Charge-neutral Defects Research Articles

Rational Design of Cu Vacancies and Antisite Defects for Boosting the Thermoelectric Properties of CuGaTe2-Based Compounds.

CuGaTe2-based compounds show great promise in the application for high-temperature thermoelectric power generation; however, its wide bandgap feature poses a great challenge for enhancing thermoelectric performance via structural defects modulation and doping the system. Herein, it is discovered that the presence of GaCu antisite defects in the CuGaTe2 compound promotes the formation of Cu vacancies, and vice versa, which tends to form the charge-neutral structure defects combination with one GaCu antisite defect and two Cu vacancies. The accumulation of Cu vacancies in the structure of the (Cu2Te)x(Ga2Te3)1-x compounds evolves into twins and stacking faults. This in conjunction with GaCu antisite defects intensify the point defects phonon scattering, yielding a dramatic reduction on lattice thermal conductivity from 6.95 W m-1 K-1 for the pristine CuGaTe2 sample to 2.98 W m-1 K-1 for the (Cu2Te)0.45(Ga2Te3)0.55 sample at room temperature. Furthermore, the high concentration of charge-neutral defects combination narrows the band gap and increases the carrier concentration, leading to an improved power factor of 1.58 mW/mK2 at 600 K for the (Cu2Te)0.49(Ga2Te3)0.51 sample, which is 41% higher than for the pristine CuGaTe2 sample. Consequently, the highest ZT value of 0.82 is achieved at 915 K for Cu0.015(Cu2Te)0.48(Ga2Te3)0.52, which represents an enhancement of about 22% over that of the pristine CuGaTe2 compound.

Doped graphene characterized via Raman spectroscopy and magneto-transport measurements

Functionalizing graphene beyond its intrinsic properties has been a key concept since the first successful realization of this archetype monolayer system. While various concepts, such as doping, co-doping, and layered device design, have been proposed, the often complex structural and electronic changes are often jeopardizing simple functionalization attempts. Here, we present a thorough analysis of the structural and electronic properties of co-doped graphene via Raman spectroscopy as well as magneto-transport and Hall measurements. The results highlight the challenges in understanding its microscopic properties beyond the simple preparation of such devices. It is discussed how co-doping with N and B dopants leads to effective charge-neutral defects acting as short-range scatterers, while charged defects introduce more long-range scattering centers. Such distinct behavior may obscure or alter the desired structural as well as electronic properties not anticipated initially. Exploring further the preparation of effective pn-junctions, we highlight step by step how the preparation process may lead to alterations in the intrinsic properties of the individual layers. Importantly, it is highlighted in all steps how the inhomogeneities across individual graphene sheets may challenge simple interpretations of individual measurements.

Radiative properties of quantum emitters in boron nitride from excited state calculations and Bayesian analysis

Point defects in hexagonal boron nitride (hBN) have attracted growing attention as bright single-photon emitters. However, understanding of their atomic structure and radiative properties remains incomplete. Here we study the excited states and radiative lifetimes of over 20 native defects and carbon or oxygen impurities in hBN using ab initio density functional theory and GW plus Bethe-Salpeter equation calculations, generating a large data set of their emission energy, polarization and lifetime. We find a wide variability across quantum emitters, with exciton energies ranging from 0.3 to 4 eV and radiative lifetimes from ns to ms for different defect structures. Through a Bayesian statistical analysis, we identify various high-likelihood charge-neutral defect emitters, among which the native VNNB defect is predicted to possess emission energy and radiative lifetime in agreement with experiments. Our work advances the microscopic understanding of hBN single-photon emitters and introduces a computational framework to characterize and identify quantum emitters in 2D materials.

Charge-neutral defects control conductivity.

The generation of charge-neutral anti-Frenkel defects in a complex transition metal oxide provides a useful pathway for controlling electronic conductivity while minimizing the impact on existing functions.

