Despite the great success that theoretical approaches based on density functional theory have in describing properties of solid compounds, accurate predictions of the enthalpies of formation ( delta ...Hsubf) of insulating and semiconducting solids still remain a challenge. In this paper we present an approach based on GGA + U calculations, including the spin-orbit coupling, which involves fitted elemental-phase reference energies (FERE) and which significantly improves the error cancellation resulting in accurate values for the compound enthalpies of formation. The FERE method, hence, represents a simple and general approach, as it is computationally equivalent to the cost of pure GGA calculations and applies to virtually all insulating and semiconducting compounds, for predicting compound ( delta Hsubf) values with chemical accuracy. We also show that by providing accurate ( delta Hsubf) the FERE approach can be applied for accurate predictions of the compound thermodynamic stability or for predictions of Li-ion battery voltages.
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Self-trapped excitons (STEs) in metal halide materials are attracting an increasing level of interest due to their unique light emission properties. Light emission from STEs in metal halides is ...usually associated with excited-state structural deformation, which lowers the symmetry of local structures, as seen for the STEs in a wide range of materials systems. Here, we reveal a prototypic STE-associated structural “distortion” that, however, enhances the symmetry of local structures, in a series of all-inorganic copper(I)-based halides Cs3Cu2X5 (X = Cl, Br, or I). We further find that the emission peaks of Cs3Cu2X5 blue-shift when the halogen changes from Cl to Br to I, which is the opposite of the trends found in traditional halide perovskites. This phenomenon is attributed to a synergetic combination of the significant change in band gap associated with structural deformation and a strong excitonic effect. Due to the highly localized electron and hole upon photoexcitation, Cs3Cu2Cl5 shows an extremely long and temperature-sensitive photoluminescence (PL) lifetime among metal halide materials with STEs. Remarkably, strong green emission with a PL quantum yield exceeding 90% is found in Cs3Cu2Cl5, opening the way to designing light emission compounds based on local symmetry-enhancing STE mechanisms.
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Two-dimensional (2D) ferromagnetism is critical for both scientific investigation and technological development owing to its low-dimensionality that brings in quantization of electronic states as ...well as free axes for device modulation. However, the scarcity of high-temperature 2D ferromagnets has been the obstacle of many research studies, such as the quantum anomalous Hall effect (QAHE) and thin-film spintronics. Indeed, in the case of the isotropic Heisenberg model with finite-range exchange interactions as an example, low-dimensionality is shown to be contraindicated with ferromagnetism. However, the advantages of low-dimensionality for micro-scale patterning could enhance the Curie temperature (T
) of 2D ferromagnets beyond the T
of bulk materials, opening the door for designing high-temperature ferromagnets in the 2D limit. In this paper, we review the recent advances in the field of 2D ferromagnets, including their material systems, physical properties, and potential device applications.
Radioluminescent materials (scintillators) are widely applied in medical imaging, nondestructive testing, security inspection, nuclear and radiation industries, and scientific research. Recently, ...all‐inorganic lead halide perovskite nanocrystal (NC) scintillators have attracted great attention due to their facile solution processability and ultrasensitive X‐ray detection, which allows for large area and flexible X‐ray imaging. However, the light yield of these perovskite NCs is relatively low because of the strong self‐absorption that reduces the light out‐coupling efficiency. Here, NCs with self‐trapped excitons emission are demonstrated to be sensitive, reabsorption‐free scintillators. Highly luminescent and stable Cs3Cu2I5 NCs with a photoluminescence quantum yields of 73.7%, which is a new record for blue emission lead‐free perovskite or perovskite‐like NCs, is produced with the assistance of InI3. The PL peak of the Cs3Cu2I5 NCs locates at 445 nm that matches with the response peak of a silicon photomultiplier. Thus, Cs3Cu2I5 NCs are demonstrated as efficient scintillators with zero self‐absorption and extremely high light yield (≈79 279 photons per MeV). Both Cs3Cu2I5 NC colloidal solution and film exhibit strong radioluminescence under X‐ray irradiation. The potential application of Cs3Cu2I5 NCs as reabsorption‐free, low cost, large area, and flexible scintillators is demonstrated by a prototype X‐ray imaging with a high spatial resolution.
