Suchergebnisse

Although lead-free halide double perovskites are considered as promising alternatives to lead halide perovskites for optoelectronic applications, state-of-the-art double perovskites are limited by their large bandgap. The doping/alloying strategy, key to bandgap engineering in traditional semiconductors, has also been employed to tune the bandgap of halide double perovskites. However, this strategy has yet to generate new double perovskites with suitable bandgaps for practical applications, partially due to the lack of fundamental understanding of how the doping/alloying affects the atomic-level structure. Here, we take the benchmark double perovskite Cs2AgInCl6 as an example to reveal the atomic-level structure of double perovskite alloys (DPAs) Cs2AgIn1-xFexCl6 (x = 0-1) by employing solid-state nuclear magnetic resonance (ssNMR). The presence of paramagnetic alloying ions (e.g. Fe3+ in this case) in double perovskites makes it possible to investigate the nuclear relaxation times, providing a straightforward approach to understand the distribution of paramagnetic alloying ions. Our results indicate that paramagnetic Fe3+ replaces diamagnetic In3+ in the Cs2AgInCl6 lattice with the formation of [FeCl6](3-)center dot[AgCl6](5-) domains, which show different sizes and distribution modes in different alloying ratios. This work provides new insights into the atomic-level structure of bandgap engineered DPAs, which is of critical significance in developing efficient optoelectronic/spintronic devices. ; Funding Agencies|Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Swedish Energy AgencySwedish Energy Agency [2018-004357]; VR Starting Grant [2019-05279]; Carl Tryggers Stiftelse; Olle Engkvist Byggmastare Stiftelse; STINT grant [CH2018-7655]; National Natural Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [61704078]; Grant Agency of the Czech RepublicGrant Agency of the Czech Republic [GA19-05259S]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]; China Scholarship Council (CSC)China Scholarship Council

We show by electron spin resonance (ESR) and Raman spectroscopies that the crystal phase transition of the lead-free double-perovskite Cs2AgBiBr6 has a profound symmetry-breaking effect on the high spin states of, for example, a transition-metal ion Fe3+ and the vibrational modes. It lifts their degeneracy when the crystal undergoes the cubic-tetragonal phase transition, splitting the six-fold degenerate S = 5/2 state of Fe3+ to three Kramer doublets and the enharmonic breathing mode T-g of the MBr6 octahedra (M = Ag, Bi, Fe) into E-g + A(g). The magnitudes of both spin and Raman line splitting are shown to directly correlate with the strength of the tetragonal strain field. This work, in turn, demonstrates the power of the ESR and Raman spectroscopies in probing structural phase transitions and in providing in-depth information on the interplay between the structural, spin, and vibrational properties of lead-free double perovskites, a newly emerging and promising class of materials for low-cost and high-efficiency photovoltaics and optoelectronics. ; Funding Agencies|Swedish Research CouncilSwedish Research Council [VR-2017-05285]; Linkoping University; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW 2019.0082]

Lead-free halide double perovskites with diverse electronic structures and optical responses, as well as superior material stability show great promise for a range of optoelectronic applications. However, their large bandgaps limit their applications in the visible light range such as solar cells. In this work, an efficient temperature-derived bandgap modulation, that is, an exotic fully reversible thermochromism in both single crystals and thin films of Cs2AgBiBr6 double perovskites is demonstrated. Along with the thermochromism, temperature-dependent changes in the bond lengths of Ag Symbol of the Klingon Empire Br (R-Ag Symbol of the Klingon Empire Br) and Bi Symbol of the Klingon Empire Br (R-Bi Symbol of the Klingon Empire Br) are observed. The first-principle molecular dynamics simulations reveal substantial anharmonic fluctuations of the R-Ag Symbol of the Klingon Empire Br and R-Bi Symbol of the Klingon Empire Br at high temperatures. The synergy of anharmonic fluctuations and associated electron-phonon coupling, and the peculiar spin-orbit coupling effect, is responsible for the thermochromism. In addition, the intrinsic bandgap of Cs2AgBiBr6 shows negligible changes after repeated heating/cooling cycles under ambient conditions, indicating excellent thermal and environmental stability. This work demonstrates a stable thermochromic lead-free double perovskite that has great potential in the applications of smart windows and temperature sensors. Moreover, the findings on the structure modulation-induced bandgap narrowing of Cs2AgBiBr6 provide new insights for the further development of optoelectronic devices based on the lead-free halide double perovskites. ; Funding Agencies|Knut and Alice Wallenberg Foundation; National Natural Science Foundation of China [61704078, 61722403]; Natural Science Foundation of Jiangsu Province of China [BK20160990]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [200900971]; European Commission Marie Skodowska-Curie actions [691210]; European Commission SOLAR-ERA.NET; Swedish Energy Agency (Energimyndigheten); Swedish Research Council (FORMAS); China Scholarship Council; Recruitment Program of Global Youth Experts in China; National Key Research and Development Program of China [2016YFB0201204]; Program for JLU Science and Technology Innovative Research Team; Swedish Research Council (VR) [2014-4750]; Ministry of Education and Science of the Russian Federation [074-02-2018-327]

