arXiv subjects

Emmanouil Kioupakis

Publications and source records attributed to Emmanouil Kioupakis.

At least 37 records · Page 2Linked to original sources

arXiv2023

Increased light-emission efficiency in disordered InGaN through the correlated reduction of recombination rates

Experiments have shown that the light-emission efficiency of indium gallium nitride (InGaN) light-emitting diodes improves with increasing indium concentration. It is widely thought that compositional fluctuations due to indium incorporation suppress diffusion of carriers to non-radiative centers, thus leading to defect-insensitive emission. However, recent experiments have challenged this hypothesis by revealing unexpectedly long diffusion lengths at room temperature. Here, we demonstrate an alternative mechanism involving the correlated reduction in radiative and non-radiative recombination rates that explains the increase in light-emission efficiency of InGaN with increasing indium concentration, without invoking the suppression of carrier diffusion. Our analysis challenges the notion that carrier localization gives rise to defect tolerance in InGaN.

physics.optics↗

arXiv2023

Electronic and optical properties of 4H Si from first principles

The cubic polytype of silicon (Si) is the most commercialized semiconductor material and finds applications in numerous electronic and optoelectronic devices such as solar cells. However, recent reports on the synthesis of the hexagonal 4H Si polytype have attracted the attention of the scientific community to understand its functional properties. Here we report the electronic, vibrational, and optical properties of the 4H Si polytype obtained with predictive first-principles calculations. We find that, compared to the cubic polytype, 4H Si shows a slightly narrower indirect gap by $\sim$ 0.05 eV. By calculating its direct and phonon-assisted optical spectra, we show that 4H Si exhibits a stronger absorption coefficient than cubic Si across the visible and IR spectral regions. We further evaluate the short-circuit current density of textured thin-films, and we demonstrate that 4H Si can achieve the same short-circuit current density for a five times thinner film compared to the cubic polytype. Our work demonstrates the advantages of 4H Si for thin-film silicon-based solar-cell applications.

cond-mat.mtrl-sci↗

arXiv2023

Phonon-assisted Auger-Meitner Recombination in Silicon from First Principles

We present a consistent first-principles methodology to study both direct and phonon-assisted Auger-Meitner recombination (AMR) in indirect-gap semiconductors that we apply to investigate the microscopic origin of AMR processes in silicon. Our results are in excellent agreement with experimental measurements and show that phonon-assisted contributions dominate the recombination rate in both n-type and p-type silicon, demonstrating the critical role of phonons in enabling AMR. We also decompose the overall rates into contributions from specific phonons and electronic valleys to further elucidate the microscopic origins of AMR. Our results highlight potential pathways to modify the AMR rate in silicon via strain engineering.

cond-mat.mtrl-sci↗

arXiv2023

Electron-phonon physics from first principles using the EPW code

EPW is an open-source software for $\textit{ab initio}$ calculations of electron-phonon interactions and related materials properties. The code combines density functional perturbation theory and maximally-localized Wannier functions to efficiently compute electron-phonon coupling matrix elements on ultra-fine Brillouin zone grids. This data is employed for predictive calculations of temperature-dependent properties and phonon-assisted quantum processes in bulk solids and low-dimensional materials. Here, we report on significant new developments in the code that occurred during the period 2016-2022, namely: a transport module for the calculation of charge carrier mobility and conductivity under electric and magnetic fields within the $\textit{ab initio}$ Boltzmann transport equation; a superconductivity module for the calculation of critical temperature and gap structure in phonon-mediated superconductors within the $\textit{ab initio}$ anisotropic multi-band Eliashberg theory; an optics module for calculations of phonon-assisted indirect transitions; a module for the calculation of small and large polarons without supercells using the $\textit{ab initio}$ polaron equations; and a module for calculating electron-phonon couplings, band structure renormalization, and temperature-dependent optical spectra using the special displacement method. For each capability, we outline the methodology and implementation, and provide example calculations. We describe recent code refactoring to prepare EPW for exascale architectures, we discuss efficient parallelization strategies, and report on extreme parallel scaling tests.

