arXiv subjects

Geoffroy Hautier

Publications and source records attributed to Geoffroy Hautier.

At least 55 records · Page 3Linked to original sources

arXiv2023

FeMnNiAlCr High Entropy Alloys with High-Efficiency Surface Oxide Solar Absorbers for Concentrating Solar Power Systems

High entropy alloys (HEAs) have attracted substantial interest in recent years. Thus far, most investigations have focused on their applications as structural materials rather than functional materials. In this paper, we show that FeMnNiAlCr HEAs can potentially be applied as both a structural and functional material for high-efficiency concentrated solar thermal power (CSP) systems working at >700 degrees C. The HEA itself would be used in high-temperature tubing to carry working fluids, while its surface oxide would act as a high-efficiency solar thermal absorber. These HEAs have demonstrated yield strengths 2-3x greater than that of stainless steel at 700 degrees C and a creep lifetime >800 h at 700 degrees C under a typical CSP tubing mechanical load of 35 MPa. Their Mn-rich surface oxides maintain a high optical-to-thermal conversion efficiency of ~87% under 1000x solar concentration for 20 simulated day-night thermal cycles between 750 degrees C and environmental temperature. These HEAs have also sustained immersion in unpurified bromide molten salts for 14 days at 750°C with <2% weight loss, in contrast to 70% weight loss from a 316 stainless steel reference. The simultaneous achievement of promising mechanical, optical, and thermochemical properties in this FeMnNiAlCr system opens the door to new applications of HEAs in solar energy harvesting.

cond-mat.mtrl-sci↗

arXiv2023

Unravelling Ultralow Thermal Conductivity in Double Perovskite Cs2AgBiBr6: Dominant Wave-like Phonon Tunnelling, Strong Quartic Anharmonicity and Lattice Instability

In this work, we investigate the microscopic mechanisms of anharmonic lattice dynamics and thermal transport in lead-free halide double perovskite Cs2AgBiBr6 from first principles. We combine self-consistent phonon calculations with bubble diagram correction and a unified theory of lattice thermal transport that considers both the particle-like phonon propagation and wave-like tunnelling of phonons. An ultra-low thermal conductivity at room temperature (~0.21 Wm-1K-1) is predicted with weak temperature dependence(~T-0.45), in sharp contrast to the conventional ~T-1 dependence. Particularly, the vibrational properties of Cs2AgBiBr6 are featured by strong anharmonicity and wave-like tunnelling of phonons. Anharmonic phonon renormalization from both the cubic and quartic anharmonicities are found essential in precisely predicting the phase transition temperature in Cs2AgBiBr6 while the negative phonon energy shifts induced by cubic anharmonicity has a significant influence on particle-like phonon propagation. Further, the contribution of the wave-like tunnelling to the total thermal conductivity surpasses that of the particle-like propagation above around 340 K, indicating the breakdown of the phonon gas picture conventionally used in the Peierls-Boltzmann Transport Equation. Importantly, further including four-phonon scatterings is required in achieving the dominance of wave-like tunnelling, as compared to the dominant particle-like propagation channel when considering only three-phonon scatterings. Our work highlights the importance of lattice anharmonicity and wave-like tunnelling of phonons in the thermal transport in lead-free halide double perovskites.

cond-mat.mtrl-sci↗

arXiv2023

Wave-like Tunneling of Phonons Dominates Glass-like Thermal Transport in Quasi-1D Copper Halide CsCu2I3

