Nonlinear Optical Glass‐Ceramic From a New Polar Phase‐Transition Organic‐Inorganic Hybrid Crystal

Abstract

AbstractMelt‐quenched glasses of organic–inorganic hybrid crystals, i.e., hybrid glasses, have attracted increasing attention as an emerging class of hybrid materials with beneficial processability and formability in the past years. Herein, we present a new hybrid crystal, (Ph3PEt)3[Ni(NCS)5] (1, Ph3PEt+=ethyl(triphenyl)phosphonium), crystallizing in a polar space groupP1 and exhibiting thermal‐induced reversible crystal‐liquid‐glass‐crystal transitions with relatively low melting temperature of 132 °C, glass‐transition temperature of 40 °C, and recrystallization on‐set temperature of 78 °C, respectively. Taking advantage of such mild conditions, we fabricated an unprecedented hybrid glass‐ceramic thin film, i.e., a thin glass uniformly embedding inner polar micro‐crystals, which exhibits a much enhanced intrinsic second‐order nonlinear optical effect, beingca. 25.6 and 3.1 times those of poly‐crystalline1and KH2PO4, respectively, without any poling treatments.