelectronic devices, terahertz devices, and energy harvesting systems,
etc1–4. The MIT is considered to be accompanied by a structural phase transition from monoclinic to rutile.
Recently, the formation of a metastable monoclinic phase of VO2 during the phase transition has attracted much
attention, not only from the point of view of the theoretical understanding of the MIT mechanism, but also from
the technological consideration in control of the transition properties for device applications. The most stable
monoclinic phase of VO2 at room temperature is referred to as the M1 phase, with the b-angle of the unit cell as
122.6u. In this structure, the V atoms are paired and twisted across the octahedral edges5. The localized electron
state in this structure is considered to induce the insulating state. However, during the MIT of the insulating M1
phase to the metallic rutile phase, another metastable monoclinic phase with the b-angle of 91.88u, named as the
M2 phase, has been reported. This metastable M2 phase is normally induced by either doping or strain. In the M2
structure, half of the V atoms pair but do not twist as in the M1 phase. In contrast, the other half of the vanadium
atoms twist, but remain equidistant along the resulting zigzag chain5–8.
To understand the nature of the M2 phase, both theoretical and experimental efforts have been initiated. It was
proposed that the uniaxial stress along [110]R direction would stabilize the M2 phase7. Experimentally, investi-
gations on the M1-M2 transition were mainly focused on single crystalline one-dimensional nanostructures
because it is easier to apply a mechanical stress on these structures6,9–12. There are only a few reports on the
observation of the M2 phase in the VO2 thin films, although stress is widely considered as an important feature in
thin film systems. Okimura et al. conducted in situ X-ray diffraction (XRD) studies on the epitaxial VO2 films on
Al2O3 (0001) grown by pulsed laser deposition, indicating the formation of the M2 phase during the heating
process13. More recently, they also found that the M2 phase could be stabilized in polycrystalline thin films at
room temperature by using a sputtering technique with inductively coupled plasma14,15. These results have clearly
demonstrated that thin film VO2 would be a good model system to study the intermediate phase. However, due to
the very complex microstructures of VO2 thin films and related phase transitions, fundamental understanding of
the correlations between the microstructures and the occurrence of the M2 phase in VO2 thin films is still lacking.
In this paper, we report our effort to systematically study the occurrence of the M2 phase in epitaxial VO2 thin

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Figure 1 | (a) XRD h 2 2h scans for samples Th90 and Th150, respectively;
(b) XRD w scans for samples Th90 and Th150, respectively.

films, using both Raman and Fourier transform infrared (FTIR)

spectroscopies at various temperatures. To fully understand the
mechanisms of the formation of the M2 phase, the high resolution
X-ray diffraction (HRXRD) technique was employed to analyze the
strain states and the microstructures.

Results
Briefly, the VO2 thin films were grown on Al2O3 (0001) substrates by
using a polymer-assisted deposition (PAD) technique as reported
earlier16–18. Different thicknesses of VO2 films were synthesized:
one set of the sample (labeled as sample Th90) had a thickness of
90 nm and the other set of the sample (labeled as sample Th150) had
a thickness of 150 nm. Figs. 1 (a) and (b) show the XRD patterns
from h 2 2h and w scans on the films, respectively. The results Figure 2 | (a) Raman spectra for samples Th90 and Th150 at room
indicate that both samples are crystallized in monoclinic VO2 phase temperature, respectively; (b) Raman spectra for sample Th90 at
(M1) at room temperature and epitaxially grown on the substrates. temperatures ranging from 300 to 360 K; (c) Raman spectra for sample
The epitaxial relationship between the thin film and the substrate was Th150 at temperatures ranging from 300 to 360 K.
determined to be VO2 (001)jjAl2O3 (0001) and VO2 [010]jjAl2O3
[11 20]. identical to those from the pure M1 phase in the bulk single crystal-
Raman spectroscopy was carried out at various temperatures to line VO219,20. This result is reasonable considering the good crystal-
check the occurrence of the M2 phase. Samples were heated from 300 line quality of the as-prepared epitaxial films. With the increase of the
to 370 K during the measurement. Each data point was the average temperature, as shown in Figs. 2(b) and (c), the peaks in the Raman
from 10 repeated records with the integral time of 10 s. The variation spectrum become weaker and finally disappear. This corresponds to
of the temperature was controlled to be less than 0.5 K during the the first order transition of crystalline structure from the low sym-
measurement. According to the reported results10,12, the fingerprint metry of monoclinic to the high symmetry of rutile. If we look at the
for the M1–M2 phase transition is the blueshift of the Raman peak detailed Raman spectra during the temperature increase, it is inter-
from 618 cm21 (the M1 phase) to 642 cm21 (the M2 phase). The esting to notice the difference between Th90 and Th150 at around
blueshift is resulted from the change of Ag vibrate mode in VO2 unit 334 K. Specifically, occurrence of the M2 phase of VO2 with the
cell. As shown in Fig 2(a), both samples (Th90 and Th150) exhibit Raman peak shifting from 618 cm21 to 642 cm21 could be clearly
almost the same spectra at room temperature. The spectra are observed in sample Th150 instead of sample Th90, as shown in

