钙钛矿氮化物 LnWN3(Ln=La, Pr, Nd) 的高温高压制备与研究

钙钛矿氮化物拥有奇特的晶体结构且具有潜在的丰富物理性质。然而，由于氮的高电子亲和能，常压下制备钙钛矿氮化物样品非常困难，导致钙钛矿氮化物的晶体结构尚存在一定的争议，基本物性的研究还不全面。因此，我们基于三种新型钙钛矿氮化物LaWN_3-δ、PrWN_3-δ和NdWN_3-δ展开研究。首先利用高温高压法制备了高质量的LaWN_3-δ、PrWN_3-δ和NdWN_3-δ样品，结合X射线衍射、中子衍射和电子衍射，解析得到三种样品的晶体结构均为Pna2₁空间群，并伴随一定的N空位，导致前两者的成分分别为LaWN_2.60、PrWN_2.59。基于高质量的钙钛矿氮化物样品，我们开展了基本物性的系统研究。发现常压下三者均呈现半导体性质并具有良好的导电性，其中LaWN_2.60和PrWN_2.59还表现出优异的力学性能与热稳定性。高压下PrWN_2.59发生结构相变，从半导体变成半金属。

结合理论计算，发现LaWN_3-δ通过姜-泰勒(SOJT)效应形成强W-N杂化使其结构产生畸变并打开带隙。通过比较引入N空位后的R3c和Pna2₁-LaWN_3-δ的形成能，发现N空位所引起的电子掺杂有利于LaWN_3-δ的结构由R3c向Pna2₁转变，从而使Pna2₁-LaWN_2.60结构稳定。同时，N空位的存在也导致了LaWN_3-δ的带隙减小，铁电性受到压制，使Pna2₁-LaWN_2.60具有良好的电导率且未表现出铁电性。

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