# Influence of nanoscale regions on Raman spectra of complex perovskites

## I Introduction

Complex perovskites form vast and promising group of compounds for microelectronics, yet many features they show are still a battlefield for scientists. Among the compounds with a well-known general formula $`AB_x^{}B_{1x}^{\prime \prime }O_3`$ one can find a spectrum of cases, from relaxor ferroelectrics (or ferroelectrics with diffuse phase transition), such as $`PbMg_{1/3}Nb_{2/3}O_3`$ (PMN) and $`PbSc_{1/2}Ta_{1/2}O_3`$ (PST) to antiferroelectrics ($`PbMg_{1/2}W_{1/2}O_3`$ (PMW) for example) . Historically, PMN and PST are most widely studied, due to their relaxor behaviour. Numerous structural studies of such compounds were performed by different techniques (x-ray scattering (see, for example, ), HRTEM, dark field images ) together with neutron scattering , synchrotron studies , and NMR studies , but still there is no unanimous point of view on ”what makes a relaxor to be a relaxor”. In some sense, the results of Raman studies make the problem even more confusing.

Every Raman study of a dielectric crystal leads to a question: to what space group does this compound belong? To make a line assignment one needs at least to determine a ”basis” for that procedure, i.e. to deconvolute the spectrum (and to prove whether this spectrum as a whole or a given part of the spectrum is of first order). In some cases this part of the task is not challenging, but for relaxors. As a matter of fact, in general, complex perovskites’ unit sell belongs to $`Pm3m`$ space group for which no first order Raman scattering is allowed by group theory analysis . But it is well known that these compounds do exhibit first order Raman spectra . Several attempts to make line assignment were maid, and the most common point of view is that they are consistent with $`Fm3m`$ space group . Such studies were performed both on raw  and reduced Raman spectra  (although due to a presence of a very low-frequency line raw spectra are not so informative), but these studies suffered from one and the same problem, namely, the problem of extra lines. Different ways to overcome this difficulty were suggested, and such lines were treated either as arising due to distortions, or as second order regions of spectra. Another surpassing detail for relaxors is that the lines are unusually broad (40 cm<sup>-1</sup> as a FWHM is a normal value for relaxors) and posses a complex structure of lines, that seems to be nearly a characteristic feature of Raman spectra of the compounds understudy. Also some of Raman lines are obviously asymmetric.

Besides, extensive study of temperature behaviour of Raman spectra of PMN and PST crystals showed that the spectra are temperature dependent and anomalies correlated with other phenomena (such as specific temperature behaviour of the acoustic phonon damping revealed by Brillouin scattering studies and sensitivity of PMN spectra for anomalies in complex dielectric response) were observed .

The present work is aimed on suggestion of a new approach to Raman spectra of $`AB_x^{}B_{1x}^{\prime \prime }O_3`$ complex perovskites.

## II Experimental

Diagonal and parallel Raman spectra of PMN (X(ZZ)Y and X(ZX)Y) and PST (Z(XX)Y and Z(XY)Y) crystals were measured with X, Y and Z being along the fourfold cubic axes. PST crystals were obtained for two levels of ordering. Investigations were carried out in a wide temperature range for both compounds. The details of sample preparation and experiment setup can be found elsewhere .

## III Raman spectra of PMN and PST crystals

Examples of Stokes parts of polarized Raman spectra of PMN and disordered PST are presented in Fig. 1. In this paper only reduced Raman spectra are discussed, so the word ”spectrum” is actually for ”reduced spectrum” unless specially stated. The reason is that dealing with complex perovskites one inevitably has to deal with low frequency region where Bose-Einstein population factor can not be neglected. Another peculiarity to be mentioned beforehand is that, being well acquainted to the results of group theory analysis and mode assignment performed for these compounds, the author deliberately tries to avoid using appropriate mode identifications (such as $`F_{2g}`$, $`E_g`$ and $`A_{1g}`$) when speaking of some part of a spectrum. This may look rather clumsy through the text but is believed to be necessary for a presentation of the approach.