cond-mat.mtrl-sci↗

arXiv2023

Phonon-assisted optical absorption of SiC polytypes from first principles

Silicon carbide (SiC) is an indirect-gap semiconductor material widely used in electronic and optoelectronic applications. While experimental measurements of the phonon-assisted absorption coefficient of SiC across its indirect gap have existed for more than fifty years, theoretical investigations of phonon-assisted absorption have been hampered by their excessive computational cost. In this work, we calculate the phonon-assisted temperature-dependent optical absorption spectra of the commonly occurring SiC polytypes (3C, 2H, 4H and 6H), using first-principles approaches based on density functional theory and related techniques. We show that our results agree with experimentally determined absorption coefficients in the spectral region between the direct and indirect band gaps. The temperature dependence of the spectra can be well-predicted with taking the temperature-dependence of the band gaps into account. Lastly, we compare the spectra obtained with second-order perturbation theory to those determined by the special displacement method, and we show that the full consideration of the electronic energy renormalization due to temperature is important to further improve the prediction of the phonon-assisted absorption in SiC. Our insights can be applied to predict the optical spectra of the less common SiC polytypes and other indirect-gap semiconductors in general.

cond-mat.mes-hall↗

arXiv2023

Ab initio calculation of carrier mobility in semiconductors including ionized-impurity scattering

The past decade has seen the emergence of ab initio computational methods for calculating phonon-limited carrier mobilities in semiconductors with predictive accuracy. More realistic calculations ought to take into account additional scattering mechanisms such as, for example, impurity and grain-boundary scattering. In this work, we investigate the effect of ionized-impurity scattering on the carrier mobility. We model the impurity potential by a collection of randomly distributed Coulomb scattering centers, and we include this relaxation channel into the ab initio Boltzmann transport equation, as implemented in the EPW code. We demonstrate this methodology by considering silicon, silicon carbide, and gallium phosphide, for which detailed experimental data are available. Our calculations agree reasonably well with experiments over a broad range of temperatures and impurity concentrations. For each compound investigated here, we compare the relative importance of electron-phonon scattering and ionized-impurity scattering, and we critically assess the reliability of Matthiessen's rule. We also show that an accurate description of dielectric screening and carrier effective masses cam improve quantitative agreement with experiments.

cond-mat.mtrl-sci↗

arXiv2022

Origin of the injection-dependent emission blueshift and linewidth broadening of III-nitride light-emitting diodes

III-nitride light-emitting diodes (LEDs) exhibit an injection-dependent emission blueshift and linewidth broadening that is severely detrimental to their color purity. Using first-principles multi-scale modelling that accurately captures the competition between polarization-charge screening, phase-space filling, and many-body plasma renormalization, we explain the current-dependent spectral characteristics of polar III-nitride LEDs fabricated with state-of-the-art quantum wells. Our analysis uncovers a fundamental connection between carrier dynamics and the injection-dependent spectral characteristics of light-emitting materials. For example, polar III-nitride LEDs offer poor control over their injection-dependent color purity due to their poor hole transport and slow carrier recombination dynamics, which forces them to operate at or near degenerate carrier densities. Designs that accelerate carrier recombination and transport and reduce the carrier density required to operate LEDs at a given current density lessen their injection-dependent wavelength shift and linewidth broadening.

physics.app-ph↗

arXiv2022

Ab initio theory of free-carrier absorption in semiconductors

The absorption of light by free carriers in semiconductors results in optical loss for all photon wavelengths. Since free-carrier absorption competes with optical transitions across the band gap, it also reduces the efficiency of optoelectronic devices such as solar cells because it does not generate electron-hole pairs. In this work, we develop a first-principles theory of free-carrier absorption taking into account both single-particle excitations and the collective Drude term, and we demonstrate its application to the case of doped Si. We determine the free-carrier absorption coefficient as a function of carrier concentration and we obtain excellent agreement with experimental data. We identify the dominant processes that contribute to free-carrier absorption at various photon wavelengths, and analyze the results to evaluate the impact of this loss mechanism on the efficiency of Si-based optoelectronic devices.

cond-mat.mtrl-sci↗

arXiv2022

Increasing the mobility and power-electronics figure of merit of AlGaN with atomically thin AlN/GaN digital-alloy superlattices

