Quantum-confinement effect on the linewidth broadening of metal halide perovskite-based quantum dots.

The linewidth broadening caused by various physicochemical effects does limit the well-known advantage of ultrahigh color purity of metal halide perovskites (MHPs) for use in next-generation light-emitting diodes (LEDs). We have theoretically examined the quantum- and dielectric-confinement effects of a quantum dot (QD) on the degree of photoluminescence linewidth broadening. It is predicted that the linewidth (ΔλQC) is mainly contributed by the two opposing effects: (i) the linewidth broadening due to the repulsive kinetic energy of confined excitons (ΔλQCKE) and (ii) the overall linewidth narrowing caused by the attractive Coulomb interaction (ΔλQCCoul). It is shown that the relative contribution essentially remains at a constant value and is evaluated asΔλQCCoul/ΔλQCKE=0.42, which is independent of the QD size and the chemical nature of semiconducting emitter. We have computed ΔλQCfor various QD sizes of the prototypical MHP emitter, MAPbBr3, where MA denotes a methylammonium (CH3NH3) organic cation. The calculated results show that the linewidth broadening due to the quantum confinement (ΔλQC) increases rapidly beginning at the QD radius approximately equal to 6.5 nm but ΔλQCis less than 2 nm even atR= 1.5 nm. Thus, ΔλQCis much narrower than the linewidth caused by the exciton-LO phonon Fröhlich coupling (∼23.4 nm) which is known as the predominant mechanism of linewidth broadening in hybrid MHPs. Thus, the linewidth broadening due to the quantum confinement (ΔλQC) is not a risk factor in the realization of MHP-based ultrahigh-quality next-generation LEDs.

Proton-transfer-induced 3D/2D hybrid perovskites suppress ion migration and reduce luminance overshoot.

Perovskite light-emitting diodes (PeLEDs) based on three-dimensional (3D) polycrystalline perovskites suffer from ion migration, which causes overshoot of luminance over time during operation and reduces its operational lifetime. Here, we demonstrate 3D/2D hybrid PeLEDs with extremely reduced luminance overshoot and 21 times longer operational lifetime than 3D PeLEDs. The luminance overshoot ratio of 3D/2D hybrid PeLED is only 7.4% which is greatly lower than that of 3D PeLED (150.4%). The 3D/2D hybrid perovskite is obtained by adding a small amount of neutral benzylamine to methylammonium lead bromide, which induces a proton transfer from methylammonium to benzylamine and enables crystallization of 2D perovskite without destroying the 3D phase. Benzylammonium in the perovskite lattice suppresses formation of deep-trap states and ion migration, thereby enhances both operating stability and luminous efficiency based on its retardation effect in reorientation.

Author Correction: Lattice strain-enhanced exsolution of nanoparticles in thin films.

The original version of this Article contained an error in the Data Availability section, which incorrectly read 'The data that support the findings of this study are available from the corresponding authors upon request.' The correct version replaces this sentence with 'The research data underpinning this publication can be accessed at https://doi.org/10.17630/21d12144-58ef-4f82-acd0-ba3c9a44ed72'. This has been corrected in both the PDF and HTML versions of the Article.

Facet-Dependent in Situ Growth of Nanoparticles in Epitaxial Thin Films: The Role of Interfacial Energy.

Nucleation of nanoparticles using the exsolution phenomenon is a promising pathway to design durable and active materials for catalysis and renewable energy. Here, we focus on the impact of surface orientation of the host lattice on the nucleation dynamics to resolve questions with regards to "preferential nucleation sites". For this, we carried out a systematic model study on three differently oriented perovskite thin films. Remarkably, in contrast to the previous bulk powder-based study suggesting that the (110)-surface is a preferred plane for exsolution, we identify that other planes such as (001)- and (111)-facets also reveal vigorous exsolution. Moreover, particle size and surface coverage vary significantly depending on the surface orientation. Exsolution of (111)-oriented film produces the largest number of particles, the smallest particle size, the deepest embedment, and the smallest and most uniform interparticle distance among the oriented films. Based on classic nucleation theory, we elucidate that the differences in interfacial energies as a function of substrate orientation play a crucial role in controlling the distinct morphology and nucleation behavior of exsolved nanoparticles. Our finding suggests new design principles for tunable solid-state catalyst or nanoscale metal decoration.

