Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userCs$_2$InAgCl$_6$: A new lead-free halide double perovskite with direct band gap
141
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
A$_2$BB$^prime$X$_6$ halide double perovskites based on bismuth and silver have recently been proposed as potential environmentally-friendly alternatives to lead-based hybrid halide perovskites. In particular, Cs$_2$BiAgX$_6$ (X = Cl, Br) have been synthesized and found to exhibit band gaps in the visible range. However, the band gaps of these compounds are indirect, which is not ideal for applications in thin film photovoltaics. Here, we propose a new class of halide double perovskites, where the B$^{3+}$ and B$^{+}$ cations are In$^{3+}$ and Ag$^{+}$, respectively. Our first-principles calculations indicate that the hypothetical compounds Cs$_2$InAgX$_6$ (X = Cl, Br, I) should exhibit direct band gaps between the visible (I) and the ultraviolet (Cl). Based on these predictions, we attempt to synthesize Cs$_2$InAgCl$_6$ and Cs$_2$InAgBr$_6$, and we succeed to form the hitherto unknown double perovskite Cs$_2$InAgCl$_6$. X-ray diffraction yields a double perovskite structure with space group $Fmoverline{3}m$. The measured band gap is 3.3 eV, and the compound is found to be photosensitive and turns reversibly from white to orange under ultraviolet illumination. We also perform an empirical analysis of the stability of Cs$_2$InAgX$_6$ and their mixed halides based on Goldschmidts rules, and we find that it should also be possible to form Cs$_2$InAg(Cl$_{1-x}$Br$_{x}$)$_6$ for $x<1$. The synthesis of mixed halides will open the way to the development of lead-free double perovskites with direct and tunable band gaps.
rate research
Read More
Methylammonium lead iodide perovskites are considered direct bandgap semiconductors. Here we show that in fact they present a weakly indirect bandgap 60 meV below the direct bandgap transition. This is a consequence of spin-orbit coupling resulting in Rashba-splitting of the conduction band. The indirect nature of the bandgap explains the apparent contradiction of strong absorption and long charge carrier lifetime. Under hydrostatic pressure from ambient to 325 MPa, Rashba splitting is reduced due to a pressure induced ordering of the crystal structure. The nature of the bandgap becomes increasingly more direct, resulting in five times faster charge carrier recombination, and a doubling of the radiative efficiency. At hydrostatic pressures above 325 MPa, MAPI undergoes a reversible phase transition resulting in a purely direct bandgap semiconductor. The pressure-induced changes suggest epitaxial and synthetic routes to higher efficiency optoelectronic devices.
We present a new member of the multiferroic oxides, Lu$_2$MnCoO$_6$, which we have investigated using X-ray diffraction, neutron diffraction, specific heat, magnetization, electric polarization, and dielectric constant measurements. This material possesses an electric polarization strongly coupled to a net magnetization below 35 K, despite the antiferromagnetic ordering of the $S = 3/2$ Mn$^{4+}$ and Co$^{2+}$ spins in an $uparrow uparrow downarrow downarrow$ configuration along the c-direction. We discuss the magnetic order in terms of a condensation of domain boundaries between $uparrow uparrow$ and $downarrow downarrow$ ferromagnetic domains, with each domain boundary producing a net electric polarization due to spatial inversion symmetry breaking. In an applied magnetic field the domain boundaries slide, controlling the size of the net magnetization, electric polarization, and magnetoelectric coupling.
Lead-free double perovskite halides are emerging optoelectronic materials that are alternatives to lead-based perovskite halides. Recently, single-crystalline double perovskite halides were synthesized, and their intriguing functional properties were demonstrated. Despite such pioneering works, lead-free double perovskite halides with better crystallinity are still in demand for applications to novel optoelectronic devices. Here, we realized highly crystalline Cs2AgBiBr6 single crystals with a well-defined atomic ordering on the microscopic scale. We avoided the formation of Ag vacancies and the subsequent secondary Cs3Bi2Br9 by manipulating the initial chemical environments in hydrothermal synthesis. The suppression of Ag vacancies allows us to reduce the trap density in the as-grown crystals and to enhance the carrier mobility further. Our design strategy is applicable for fabricating other lead-free halide materials with high crystallinity.
We report a strongly temperature dependent luminescence Stokes shift in the electronic spectra of both hybrid and inorganic lead-bromide perovskite single crystals. This behavior stands in stark contrast to that exhibited by more conventional crystalline semiconductors. We correlate the electronic spectra with the anti-Stokes and Stokes Raman vibrational spectra. Dielectric solvation theories, originally developed for excited molecules dissolved in polar liquids, reproduce our experimental observations. Our approach, which invokes a classical Debye-like relaxation process, captures the dielectric response originating from an anharmonic LO phonon at about 20 meV (160 cm-1) in the lead-bromide framework. We reconcile the liquid-like picture with more standard solid-state theories of the Stokes shift in crystalline semiconductors.
Efficient charge separation at the interfaces between the perovskite and with the carrier transport layers is crucial for perovskite solar cells to achieve high power conversion efficiency. We systematically investigate the hole injection dynamics from MAPbI$_3$ perovskite to three typical hole transport materials (HTMs) PEDOT:PSS, PTAA and NiO$_x$ by means of pump-probe transmission measurements. We photoexcite only near the MAPbI$_3$/HTM interface or near the back surface, and measure the differential transient transmission between the two excitation configurations to extract the carrier dynamics directly related to the hole injection. The differential transmission signals directly monitor the hole injections to PTAA and PEDOT:PSS being complete within 1 and 2 ps, respectively, and that to NiO$_x$ exhibiting an additional slow process of 40 ps time scale. The obtained injection dynamics are discussed in comparison with the device performance of the solar cells containing the same MAPbI$_3$/HTM interfaces.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