Environmentally friendly halide double perovskites with improved stability are regarded as a promising alternative to lead halide perovskites. The benchmark double perovskite, Cs2AgBiBr6, shows attractive optical and electronic features, making it promising for high-efficiency optoelectronic devices. However, the large band gap limits its further applications, especially for photovoltaics. Herein, we develop a novel crystal-engineering strategy to significantly decrease the band gap by approximately 0.26 eV, reaching the smallest reported band gap of 1.72 eV for Cs(2)AgBiBr(6)under ambient conditions. The band-gap narrowing is confirmed by both absorption and photoluminescence measurements. Our first-principles calculations indicate that enhanced Ag-Bi disorder has a large impact on the band structure and decreases the band gap, providing a possible explanation of the observed band-gap narrowing effect. This work provides new insights for achieving lead-free double perovskites with suitable band gaps for optoelectronic applications. ; Funding Agencies|Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Swedish Energy AgencySwedish Energy Agency [2018-004357]; VR Starting Grant [2019-05279]; Carl Tryggers Stiftelse; Olle Engkvist Byggmastare Stiftelse; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Swedish Energy AgencySwedish Energy Agency; SSFSwedish Foundation for Strategic Research; China Scholarship Council (CSC)China Scholarship Council; Ministry of Science and High Education of the Russian Federation [075-15-2019-872 (14.Y26.31.0027/074-02-2018-327)]; Swedish Research Council (VR)Swedish Research Council [2019-05551]; Swedish Research CouncilSwedish Research Council [2016-07213]

Solution-processed metal halide perovskites (MHPs) have demonstrated great advances on achieving high-performance photodetectors. However, the intrinsic material instability and the toxicity of lead still hinder the practical applications of MHPs-based photodetectors. In this work, the first highly sensitive and fast-response lead-free perovskite photodetectors based on Cs2AgBiBr6 double perovskite films are demonstrated. A convenient solution method is developed to deposit high-quality Cs2AgBiBr6 film with large grain sizes, low trap densities, and long charge carrier lifetimes. Incorporated within a photodiode device architecture comprised of optimized hole- and electron-transporting layers, lead-free perovskite photodetectors are achieved exhibiting a high detectivity of 3.29 x 10(12) Jones, a large linear dynamic range of 193 dB, and a fast response time of approximate to 17 ns. All the key figures of merit of the devices are comparable with the reported best-performing photodetectors based on lead halide perovskites. In addition, the resulting devices exhibit excellent thermal and environmental stability. The nonencapsulated devices show negligible degradation after thermal stressing at 150 degrees C and less than 5% degradation in the photoresponsivity after storage in ambient air for approximate to 2300 h. The results demonstrate the great potential of the lead-free Cs2AgBiBr6 double perovskite in applications for environmentally friendly and high-performance photodetectors. ; Funding Agencies|National Natural Science Foundation of China [51472164]; 1000 Talents Program for Young Scientists of China, Shenzhen Peacock Plan [KQTD2016053112042971]; Educational Commission of Guangdong Province [2015KGJHZ006, 2016KCXTD006]; Science and Technology Planning Project of Guangdong Province [2016B050501005]; China Postdoctoral Science Foundation [2017M622744, 2018T110886]; Swedish Research Council FORMAS [942-2015-1253]; European Commission Marie Sklodowska-Curie Actions [691210]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]

Spintronics holds great potential for next-generation high-speed and low-power consumption information technology. Recently, lead halide perovskites (LHPs), which have gained great success in optoelectronics, also show interesting magnetic properties. However, the spin-related properties in LHPs originate from the spin-orbit coupling of Pb, limiting further development of these materials in spintronics. Here, we demonstrate a new generation of halide perovskites, by alloying magnetic elements into optoelectronic double perovskites, which provide rich chemical and structural diversities to host different magnetic elements. In our iron-alloyed double perovskite, Cs2Ag(Bi:Fe)Br-6, Fe3+ replaces Bi3+ and forms FeBr6 clusters that homogenously distribute throughout the double perovskite crystals. We observe a strong temperature-dependent magnetic response at temperatures below 30 K, which is tentatively attributed to a weak ferromagnetic or antiferromagnetic response from localized regions. We anticipate that this work will stimulate future efforts in exploring this simple yet efficient approach to develop new spintronic materials based on lead-free double perovskites. ; Funding Agencies|Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW 2019.0082]; Swedish Energy AgencySwedish Energy Agency [2018004357, P43288-1]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]; Grant Agency of the Czech RepublicGrant Agency of the Czech Republic [GA19-05259S]; China Scholarship Council (CSC)China Scholarship Council; U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering DivisionUnited States Department of Energy (DOE); European CommunityEuropean Community (EC) [312284]; Czech Ministry of EducationMinistry of Education, Youth & Sports - Czech Republic [LM2015057]; CERIC users grant; International Synchrotron Access Program of the Australian Synchrotron