One can easily observe some common features of these spectra. (Mind that at 495 K PMN is in ferrophase and at 373 K a disordered PST is in paraphase.) The striking detail is that the likely regions of spectra have practically the same frequency shifts. For example, apart from such obvious lines as those at approximately 50 cm<sup>-1</sup> and 800 cm<sup>-1</sup>, the bands in the regions of 100 - 300 cm<sup>-1</sup> and 500 - 600 cm<sup>-1</sup> are more or less likely. The lines at approximately 380 and 550 cm<sup>-1</sup> in Z(YZ)X polarization are clearly resolved only for PST. According to dielectric response data, disordered PST is a relaxor as well as PMN. Temperature evolution at least of the low frequency region of PMN was already reported, so this time let us consider the temperature evolution of Z(YY)X spectra of PST (Fig. 2). Quite obviously the spectrum at 292 K differs from one at 741 K, and also a specific temperature evolution is seen. As the population factor is already taken into account, one can suppose that the whole spectra are the first order Raman spectra since no band performs a drastically different temperature behaviour.

So, there are first order Raman spectra exhibiting unusually broad and asymmetric lines and specific temperature evolution obtained from compounds for which no first order Raman scattering is allowed.

## IV Interpretation of Raman spectra

The considerations stated above already lead to conclusion that there is a factor, which violates the Raman selection rules thus allowing the existence of forbidden spectra. It means that for some reason the scattering observed originates not only from the center of the Brillouin zone but from other points of the Brillouin zone as well. As additional evidences for violation of selection rules one can recall that the IR spectra  of PMN (as well as neutron diffraction studies ) revealed practically the same set of modes as for Raman spectra. Another fact, which is worth mentioning, is that structural studies performed for PST showed that there are significant deviations from $`Fm3m`$ symmetry . And nevertheless these compounds exhibit practically identical spectra. Many studies revealed the existence of nanoregions in PMN and PST . Although the nature of such regions is still under discussion and quite contradictory interpretations are suggested , nowadays the presence of nanoscale structure in relaxors can not be denied. Recently on the basis of similarity of Raman spectra of $`BaMg_{1/3}Ta_{2/3}O_3`$ (BMT) crystals and ceramics it was suggested that the Raman scattering in BMT is determined by the short-range order in the nanoscale microstructures .

The smallness of nanoregions can be, in principle, the factor, which violates Raman selection rules. Indeed, in ideal infinite crystal only phonons at the center of the Brillouin zone (with $`\stackrel{}{q}0`$) can be observed due to crystal momentum conservation. In an imperfect crystal (and there are no reasons to treat a complex perovskite as an ideal crystal) phonons can be confined in space. Thus, according to the uncertainty relation, there appears an uncertainty in the phonon momentum and phonons with $`\stackrel{}{q}>0`$ can contribute to Raman signal. Provided that the region of scattering is very small, scattering from practically the entire Brillouin zone is allowed to contribute to the signal. To describe a frequency shift and broadening of lines in Raman spectra in the case of scattering from sufficiently small regions a model was developed nowadays known as spatial correlation or phonon-confinement model . This model is outlined briefly below.

The wave function of a phonon with a wave vector in an infinite perfect crystal is

$$\varphi (\stackrel{}{q}_0,\stackrel{}{r})=u(\stackrel{}{q}_0,r)\mathrm{exp}\left(i\stackrel{}{q}_0\stackrel{}{r}\right),$$
(1)   
where $`u(\stackrel{}{q}_0,\stackrel{}{r})`$ is the periodicity of the lattice. Let us suppose that the phonon is confined to the sphere of diameter $`L`$. Such confinement can be accounted for by writing another wave function $`\psi `$ instead of $`\varphi `$

$$\psi (\stackrel{}{q}_0,\stackrel{}{r})=A\mathrm{exp}\left\{\frac{r^2}{2}/\left(\frac{L}{2}\right)^2\right\}\varphi (\stackrel{}{q}_0,\stackrel{}{r})=\psi ^{}(\stackrel{}{q}_0,\stackrel{}{r})u(\stackrel{}{q}_0,\stackrel{}{r}),$$
(2)   
where