Nanocrystals (NCs) with self‐trapped excitons emission are demonstrated to be sensitive, reabsorption‐free scintillators. Highly blue‐emissive and stable Cs3Cu2I5 NCs with a photoluminescence quantum yield of 73.7% are produced. These Cs3Cu2I5 NCs show a strong and reabsorption‐free radioluminescence under X‐ray irradiation with an extremely high light yield, which makes them promising scintillators for low cost, large area, and flexible X‐ray imaging.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Intriguing physical properties of materials stem from their chemical constituents, whereas the connection between them is often not clear. Here, we uncover a general chemical classification for the ...two quantum phases in the honeycomb ABX structuretopological insulator (TI) and topological Dirac semimetal (TDSM). First, we find among the 816 (existing as well as hypothetical) calculated compounds, 160 TIs (none were noted before), 96 TDSMs, 282 normal insulators (NIs), and 278 metals. Second, based on this classification, we have distilled a simple chemical regularity based on compound formulas for the selectivity between TI and TDSM: the ABX compounds that are TDSM have B atoms (part of the BX honeycomb layers) that come from the periodic table columns XI (Cu, Ag, Au) or XII (Zn, Cd, Hg), or Mg (group II), whereas the ABX compounds whose B atoms come from columns I (Li, Na, K, Rb, Cs) or II (Ca, Sr, Ba) are TIs. Third, focusing on the ABX bismide compounds that are thermodynamically stable, we find a structural motif that delivers topological insulation and stability at the same time. This study opens the way to simultaneously design new topological materials based on the compositional rules indicated here.
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Spin-orbit coupling can induce spin polarization in nonmagnetic 3D crystals when the inversion symmetry is broken, as manifested by the bulk Rashba and Dresselhaus effects. We establish that these ...spin-polarization effects originate fundamentally from specific atomic site asymmetries, rather than, as generally accepted, from the asymmetry of the crystal space group. This understanding leads to the recognition that a previously overlooked hidden form of spin polarization should exist in centrosymmetric crystals. Although all energy bands must be doubly degenerate in centrosymmetric materials, we find that the two components of such doubly degenerate bands could have opposite polarizations, each spatially localized on one of the two separate sectors forming the inversion partners. We demonstrate such hidden spin polarizations in particular centrosymmetric crystals by first-principles calculations. This new understanding could considerably broaden the range of currently useful spintronic materials and enable the control of spin polarization by means of operations on the atomic scale.
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2D nonlayered materials that possess appealing properties are entering the researchers' vision. However, direct access to the 2D level of these materials is still a great challenge due to the ...instrinsic isotropic chemical bond. This work presents the initially self‐limited epitaxial growth of ultrathin nonlayered CdS flakes (as thin as 6 nm) on mica substrate with a large domain size (>40 µm) by employing In2S3 as the passivation agent. Besides, the thickness and sizes of the products could be tunable by the addition level of In2S3 amount. The growth mechanism is evidenced via experiments and theoretical calculations, which is attributed to the surface distortion effect of In–S motif and the preference of local environments for In on the CdS (0001) surface. The photodetector designed on CdS flake demonstrates a high photoswitching ratio (up to 103), a high detectivity (D* ≈ 2.71 × 109 Jones), and fast photoresponse speed (τR = 14 ms, τD = 8 ms). The as‐proposed self‐limited epitaxial growth method opens a new avenue to synthetize 2D nonlayered materials and will promote their further applications in novel optoelectronic devices.