Fundamental understanding of thermal transport in compounds with ultra-low thermal conductivity remains challenging, primarily due to the limitations of conventional lattice dynamics and heat transport models. In this study, we investigate the thermal transport in quasi-one-dimensional (1D) copper halide CsCu2I3 by employing a combination of first principles-based self-consistent phonon calculations and a dual-channel thermal transport model. Our results show that the 0-K unstable soft modes, primarily dominated by Cs and I atoms in CsCu2I3, can be an-harmonically stabilized at ~ 75 K. Furthermore, we predict an ultra-low thermal conductivity of 0.362 Wm^(-1) K^(-1) along the chain axis and 0.201 Wm^(-1) K^(-1) along cross chain direction in CsCu2I3 at 300 K. Importantly, we find that an unexpected anomalous trend of increasing cross-chain thermal conductivity with increasing temperature for CsCu2I3, following a temperature dependence of ~T 0.106, which is atypical for a single crystal and classified as an abnormal glass-like behavior. The peculiar temperature-dependent behavior of thermal conductivity is elucidated by the dominant wave-like tunnelling of phonons in thermal transport of CsCu2I3 along cross-chain direction. In contrast, particle-like phonon propagation primarily contributes to the chain-axis thermal conductivity across the entire temperature range of 300-700 K. The sharp difference in the dominant thermal transport channels between the two crystallographic directions can be attributed to the unique chain-like quasi-1D structure of CsCu2I3. Our study not only illustrates the microscopic mechanisms of thermal transport in CsCu2I3 but also paves the way for searching for and designing materials with ultra-low thermal conductivity.

cond-mat.mtrl-sci↗

arXiv2023

Discovery of the Zintl-phosphide BaCd$_{2}$P$_{2}$ as a long carrier lifetime and stable solar absorber

Thin-film photovoltaics offers a path to significantly decarbonize our energy production. Unfortunately, current materials commercialized or under development as thin-film solar cell absorbers are far from optimal as they show either low power conversion efficiency or issues with earth-abundance and stability. Entirely new and disruptive materials platforms are rarely discovered as the search for new solar absorbers is traditionally slow and serendipitous. Here, we use first principles high-throughput screening to accelerate this process. We identify new solar absorbers among known inorganic compounds using considerations on band gap, carrier transport, optical absorption but also on intrinsic defects which can strongly limit the carrier lifetime and ultimately the solar cell efficiency. Screening about 40,000 materials, we discover the Zintl-phosphide BaCd$_{2}$P$_{2}$ as a potential high-efficiency solar absorber. Follow-up experimental work confirms the predicted promises of BaCd$_{2}$P$_{2}$ highlighting an optimal band gap for visible absorption, bright photoluminescence, and long carrier lifetime of up to 30 ns even for unoptimized powder samples. Importantly, BaCd$_{2}$P$_{2}$ does not contain any critical elements and is highly stable in air and water. Our work opens an avenue for a new family of stable, earth-abundant, high-performance Zintl-based solar absorbers. It also demonstrates how recent advances in first principles computation can accelerate the search of photovoltaic materials by combining high-throughput screening with experiment.

cond-mat.mtrl-sci↗

arXiv2023

First-principles study of intrinsic and hydrogen point defects in the earth-abundant photovoltaic absorber Zn3P2

Zinc phosphide (Zn3P2) has had a long history of scientific interest largely because of its potential for earth-abundant photovoltaics. To realize high-efficiency Zn3P2 solar cells, it is critical to understand and control point defects in this material. Using hybrid functional calculations, we assess the energetics and electronic behavior of intrinsic point defects and hydrogen impurities in Zn3P2. All intrinsic defects are found to act as compensating centers in p-type Zn3P2 and have deep levels in the band gap, except for zinc vacancies which are shallow acceptors and can act as a source of doping. Our work highlights that zinc vacancies rather than phosphorus interstitials are likely to be the main source of p-type doping in as-grown Zn3P2. We also show that Zn-poor and P-rich growth conditions, which are usually used for enhancing p-type conductivity of Zn3P2, will facilitate the formation of certain deep-level defects (P_Zn and P_i) which might be detrimental to solar cell efficiency. For hydrogen impurities, which are frequently present in the growth environment of Zn3P2, we study interstitial hydrogen and hydrogen complexes with vacancies. The results suggest small but beneficial effects of hydrogen on the electrical properties of Zn3P2.

