An intriguing intermediate state is revealed as a bridge between conventional antiferroelectric and ferroelectric states in PbZrO₃-based perovskites

Negative thermal expansion (NTE), referring to the lattice contraction upon heating, has been an attractive topic of solid-state chemistry and functional materials. The response of a lattice to the temperature field is deeply rooted in its structural features and is inseparable from the physical properties. For the past 30 years, great efforts have been made to search for NTE compounds and control NTE performance. The demands of different applications give rise to the prominent development of new NTE systems covering multifarious chemical substances and many preparation routes. Even so, the intelligent design of NTE structures and efficient tailoring for lattice thermal expansion are still challenging. However, the diverse chemical routes to synthesize target compounds with featured structures provide a large number of strategies to achieve the desirable NTE behaviors with related properties. The chemical diversity is reflected in the wide regulating scale, flexible ways of introduction, and abundant structure–function insights. It inspires the rapid growth of new functional NTE compounds and understanding of the physical origins. In this review, we provide a systematic overview of the recent progress of chemical diversity in the tailoring of NTE. The efficient control of lattice and deep structural deciphering are carefully discussed. This comprehensive summary and perspective for chemical diversity are helpful to promote the creation of functional zero-thermal-expansion (ZTE) compounds and the practical utilization of NTE.

Metallic materials that exhibit negligible thermal expansion or zero thermal expansion (ZTE) have great merit for practical applications, but these materials are rare and their thermal expansions are difficult to control. Here, we successfully tailored the thermal expansion behaviors from strongly but abruptly negative to zero over wide temperature ranges in a series of (Gd,R)­(Co,Fe)2 (R = Dy, Ho, Er) intermetallic compounds by tuning the composition to bring the first-order magnetic phase transition to second-order. Interestingly, an unusual isotropic ZTE property with a coefficient of thermal expansion of α l = 0.16(0) × 10–6 K–1 was achieved in cubic Gd0.25Dy0.75Co1.93Fe0.07 (GDCF) in the temperature range of 10–275 K. The short-wavelength neutron powder diffraction, synchrotron X-ray diffraction, and magnetic measurement studies evidence that this ZTE behavior was ascribed to the rare-earth-moment-dominated spontaneous volume magnetostriction, which can be controlled by an adjustable magnetic phase transition. The present work extends the scope of the ZTE family and provides an effective approach to exploring ZTE materials, such as by adjusting the magnetism or ferroelectricity-related phase transition in the family of functional materials.