Phase transitions and thermal-stress-induced structural changes in a ferroelectric Pb(Zr0.80Ti0.20)O3 single crystal

TL;DR

This study investigates the structural and domain boundary stability of a PZT single crystal across phase transitions using Raman scattering, revealing persistent domain boundaries and reversible boundary formation with implications for memory devices.

Contribution

It demonstrates the stability of certain domain boundaries at high temperatures and proposes a layered model explaining thermal-stress-induced structural changes in PZT.

Findings

Domain boundaries remain stable above the ferroelectric transition temperature.

Reversible formation and disappearance of boundary types between 573 K and 673 K.

Implication for restoring ferroelectric states after phase transformation.

Abstract

A single crystal of lead-zirconate-titanate (PZT), composition Pb(Zr0.80Ti0.20)O3, was studied by polarized-Raman scattering as a function of temperature. Raman spectra reveal that the local structure deviates from the average structure in both ferroelectric and paraelectric phases. We show that the crystal possesses several, inequivalent complex domain boundaries which show no sign of instability even 200 K above the ferroelectric-to-paraelectric phase transition temperature TC. Two types of boundaries are addressed. The first boundary was formed between ferroelectric domains below TC. This boundary remained stable up to the highest measurement temperatures, and stabilized the domains so that they had the same orientation after repeated heating and cooling cycles. These domains transformed normally to the cubic paraelectric phase. Another type of boundary was formed at 673 K and exhibited no signs of instability up to 923 K. The boundary formation was reversible: it formed and vanished between 573 and 673 K during heating and cooling, respectively. A model in which the crystal is divided into thin slices with different Zr/Ti ratios is proposed. The physical mechanism behind the thermal-stress-induced structural changes is related to the different thermal expansion of the slices, which forces the domain to grow similarly after each heating and cooling cycle. The results are interesting for non-volatile memory development, as it implies that the original ferroelectric state can be restored after the material has been transformed to the paraelectric phase. It also suggests that a low-symmetry structure, stable up to high-temperatures, can be prepared through controlled deposition of layers with desired compositions.