cond-mat.mtrl-sci↗

arXiv2023

A map of single-phase high-entropy alloys

High-entropy alloys have shown much interest and unusual materials properties. The stability of equimolar single-phase solid solution of five or more elements is likely to be rare and identifying the existence of such alloys has been very challenging because of the very large space of possible combinations. Herein, based on high-throughput density-functional theory calculations, we construct a chemical map of single-phase equimolar high entropy alloys by investigating over 650000 equimolar quinary alloys through a binary regular solid-solution model. We identify more than 30000 potential single-phase equimolar alloys (5% of the possible combinations) forming mainly in body-centered cubic structures. We unveil the chemistries that are likely to form high-entropy alloys, and identify the complex interplay among mixing enthalpy, intermetallics formation, and melting point that drives the formation of these solid solutions. We demonstrate the power of our method by predicting the existence of two new high entropy alloys, i.e. the body-centered cubic AlCoMnNiV and the face-centered cubic CoFeMnNiZn, which are successfully synthesized.

cond-mat.mtrl-sci↗

arXiv2023

Designing transparent conductors using forbidden optical transitions

Many semiconductors present weak or forbidden transitions at their fundamental band gaps, inducing a widened region of transparency. This occurs in high-performing n-type transparent conductors (TCs) such as Sn-doped In2O3 (ITO), however thus far the presence of forbidden transitions has been neglected in searches for new p-type TCs. To address this, we first compute high-throughput absorption spectra across ~18,000 semiconductors, showing that over half exhibit forbidden or weak optical transitions at their band edges. Next, we demonstrate that compounds with highly localized band edge states are more likely to present forbidden transitions. Lastly, we search this set for p-type and n-type TCs with forbidden or weak transitions. Defect calculations yield unexplored TC candidates such as ambipolar BeSiP2, Zr2SN2 and KSe, p-type BAs, Au2S, and AuCl, and n-type Ba2InGaO5, GaSbO4, and KSbO3, among others. We share our data set via the MPContribs platform, and we recommend that future screenings for optical properties use metrics representative of absorption features rather than band gap alone.

cond-mat.mtrl-sci↗

arXiv2023

High-throughput identification of spin-photon interfaces in silicon

Color centers in host semiconductors are prime candidates for spin-photon interfaces that would enable numerous quantum applications. The discovery of an optimal spin-photon interface in silicon would move quantum information technologies towards a mature semiconductor technology. However, the space of possible charged defects in a host is very large, making the identification of promising quantum defects from experiments only extremely challenging. Here, we use high-throughput first principles computational screening to identify spin-photon interfaces among more than 1000 substitutional and interstitial charged defects in silicon. We evaluate the most promising defects by considering their optical properties, spin multiplicity, and formation energies. The use of a single-shot hybrid functional approach is critical in enabling the screening of a large number of defects with a reasonable accuracy in the calculated optical and electronic properties. We identify three new promising spin-photon interface as potential bright emitters in the telecom band: $\rm Ti_{i}^{+}$, $\rm Fe_{i}^{0}$, and $\rm Ru_{i}^{0}$. These candidates are excited through defect-bound excitons, stressing the importance of considering these type of defects in silicon if operations in the telecom band is targeted. Our work paves the way to further large scale computational screening for quantum defects in silicon and other hosts.

quant-ph↗

arXiv2023

Midgap state requirements for optically active quantum defects

Optically active quantum defects play an important role in quantum sensing, computing, and communication. The electronic structure and the single-particle energy levels of these quantum defects in the semiconducting host have been used to understand their opto-electronic properties. Optical excitations that are central for their initialization and readout are linked to transitions between occupied and unoccupied single-particle states. It is commonly assumed that only quantum defects introducing levels well within the band gap and far from the band edges are of interest for quantum technologies as they mimic an isolated atom embedded in the host. In this perspective, we contradict this common assumption and show that optically active defects with energy levels close to the band edges can display similar properties. We highlight quantum defects that are excited through transitions to or from a band-like level (bound exciton), such as the T center and Se$\rm _{Si}^+$ in silicon. We also present how defects such as the silicon divacancy in diamond can involve transitions between localized levels that are above the conduction band or below the valence band. Loosening the commonly assumed requirement on the electronic structure of quantum defects offers opportunities in quantum defects design and discovery, especially in smaller band gap hosts such as silicon. We discuss the challenges in terms of operating temperature for photoluminescence or radiative lifetime in this regime. We also highlight how these alternative type of defects bring their own needs in terms of theoretical developments and fundamental understanding. This perspective clarifies the electronic structure requirement for quantum defects and will facilitate the identification and design of new color centers for quantum applications especially driven by first principles computations.