$$\left|\psi \right|^2=A^2\mathrm{exp}\left\{r^2/\left(\frac{L}{2}\right)^2\right\}.$$
(3)   
That means that $`\psi `$ is confined to $`\left|r\right|L`$ in the form of Gauss distribution of width $`\sqrt{\mathrm{ln}2L}.And\psi ^{}`$ might be expanded in a Fourier series:

$$\psi (\stackrel{}{q}_0,\stackrel{}{r})=d^3qC(\stackrel{}{q}_0,\stackrel{}{q})\mathrm{exp}\left(i\stackrel{}{q}\stackrel{}{r}\right),$$
(4)   
where the Fourier coefficients are given by

$$C(\stackrel{}{q}_0,\stackrel{}{q})=\frac{1}{(2\pi )^3}d^3r\psi ^{}(\stackrel{}{q}_0,\stackrel{}{r})\mathrm{exp}\left(i\stackrel{}{q}\stackrel{}{r}\right).$$
(5)   
Substitution of $`\psi ^{}`$ from (2) to into (5) yields

$$C(\stackrel{}{q}_0,\stackrel{}{q})=\frac{AL}{\left(2\pi \right)^{3/2}}\mathrm{exp}\left\{\frac{1}{2}\left(\frac{L}{2}\right)^2\left(\stackrel{}{q}\stackrel{}{q}_0\right)^2\right\}.$$
(6)   
Thus the $`\psi ^{}`$ and $`\psi `$ seize to be Eigenfunctions of a phonon wave vector $`\stackrel{}{q}_0`$, and become a superposition of Eigenfunctions with $`\stackrel{}{q}`$ vectors in an interval $`\left|qq_0\right|\frac{1}{2L}`$ centered at $`\stackrel{}{q}_0`$. For the chosen form of confinement (3) the Eigenfunctions are weighted through the coefficients $`C(\stackrel{}{q}_0,\stackrel{}{q})`$, according to a Gauss distribution.

Thus, it is supposed that for the phonon transition matrix elements $`\left|\stackrel{}{q}_0\left|\widehat{o}\right|\stackrel{}{q}\right|^2`$ there appear non-vanishing values also for $`\stackrel{}{q}\stackrel{}{q}_0`$ according to:

$$\left|\stackrel{}{q}_0\left|\widehat{o}\right|\stackrel{}{q}\right|^2=\left|\stackrel{}{q}_0\left|\widehat{o}\right|\stackrel{}{q}_0\right|^2C(\stackrel{}{q}_0,\stackrel{}{q}),$$
(7)   
where $`\left|\widehat{o}\right|`$ is the phonon-phonon interaction operator. To simplify the equation, when writing (7) it was assumed that $`u(\stackrel{}{q},\stackrel{}{r})=u(\stackrel{}{q}_0,\stackrel{}{r})`$. Thus the phonon confinement leads to relaxation of $`\mathrm{\Delta }q=0`$ selection rule.

Normally when speaking of Raman spectra we actually deal with the excited optical phonon in the center of the Brillouin zone $`\left(\stackrel{}{q}=0\right)`$. In case of allowed $`\stackrel{}{q}o`$ transiotions contributions with $`\omega `$ determined by the dispersion relations $`\omega \left(\stackrel{}{q}\right)`$ will add to the Raman spectrum. Obviously, the additional transitions with $`\stackrel{}{q}0`$ lead to a broadening of a Raman line and its shift towards higher or lower frequencies. The direction of such frequency shift depends on a dispersion relation for each phonon brunch and will be examined in more details further on.

