Showing papers on "Electronic structure published in 2019"

Quantum Chemistry in the Age of Quantum Computing.

Abstract: Practical challenges in simulating quantum systems on classical computers have been widely recognized in the quantum physics and quantum chemistry communities over the past century. Although many approximation methods have been introduced, the complexity of quantum mechanics remains hard to appease. The advent of quantum computation brings new pathways to navigate this challenging and complex landscape. By manipulating quantum states of matter and taking advantage of their unique features such as superposition and entanglement, quantum computers promise to efficiently deliver accurate results for many important problems in quantum chemistry, such as the electronic structure of molecules. In the past two decades, significant advances have been made in developing algorithms and physical hardware for quantum computing, heralding a revolution in simulation of quantum systems. This Review provides an overview of the algorithms and results that are relevant for quantum chemistry. The intended audience is both quantum chemists who seek to learn more about quantum computing and quantum computing researchers who would like to explore applications in quantum chemistry.

Maximized electron interactions at the magic angle in twisted bilayer graphene

Abstract: The electronic properties of heterostructures of atomically thin van der Waals crystals can be modified substantially by moire superlattice potentials from an interlayer twist between crystals1,2. Moire tuning of the band structure has led to the recent discovery of superconductivity3,4 and correlated insulating phases5 in twisted bilayer graphene (TBG) near the ‘magic angle’ of twist of about 1.1 degrees, with a phase diagram reminiscent of high-transition-temperature superconductors. Here we directly map the atomic-scale structural and electronic properties of TBG near the magic angle using scanning tunnelling microscopy and spectroscopy. We observe two distinct van Hove singularities (VHSs) in the local density of states around the magic angle, with an energy separation of 57 millielectronvolts that drops to 40 millielectronvolts with high electron/hole doping. Unexpectedly, the VHS energy separation continues to decrease with decreasing twist angle, with a lowest value of 7 to 13 millielectronvolts at a magic angle of 0.79 degrees. More crucial to the correlated behaviour of this material, we find that at the magic angle, the ratio of the Coulomb interaction to the bandwidth of each individual VHS (U/t) is maximized, which is optimal for electronic Cooper pairing mechanisms. When doped near the half-moire-band filling, a correlation-induced gap splits the conduction VHS with a maximum size of 6.5 millielectronvolts at 1.15 degrees, dropping to 4 millielectronvolts at 0.79 degrees. We capture the doping-dependent and angle-dependent spectroscopy results using a Hartree–Fock model, which allows us to extract the on-site and nearest-neighbour Coulomb interactions. This analysis yields a U/t of order unity indicating that magic-angle TBG is moderately correlated. In addition, scanning tunnelling spectroscopy maps reveal an energy- and doping-dependent three-fold rotational-symmetry breaking of the local density of states in TBG, with the strongest symmetry breaking near the Fermi level and further enhanced when doped to the correlated gap regime. This indicates the presence of a strong electronic nematic susceptibility or even nematic order in TBG in regions of the phase diagram where superconductivity is observed. Scanning tunnelling spectroscopy is used to map the atomic-scale electronic structure of magic-angle twisted bilayer graphene, finding multiple signatures of electron correlations and thus providing insight into the sought-after mechanism behind superconductivity in graphene.

Atomic and electronic reconstruction at the van der Waals interface in twisted bilayer graphene

Abstract: Control of the interlayer twist angle in two-dimensional van der Waals (vdW) heterostructures enables one to engineer a quasiperiodic moire superlattice of tunable length scale1–8. In twisted bilayer graphene, the simple moire superlattice band description suggests that the electronic bandwidth can be tuned to be comparable to the vdW interlayer interaction at a ‘magic angle’9, exhibiting strongly correlated behaviour. However, the vdW interlayer interaction can also cause significant structural reconstruction at the interface by favouring interlayer commensurability, which competes with the intralayer lattice distortion10–16. Here we report atomic-scale reconstruction in twisted bilayer graphene and its effect on the electronic structure. We find a gradual transition from an incommensurate moire structure to an array of commensurate domains with soliton boundaries as we decrease the twist angle across the characteristic crossover angle, θc ≈ 1°. In the solitonic regime (θ < θc) where the atomic and electronic reconstruction become significant, a simple moire band description breaks down and the secondary Dirac bands appear. On applying a transverse electric field, we observe electronic transport along the network of one-dimensional topological channels that surround the alternating triangular gapped domains. Atomic and electronic reconstruction at the vdW interface provide a new pathway to engineer the system with continuous tunability. An investigation of the structural and transport properties of bilayer graphene as a function of the twist angle between the layers reveals atomic-scale reconstruction for twist angles smaller than a critical value.

