Journal of Applied Spectroscopy, Vol. 80, No. 3, July, 2013 (Russian Original Vol. 80, No.

3, MayJune, 2013)

X-RAY DIFFRACTION, ATOMIC FORCE MICROSCOPY AND RAMAN

SPECTROSCOPY STUDIES OF MICROSTRUCTURE OF BiFeO3 THIN FILMS
ON Pt/Ti/SiO2/Si (111) SUBSTRATES

Fei Fan,* Bingcheng Luo, Mengmeng Duan, and Changle Chen UDC 539.216.2

A set of BiFeO3 (BFO) thin films with different thicknesses deposited on Pt/Ti/SiO2/Si (111) substrates and LaNiO3
(LNO)-buffered Pt/Ti/SiO2/Si (111) substrates using a radio-frequency magnetron sputtering technique was studied
by X-ray diffraction (XRD), atomic force microscopy (AFM) and Raman spectroscopy. The XRD patterns demostrated
that all BFO thin films were polycrystalline with a distorted rhombohedral structure even though there were distinct
changes in the main peak positions and intensities. The AFM topography images also clearly illustrated the different
surface profiles of these thin films. The grain size of thin films deposited on LNO-buffered subtrates was greatly
decreased compared to that of thin films deposited directly on Pt/Ti/SiO2/Si (111) substrates. Raman-active modes,
which can be classified as 4A1 and 9E modes, have been observed in the Raman spectra of the BFO thin films.
Variations in the Raman shift and bandwidth of different BFO thin films reveal the influence of the thin film and buffer
layer thicknesses on the film microsturcture.

Keywords: X-ray diffraction, atomic force microscopy, Raman spectroscopy, buffer layer, thin film thickness.
Introduction. Multiferroic materials have attracted great interest and attention due to their basic physical properties
and potential applications in new type data-storage devices [13]. Among these materials, bismuth ferrite, BiFeO3 (BFO),
is the only material that shows multiferroism at room temperature [4]. It shows simultaneously an antiferromagnetic and
ferroelectric order with high transition temperatures, TN ~ 370C and TC ~ 830C. The main interest of BFO, besides its re-
markable ferroelectric characteristics [5], resides in the possible use of its magnetoelectric properties that allows us to write
magnetic information electrically [68]. Until now, plenty of theoretical and experimental researches have been performed
on physical properties of BFO as well as its structure [916]. In bulk, BFO has a distorted perovskite structure, i.e., it is a
rhombohedrally distorted ferroelectric, belonging to the space group R3c, with a superimposed cycloidal modulation with
a period of bulk = 620 [17]. The pseudo-cubic cell parameters are a = 3.96 and = 89.4 [18, 19]. Yang et al. [4] re-
ported differences between the Raman spectra with respect to the spectroscopic linewidth, line intensity, and peak position
for different depths of BFO thin films along the growth direction, which was associated with the residual strain and thin film
microstructure. Wu et al. [20] reported the effects of film deposition temperature on the degree of (111) orientation and mi-
crostructure of the film. Data obtained using -ray diffraction (XRD) and Raman spectra have revealed that the ferroelectric
behavior, leakage current, and fatigue endurance of BFO thin films strongly depend on the (111) orientation degree. Obvi-
ously, the physical properties of BFO thin films are closely relevant to their microstructure [14], and Raman spectroscopy
has been successfully adopted to study elementary excitation processes and their interactions in solid-state materials [2125].
However, up to now, little research has been reported concerning the influence of the thin film and buffer layer thickness on
the film surface profile and microstructure, which are important factors affecting thin film physical properties. Therefore in
this work, we discuss the effect of the thickness of BFO thin films and the buffer layer of LaNiO3 (LNO) on the film surface
profile and microstructure using XRD and Raman spectroscopy. Variations in the Raman shift and bandwidth in the spectra
of different films imply different tensile stresses in the BFO films. The results can be used to interpret the physical properties
of the BFO films and prepare good quality film devices.

_____________________
*
To whom correspondence should be addressed.

Northwestern Polytechnical University, Shaanxi Key Laboratory of Condensed Matter Structures and Properties,
Xian 710072, P R China; e-mail: fanfei86919@163.com. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 80, No. 3, pp.
391396, MayJune, 2013. Original article submitted May 30, 2012.

