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Lead-free halide double perovskites (HDPs) have emerged as a new generation of thermochromic materials. However, further materials development and mechanistic understanding are required. Here, a highly stable HDP Cs2NaFeCl6 single crystal is synthesized, and its remarkable and fully reversible thermochromism with a wide color variation from light-yellow to black over a temperature range of 10 to 423 K is investigated. First-principles, density functional theory (DFT)-based calculations indicate that the thermochromism in Cs2NaFeCl6 is an effect of electron-phonon coupling. The temperature sensitivity of the bandgap in Cs2NaFeCl6 is up to 2.52 meVK(-1) based on the Varshni equation, which is significantly higher than that of lead halide perovskites and many conventional group-IV, III-V semiconductors. Meanwhile, this material shows excellent environmental, thermal, and thermochromic cycle stability. This work provides valuable insights into HDPs' thermochromism and sheds new light on developing efficient thermochromic materials.

Reversible optical property changes in lead-free perovskites have recently received great interest due to their potential applications in smart windows, sensors, data encryption, and various on-demand devices. However, it is challenging to achieve remarkable color changes in their thin films. Here, methylamine gas (CH3NH2, MA0) induced switchable optical bleaching of bismuth (Bi)-based perovskite films is demonstrated for the first time. By exposure to an MA0 atmosphere, the color of Cs2AgBiBr6 (CABB) films changes from yellow to transparent, and the color of Cs3Bi2I9 (CBI) films changes from dark red to transparent. More interestingly, the underlying reason is found to be the interactions between MA0 and Bi3+ with the formation of an amorphous liquefied transparent intermediate phase, which is different from that of lead-based perovskite systems. Moreover, the generality of this approach is demonstrated with other amine gases, including ethylamine (C2H5NH2, EA0) and butylamine (CH3(CH2)3NH2, BA0), and another compound, Cs3Sb2I9, by observing a similar reversible optical bleaching phenomenon. The potential for the application of CABB and CBI films in switchable smart windows is investigated. This study provides valuable insights into the interactions between amine gases and lead-free perovskites, opening up new possibilities for high-efficiency optoelectronic and stimuli-responsive applications of these emerging Bi-based materials.

Solution-processable semiconductors with antiferromagnetic (AFM) order are attractive for future spintronics and information storage technology. Halide perovskites containing magnetic ions have emerged as multifunctional materials, demonstrating a cross-link between structural, optical, electrical, and magnetic properties. However, stable optoelectronic halide perovskites that are antiferromagnetic remain sparse, and the critical design rules to optimize magnetic coupling still must be developed. Here, we combine the complementary magnetometry and electron-spin-resonance experiments, together with first-principles calculations to study the antiferromagnetic coupling in stable Cs2(Ag:Na)FeCl6 bulk semiconductor alloys grown by the hydrothermal method. We show the importance of nonmagnetic monovalence ions at the BI site (Na/Ag) in facilitating the superexchange interaction via orbital hybridization, offering the tunability of the Curie-Weiss parameters between -27 and -210 K, with a potential to promote magnetic frustration via alloying the nonmagnetic BI site (Ag:Na ratio). Combining our experimental evidence with first-principles calculations, we draw a cohesive picture of the material design for B-site-ordered antiferromagnetic halide double perovskites.

Semiconducting nanowires (NWs) fabricated from III-V materials have gained significant attention for their application in advanced optoelectronic devices. Here, the growth of GaAs/GaInNAs/GaAs core-multishell NWs with a triple quantum-well structure, having about 2% N and 20% In, is reported. The NWs are grown via selective area plasma-assisted molecular beam epitaxy on patterned Si(111) substrates with SiO2 mask holes. The nucleation and growth of the GaAs nanowires' core are carried out by Ga-induced vapor-liquid-solid growth at the open holes. Finely controlled, vertically aligned, regular core-multishell NWs with uniform wire length and diameter are obtained with a 96% yield and targeted nitrogen concentrations of 0%, 2%, and 3%. The GaInNAs NWs exhibit a spectral red shift relative to the GaAs NWs' peak. Their emission wavelength increases with the N content reaching up to 1.26 mu m, which makes them a promising tool in telecommunication light sources.