Experimental Realization of an Intrinsic Magnetic Topological Insulator

Abstract: An intrinsic magnetic topological insulator (TI) is a stoichiometric magnetic compound possessing both inherent magnetic order and topological electronic states. Such a material can provide a shortcut to various novel topological quantum effects but remained elusive experimentally for a long time. Here we report the experimental realization of thin films of an intrinsic magnetic TI, MnBi 2 Te 4 , by alternate growth of a Bi 2 Te 3 quintuple layer and a MnTe bilayer with molecular beam epitaxy. The material shows the archetypical Dirac surface states in angle-resolved photoemission spectroscopy and is demonstrated to be an antiferromagnetic topological insulator with ferromagnetic surfaces by magnetic and transport measurements as well as first-principles calculations. The unique magnetic and topological electronic structures and their interplays enable the material to embody rich quantum phases such as quantum anomalous Hall insulators and axion insulators at higher temperature and in a well-controlled way.

Unifying machine learning and quantum chemistry with a deep neural network for molecular wavefunctions

Abstract: Machine learning advances chemistry and materials science by enabling large-scale exploration of chemical space based on quantum chemical calculations. While these models supply fast and accurate predictions of atomistic chemical properties, they do not explicitly capture the electronic degrees of freedom of a molecule, which limits their applicability for reactive chemistry and chemical analysis. Here we present a deep learning framework for the prediction of the quantum mechanical wavefunction in a local basis of atomic orbitals from which all other ground-state properties can be derived. This approach retains full access to the electronic structure via the wavefunction at force-field-like efficiency and captures quantum mechanics in an analytically differentiable representation. On several examples, we demonstrate that this opens promising avenues to perform inverse design of molecular structures for targeting electronic property optimisation and a clear path towards increased synergy of machine learning and quantum chemistry. Machine learning models can accurately predict atomistic chemical properties but do not provide access to the molecular electronic structure. Here the authors use a deep learning approach to predict the quantum mechanical wavefunction at high efficiency from which other ground-state properties can be derived.

All‐Inorganic CsCu2I3 Single Crystal with High‐PLQY (≈15.7%) Intrinsic White‐Light Emission via Strongly Localized 1D Excitonic Recombination

Abstract: Energy-saving white lighting from the efficient intrinsic emission of semiconductors is considered as a next-generation lighting source. Currently, white-light emission can be composited with a blue light-emitting diode and yellow phosphor. However, this solution has an inevitable light loss, which makes the improvement of the energy utilization efficiency more difficult. To deal with this problem, intrinsic white-light emission (IWE) in a single solid material gives a possibility. Here, an all-inorganic lead-free CsCu2 I3 perovskite single crystal (SC) with stable and high photoluminescence quantum yield (≈15.7%) IWE through strongly localized 1D exciton recombination is synthesized. In the CsCu2 I3 , the Cu-I octahedron, which provides most of electron states, is isolated by Cs atoms in two directions to form a 1D electronic structure, resulting a high radiation recombination rate of excitons. With this electronic structure design, the CsCu2 I3 SCs have great potential in energy-saving white lighting.

Variational Quantum Computation of Excited States

Abstract: The calculation of excited state energies of electronic structure Hamiltonians has many important applications, such as the calculation of optical spectra and reaction rates. While low-depth quantum algorithms, such as the variational quantum eigenvalue solver (VQE), have been used to determine ground state energies, methods for calculating excited states currently involve the implementation of high-depth controlled-unitaries or a large number of additional samples. Here we show how overlap estimation can be used to deflate eigenstates once they are found, enabling the calculation of excited state energies and their degeneracies. We propose an implementation that requires the same number of qubits as VQE and at most twice the circuit depth. Our method is robust to control errors, is compatible with error-mitigation strategies and can be implemented on near-term quantum computers.