Alloy scattering in random AlGaN alloys drastically reduces the electron mobility and therefore the power-electronics figure of merit. As a result, Al compositions greater than 75% are required to obtain even a two-fold increase of the Baliga figure of merit compared to GaN. However, beyond approximately 80% Al composition, donors in AlGaN undergo the DX transition which makes impurity doping increasingly more difficult. Moreover, the contact resistance increases exponentially with increasing Al content, and integration with dielectrics becomes difficult due to the upward shift of the conduction band. Atomically thin superlattices of AlN and GaN, also known as digital alloys, are known to grow experimentally under appropriate growth conditions. These chemically ordered nanostructures could offer significantly enhanced figure of merit compared to their random-alloy counterparts due to the absence of alloy scattering, as well as better integration with contact metals and dielectrics. In this work, we investigate the electronic structure and phonon-limited electron mobility of atomically thin AlN/GaN digital-alloy superlattices using first-principles calculations based on density-functional and many-body perturbation theory. The band gap of the atomically thin superlattices reaches 4.8 eV, and the in-plane (out-of-plane) mobility is 369 (452) cm$^2$ V$^{-1}$ s$^{-1}$. Using the modified Baliga figure of merit that accounts for the dopant ionization energy, we demonstrate that atomically thin AlN/GaN superlattices with a monolayer sublattice periodicity have the highest modified Baliga figure of merit among several technologically relevant ultra-wide band-gap materials, including random AlGaN, $β$-Ga$_{2}$O$_{3}$, cBN, and diamond.

cond-mat.mtrl-sci↗

arXiv2021

Cation-size mismatch as a predictive descriptor for structural distortion, configurational disorder, and valence-band splitting in II-IV-N$_2$ semiconductors

The II-IV-N$_2$ class of heterovalent ternary nitrides have gained significant interest as alternatives to the III-nitrides for electronic and optoelectronic applications. In this study, we apply first-principles calculations based on density functional theory to systematically investigate the effects of structural distortions due to cation size mismatch on the configurational disorder of the cation sublattice and the valence band structure in this class of materials. We find that larger size mismatch between the group-II and the group-IV cations results in stronger lattice distortions from the ideal hexagonal ratio, which in turn inhibits the propensity of these materials towards octet-rule violating cation disorder. We also demonstrate that the formation energy of a single cation antisite pair, which is fast and simple to calculate, is a strong indicator of a material's propensity towards disorder. Furthermore, the breaking of in-plane symmetry leads to a splitting of the top three valence bands at $Γ$, which is also directly related to the magnitude of structural distortions. Our work demonstrates that the structural and functional properties of the II-IV-N$_2$ materials can be finely tuned through controllable structural distortions that stem from the choice of cations.

cond-mat.mtrl-sci↗

arXiv2021

Phonon- and defect-limited electron and hole mobility of diamond and cubic boron nitride: a critical comparison

Diamond and cBN are two of the most promising ultra-wide-band-gap (UWBG) semiconductors for applications in high-power high-frequency electronic devices. Yet despite extensive studies on carrier transport in these materials, there are large discrepancies in their reported carrier mobilities. In this work, we investigate the phonon- and dopant-limited electron and hole mobility of cBN and diamond with atomistic first-principles calculations in order to understand their fundamental upper bounds to carrier transport. Our results show that although the phonon-limited electron mobilities are comparable between cBN and diamond, the hole mobility is significantly lower in cBN due to its heavier hole effective mass. Moreover, although lattice scattering dominates the mobility at low doping, neutral impurity scattering becomes the dominant scattering mechanism at higher dopant concentrations due to the high dopant ionization energies. Our analysis provides critical insights and reveals the intrinsic upper limits to the carrier mobilities of diamond and cBN as a function of doping and temperature for applications in high-power electronic devices.

cond-mat.mtrl-sci↗

arXiv2021

Semiconducting character of LaN: magnitude of the band gap, and origin of the electrical conductivity