Phonon-phonon and electron/exciton-phonon coupling play a vitally important role in thermal, electronic, as well as optical properties of metal halide perovskites. In this work, we evaluate phonon anharmonicity and coupling between electronic and vibrational excitations in novel double perovskite Cs2NaFeCl6 single crystals. By employing comprehensive Raman measurements combined with first-principles theoretical calculations, we identify four Raman-active vibrational modes. Polarization properties of these modes imply Fm (3) over barm symmetry of the lattice, indicative for on average an ordered distribution of Fe and Na atoms in the lattice. We further show that temperature dependence of the Raman modes, such as changes in the phonon line width and their energies, suggests high phonon anharmonicity, typical for double perovskite materials. Resonant multiphonon Raman scattering reveals the presence of high-lying band states that mediate strong electron-phonon coupling and give rise to intense nA(1g) overtones up to the fifth order. Strong electron-phonon coupling in Cs2NaFeCl6 is also concluded based on the Urbach tail analysis of the absorption coefficient and the calculated Frohlich coupling constant. Our results, therefore, suggest significant impacts of phonon-phonon and electron-phonon interactions on electronic properties of Cs2NaFeCl6, important for potential applications of this novel material.

Record power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have been obtained with the organic hole transporter 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD). Conventional doping of spiro-OMeTAD with hygroscopic lithium salts and volatile 4-tert-butylpyridine is a time-consuming process and also leads to poor device stability. We developed a new doping strategy for spiro-OMeTAD that avoids post-oxidation by using stable organic radicals as the dopant and ionic salts as the doping modulator (referred to as ion-modulated radical doping). We achieved PCEs of >25% and much-improved device stability under harsh conditions. The radicals provide hole polarons that instantly increase the conductivity and work function (WF), and ionic salts further modulate the WF by affecting the energetics of the hole polarons. This organic semiconductor doping strategy, which decouples conductivity and WF tunability, could inspire further optimization in other optoelectronic devices.

A common way of determining the majority charge carriers of pristine and doped semiconducting polymers is to measure the sign of the Seebeck coefficient. However, a polarity change of the Seebeck coefficient has recently been observed to occur in highly doped polymers. Here, it is shown that the Seebeck coefficient inversion is the result of the density of states filling and opening of a hard Coulomb gap around the Fermi energy at high doping levels. Electrochemical n-doping is used to induce high carrier density (>1 charge/monomer) in the model system poly(benzimidazobenzophenanthroline) (BBL). By combining conductivity and Seebeck coefficient measurements with in situ electron paramagnetic resonance, UV-vis-NIR, Raman spectroelectrochemistry, density functional theory calculations, and kinetic Monte Carlo simulations, the formation of multiply charged species and the opening of a hard Coulomb gap in the density of states, which is responsible for the Seebeck coefficient inversion and drop in electrical conductivity, are uncovered. The findings provide a simple picture that clarifies the roles of energetic disorder and Coulomb interactions in highly doped polymers and have implications for the molecular design of next-generation conjugated polymers.

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., QC 20201201

Doping of organic semiconductors is crucial for the operation of organic (opto)electronic and electrochemical devices. Typically, this is achieved by adding heterogeneous dopant molecules to the polymer bulk, often resulting in poor stability and performance due to dopant sublimation or aggregation. In small-molecule donor-acceptor systems, charge transfer can yield high and stable electrical conductivities, an approach not yet explored in all-conjugated polymer systems. Here, we report ground-state electron transfer in all-polymer donor-acceptor heterojunctions. Combining low-ionization-energy polymers with high-electron-affinity counterparts yields conducting interfaces with resistivity values five to six orders of magnitude lower than the separate single-layer polymers. The large decrease in resistivity originates from two parallel quasi-two-dimensional electron and hole distributions reaching a concentration of similar to 10(13) cm(-2). Furthermore, we transfer the concept to three-dimensional bulk heterojunctions, displaying exceptional thermal stability due to the absence of molecular dopants. Our findings hold promise for electro-active composites of potential use in, for example, thermoelectrics and wearable electronics. Doping through spontaneous electron transfer between donor and acceptor polymers is obtained by selecting organic semiconductors with suitable electron affinity and ionization energy, achieving high conductivity in blends and bilayer configuration.