Topological Electronic Structure and Its Temperature Evolution in Antiferromagnetic Topological Insulator MnBi2Te4

Abstract: Topological quantum materials coupled with magnetism can provide a platform for realizing rich exotic physical phenomena, including quantum anomalous Hall effect, axion electrodynamics and Majorana fermions. However, these unusual effects typically require extreme experimental conditions such as ultralow temperature or sophisticate material growth and fabrication. Recently, new intrinsic magnetic topological insulators were proposed in MnBi2Te4-family compounds - on which rich topological effects could be realized under much relaxed experimental conditions. However, despite the exciting progresses, the detailed electronic structures observed in this family of compounds remain controversial up to date. Here, combining the use of synchrotron and laser light sources, we carried out comprehensive and high resolution angle-resolved photoemission spectroscopy studies on MnBi2Te4, and clearly identified its topological electronic structures including the characteristic gapless topological surface states. In addition, the temperature evolution of the energy bands clearly reveals their interplay with the magnetic phase transition by showing interesting differences for the bulk and surface states, respectively. The identification of the detailed electronic structures of MnBi2Te4 will not only help understand its exotic properties, but also pave the way for the design and realization of novel phenomena and applications.

Topological Electronic Structure and Its Temperature Evolution in Antiferromagnetic Topological Insulator MnBi 2 Te 4

Abstract: The intrinsic magnetic topological insulator MnBi2Te4 exhibits rich topological effects such as quantum anomalous Hall effect and axion electrodynamics. Here, by combining the use of synchrotron and laser light sources, we carry out comprehensive and high-resolution angle-resolved photoemission spectroscopy studies on MnBi2Te4 and clearly identify its topological electronic structure. In contrast to theoretical predictions and previous studies, we observe topological surface states with diminished gap forming a characteristic Dirac cone. We argue that the topological surface states are mediated by multidomains of different magnetization orientations. In addition, the temperature evolution of the energy bands clearly reveals their interplay with the magnetic phase transition by showing interesting differences between the bulk and surface states, respectively. The investigation of the detailed electronic structure of MnBi2Te4 and its temperature evolution provides important insight into not only the exotic properties of MnBi2Te4, but also the generic understanding of the interplay between magnetism and topological electronic structure in magnetic topological quantum materials.

Charge Density Wave State Suppresses Ferromagnetic Ordering in VSe2 Monolayers

Abstract: Ferromagnetic ordering of monolayer vanadium dichalcogenides (VSe2 and VS2) has been predicted by density functional theory (DFT), and suggestive experimental evidence for magnetic ordering in VSe2 monolayers has been reported. However, such ferromagnetic ordering would be in stark contradiction to the known paramagnetic nature of the bulk VSe2. Herein, we investigate the electronic structure of VSe2 monolayers by angle-resolved photoemission spectroscopy (ARPES) and first-principles DFT. The ARPES measurements demonstrate the absence of spin-polarized bands for monolayers in close correspondence to nonmagnetic nature of the bulk VSe2. We demonstrate that the stabilization of the nonmagnetic state occurs due to the appearance of a charge density wave (CDW) state in VSe2 monolayers. In contrast to well-established 4 × 4 × 3 periodicity of the CDW in bulk VSe2, we identify a √3 × √7 unit cell for VSe2 monolayers from both scanning tunneling microscopy imaging and first-principles calculations. Moreover, DFT...

Synthesis and Characterization of π-Extended Triangulene

Abstract: The electronic and magnetic properties of nanographenes strongly depend on their size, shape and topology. While many nanographenes present a closed-shell electronic structure, certain molecular topologies may lead to an open-shell structure. Triangular-shaped nanographenes with zigzag edges, which exist as neutral radicals, are of considerable interest both in fundamental science and for future technologies aimed at harnessing their intrinsic high-spin magnetic ground states for spin-based operations and information storage. Their synthesis, however, is extremely challenging owing to the presence of unpaired electrons, which confers them with enhanced reactivity. We report a combined in-solution and on-surface synthesis of π-extended triangulene, a non-Kekule nanographene with the structural formula C33H15, consisting of ten benzene rings fused in a triangular fashion. The distinctive topology of the molecule entails the presence of three unpaired electrons that couple to form a spin quartet ground state...

Analogue quantum chemistry simulation.

Abstract: Computing the electronic structure of molecules with high precision is a central challenge in the field of quantum chemistry. Despite the success of approximate methods, tackling this problem exactly with conventional computers remains a formidable task. Several theoretical1,2 and experimental3–5 attempts have been made to use quantum computers to solve chemistry problems, with early proof-of-principle realizations done digitally. An appealing alternative to the digital approach is analogue quantum simulation, which does not require a scalable quantum computer and has already been successfully applied to solve condensed matter physics problems6–8. However, not all available or planned setups can be used for quantum chemistry problems, because it is not known how to engineer the required Coulomb interactions between them. Here we present an analogue approach to the simulation of quantum chemistry problems that relies on the careful combination of two technologies: ultracold atoms in optical lattices and cavity quantum electrodynamics. In the proposed simulator, fermionic atoms hopping in an optical potential play the role of electrons, additional optical potentials provide the nuclear attraction, and a single-spin excitation in a Mott insulator mediates the electronic Coulomb repulsion with the help of a cavity mode. We determine the operational conditions of the simulator and test it using a simple molecule. Our work opens up the possibility of efficiently computing the electronic structures of molecules with analogue quantum simulation. An analogue quantum simulator based on ultracold atoms in optical lattices and cavity quantum electrodynamics is proposed for the solution of quantum chemistry problems and tested numerically for a simple molecule.

