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

Despite rapid improvements in efficiency and brightness of perovskite light-emitting diodes (PeLEDs), the poor operational stability remains a critical challenge hindering their practical applications. Here, we demonstrate greatly improved operational stability of high-efficiency PeLEDs, enabled by incorporating dicarboxylic acids into the precursor for perovskite depositions. We reveal that the dicarboxylic acids efficiently eliminate reactive organic ingredients in perovskite emissive layers through an in situ amidation process, which is catalyzed by the alkaline zinc oxide substrate. The formed stable amides prohibit detrimental reactions between the perovskites and the charge injection layer underneath, stabilizing the perovskites and the interfacial contacts and ensuring the excellent operational stability of the resulting PeLEDs. Through rationally optimizing the amidation reaction in the perovskite emissive layers, we achieve efficient PeLEDs with a peak external quantum efficiency of 18.6% and a long half-life time of 682 h at 20 mA cm(-2), presenting an important breakthrough in PeLEDs. ; Funding Agencies|ERC Starting grantEuropean Research Council (ERC) [717026]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; China Scholarship Council (CSC)China Scholarship Council

Lead-free halide double perovskites (A(2)B(I)B(III)X(6)) with attractive optical and electronic features are considered to be a promising candidate to overcome the toxicity and stability issues of lead halide perovskites (APbX(3)). However, their poor absorption profiles limit device performance. Here the absorption band edge of Cs(2)AgBiBr(6)double perovskite to the near-infrared range is significantly broadened by developing doped double perovskites, Cs-2(Ag:Cu)BiBr6. The partial replacement of Ag ions by Cu ions in the crystal lattice is confirmed by the X-ray photoelectron spectroscopy (XPS) and solid-state nuclear magnetic resonance (ssNMR) measurements. Cu doping barely affects the bandgap of Cs2AgBiBr6; instead it introduces subbandgap states with strong absorption to the near-infrared range. More interestingly, the near-infrared absorption can generate band carriers upon excitation, as indicated by the photoconductivity measurement. This work sheds new light on the absorption modulation of halide double perovskites for future efficient optoelectronic devices. ; Funding Agencies|Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW 2019.0082]; Swedish Energy AgencySwedish Energy Agency [2018-004357]; Grant Agency of the Czech RepublicGrant Agency of the Czech Republic [GA19-05259S]; 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]; China Scholarship Council (CSC)China Scholarship Council; Ministry of Science and Higher Education of the Russian Federation of NUST "MISIS" [K2-2019-001, 211]; Swedish Research Council (VR)Swedish Research Council [2019-05551]; Swedish Research CouncilSwedish Research Council [2016-07213]

Although perovskite light-emitting diodes (PeLEDs) have recently experienced significant progress, there are only scattered reports of PeLEDs with both high efficiency and long operational stability, calling for additional strategies to address this challenge. Here, we develop perovskite-molecule composite thin films for efficient and stable PeLEDs. The perovskite-molecule composite thin films consist of in-situ formed high-quality perovskite nanocrystals embedded in the electron-transport molecular matrix, which controls nucleation process of perovskites, leading to PeLEDs with a peak external quantum efficiency of 17.3% and half-lifetime of approximately 100 h. In addition, we find that the device degradation mechanism at high driving voltages is different from that at low driving voltages. This work provides an effective strategy and deep understanding for achieving efficient and stable PeLEDs from both material and device perspectives. ; Funding Agencies|ERC Starting GrantEuropean Research Council (ERC) [717026]; European Commission Marie Skodowska-Curie Actions [691210]; Swedish Foundation for International Cooperation in Research and Higher Education [CH2018-7736]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]; China Scholarship CouncilChina Scholarship Council; Jardine Foundation; Cambridge Trust; Linkoping University

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

Multidentate molecular additives are widely used to passivate perovskite, yet the role of chelate effect is still unclear. Here, the authors investigate a wide range of additives with different coordination number and functional moieties to establish correlation between coordination affinity and perovskite crystallisation dynamics. Molecular additives are widely utilized to minimize non-radiative recombination in metal halide perovskite emitters due to their passivation effects from chemical bonds with ionic defects. However, a general and puzzling observation that can hardly be rationalized by passivation alone is that most of the molecular additives enabling high-efficiency perovskite light-emitting diodes (PeLEDs) are chelating (multidentate) molecules, while their respective monodentate counterparts receive limited attention. Here, we reveal the largely ignored yet critical role of the chelate effect on governing crystallization dynamics of perovskite emitters and mitigating trap-mediated non-radiative losses. Specifically, we discover that the chelate effect enhances lead-additive coordination affinity, enabling the formation of thermodynamically stable intermediate phases and inhibiting halide coordination-driven perovskite nucleation. The retarded perovskite nucleation and crystal growth are key to high crystal quality and thus efficient electroluminescence. Our work elucidates the full effects of molecular additives on PeLEDs by uncovering the chelate effect as an important feature within perovskite crystallization. As such, we open new prospects for the rationalized screening of highly effective molecular additives. ; Funding Agencies|ERC Starting GrantEuropean Research Council (ERC) [717026]; Swedish Energy Agency EnergimyndighetenSwedish Energy Agency [48758-1, 44651-1]; Swedish Research Council VRSwedish Research Council; NanoLund; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]; National Natural Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [91833303, 61974098, 62005126]; National Key Research and Development Program [2016YFA0201900]; Jiangsu High Educational Natural Science Foundation [18KJA430012]; 111 ProgramMinistry of Education, China - 111 Project; Collaborative Innovation Center of Suzhou Nano Science and Technology; Collaborative Innovation Center of Suzhou Nano Science Technology; Research Foundation - Flanders (FWO)FWO [12Y7218N, 12Y7221N, G098319N]; KU Leuven Research FundKU Leuven [C14/19/079, 201806920071, 201906830040, 201608530162, 201806460021]; China Scholarship CouncilChina Scholarship Council