It is possible to write an expression for a Raman line on the basis of the above mentioned considerations.The wave function of the confined phonon can be expressed via the wave functuion of a phonon in an ideal infinite crystal as (here the notations of  are used):

$$\psi (\stackrel{}{q}_0,\stackrel{}{r})=W(\stackrel{}{r},L)\varphi (\stackrel{}{q}_0,\stackrel{}{r})=\psi ^{}(\stackrel{}{q}_0,\stackrel{}{r})u(\stackrel{}{q}_0,\stackrel{}{r}),$$
(8)   
where $`W(\stackrel{}{r},L)`$ describes confinement. Then the Fourier coefficients are

$$C(\stackrel{}{q}_0,\stackrel{}{q})=\frac{1}{(2\pi )^3}d^3r\psi ^{}(\stackrel{}{q}_0,\stackrel{}{r})\mathrm{exp}\left(i\stackrel{}{q}\stackrel{}{r}\right)$$
(9)   
$`={\displaystyle \frac{1}{(2\pi )^3}}{\displaystyle d^3rW(\stackrel{}{r},L)\mathrm{exp}\left(i\left(\stackrel{}{q}\stackrel{}{q}_0\right)\stackrel{}{r}\right)}.`$

Let us stress again that the confined phonon wave function is a superposition of plane waves with wave vectors $`\stackrel{}{q}`$ centered at $`\stackrel{}{q}_0`$. The Raman lineshape appears to be constructed by superposition of Lorentzian line shapes (with the linewidth of an imagined ideal crystalline media for the compound understudy) centerd at $`\omega \left(\stackrel{}{q}\right)`$ and weighted by the wave-vector uncertainty caused by confinement:

$$I\left(\omega \right)\frac{_o^1\frac{d^3\stackrel{}{q}\left|C(0,\stackrel{}{q})\right|^2}{\left[\omega \omega \left(\stackrel{}{q}\right)\right]^2\left(\frac{\mathrm{\Gamma }_0}{2}\right)^2}}{_0^1d^3\stackrel{}{q}\left|C(0,\stackrel{}{q})\right|^2},$$
(10)   
where $`\omega \left(\stackrel{}{q}\right)`$ is the phonon-dispersion curve, and $`\mathrm{\Gamma }_0`$ is the imagined linewidth of an ideal crystalline media for the compound understudy. It is important to notice that, unlike crystals like $`KTaO_3`$, $`K_{1x}Li_xTaO_3`$ in case of complex perovskites we have no sample compound that can give us the exact value of $`\mathrm{\Gamma }_0`$. $`\stackrel{}{q}=0`$ corresponds to the scattering from the center of the Brillouin zone and the integration is carried over the entire Brillouin zone. With $`L\mathrm{}`$, $`C(0,\stackrel{}{q})=\delta \left(\stackrel{}{q}\right)`$ and $`I\left(\omega \right)`$ is a Lorentzian centerd at $`\omega \left(0\right)`$ and with a linewidth of $`\mathrm{\Gamma }_0`$. Different functions can be chosen to describe the localization, but, according to , for the case of sampling a signal from a number of regions of localization a Gaussian (provided that the amplitude is $`0`$ on a border of a region) is the most successful. Thus we have

$$W(\stackrel{}{r},L)=\mathrm{exp}\left[\frac{8\pi ^2r^2}{L^2}\right],$$
(11)   
$$\text{ }\left|C(0,\stackrel{}{q})\right|^2\mathrm{exp}\left[\frac{q^2L^2}{4}\right],$$
(12)   
where $`q`$ is given in units of $`2\pi /a`$, where $`a`$ is the lattice constant (approximately 4 Å for complex perovskites), and $`L`$ is given in units of $`a`$.

Mind that further on instead of arbitrary intensity $`I\left(\omega \right)`$ Raman suscptibility $`\chi \left(\omega \right)`$ will be considered obtained as

$$\chi \left(\omega \right)=\frac{I\left(\omega \right)}{F(\omega ,T)},$$
(13)   
where $`F(\omega ,T)=\left[n(\omega ,T)+1\right]`$ for Stokes part of spectra and $`F(\omega ,T)=n(\omega ,T)`$ for anti-Stokes part respectively, and

$$n(\omega ,T)=\left[\mathrm{exp}\left(\mathrm{}\omega /kT\right)1\right]^1,$$
(14)   
where $`\omega `$ is the Raman shift and $`T`$ is the temperature.