First-principles study on the effect of Sn doping in Cu2S—Acanthite phase as a substitute to low chalcocite for modeling complex doping

The major challenge in the application of Cu2S, as a solar absorber for photovoltaic, is its excessive Cu-vacancy formation tendency within the crystal structure that makes it a degenerate semiconductor. A recent study on Ag alloyed Cu2S acanthite phase has shown a reduced Cu-vacancy formation and a high Cu diffusion barrier. Though low chalcocite is the experimentally known ground state phase at room temperature, its low crystallinity makes it computationally expensive for complex doping modeling. In this work, we first establish the structural correspondence between a newly predicted acanthite and experimentally known low chalcocite phases of Cu2S. This study shows that the acanthite crystal structure of Cu2S can be used to model complex doping in the low chalcocite. The simulated pair distribution functions and diffusions of Cu at room temperature in acanthite and low chalcocite phases of Cu2S show that they have similar structural behavior. Pristine band structures and density of state plots of these two phases also show similarity. Next, we report density functional theory based first-principles investigations of Cu2−xSnxS systems for x = 0 to 0.31 in the acanthite phase for thermodynamic, electronic, and optical properties. We have found that Sn doping coupled with Cu vacancies creates charge-neutral defects and results in higher photoabsorption in the visible light spectra. It was found from these detailed studies that a low concentration of Sn doping is preferable. Then, Sn doping and Cu-vacancy related defects in low chalcocite Cu2S are also studied. Ab initio molecular dynamics simulations show that these compound defects in Cu2S do not negatively affect Cu diffusion inside the crystal. We propose a possible route to synthesize Sn doped acanthite like Cu2S.

Anion Exchange and the Quantum-Cutting Energy Threshold in Ytterbium-Doped CsPb(Cl1- xBr x)3 Perovskite Nanocrystals.

Colloidal halide perovskite nanocrystals of CsPbCl3 doped with Yb3+ have demonstrated remarkably high sensitized photoluminescence quantum yields (PLQYs), approaching 200%, attributed to a picosecond quantum-cutting process in which one photon absorbed by the nanocrystal generates two photons emitted by the Yb3+ dopants. This quantum-cutting process is thought to involve a charge-neutral defect cluster within the nanocrystal's internal volume. We demonstrate that Yb3+-doped CsPbCl3 nanocrystals can be converted postsynthetically to Yb3+-doped CsPb(Cl1- xBr x)3 nanocrystals without compromising the desired high PLQYs. Nanocrystal energy gaps can be tuned continuously from Eg ≈ 3.06 eV (405 nm) in CsPbCl3 down to Eg ≈ 2.53 eV (∼490 nm) in CsPb(Cl0.25Br0.75)3 while retaining a constant PLQY above 100%. Reducing Eg further causes a rapid drop in PLQY, interpreted as reflecting an energy threshold for quantum cutting at approximately twice the energy of the Yb3+2F7/2 → 2F5/2 absorption threshold. These data demonstrate that very high quantum-cutting energy efficiencies can be achieved in Yb3+-doped CsPb(Cl1- xBr x)3 nanocrystals, offering the possibility to circumvent thermalization losses in conventional solar technologies. The presence of water during anion exchange is found to have a deleterious effect on the Yb3+ PLQYs but does not affect the nanocrystal shapes or morphologies, or even reduce the excitonic PLQYs of analogous undoped CsPb(Cl1- xBr x)3 nanocrystals. These results provide valuable information relevant to the development and application of these unique materials for spectral-shifting solar energy conversion technologies.