Lanthanum nitride (LaN) has attracted research interest in catalysis due to its ability to activate the triple bonds of N$_2$ molecules, enabling efficient and cost-effective synthesis of ammonia from N$_2$ gas. While exciting progress has been made to use LaN in functional applications, the electronic character of LaN (metallic, semi-metallic, or semiconducting) and magnitude of its band gap have so far not been conclusively determined. Here, we investigate the electronic properties of LaN with hybrid density functional theory calculations. In contrast to previous claims that LaN is semi-metallic, our calculations show that LaN is a direct-band-gap semiconductor with a band-gap value of 0.62 eV at the X point of the Brillouin zone. The dispersive character of the bands near the band edges leads to light electron and hole effective masses, making LaN promising for electronic and optoelectronic applications. Our calculations also reveal that nitrogen vacancies and substitutional oxygen atoms are two unintentional shallow donors with low formation energies that can explain the origin of the previously reported electrical conductivity. Our calculations clarify the semiconducting nature of LaN and reveal candidate unintentional point defects that are likely responsible for its measured electrical conductivity.

cond-mat.mtrl-sci↗

arXiv2020

Electron and hole mobility of rutile GeO$_2$ from first principles: an ultrawide-band-gap semiconductor for power electronics

Rutile germanium dioxide (r-GeO$_2$) is a recently predicted ultrawide-band-gap semiconductor with potential applications in high-power electronic devices, for which the carrier mobility is an important material parameter that controls the device efficiency. We apply first-principles calculations based on density functional and density functional perturbation theory to investigate carrier-phonon coupling in r-GeO$_2$ and predict its phonon-limited electron and hole mobilities as a function of temperature and crystallographic orientation. The calculated carrier mobilities at 300 K are $μ_{\text{elec},\perp \vec{c}}$=244 cm$^2$ V$^{-1}$ s$^{-1}$, $μ_{\text{elec},||\vec{c}}$=377 cm$^2$ V$^{-1}$ s$^{-1}$, $μ_{\text{hole},\perp \vec{c}}$=27 cm$^2$ V$^{-1}$ s$^{-1}$, and $μ_{\text{hole},||\vec{c}}$=29 cm$^2$ V$^{-1}$ s$^{-1}$. At room temperature, carrier scattering is dominated by the low-frequency polar-optical phonon modes. The predicted Baliga figure of merit of n-type r-GeO$_2$ surpasses several incumbent semiconductors such as Si, SiC, GaN, and $β$-Ga$_2$O$_3$, demonstrating its superior performance in high-power electronic devices.

cond-mat.mtrl-sci↗

arXiv2019

Optical properties of cubic boron arsenide

The ultrahigh thermal conductivity of boron arsenide makes it a promising material for next-generation electronics and optoelectronics. In this work, we report measured optical properties of cubic boron arsenide crystals including the complex dielectric function, refractive index, and absorption coefficient in the ultraviolet, visible, and near-infrared wavelength range. The data were collected at room temperature using spectroscopic ellipsometry as well as transmission and reflection spectroscopy. We further calculate the optical response using density functional and many-body perturbation theory, considering quasiparticle and excitonic corrections. The computed values for the direct and indirect band gaps (4.25 eV and 2.07 eV) agree well with the measured results (4.12 eV and 2.02 eV). Our findings contribute to the effort of using boron arsenide in novel electronic and optoelectronic applications that take advantage of its demonstrated ultrahigh thermal conductivity and predicted high ambipolar carrier mobility.

cond-mat.mtrl-sci↗

arXiv2019

Thermal conductivity of AlN, GaN, and Al$_x$Ga$_{1-x}$N alloys as a function of composition, temperature, crystallographic direction, and isotope disorder from first principles

Ultra-wide-band-gap group-III nitrides are of interest for applications in deep-ultraviolet optoelectronics and power electronics. Such devices must be able to efficiently dissipate heat generated from their operation, making the thermal conductivity of the constituent materials an important parameter for high-power applications. We have investigated the phonon-limited thermal conductivity of AlN, GaN, and Al$_x$Ga$_{1-x}$N using first-principles calculations, with a focus on the effects of compositional and isotopic disorder. Our Boltzmann-transport-equation calculations show that the maximum thermal conductivity for AlN (GaN) is 348 W m$^{-1}$ K$^{-1}$ (235 W m$^{-1}$ K$^{-1}$) for with pure $^{14}$N, and 292 W m$^{-1}$ K$^{-1}$ for GaN with pure $^{71}$Ga. Al$_x$Ga$_{1-x}$N alloys reach a minimum thermal conductivity at Al mole fractions of x = 0.60 to 0.71 over the 100-1000K temperature range. Our results provide understanding on the effects of isotope disorder on the thermal conductivity of AlN and GaN. We also present an analytical model for the evaluation of the thermal conductivity of Al$_x$Ga$_{1-x}$N alloys for arbitrary composition and temperature, which can be applied for the thermal design of AlGaN-based electronic and optoelectronic devices.