Direct comparison of many-body methods for realistic electronic Hamiltonians

Abstract: A large collaboration carefully benchmarks 20 first principles many-body electronic structure methods on a test set of 7 transition metal atoms, and their ions and monoxides. Good agreement is attained between the 3 systematically converged methods, resulting in experiment-free reference values. These reference values are used to assess the accuracy of modern emerging and scalable approaches to the many-electron problem. The most accurate methods obtain energies indistinguishable from experimental results, with the agreement mainly limited by the experimental uncertainties. Comparison between methods enables a unique perspective on calculations of many-body systems of electrons.

Flat bands in twisted bilayer transition metal dichalcogenides

Abstract: The crystal structure of a material creates a periodic potential that electrons move through giving rise to the electronic band structure of the material. When two-dimensional materials are stacked, the twist angle between the layers becomes an additional degree freedom for the resulting heterostructure. As this angle changes, the electronic band structure is modified leading to the possibility of flat bands with localized states and enhanced electronic correlations. In transition metal dichalcogenides, flat bands have been theoretically predicted to occur for long moire wavelengths over a range of twist angles around 0 and 60 degrees giving much wider versatility than magic angle twisted bilayer graphene. Here we show the existence of a flat band in the electronic structure of 3° and 57.5° twisted bilayer WSe2 samples using scanning tunneling spectroscopy. Direct spatial mapping of wavefunctions at the flat band energy have shown that the flat bands are localized differently for 3° and 57.5°, in excellent agreement with first-principle density functional theory calculations.

Constrained Variational Quantum Eigensolver: Quantum Computer Search Engine in the Fock Space.

Abstract: Variational quantum eigensolver (VQE) is an efficient computational method promising chemical accuracy in electronic structure calculations on a universal-gate quantum computer. However, such a sim...

Cyclo[18]carbon: Insight into Electronic Structure, Aromaticity, and Surface Coupling.

Abstract: Cyclo[18]carbon (C18) is studied computationally at the density functional theory (DFT) and ab initio levels to obtain insight into its electronic structure, aromaticity, and adsorption properties ...

Electronic Structure of the Plasmons in Metal Nanocrystals: Fundamental Limitations for the Energy Efficiency of Hot Electron Generation

Abstract: This Review discusses the electronic structure of plasmonic resonances in metal nanostructures, clarifying existing misconceptions on the topic. Here we underscore the key property of the plasmonic response in metal nanocrystals: the plasmon and its wave function are mostly composed of a large number of low-energy excitations, which involve electrons near the Fermi level. Simultaneously, some number of high-energy hot electrons are excited in a nanocrystal due to the scattering of electrons by surfaces and in hot spots. It is an established fact that plasmon excitations are well described by classical frameworks, considering the collective oscillation of low-energy carriers moving as the result of classical acceleration. This classical motion is intrinsically dissipative and leads to heating. On the other hand, the generation of hot electrons in nanocrystals is a quantum surface effect. The energy efficiency of such hot-electron processes is always limited. However, there are interesting possibilities for...

Phase stability and electronic structure of iridium metal at the megabar range

Abstract: The 5d transition metals have attracted specific interest for high-pressure studies due to their extraordinary stability and intriguing electronic properties. In particular, iridium metal has been proposed to exhibit a recently discovered pressure-induced electronic transition, the so-called core-level crossing transition at the lowest pressure among all the 5d transition metals. Here, we report an experimental structural characterization of iridium by x-ray probes sensitive to both long- and short-range order in matter. Synchrotron-based powder x-ray diffraction results highlight a large stability range (up to 1.4 Mbar) of the low-pressure phase. The compressibility behaviour was characterized by an accurate determination of the pressure-volume equation of state, with a bulk modulus of 339(3) GPa and its derivative of 5.3(1). X-ray absorption spectroscopy, which probes the local structure and the empty density of electronic states above the Fermi level, was also utilized. The remarkable agreement observed between experimental and calculated spectra validates the reliability of theoretical predictions of the pressure dependence of the electronic structure of iridium in the studied interval of compressions.

