Considerable research interests have been paid to the rare-earth (RE) Yb³⁺-doped Y₂O₃ crystal which is of great potential for application as a solid-state laser because of its remarkable optoelectronic and physical properties. However, the detailed information of its microstructure is still lacking. Here, we have performed a systematically study of the structural evolution and electronic features of Yb³⁺-doped Y₂O₃ crystal by using the CALYPSO method and first-principle calculations. A novel stable phase of Yb³⁺-doped Y₂O₃ with R-3 space group has been uncovered for the first time. The obtained crystal structure indicates that the impurity Yb³⁺ ions are likely to substitute the Y³⁺ ions, forming a cage-like structure. Our simulated X-ray diffraction patterns of the lowest-energy structure show excellent agreement with the observed data, which demonstrates the accuracy of the present calculation. By analyzing the electronic band structures, we found the elimination of the insulated characters of Yb³⁺-doped Y₂O₃, resulting in an energy gap of 1.64 eV. The electron localization function and Bader charge analysis of Yb³⁺-doped Y₂O₃ are calculated and the results suggest that the Y-O bonds in Y₂O₃:Yb are ionic. These results can offer significant information of RE doped laser materials and serve as guides for the further investigation of such materials.

掺稀土（Y ）Yb ^3+的Y ₂ O ₃晶体引起了相当大的研究兴趣，由于其卓越的光电和物理性能，其具有作为固态激光器应用的巨大潜力。但是，仍然缺乏其微观结构的详细信息。在这里，我们使用CALYPSO方法和第一性原理计算系统地研究了Yb ³⁺掺杂Y ₂ O ₃晶体的结构演化和电子特征。Yb ³⁺掺杂的Y ₂ O _3的新型稳定相R-3太空舱首次被发现。所获得的晶体结构表明，杂质Yb ³⁺离子很可能替代Y ³⁺离子，从而形成笼状结构。我们的最低能级结构的模拟X射线衍射图显示出与观察到的数据极好的一致性，这证明了本计算的准确性。通过分析电子能带结构，我们发现消除了Yb ³⁺掺杂的Y ₂ O ₃的绝缘特性，从而形成了1.64 eV的能隙。掺Yb ^3+的Y ₂ O ₃的电子定位功能和Bader分析计算结果表明Y ₂ O ₃：Yb中的YO键是离子性的。这些结果可以提供稀土掺杂激光材料的重要信息，并为进一步研究此类材料提供指导。