This work presents the initially self‐limited epitaxial growth of ultrathin nonlayered CdS flakes (≈6 nm) on mica substrate with a large domain size (>40 µm) by employing In2S3 as the passivation agent. The growth mechanism is attributed to the surface distortion effect of In–S motif and the preference of local environments for In on the CdS (0001) surface.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Electronic structure theory has recently been used to propose hypothetical compounds in presumed crystal structures, seeking new useful functional materials. In some cases, such hypothetical ...materials are metastable, albeit with technologically useful long lifetimes. Yet, in other cases, suggested hypothetical compounds may be significantly higher in energy than their lowest‐energy crystal structures or competing phases, making their synthesis and eventual device‐stability questionable. By way of example, the focus here is on the family of 1:1:1 compounds ABX called “filled tetrahedral structure” (sometimes called Half‐Heusler) in the four groups with octet electron count: I‐I‐VI (e.g., CuAgSe), I‐II‐V (e.g., AgMgAs), I‐III‐IV (e.g., LiAlSi), and II‐II‐IV (e.g., CaZnSn). First‐principles thermodynamics is used to sort the lowest‐energy structure and the thermodynamic stability of the 488 unreported hypothetical ABX compounds, many of which were previously proposed to be useful technologically. It is found that as many as 235 of the 488 are unstable with respect to decomposition (hence, are unlikely to be viable technologically), whereas other 235 of the unreported compounds are predicted to be thermodynamically stable (hence, potentially interesting new materials). 18 additional materials are too close to determine. The electronic structures of these predicted stable compounds are evaluated, seeking potential new material functionalities.
First‐principles thermodynamics is used to determine the lowest‐energy structures and stability with respect to decomposition of 488 hypothetical ABX Half‐Heusler compounds from the groups I‐I‐VI, I‐II‐V, I‐III‐IV, II‐II‐IV and it is found that 235 are unstable against decomposition and 18 are too close to determine. 235 other unreported (UR) compounds are predicted to be new stable phases. The electronic structures of these predicted new compounds are evaluated, seeking potential new material functionalities.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Chemists and material scientists have often focused on the properties of previously reported compounds, but neglect numerous unreported but chemically plausible compounds that could have interesting ...properties. For example, the 18-valence electron ABX family of compounds features examples of topological insulators, thermoelectrics and piezoelectrics, but only 83 out of 483 of these possible compounds have been made. Using first-principles thermodynamics we examined the theoretical stability of the 400 unreported members and predict that 54 should be stable. Of those previously unreported 'missing' materials now predicted to be stable, 15 were grown in this study; X-ray studies agreed with the predicted crystal structure in all 15 cases. Among the predicted and characterized properties of the missing compounds are potential transparent conductors, thermoelectric materials and topological semimetals. This integrated process-prediction of functionality in unreported compounds followed by laboratory synthesis and characterization-could be a route to the systematic discovery of hitherto missing, realizable functional materials.
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As an emerging type of optically active materials, chiral molecules-stabilized semiconductor quantum dots (QDs) have achieved extensive attention. Unfortunately, understanding of the optical ...characteristics of chiral QDs observed by circular dichroism (CD) spectroscopy remains a great challenge due to their rather weak signals. Herein, we successfully achieve much enhanced CD responses from l- or d-cysteine-stabilized wurtzite CdSe quantum rods (QRs) thanks to their unique optical anisotropy. Furthermore, the optical activity of CdSe QRs is explored to be improved and subsequently become stable with the geometrical aspect ratio (AR) increasing, and such change matches well with alternation of the polarization factor of CdSe QRs. A non-degenerate coupled-oscillator (NDCO) model is established to elucidate the optical activity of chiral QRs, and the positive and negative natures of the CD peaks appearing at the first exciton band are clearly assigned to different transition polarization along 4p z,Se → 5sCd and 4p(x,y),Se → 5sCd, respectively. This work opens the door toward comprehension and design of optically active semiconductor nanomaterials.
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