Digital quantum simulation of molecular vibrations.

Abstract: Molecular vibrations underpin important phenomena such as spectral properties, energy transfer, and molecular bonding. However, obtaining a detailed understanding of the vibrational structure of even small molecules is computationally expensive. While several algorithms exist for efficiently solving the electronic structure problem on a quantum computer, there has been comparatively little attention devoted to solving the vibrational structure problem with quantum hardware. In this work, we discuss the use of quantum algorithms for investigating both the static and dynamic vibrational properties of molecules. We introduce a physically motivated unitary vibrational coupled cluster ansatz, which also makes our method accessible to noisy, near-term quantum hardware. We numerically test our proposals for the water and sulfur dioxide molecules.

Geometry and electronic structure of monolayer, bilayer, and multilayer Janus WSSe

Abstract: Newly synthesized Janus transition-metal dichalcogenides MXY ($M=\mathrm{Mo}$, W; $X\ensuremath{ e}Y=\mathrm{S}$, Se, Te) possess intrinsic Rashba spin splitting and out-of-plane dipole moment due to the breaking of mirror symmetry. Taking WSSe as an example, we present a first-principles investigation of the structural stability and electronic properties of mono-, bi-, and multilayer MXY. Results show that S atoms contribute more than Se atoms in the valence-band maximum at the $\mathrm{\ensuremath{\Gamma}}$ point, which can be greatly affected by interlayer interactions. The high-symmetry AA\ensuremath{'} stacking is still the most stable pattern, but there are various orders of chalcogen atomic layers in each stacking. The most preferred order of two adjacent layers is S-Se-Se-S, followed by Se-S-Se-S. The Se-S-Se-S--ordered WSSe bilayer is found to have significant layer splitting due to the net dipole moment, which has great potential for solar cells. Layer-dependent Rashba splittings exist in asymmetry-ordered WSSe bilayers, that can be tuned by changing the interlayer distance, originating from the regulation of interlayer electrostatic interaction. However, there is not layer splitting in a symmetrically stacked WSSe bilayer and opposite Rashba splitting appears in the two layers at a sufficiently large interlayer distance. The electronic structures and spin splittings can be easily modulated by controlling the chalcogen atomic-layer order, so that we can obtain the desired properties from mono-, bi-, and multilayer MXY.

Two-Dimensional Kagome Lattices Made of Hetero Triangulenes Are Dirac Semimetals or Single-Band Semiconductors

Abstract: Here we discuss, based on first-principles calculations, two-dimensional (2D) kagome lattices composed of polymerized heterotriangulene units, planar molecules with D3h point group containing a B, C, or N center atom and CH2, O, or CO bridges. We explore the design principles for a functional lattice made of 2D polymers, which involves control of π-conjugation and electronic structure of the knots. The former is achieved by the chemical potential of the bridge groups, while the latter is controlled by the heteroatom. The resulting 2D kagome polymers have a characteristic electronic structure with a Dirac band sandwiched by two flat bands and are either Dirac semimetals (C center), or single-band semiconductors—materials with either exclusively electrons (B center) or holes (N center) as charge carriers of very high mobility, reaching values of up to ∼8 × 103 cm2 V–1 s–1, which is comparable to crystalline silicon.

Cu-Doped ZnO Electronic Structure and Optical Properties Studied by First-Principles Calculations and Experiments

Abstract: The band structure, the density of states and optical absorption properties of Cu-doped ZnO were studied by the first-principles generalized gradient approximation plane-wave pseudopotential method based on density functional theory. For the Zn1-xCuxO (x = 0, x = 0.0278, x = 0.0417) original structure, geometric optimization and energy calculations were performed and compared with experimental results. With increasing Cu concentration, the band gap of the Zn1-xCuxO decreased due to the shift of the conduction band. Since the impurity level was introduced after Cu doping, the conduction band was moved downwards. Additionally, it was shown that the insertion of a Cu atom leads to a red shift of the optical absorption edge, which was consistent with the experimental results.