cond-mat.mtrl-sci↗

arXiv2019

Room-temperature stability of excitons and transverse-electric polarized deep-ultraviolet luminescence in atomically thin GaN quantum wells

Quantum confinement profoundly affects the properties and interactions of electrons, holes, and excitons in nanomaterials. We apply first-principles calculations to study the effects of extreme quantum confinement on the electronic, excitonic, and radiative properties of atomically thin GaN quantum wells with a thickness of 1 to 4 atomic monolayers embedded in AlN. We determine the quasiparticle band gaps, exciton energies and wave functions, radiative lifetimes, and Mott critical densities as a function of well and barrier thickness. Our results show that quantum confinement in GaN monolayers increases the band gap up to 5.44 eV and the exciton binding energy up 215 meV, indicating the thermal stability of excitons at room temperature. Exciton radiative lifetimes range from 1 to 3 nanoseconds at room temperature, while the Mott critical density for exciton dissociation is approximately 10$^{13}$ cm$^{-2}$. The luminescence is transverse-electric polarized, which facilitates light extraction from c-plane heterostructures. We also introduce a simple approximate model for calculating the exciton radiative lifetime based on the free-carrier bimolecular radiative recombination coefficient and the exciton radius, which agrees well with our results obtained with the Bethe-Salpeter equation predictions. Our results demonstrate that atomically thin GaN quantum wells exhibit stable excitons at room temperature for potential applications in efficient light emitters in the deep ultraviolet, as well as room-temperature excitonic devices.

cond-mat.mtrl-sci↗

arXiv2019

Boron Arsenide Heterostructures: Lattice-Matched Heterointerfaces, and Strain Effects on Band Alignments and Mobility

BAs is III-V semiconductor with ultra-high thermal conductivity, but many of its electronic properties are unknown. This work applies predictive atomistic calculations to investigate the properties of BAs heterostructures, such as strain effects on band alignments and carrier mobility, considering BAs as both a thin film and a substrate for lattice-matched materials. The results show that strain decreases the band gap independent of sign or direction. In addition, biaxial tensile strain increases the in-plane electron and hole mobilities by more than 60% compared to the unstrained values due to a reduction of the electron effective mass and of hole interband scattering. Moreover, BAs is shown to be nearly lattice-matched with InGaN and ZnSnN2, two important optoelectronic semiconductors with tunable band gaps by alloying and cation disorder, respectively. The results predict type-II band alignments and determine the absolute band offsets of these two materials with BAs. The combination of the ultra-high thermal conductivity and intrinsic p-type character of BAs, with its high electron and hole mobilities that can be further increased by tensile strain, as well as the lattice-match and the type-II band alignment with intrinsically n-type InGaN and ZnSnN2 demonstrate the potential of BAs heterostructures for electronic and optoelectronic devices.

cond-mat.mtrl-sci↗

arXiv2019

BAlGaN alloys nearly lattice-matched to AlN for efficient UV LEDs

The lattice mismatch between AlGaN and AlN substrates limits the design and efficiency of UV LEDs, but it can be mitigated by the co-incorporation of boron. We employ hybrid density functional theory to investigate the thermodynamic, structural, and electronic properties of BAlGaN alloys. We show that BAlGaN can lattice match AlN with band gaps that match AlGaN of the same gallium content. We predict that BAlGaN emits transverse-electric polarized for gallium content of ~45% or more. Our results indicate that BAlGaN alloys are promising materials for higher efficiency UV optoelectronic devices on bulk AlN substrates.

cond-mat.mtrl-sci↗