Stress-Induced Multi-Stimulus-Responsive Mechanoluminescence in Mn2+ Doped Double Perovskite Compound,Advanced Optical Materials

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Stress-Induced Multi-Stimulus-Responsive Mechanoluminescence in Mn2+ Doped Double Perovskite Compound
Advanced Optical Materials ( IF 8.0 ) Pub Date : 2023-10-05 , DOI: 10.1002/adom.202301796
Zhiduo Wang ₁ , Yao Xiao ₁ , Bingjun Liu ₁ , Kang Chen ₁ , Peishan Shao ₁ , Zhicong Chen ₁ , Puxian Xiong ₁ , Jiulin Gan ₁ , Dongdan Chen ₁

Affiliation

Multi-mode mechanoluminescence (ML) materials are have applications such as anti-counterfeiting, stress sensing, and information security. There is limited general consensuses on the luminescent mechanisms, even though exploring ML mechanism based on defects has shown significance in further studies exploring both ML materials design and application. Here, a deep-red to near-infrared (NIR) ML material is reported in a Mn²⁺-activated double perovskite-type compound (CaZnGe₂O₆: Mn²⁺). The abundant lattice sites within the crystal structure have enabled Mn²⁺ doping and defects. Two different photoluminescence (PL) emission bands peaked at 536 and 676 nm from ⁴T₁(⁴G)→⁶A₁(⁶S) are observed, which are attributed to the substitution of Zn²⁺ and Ca²⁺ sites by Mn²⁺, respectively. Hence, tunable emissions from green to red are realized in single Mn²⁺ doping, which can be further regulated by varying the Mn²⁺ concentration. Electrons and holes are captured by cation and anion defects (

V_{Zn}^{''} $V_{{\mathrm{Zn}}}^{\prime \prime }$

and

V_{Ca}^{''} $V_{{\mathrm{Ca}}}^{\prime \prime }$

V_{O}^{• •} $V_{\mathrm{O}}^{ \bullet \bullet }$

, vacancy of Zn, Ca and O ions), followed by the combination of such carriers to transfer energy to the Mn²⁺ 3d states to produce ML/persistent luminescence (PersL) under mechanical/thermal stimuli. Proof-of-concept applications in multi-mode anti-counterfeiting, temperature sensing, and X-ray imaging fields are demonstrated. These results will deepen the understanding of single Mn²⁺-doped multi-stimulus-responsive ML materials, inspiring the development of more high-performance ML phosphors for practical applications.

中文翻译：

Mn2+ 掺杂双钙钛矿化合物中应力诱导的多刺激响应机械发光

多模机械发光（ML）材料具有防伪、应力传感和信息安全等应用。尽管探索基于缺陷的ML机制对于探索ML材料设计和应用的进一步研究具有重要意义，但关于发光机制的普遍共识仍然有限。在此，报道了Mn ²⁺激活的双钙钛矿型化合物（CaZnGe ₂ O ₆ :Mn ²⁺ ）中的深红至近红外（NIR）ML材料。晶体结构内丰富的晶格位点使得Mn ²⁺掺杂和缺陷成为可能。从⁴ T ₁ ( ⁴ G)→ ⁶ A ₁ ( ⁶ S) 观察到两个不同的光致发光（PL）发射带，峰值在 536 和 676 nm，这归因于 Zn ²⁺和 Ca ²⁺位点被 Mn取代分别为²⁺。因此，在单一Mn ²⁺掺杂中实现了从绿光到红光的可调发射，这可以通过改变Mn ²⁺浓度来进一步调节。电子和空穴被阳离子和阴离子缺陷捕获（

V_{锌}^{''} $V_{{\mathrm{Zn}}}^{\prime \prime }$

和

V_{钙}^{''} $V_{{\mathrm{Ca}}}^{\prime \prime }$

V_{氧}^{• •} $V_{\mathrm{O}}^{ \bullet \bullet }$

，Zn、Ca 和 O 离子的空位），然后这些载流子结合，将能量转移到 Mn ²⁺ 3d 态，在机械/热刺激下产生 ML/持续发光（PersL）。演示了多模式防伪、温度传感和 X 射线成像领域的概念验证应用。这些结果将加深对单一Mn ²⁺掺杂多刺激响应ML材料的理解，激发开发更多高性能ML荧光粉用于实际应用。

更新日期：2023-10-05

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