So, the Raman line shape for the case of a phoon confined to a sphere of diameter $`L`$, and a Gaussian confinement is

$$\chi \left(\omega \right)\frac{_0^1\frac{dq\mathrm{exp}\left(q^2L^2/4\right)4\pi q^2}{\left[\omega \omega \left(q\right)\right]^2+\left(\mathrm{\Gamma }_0/2\right)^2}}{_0^1𝑑q\mathrm{exp}\left(q^2L^2/4\right)4\pi q^2},$$
(15)   
where $`\omega \left(q\right)`$ is an approximate one-dimensional phonon-dispersion curve. Unfortunately, there are no reported experimental data on phonon-dispersion curves in complex perovskites, but it can be easily shown that for such calculations the quadratic term of polinomial approximation is playing the key role and other terms can be neglected. So, the dispersion curve for (14) can be written as

$$\omega \left(q\right)=\omega _0\pm Q\omega ^2,$$
(16)   
where $`Q`$ is the quadratic term and the sign before $`Q`$ in fact determines whether the line suffers a shift to low freuencies (minus) or to higher frequencies (plus). Fig. 3 illustrates alteration of frequency position and shape of a Raman line with different $`L`$ and $`Q`$.

## V Results and discussion

The initial aim of the present study was to describe the experimental Raman spectra of PMN and PST with a fixed set of modes on the basis of spatial-correlation model. An example of such calculation is presented in Fig. 4. In the contribution only a region of 0 - 400 cm<sup>-1</sup> is considered. The results of interpretation of the rest of the frequency region (400 - 1000 cm<sup>-1</sup>) will be reported later, but it is possible to state that these results do not contradict to the suggested interpretation. Besides, such sharing of spectra regions does not lead to mistakes in calculations. Similar calculations were performed for all experimentally obtained spectra. The first important result is that the size of nanoregions is a kind of ”inborn” characteristic of the sample (or, generally speaking, of the type of compound) and is not temperature dependent. Thus, for PMN and PST disordered $`L=4`$ and for PST ordered $`L=5`$. To check the validity of such approximation in the results obtained for one of a high-temperature spectra of PST was taken equal to 12 (that value influences lineshapes not so dramatically) and both Z(YY)X and Z(YZ)X lines were calculated to make the simulated spectra effectively unpolarized. The results appeared to be in good agreement with the spectra experimentally obtained by authors of  for non-polarized spectra of crystalline BMT (Fig. 5).

One can readily notice that in the frequency range of 100 - 200 cm<sup>-1</sup> the simulated Raman lines are different from those in the frequency region of 150 - 250 cm<sup>-1</sup> on the experimentally obtained spectrum, although the number of lines is the same. It appeared that for disordered PST there are modes in the region of 100 - 200 cm<sup>-1</sup>, which demonstrate an alteration of parameters (especially of the value of the line frequency position) with temperature growth. One of these modes seems to be a ”softening” mode, because its positions changes rapidly from 260 cm<sup>-1</sup> at 550 K to 140 cm<sup>-1</sup> at 600 K, while its intensity significantly decreases in the range of 300 - 500 K. For the ordered PST also one mode with similar behaviour was found. It changes its position from 160 cm$`^{1\text{ }}`$at 300 K down to 90 cm<sup>-1</sup>at 600 K.

The analysis of the obtained parameters of the phonon modes showed some anomalies in their temperature behavior. The common feature of these anomalies is that they all happen in the region of approximately 350 - 600 K and the main temperature points appear to be in the vicinty of 400 K and 600 K. The point 400 K is in good agreement with suggested estimation of Curie-Weiss temperature performed on the basis of experimental investigation of dielectric permittivity of PST crystals . As for 600 K, anomalies of the refractive index starting at approximately 600 K were reported by the authors of .

More detailed analysis of the temperature behaviour of mode parameters will be published later.

## Acknowledgement

The work was supported by INTAS Project 96/167, INTAS Fellowship grant for Young Scientists No YSF 98-75. The author is extremely thankful to the Royal Institute of Technology for technical support and to Dr. E.Obraztsova and Dr. A.Tagantsev for helpful and inspiring discussions.

## Figure Captions