quant-ph↗

arXiv2022

Prediction of topological phases in metastable ferromagnetic MPX$_3$ monolayers

Density functional theory calculations are carried out to study the electronic and topological properties of $M$P$X_3$ ($M$ = Mn, Fe, Co, Ni, and $X$ = S, Se) monolayers in the ferromagnetic (FM) metastable magnetic state. We find that FM MnPSe$_3$ monolayers host topological semimetal signatures that are gapped out when spin-orbit coupling (SOC) is included. These findings are supported by explicit calculations of the Berry curvature and the Chern number. The choice of the Hubbard-$U$ parameter to describe the $d$-electrons is thoroughly discussed, as well as the influence of using a hybrid-functional approach. The presence of band inversions and the associated topological features are found to be formalism-dependent. Nevertheless, routes to achieve the topological phase via the application of external biaxial strain are demonstrated. Within the hybrid-functional picture, topological band structures are recovered under a pressure of 15% (17 GPa). The present work provides a potential avenue for uncovering new topological phases in metastable ferromagnetic phases.

cond-mat.mtrl-sci↗

arXiv2022

Indistinguishable photons from an artificial atom in silicon photonics

Silicon is the ideal material for building electronic and photonic circuits at scale. Spin qubits and integrated photonic quantum technologies in silicon offer a promising path to scaling by leveraging advanced semiconductor manufacturing and integration capabilities. However, the lack of deterministic quantum light sources, two-photon gates, and spin-photon interfaces in silicon poses a major challenge to scalability. In this work, we show a new type of indistinguishable photon source in silicon photonics based on an artificial atom. We show that a G center in a silicon waveguide can generate high-purity telecom-band single photons. We perform high-resolution spectroscopy and time-delayed two-photon interference to demonstrate the indistinguishability of single photons emitted from a G center in a silicon waveguide. Our results show that artificial atoms in silicon photonics can source highly coherent single photons suitable for photonic quantum networks and processors.

quant-ph↗

arXiv2022

Nonunique fraction of Fock exchange for defects in two-dimensional materials

By investigating the vacancy and substitutional defects in monolayer WS$_2$ with hybrid functionals, we find that there is no unique amount of Fock exchange that concurrently satisfies the generalized Koopmans' condition and reproduces the band gap and band-edge positions. Fixing the mixing parameter of Fock exchange based upon the band gap can lead to qualitatively incorrect defect physics in two-dimensional materials. Instead, excellent agreement is achieved with experiment and many-body perturbation theory within $GW$ approximation once the mixing parameters are tuned individually for the defects and the band edges. We show the departure from a unique optimized mixing parameter is inherent to two-dimensional systems as the band edges experience a reduced screening whilst the localized defects are subject to bulklike screening.

cond-mat.mtrl-sci↗

arXiv2022

SnP$_2$S$_6$: A Promising Infrared Nonlinear Optical Crystal with Strong Non-Resonant Second Harmonic Generation and Phase-matchability

High-power infrared laser systems with broadband tunability are of great importance due to their wide range of applications in spectroscopy and free-space communications. These systems require nonlinear optical (NLO) crystals for wavelength up/down conversion using sum/difference frequency generation, respectively. NLO crystals need to satisfy many competing criteria, including large nonlinear optical susceptibility, large laser induced damage threshold (LIDT), wide transparency range and phase-matchability. Here, we report bulk single crystals of SnP_2S_6 with a large non-resonant SHG coefficient of d33= 53 pm/V at 1550nm and a large LIDT of 350 GW/cm^2 for femtosecond laser pulses. It also exhibits a broad transparency range from 0.54 μm to 8.5μm (bandgap of ~2.3 eV) and can be both Type I and Type II phase-matched. The complete linear and SHG tensors are measured as well as predicted by first principles calculations, and they are in excellent agreement. A proximate double-resonance condition in the electronic band structure for both the fundamental and the SHG light is shown to enhance the non-resonant SHG response. Therefore, SnP2S6 is an outstanding candidate for infrared laser applications.