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Figs. 2(b) and (c). To verify the results, the Raman spectra between temperatures. In other words, both the amount of the M2 phase
520 and 720 cm21 for both samples measured at various tempera- and the temperature window for the occurrence of the M2 phase
tures were carefully fit with Lorentz functions. Figs. 3(a) and (b) show are larger in Th150 than Th90 during the MIT.
the fitting results for Th90 and Th150, respectively. The peaks cen- To have a better understanding of the phase transition, IR trans-
tered at 577, 618, 642 cm21 correspond to the characteristic Raman mission properties of the samples were measured by using the IR
peaks from the Eg mode of sapphire, and the Ag modes of the M1 and light with different wavelengths at different temperatures. Both the
M2 phases of VO2, respectively. It is found that both samples are as-prepared samples, Th90 and Th150, exhibit strong modulation of
actually composed of mixing phases of M1 and M2 during the MIT. IR transmission at room temperature in the wavelength range from
However, the M2 peak started to occur at a much lower temperature 2500 to 5000 nm, as shown in Fig. 4(a). The transmittance becomes
for sample Th150 (305 K) than Th90 (332 K). Moreover, the M2 lower as the film thickness increases, possibly due to the stronger
peak is comparable or even higher than the M1 peak for Th150 when absorption from a thicker film. Fig. 4(b) is the IR transmittance
the temperature is higher than 330 K. On the contrary, for Th90, the measured at various temperatures with a wavelength of 4000 nm.
M1 peak is dominant throughout the whole measuring range of Hysteresis loops were observed from both samples as the results of

Figure 3 | Lorentz fitting results for the Raman spectra in the range from 520 cm21 to 720 cm21 measured at various temperatures for samples Th90 (a)
and Th150 (b), respectively. (Black dots are the original data, black lines are the Lorentz fitting line, purple lines indicate the Eg mode of sapphire, red lines
indicate the Ag mode of the M1 phase of VO2, and blue lines indicate the Ag mode of the M2 phase of VO2.)

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using HRXRD. Similar to the strain distribution analysis for the other
epitaxial oxide thin films21–26, the strain states can be determined by
characterizing the changes in related diffraction peak positions,
which reflect the changes in the lattice parameters. The reciprocal
space maps (RSMs) were recorded around Al2O3 (0006) and VO2
(002) for samples Th90 and Th150, as shown in Figs. 5(a) and (b),
respectively. It is found that the positions of VO2 (002) for both
samples are almost the same, i.e., at about 3400 arcseconds lower
than the diffraction spots from Al2O3 (0006). The lattice parameters
of the c-axis for both samples (Th90 and Th150) are estimated to be
5.3730 Å. Comparing to the lattice parameter of bulk VO2, 5.3820 Å
(JCPDS 82-0661), a compressive strain of 20.17% was found along
the c-axis for both samples. Under the assumption of constant unit-
cell volume, a tensile strain along [011]M1 is expected. By tilting the
samples with the setting of x 5 44.8416u, XRD h 2 2h scanning
patterns were collected to measure the in-plane lattice parameters
along the [011]M1 direction of the as-prepared VO2 thin films, as
shown in Fig. 5(c). The [011]M1 lattice parameters were determined
to be 3.208 Å and 3.209 Å for samples Th90 and Th150, respectively.
Comparing with its bulk parameter (3.2034 Å), tensile strains of
0.14% and 0.17% for samples Th90 and Th150 were estimated along
the [011]M1 direction, respectively.