378 0021-9037/13/8003-0378 2013 Springer Science+Business Media New York

TABLE 1. Root Mean Square (RMS) Roughness Values and Average Grain Size (AGS) of the Samples. Thickness of the BFO
Layer in All Samples of Group B is 200 nm

RMS, AGS,
Sample Thickness, nm RMS, nm AGS, nm Sample Thickness, nm
nm nm
A-1 450 (BFO layer) 13.727 125.0 B-1 240 (LNO layer) 3.034 50.0
A-2 200 (BFO layer) 8.088 90.9 B-2 100 (LNO layer) 3.145 52.6
A-3 50 (BFO layer) 13.514 100.0 B-3 30 (LNO layer) 6.599 62.5

Experiments. BFO thin films were deposited by a radio-frequency magnetron sputtering technique on Pt/Ti/SiO2/Si
(111) and LNO-buffered Pt/Ti/SiO2/Si (111) substrates, which are classified as groups A and B, respectively. The LNO buffer
layers were deposited at 450C under dynamic gas (Ar and O2) pressure of 2.0 Pa, while all BFO layers in the two groups
were deposited at 610C. The thicknesses of the BFO layers and LNO buffer layers were estimated through the deposition
speed and time and listed in Table 1. The phase structures were characterized using an X-ray diffractometer (XRD, Rigaku
D/max-2400, CuKa radiation, = 0.15432 nm, Japan). The topography was monitored by an atomic force microscope (AFM,
Asylum Research MFP-3D, USA) with Pt/Ir coated tips (Al reflex coated, 70 kHz resonant frequency, ~320 kHz contact
resonance frequency). The Raman spectra of the BFO thin films were obtained at room temperature using a laser microscopic
Raman spectrometer (inVia Raman Microscope, Renishaw, las = 514.5 nm, UK).
Results and Discussions. Figure 1 shows the XRD patterns of the BFO thin films deposited on the Pt/Ti/SiO2/Si (111)
and LaNiO3-buffered Pt/Ti/SiO2/Si (111) substrates. All detectable diffraction peaks match well with those of the distorted
rhombohedral structure. We observed the expected characteristic peaks corresponding to (101), (110), (003), (202), (113),
and (104) planes of the BFO thin film at 22.490, 32.136, 39.072, 45.816, 51.376, and 56.439, respectively. The BFO
layer has a polycrystalline structure, showing a mixed pattern with no preferred orientation within 2 ranging from 20 to
65. The peak intensity increases with the thickness of the BFO thin films in Fig. 1a, which was attributed to the fact that the
tensile stress due to the lattice mismatch between the BFO layer and Pt/Ti/SiO2/Si substrate at the interface was released with
increasing thickness. Similarly, in Fig. 1b, the intensity of the peaks also increases with the thickness of the LNO buffer layer.
Comparing Fig. 1a and b, it is found that when the substrates were buffered by LNO, the main peaks of the BFO thin films
have changed from (110) and (101) to (101) and (202) respectively. The intensities of the (113) and (104) peaks decrease and
the (003) peak even disappears. Evidently, the LNO buffer layer greatly changed the growth orientation of the BFO thin films
and effectively reduced the lattice mismatch between the BFO layer and the Pt/Ti/SiO2/Si (111) substrate, since the lattice
constant of LNO (a = 0.384 nm) is smaller than that of BFO (a = 0.396 nm) and they belong to the same space group R3c [4].
Typical AFM topography images of the six thin films over 1 1 m are shown in Fig. 2. Values of the corresponding
root mean square (RMS) roughness and the average grain size (AGS) are displayed in Table 1. A comparison of the AFM
images of the group A samples shows that the sample in Fig. 2b has a relatively good surface profile of the most uniform and
compact grains with the smallest RMS roughness and AGS values among the three samples. Apparently, the thinnest BFO
film insufficiently reduces the lattice mismatch between the BFO layer and the substrate, and thus the grain does not grow
uniformly, as seen in Fig. 2c. In contrast, the grains could grow much larger with a further increase in the BFO thin film thick-
ness, as shown in Fig. 2a. Therefore, 200 nm was the optimum thickness for growth of the BFO thin films.
In contrast, in group B, all the BFO thin films deposited on the LNO buffer layer had 200 nm thickness, but the
thicknesses of the LNO layers were different. Based on Table 1 and Fig. 2d and e, the RMS roughness and AGS values of the
samples in group B decreased remarkably compared to those of sample A-2, demonstrating the efficiency of the LNO layer
buffering in the growth of the BFO thin film. As discussed above, LNO and BFO belong to the same space group R3c and
have similar lattice constants, so it is clear that the lattice mismatch is greatly reduced to improve the film growth. Addition-
ally, an increase in the LNO buffer layer thickness also improves the thin film growth, which is consistent with the XRD
pattern results. A too-thin LNO buffer layer cannot effectively release the tensile stress resulting from the lattice mismatch at
the interface, and some BFO crystalline grains cannot acquire enough energy to freely move to the stable equilibrium lattice
position. With rise in the buffer layer thickness, the tensile stress due to the lattice mismatch was gradually released, and the
surface profile of the BFO thin films could be prominently enhanced.
The Raman spectra of the BFO thin films shown in Fig. 3 further confirm the crystal structure of the BFO thin film.
According to group theory analysis, 13 Raman-active modes are classified as 4 A1 and 9 E modes for R3c symmetry. Four

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