Polymorphism in Cu2ZnSnS4 and New Off-Stoichiometric Crystal Structure Types

Cu2ZnSnS4 (CZTS) is a very promising material for the absorber layer in sustainable thin-film solar cells. Its photovoltaic performance is currently limited by crystal structure disorder, which causes fluctuations in electrostatic potential that decrease open-circuit voltage. The origin of this disorder is still not fully understood. This work investigates five samples of CZTS over a range of compositions, fabricated by solid-state reaction. Their crystal structures are conclusively identified using high-resolution anomalous X-ray diffraction. Three of the samples display two distinct CZTS phases, evident in minute splitting of some diffraction peaks (by ∼0.02°) due to different c/a lattice parameter ratios. These are attributed to different composition types of CZTS, defined by different charge-neutral defect complexes. In addition to such types previously reported, two new types are proposed: G-type, in which [2CuSn3– + CuZn– + Cui+ + 3VS2+] defects are prevalent, and H-type, in which [3Si2– + VCu– + ZnCu+ + 2SnCu3+] defects are prevalent. In both cases, the defects probably do not form a single complex due to their large number. Above the order–disorder phase transition the two CZTS phases generally converge to a single phase. A mechanism of phase formation in CZTS is thus proposed. This is the first time CZTS crystal structures have been investigated with sufficiently high resolution to distinguish these different CZTS phases, thereby establishing polymorphic behavior in CZTS.

Importance of elastic finite-size effects: Neutral defects in ionic compounds

Small system sizes are a well-known source of error in density functional theory (DFT) calculations, yet computational constraints frequently dictate the use of small supercells, often as small as 96 atoms in oxides and compound semiconductors. In ionic compounds, electrostatic finite-size effects have been well characterized, but self-interaction of charge-neutral defects is often discounted or assumed to follow an asymptotic behavior and thus easily corrected with linear elastic theory. Here we show that elastic effects are also important in the description of defects in ionic compounds and can lead to qualitatively incorrect conclusions if inadequately small supercells are used; moreover, the spurious self-interaction does not follow the behavior predicted by linear elastic theory. Considering the exemplar cases of metal oxides with fluorite structure, we show that numerous previous studies, employing 96-atom supercells, misidentify the ground-state structure of (charge-neutral) Schottky defects. We show that the error is eliminated by employing larger cells (324, 768, and 1500 atoms), and careful analysis determines that elastic, not electrostatic, effects are responsible. The spurious self-interaction was also observed in nonoxide ionic compounds irrespective of the computational method used, thereby resolving long-standing discrepancies between DFT and force-field methods, previously attributed to the level of theory. The surprising magnitude of the elastic effects is a cautionary tale for defect calculations in ionic materials, particularly when employing computationally expensive methods (e.g., hybrid functionals) or when modeling large defect clusters. We propose two computationally practicable methods to test the magnitude of the elastic self-interaction in any ionic system. In commonly studied oxides, where electrostatic effects would be expected to be dominant, it is the elastic effects that dictate the need for larger supercells: greater than 96 atoms.

Local phonon mode in thermoelectric Bi2Te2Se from charge neutral antisites

Local modes caused by defects play a significant role in the thermal transport properties of thermoelectrics. Of particular interest are charge-neutral defects that suppress thermal conductivity, without significantly reducing electrical transport. Here, we report a temperature dependent Raman study that identifies such a mode in a standard thermoelectric material, Bi2Te2Se. One of the modes observed, whose origin has been debated for decades, was shown most likely to be an antisite defect induced local mode. The anomalous temperature independent broadening of the local mode is ascribed to the random arrangement of Se atoms. The temperature renormalization of all modes is well explained by an anharmonic model–Klemens's model.

Band structures and native defects of ammonia borane

Band structures and native defects in molecular solid ammonia borane (AB) are investigated by using first-principles calculations based on the density-functional theory (DFT). The native defects include ${\text{NH}}_{3}$ and ${\text{BH}}_{3}$ antisites, interstitials, and vacancies in the various charge states. Despite that the AB crystal is an insulator with a DFT band gap larger than 6 eV, some of the charge-neutral native defects can be abundant, especially at the ${\text{NH}}_{3}$-rich growth conditions, due to their exceptionally low formation energies. This is in sharp contrast to defects in semiconductors for which the formation energies of charge-neutral defects are usually high and correspondingly the concentrations of those defects are low.