Pritzl Reinhard M, Buda Amalina T, Witthaut Kristian, Schmidt Peter J, Schnick Wolfgang
Department of Chemistry, University of Munich (LMU), Butenandtstraße 5-13, 81377, Munich, Germany.
Lumileds Phosphor Center Aachen (LPCA), Lumileds (Germany) GmbH, Philipsstraße 8, 52068, Aachen, Germany.
Angew Chem Int Ed Engl. 2025 Feb 24;64(9):e202420565. doi: 10.1002/anie.202420565. Epub 2024 Nov 26.
Nitridophosphates have emerged as promising host compounds in the field of solid-state lighting. Their industrial relevance has increased significantly, mainly due to recent advances in synthetic approaches under medium-pressure (MP) conditions, including ammonothermal synthesis and hot isostatic pressing (HIP). In this study, we report on the synthesis and characterization of the quaternary representatives CaLiPN (x=2, 2.7, 4) and SrLiPN, prepared via a simplified ion exchange reaction under MP conditions, starting from the nitridophosphate-based lithium ion conductor LiPN. The synthesis route allowed for the preservation of the anionic [PN] structural motif of the starting material, while simultaneously introducing potential doping sites for Eu by incorporating divalent alkaline earth cations (Ca/Sr). Upon excitation of Eu doped samples with blue light, strong luminescence due to parity-allowed 4f(F)5d→4f(S) transition can be observed in the red (CaLiPN : Eu: λ=626 nm), yellow/orange (CaLiPN : Eu: λ=506 nm, λ=592 nm and SrLiPN : Eu: λ=596 nm) and green (CaLiPN : Eu: λ=546 nm) spectral regions of the visible light. The compounds presented, together with the simplified synthetic approach, demonstrate the significant potential of ion exchange on Li ion conductors for the development of novel nitridophosphates in the future.
氮磷化物已成为固态照明领域中很有前景的主体化合物。它们的工业相关性显著增加,主要归因于中压(MP)条件下合成方法的最新进展,包括氨热合成和热等静压(HIP)。在本研究中,我们报道了通过在MP条件下从基于氮磷化物的锂离子导体LiPN开始的简化离子交换反应制备的四元化合物CaLiPN(x = 2、2.7、4)和SrLiPN的合成与表征。该合成路线能够保留起始材料的阴离子[PN]结构单元,同时通过引入二价碱土阳离子(Ca/Sr)引入潜在的Eu掺杂位点。在用蓝光激发Eu掺杂样品时,在可见光的红色(CaLiPN : Eu: λ = 626 nm)、黄色/橙色(CaLiPN : Eu: λ = 506 nm、λ = 592 nm和SrLiPN : Eu: λ = 596 nm)和绿色(CaLiPN : Eu: λ = 546 nm)光谱区域可以观察到由于宇称允许的4f(F)5d→4f(S)跃迁而产生的强烈发光。所展示的这些化合物,连同简化的合成方法,证明了离子交换对锂离子导体在未来开发新型氮磷化物方面具有巨大潜力。