High-Entropy Enhanced Negative Thermal Expansion Perfomance in Antiperovkites

The negative thermal expansion (NTE) materials, which can act as thermal-expansion compensators to counteract the positive thermal expansion, have great applications merit in precision engineering. However, the exploration of NTE behavior with a wide temperature range has reached its upper ceiling through traditional doping strategies due to composition limitations. The unique sluggish characteristic in phase transition and extended optimization space in recent high entropy systems has great potential to broaden the temperature range in electronic transitions-induced NTE materials. Mn-based anti-perovskites offer an ideal platform for the exploration of high entropy NTE material due to their abundant element selection and controllable NTE performance. In this paper, the high entropy strategy is first introduced to broaden the NTE temperature range by relaxing the abrupt phase transition in Mn-based anti-perovskite nitride. We propose an empirical screening method to synthesize the high-entropy anti-perovskite (HEAP). it is found that magnetic phase separation from anti-ferromagnetic CII to paramagnetic CI surviving in an ultra-wide temperature range of 5K<=T<=350K (Delta_T=345K), revealing a unique sluggish characteristic. Consequently, a remarkable NTE behavior (up to Delta_T=235K, 5K<=T<=240K) with a coefficient of thermal expansion of -4.7x10-6/K, has been obtained in HEAP. It is worth noting that the temperature range is two/three times wider than that of low-entropy systems. The sluggish characteristic has been further experimentally proved to come from disturbed phase transition dynamics due to distortion in atomic spacing and chemical environmental fluctuation observed by the spherical aberration-corrected electron microscope. Our demonstration provides a unique paradigm for broadening the temperature range of NTE materials induced by phase transition through entropy engineering.