Direct evidence of strong local ferroelectric ordering in a thermoelectric semiconductor

It is thought that the proposed new family of multi-functional materials namely the ferroelectric thermoelectrics may exhibit enhanced functionalities due to the coupling of the thermoelectric parameters with ferroelectric polarization in solids. Therefore, the ferroelectric thermoelectrics are expected to be of immense technological and fundamental significance. As a first step towards this direction, it is most important to identify the existing high performance thermoelectric materials exhibiting ferroelectricity. Herein, through the direct measurement of local polarization switching we show that the recently discovered thermoelectric semiconductor $AgSbSe_{2}$ has local ferroelectric ordering. Using piezo-response force microscopy, we demonstrate the existence of nanometer scale ferroelectric domains that can be switched by external electric field. These observations are intriguing as $AgSbSe_{2}$ crystalizes in cubic rock salt structure with centro-symmetric space group (Fm-3m) and therefore no ferroelectricity is expected. However, from high resolution transmission electron microscopy (HRTEM) measurement we found the evidence of local superstructure formation which, we believe, leads to local distortion of the centro-symmetric arrangement in $AgSbSe_{2}$ and gives rise to the observed ferroelectricity. Stereochemically active $5s^{2}$ lone pair of Sb can also give rise to local structural distortion, which creates ferroelectricity in $AgSbSe_{2}$.

Observation of hysteretic phase-switching in silicon by piezoresponse force microscopy

We report the observation of $180^o$ phase switching on silicon wafers by piezo-response force microscopy (PFM). The switching is hysteretic and shows remarkable similarities with polarization switching in ferroelectrics. This is always accompanied by a hysteretic amplitude vs. voltage curve which resembles the butterfly loops for piezoelectric materials. From a detailed analysis of the data obtained under different environmental and experimental conditions, we show that the hysteresis effects in phase and amplitude do not originate from ferro-electricity or piezoelectricity. This further indicates that mere observation of hysteresis effects in PFM does not confirm the existence of ferroelectric and/or piezoelectric ordering in materials. We also show that when samples are mounted on silicon for PFM measurements, the switching properties of silicon may appear on the sample even if the sample thickness is large.