Solids can be generally categorized by their structures into crystalline and amorphous states with different interactions among atoms dictating their properties. Crystalline-amorphous hybrid structures, combining the advantages of both ordered and disordered components, present a promising opportunity to design materials with emergent collective properties. Hybridization of crystalline and amorphous structures at the sublattice level with long-range periodicity has been rarely observed. Here, we report a nested order-disorder framework (NOF) constructed by a crystalline matrix with self-filled amorphous-like innards that is obtained by using pressure to regulate the bonding hierarchy of Cu₁₂Sb₄S₁₃. Combined in situ experimental and computational methods demonstrate the formation of disordered Cu sublattice which is embedded in the retained crystalline Cu framework. Such a NOF structure gives a low thermal conductivity (~0.24 W·m⁻¹·K⁻¹) and a metallic electrical conductivity (8 × 10⁻⁶ Ω·m), realizing the collaborative improvement of two competing physical properties. These findings demonstrate a category of solid-state materials to link the crystalline and amorphous forms in the sublattice-scale, which will exhibit extraordinary properties.

固体通常可以根据其结构分为晶态和非晶态，原子之间的不同相互作用决定了它们的性质。晶体-非晶杂化结构结合了有序和无序成分的优点，为设计具有新兴集体特性的材料提供了一个有前途的机会。很少观察到具有长程周期性的亚晶格水平上的晶体和非晶结构的杂化。在这里，我们报告了一种由具有自填充非晶状内部结构的晶体基质构建的嵌套有序无序框架（NOF），该框架是通过使用压力调节Cu ₁₂ Sb ₄ S ₁₃的键合层次而获得的。结合原位实验和计算方法证明了无序铜亚晶格的形成，该亚晶格嵌入保留的结晶铜框架中。这种NOF结构具有低热导率（~0.24 W·m ^-1 ·K ^-1 ）和金属电导率（8 × 10 ^-6 Ω·m），实现了两种相互竞争的物理性能的协同改进。这些发现证明了一类固态材料可以在亚晶格尺度上连接结晶和非晶形式，这将表现出非凡的性能。