熔体法制备无机钙钛矿半导体核辐射探测晶体与器件的研究进展

钙钛矿材料在太阳能电池和光电探测等领域的快速发展,带动了其在核辐射探测领域的应用研究。钙钛矿晶体结构拥有多样化的结构容忍性,如何设计组分并挖掘材料的相关特性具有很大的科学挑战。其次,针对新型钙钛矿材料特性,需要根据应用场景来优化半导体器件设计,才能最大限度地发挥其辐射探测性能。鉴于此,本文从熔体法晶体生长及半导体器件设计等角度,探讨了不同维度钙钛矿结构的材料特性及辐射探测器件性能,以期为该材料在核辐射探测领域的发展提供参考。

Defect tolerance in chalcogenide perovskite photovoltaic material BaZrS_(3)

Chalcogenide perovskites(CPs) exhibiting lower band gaps than oxide perovskites and higher stability than halide perovskites are promising materials for photovoltaic and optoelectronic applications. For such applications, the absence of deep defect levels serving as recombination centers(dubbed defect tolerance) is a highly desirable property. Here,using density functional theory(DFT) calculations, we study the intrinsic defects in BaZrS_(3), a representative CP material.We compare Hubbard-U and hybrid functional methods, both of which have been widely used in addressing the band gap problem of semi-local functionals in DFT. We find that tuning the U value to obtain experimental bulk band gap and then using the obtained U value for defect calculations may result in over-localization of defect states. In the hybrid functional calculation, the band gap of BaZrS_(3)can be accurately obtained. We observe the formation of small S-atom clusters in both methods, which tend to self-passivate the defects from forming mid-gap levels. Even though in the hybrid functional calculations several relatively deep defects are observed, all of them exhibit too high formation energy to play a significant role if the materials are prepared under thermal equilibrium.BaZrS_(3)is thus expected to exhibit sufficient defect tolerance promising for photovoltaic and optoelectronic applications.

Boosting the lithium-ion storage performance of perovskite Sr_(x)VO_(3-δ) via Sr cation and O anion deficient engineering

Perovskite SrVO_(3) has been investigated as a promising lithium storage anode where the V cation plays the role of the redox center,combining excellent cycle stability and safe operating potential versus Li metal plating,with limited capacity.Here,we demonstrate the possibility to boost the lithium storage properties,by reducing the non-redox active Sr cation content and fine-tuning the O anion vacancies while maintaining a non-stoichiometric Sr_(x)VO_(3-δ) perovskite structure.Theoretical investigations suggest that Sr vacancy can work as favorable Li^(+) storage sites and preferential transport channels for guest Li^(+) ions,contributing to the increased specific capacity and rate performance.In contrast,inducing O anion vacancy in Sr_(x)VO_(3-δ) can improve rate performance while compromising the specific capacity.Our experimental results confirm the enhancement of specific capacities by fine adjusting the Sr and O vacancies,with a maximum capacity of 444 mAh g^(-1) achieved with Sr_(0.63)VO_(3-δ),which is a 37%increase versus stoichiometric SrVO_(3).Although rich defects have been induced,Sr_(x)VO_(3-δ) electrodes maintain a stable perovskite structure during cycling versus a LiFePO_(4) cathode,and the full-cell could achieve more than 6000 discharge/charge cycles with 80%capacity retention.This result highlights the possibility to use the cation defective-based engineering approach to design high-capacity perovskite oxide anode materials.

Stable tin perovskite solar cells developed via additive engineering

Tin perovskite solar cells(TPSCs)are promising for lead-free perovskite solar cells(PSCs)and have led to extensive research;however,the poor crystallinity and chemical stability of tin perovskites are two issues that prevent stable TPSCs.In this study,we outline a new process that addresses these issues by using tin(II)acetate(Sn(Ac)2)in place of the conventional SnF2 precursor additive.Compared with SnF2,Sn(Ac)2 improves the crystallinity and stability of tin perovskite with fewer defects and better charge extraction.Using this process,we developed a device that has a higher external quantum efficiency for charge extraction compared with the control devices and a power conversion efficiency of 9.93%,which maintained more than 90%of its initial efficiency after 1000 h operation at the maximum power point under standard AM 1.5G solar illumination.