High-throughput screening for spin-gapless semiconductors in quaternary Heusler compounds

Abstract: Based on high-throughput density functional theory calculations, we performed a systematic screening for spin-gapless semiconductors (SGSs) in quaternary Heusler alloys $X{X}^{\ensuremath{'}}YZ$ ($X$, ${X}^{\ensuremath{'}}$, and $Y$ are transition metal elements except Tc, and $Z$ is one of B, Al, Ga, In, Si, Ge, Sn, Pb, P, As, Sb, and Bi). Following an empirical rule, we focused on compounds with 21, 26, or 28 valence electrons, resulting in 12 000 possible chemical compositions. After systematically evaluating the thermodynamic, mechanical, and dynamical stabilities, we have identified 70 so far unreported SGSs, confirmed by explicit electronic structure calculations with proper magnetic ground states, of which 17 candidates have a distance to the convex hull smaller than 0.10 eV/atom. It is demonstrated that all four types of SGSs can be realized, defined based on the spin characters of the bands around the Fermi energy. Type-II SGSs show promising transport properties for spintronic applications. The effect of spin-orbit coupling is investigated, resulting in large anisotropic magnetoresistance and anomalous Nernst effects.

Investigation on the electronic structure, optical, elastic, mechanical, thermodynamic and thermoelectric properties of wide band gap semiconductor double perovskite Ba2InTaO6

Abstract: In the present paper, double perovskite Ba2InTaO6 was investigated in terms of its structural, electronic, optical, elastic, mechanical, thermodynamic and thermoelectric properties using density-functional theory (DFT). The generalized gradient approximation (GGA) in the scheme of Perdew, Burke and Ernzerhof (PBE) and the modified Becke–Johnson (mBJ) potential were employed for the exchange–correlation potential. The computed lattice constant was found to be in agreement with the available experimental and theoretical results. The electronic profile shows a semiconducting nature. Further analysis of the complex dielectric constant e(ω), refractive index n(ω), reflectivity R(ω), absorption coefficient α(ω), optical conductivity (ω) and energy loss function were also reported with the incident photon energy. The elastic constants were also calculated and used to determine mechanical properties like Young's modulus (Y), the shear modulus (G), Poisson's ratio (ν) and the anisotropic factor (A). The electrical conductivity (σ/τ) and Seebeck coefficient (S) also demonstrated the semiconducting nature of the compound with electrons as the majority carriers. The value of the power factor was calculated to be 1.20 × 1012 W K−2 m−1 s−1 at 1000 K. From thermodynamic investigations, the heat capacity and Gruneisen parameter were also predicted.

Tuning the Structure and Electronic Properties of B-N Fused Dipyridylanthracene and Implications on the Self-Sensitized Reactivity with Singlet Oxygen

Abstract: We demonstrate that the modification of anthracene with B ← N Lewis pairs at their periphery serves as a highly effective tool to modify the electronic structure with important ramifications on the generation and reactivity toward singlet oxygen. A series of BN-fused dipyridylanthracenes with Me groups in different positions of the pyridyl ring have been prepared via directed electrophilic borylation. The steric and electronic effects of the substituents on the structural features and electronic properties of the isomeric borane-functionalized products have been investigated in detail, aided by experimental tools and computational studies. We find that BDPA-2Me, with Me groups adjacent to the pyridyl N, has the longest B–N distance and shows overall less structural distortions, whereas BDPA-5Me with the Me group close to the anthracene backbone experiences severe distortions that are reflected in the buckling of the anthracene framework and dislocation of the boron atoms from the planes of the phenyl ring...

Constructing the Electronic Structure of CH3NH3PbI3 and CH3NH3PbBr3 Perovskite Thin Films from Single-Crystal Band Structure Measurements

Abstract: Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH3NH3PbBr3 and CH3NH3PbI3), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced.

Spectroscopic Evidence for the Contribution of Holes to the Bleach of Cd-Chalcogenide Quantum Dots

Abstract: In transient absorption (TA) measurements on Cd-chalcogenide quantum dots (QDs), the presence of a band-edge (BE) bleach signal is commonly attributed entirely to conduction-band electrons in the 1S(e) state, neglecting contributions from BE holes. While this has been the accepted view for more than 20 years, and has often been used to distinguish electron and hole kinetics, the reason for the absence of a hole contribution to the BE-bleach has remained unclear. Here, we show with three independent experiments that holes do in fact have a significant impact on the BE-bleach of well-passivated Cd-chalcogenide QD samples. Transient absorption experiments on high photoluminescence quantum yield CdSe/CdS/ZnS core–shell–shell QDs clearly show an increase of the band-edge bleach as holes cool down to the band edge. The relative contribution of electron-to-hole bleach is 2:1, as predicted by theory. The same measurements on core-only CdSe QDs with a lower quantum yield do not show a contribution of holes to the ...