Contains fulltext : 208634.pdf (publisher's version ) (Open Access)

We investigated the influence of backbone regiochemistry on the conductivity, charge density, and polaron structure in the widely studied n-doped donor-acceptor polymer poly[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene) [P-(NDI2OD-T2)]. In contrast to classic semicrystalline polymers such as poly(3-hexylthiophene) (P3HT), the regioirregular (RI) structure of the naphthalenediimide (NDI)-bithiophene (T2) backbone does not alter the intramolecular steric demand of the chain versus the regioregular (RR) polymer, yielding RI-P(NDI2OD-T2) with similar energetics and optical features as its RR counterpart. By combining the electrical, UV-vis/infrared, X-ray diffraction, and electron paramagnetic resonance data and density functional theory calculations, we quantitatively characterized the conductivity, aggregation, crystallinity, and charge density, and simulated the polaron structures, molecular vibrations, and spin density distribution of RR-/RI-P(NDI2OD-T2). Importantly, we observed that RI-P(NDI2OD-T2) can be doped to a greater extent compared to its RR counterpart. This finding is remarkable and contrasts benchmark P3HT, allowing us to uniquely study the role of regiochemistry on the charge-transport properties of n-doped donor-acceptor polymers.

Recent developments in fabrication techniques and extensive investigations of the physical properties of III-V semiconductor nanowires (NWs), such as GaAs NWs, have demonstrated their potential for a multitude of advanced electronic and photonics applications. Alloying of GaAs with nitrogen can further enhance the performance and extend the device functionality via intentional defects and heterostructure engineering in GaNAs and GaAs/GaNAs coaxial NWs. In this work, it is shown that incorporation of nitrogen in GaAs NWs leads to formation of three-dimensional confining potentials caused by short-range fluctuations in the nitrogen composition, which are superimposed on long-range alloy disorder. The resulting localized states exhibit a quantum-dot like electronic structure, forming optically active states in the GaNAs shell. By directly correlating the structural and optical properties of individual NWs, it is also shown that formation of the localized states is efficient in pure zinc-blende wires and is further facilitated by structural polymorphism. The light emission from these localized states is found to be spectrally narrow (similar to 50-130 mu eV) and is highly polarized (up to 100%) with the preferable polarization direction orthogonal to the NW axis, suggesting a preferential orientation of the localization potential. These properties of self-assembled nano-emitters embedded in the GaNAs-based nanowire structures may be attractive for potential optoelectronic applications., Funding agencies: Financial support by the Swedish Energy Agency (grant # P40119-1) and the Swedish Research Council (grants # 2015-05532 and 2008-405) is greatly appreciated. The Knut and Alice Wallenberg Foundation is gratefully acknowledged for support of the Electron Microscopy laboratory in Linkoping.

GaNAs-based nanowires (NWs) form a novel material system of potential importance for applications in advanced optoelectronic and photonic devices, thanks to the advantages provided by band-structure engineering, one-dimensional architecture and the possibility to combine them with mainstream silicon technology. In this work we utilize the micro-Raman scattering technique to systematically study the structural properties of such GaAs/GaNAs core/shell NW structures grown by molecular beam epitaxy on a Si substrate. It is shown that the employed one-dimensional architecture allows the fabrication of a GaNAs shell with a low degree of alloy disorder and weak residual strain, at least within the studied range of nitrogen (N) compositions [N]Â