Discussion
The [011]M1 would be changed to [110]R when the monoclinic phase
M1 is changed to rutile structure27. Therefore, the tensile strains may
induce the formation of the M2 phase in both samples, Th90 and
Th15011. Nevertheless, the temperature window for the occurrence of
the M2 phase can be quite narrow due to the very weak strains.
Although the values of the tensile strain in samples Th90 (0.14%)
and Th150 (0.17%) are very close to each other, the occurrence
window for the M2 phase is very different. More exactly, the amount
of M2 phase and the temperature window for the occurrence of the
M2 phase are much larger in Th150 than Th90, leading to the clear
direct observation of M2 phase in sample Th150 rather than in Th90
under the exactly same experimental set up, as demonstrated by the
temperature dependency of Raman spectrum and FTIR spectrum
shown above.
To clarify the different occurrence window of the M2 phase in
these two epitaxial VO2 thin films, peak spreading of the as-grown
films were analyzed by HRXRD v and w scans. As shown in Figs. 5(a)
and (b), the full width at half maximum (FWHM) of v 2 2h scans
around VO2 (002) (along the y-axis in Figs. 5(a) and (b)) are almost
the same for samples Th90 and Th150, indicating the similar global
strain states of both films. However, the FWHM of the v scan (along
the x-axis in Figs. 5(a) and (b)) for the Th150 sample is much wider
than that for the Th90 sample. Similar results (as shown in Fig. 5(d))
Figure 4 | (a) FTIR spectra for samples Th90 and Th150 at 313 K and were observed in the v scan rocking curve of VO2 (011) where the
353 K, respectively; (b) IR transmittance versus temperature for samples sample was tilted by x 5 44.8416u. Theoretically, the FWHM of the v
Th90 and Th150, respectively; (c) differential curves of transmittance scan (bm) comes from several sources28:
versus temperature for samples Th90 and Th150, respectively (the dotted
b2m ~b20 zb2d zb2r zb2l zb2a ð1Þ
lines indicated the fitting results of these differential curves using Gaussian
functions). where b0 is the intrinsic width of X-ray, bd is from optical path of the
X-ray equipment, br depends on the radius of curvature of the sam-
the intrinsic MIT properties of VO2. The differential curves of the IR ple, bl depends on the grain size of the sample, and ba is the broa-
transmittance versus temperature are plotted in Fig. 4(c). If we fit dened width due to the screw dislocations of the sample. Under the
these differential curves using Gaussian functions, as shown in the same measurement set-up, equation (1) clearly suggests that the
dotted lines in Fig. 4(c), two peaks located at different temperatures difference in the FWHM of the v scan should be from the broadened
(332.1 K and 334.5 K) are observed in sample Th150 during the width induced by screw dislocations or grain boundaries, i.e. the
cooling process, whereas no such obvious split is observed in sample value of (bl 1 ba) in sample Th150 is higher than that in sample
Th90. The two peaks in sample Th150 are most likely to be related to Th90. On the other hand, it is known that the density of edge dis-
the M1–M2 transition and M2-rutile transition, respectively, which locations can be estimated from the peak broadening of the w scan.
is in good agreement with the M2 occurrence observed in the Raman As shown in Fig. 5(e), the larger FWHM of the w scan peaks for
spectra. sample Th150 than that for sample Th90 suggests higher density of
To understand the mechanism of the occurrence of M2 phases, the edge dislocations in the sample Th150. The higher densities of both
strain states/distributions of the thin films were characterized by screw dislocations and edge dislocations may induce higher density

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Figure 5 | (a) RSM around Al2O3 (0006) and VO2 (002) for sample Th90; (b) RSM around Al2O3 (0006) and VO2 (002) for sample Th150; (c) tilted XRD
h 2 2h scans (x 5 44.8416u) for samples Th90 and Th150, respectively; (d) Gaussian fittings of v rocking curves of VO2 (011) for samples Th90 and
Th150, respectively; (e) Gaussian fittings of w scans of VO2 (011) for samples Th90 and Th150, respectively.

of domain/grain boundaries in sample Th150. These domain/grain spin-coating and thermal treatment process was repeated for various times to achieve
films with different thicknesses.
boundaries may result in a strong impact on the nucleation of the M2
The XRD characterization was conducted using a Bede D1 diffractometer with Cu
phase11,20,27,29. The low energy at the domain/grain boundaries would Ka radiation (l 5 1.54060 Å). HRXRD measurements were set by adopting a Si (220)
promote the nucleation of the new phase. Thus, the richer domain/ dual channel collimator and monochromator system to provide a highly collimated
grain boundaries in sample Th150 would increase the opportunities Cu Ka1 beam with a wavelength spread less than the natural line width of Cu Ka1 and a
for the formation of the M2 phase, which either increases the amount divergence of 12 arcseconds. The detector acceptance aperture was strictly limited by
a precision slit with the width of 50 mm.
of M2 domains or broadens the temperature windows for the occur- Raman spectra were recorded at various temperatures using a Renishaw Micro-
rence of an M2 phase. This explains the clear direct observation of the Raman Spectroscopy System. The wavelength of the Raman exciting laser used in this
M2 phase during the MIT in sample Th150 rather than in sample measurement was 532 nm.
Th90. The infrared ray (IR) transmittance versus temperature was measured by using a
Fourier transform infrared spectrometer (FTIR-8400S) equipped with a home-made
In conclusion, the epitaxial VO2 thin films were prepared on temperature controlling unit.
Al2O3 (0001) using a polymer-assisted deposition technique. The
intermediate M2 phase was clearly observed in the thicker thin films
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