physics.optics↗

arXiv2022

First principles study of the T-center in Silicon

The T-center in silicon is a well-known carbon-based color center that has been recently considered for quantum technology applications. Using first principles computations, we show that the excited state is formed by a defect-bound exciton made of a localized defect state occupied by an electron to which a hole is bound. The localized state is of strong carbon \textit{p} character and reminiscent of the localization of the unpaired electron in the ethyl radical molecule. The radiative lifetime for the defect-bound exciton is calculated to be on the order of $μ$s, much longer than other quantum defects such as the NV center in diamond and in agreement with experiments. The longer lifetime is associated with the small transition dipole moment as a result of the very different nature of the localized and delocalized states forming the defect-bound exciton. Finally, we use first principles calculations to assess the stability of the T-center. We find the T-center to be stable against decomposition into simpler defects when keeping the stoichiometry fixed. However, we identify that the T-center is easily prone to (de)hydrogenation and so requires very precise annealing conditions (temperature and atmosphere) to be efficiently formed.

cond-mat.mtrl-sci↗

arXiv2022

Assessing the quality of relaxation-time approximations with fully-automated computations of phonon-limited mobilities

The mobility of carriers, as limited by their scattering with phonons, can now routinely be obtained from first-principles electron-phonon coupling calculations. However, so far, most computations have relied on some form of simplification of the linearized Boltzmann transport equation based on either the self-energy, the momentum- or constant relaxation time approximations. Here, we develop a high-throughput infrastructure and an automatic workflow and we compute 69 phonon-limited mobilities in semiconductors. We compare the results resorting to the approximations with the exact iterative solution. We conclude that the approximate values may deviate significantly from the exact ones and are thus not reliable. Given the minimal computational overhead, our work encourages to rely on this exact iterative solution and warns on the possible inaccuracy of earlier results reported using relaxation time approximations.

cond-mat.mtrl-sci↗

arXiv2021

Giant thermoelectric figure of merit in multivalley high-complexity-factor LaSO

We report a giant thermoelectric figure of merit $ZT$ (up to 6 at 1100 K) in $n$-doped lanthanum oxysulphate LaSO. Thermoelectric coefficients are computed from ab initio bands within Bloch-Boltzmann theory in an energy-, chemical potential- and temperature-dependent relaxation time approximation. The lattice thermal conductivity is estimated from a model employing the ab initio phonon and Grüneisen-parameter spectrum. The main source of the large $ZT$ is the significant power factor which correlates with a large band complexity factor. We also suggest a possible $n$-type dopant for the material based on ab initio calculations.

cond-mat.mtrl-sci↗

arXiv2021

OPTIMADE, an API for exchanging materials data

The Open Databases Integration for Materials Design (OPTIMADE) consortium has designed a universal application programming interface (API) to make materials databases accessible and interoperable. We outline the first stable release of the specification, v1.0, which is already supported by many leading databases and several software packages. We illustrate the advantages of the OPTIMADE API through worked examples on each of the public materials databases that support the full API specification.

cond-mat.mtrl-sci↗

arXiv2021

MODNet -- accurate and interpretable property predictions for limited materials datasets by feature selection and joint-learning

In order to make accurate predictions of material properties, current machine-learning approaches generally require large amounts of data, which are often not available in practice. In this work, an all-round framework is presented which relies on a feedforward neural network, the selection of physically-meaningful features and, when applicable, joint-learning. Next to being faster in terms of training time, this approach is shown to outperform current graph-network models on small datasets. In particular, the vibrational entropy at 305 K of crystals is predicted with a mean absolute test error of 0.009 meV/K/atom (four times lower than previous studies). Furthermore, joint-learning reduces the test error compared to single-target learning and enables the prediction of multiple properties at once, such as temperature functions. Finally, the selection algorithm highlights the most important features and thus helps understanding the underlying physics.

cond-mat.mtrl-sci↗