Lattice strain-enhanced exsolution of nanoparticles in thin films.

Nanoparticles formed on oxide surfaces are of key importance in many fields such as catalysis and renewable energy. Here, we control B-site exsolution via lattice strain to achieve a high degree of exsolution of nanoparticles in perovskite thin films: more than 1100 particles µm-2 with a particle size as small as ~5 nm can be achieved via strain control. Compressive-strained films show a larger number of exsolved particles as compared with tensile-strained films. Moreover, the strain-enhanced in situ growth of nanoparticles offers high thermal stability and coking resistance, a low reduction temperature (550 °C), rapid release of particles, and wide tunability. The mechanism of lattice strain-enhanced exsolution is illuminated by thermodynamic and kinetic aspects, emphasizing the unique role of the misfit-strain relaxation energy. This study provides critical insights not only into the design of new forms of nanostructures but also to applications ranging from catalysis, energy conversion/storage, nano-composites, nano-magnetism, to nano-optics.

Switchable ferroelectric photovoltaic effects in epitaxial h-RFeO3 thin films.

Ferroelectric photovoltaics (FPVs) have drawn much attention owing to their high stability, environmental safety, and anomalously high photovoltages, coupled with reversibly switchable photovoltaic responses. However, FPVs suffer from extremely low photocurrents, which is primarily due to their wide band gaps. Here, we present a new class of FPVs by demonstrating switchable ferroelectric photovoltaic effects and narrow band-gap properties using hexagonal ferrite (h-RFeO3) thin films, where R denotes rare-earth ions. FPVs with narrow band gaps suggest their potential applicability as photovoltaic and optoelectronic devices. The h-RFeO3 films further exhibit reasonably large ferroelectric polarizations (4.7-8.5 µC cm-2), which possibly reduces a rapid recombination rate of the photo-generated electron-hole pairs. The power conversion efficiency (PCE) of h-RFeO3 thin-film devices is sensitive to the magnitude of polarization. In the case of the h-TmFeO3 (h-TFO) thin film, the measured PCE is twice as large as that of the BiFeO3 thin film, a prototypic FPV. The effect of electrical fatigue on FPV responses has been further investigated. This work thus demonstrates a new class of FPVs towards high-efficiency solar cell and optoelectronic applications.

Electron-hole separation in ferroelectric oxides for efficient photovoltaic responses.

Despite their potential to exceed the theoretical Shockley-Queisser limit, ferroelectric photovoltaics (FPVs) have performed inefficiently due to their extremely low photocurrents. Incorporating Bi2FeCrO6 (BFCO) as the light absorber in FPVs has recently led to impressively high and record photocurrents [Nechache R, et al. (2015) Nat Photonics 9:61-67], which has revived the FPV field. However, our understanding of this remarkable phenomenon is far from satisfactory. Here, we use first-principles calculations to determine that such excellent performance mainly lies in the efficient separation of electron-hole (e-h) pairs. We show that photoexcited electrons and holes in BFCO are spatially separated on the Fe and Cr sites, respectively. This separation is much more pronounced in disordered BFCO phases, which adequately explains the observed exceptional PV responses. We further establish a design strategy to discover next-generation FPV materials. By exploring 44 additional Bi-based double-perovskite oxides, we suggest five active-layer materials that offer a combination of strong e-h separations and visible-light absorptions for FPV applications. Our work indicates that charge separation is the most important issue to be addressed for FPVs to compete with conventional devices.

Spin-coupling-induced Improper Polarizations and Latent Magnetization in Multiferroic BiFeO3.

Multiferroic BiFeO3 (BFO) that exhibits a gigantic off-centering polarization (OCP) is the most extensively studied material among all multiferroics. In addition to this gigantic OCP, the BFO having R3c structural symmetry is expected to exhibit a couple of parasitic improper polarizations owing to coexisting spin-polarization coupling mechanisms. However, these improper polarizations are not yet theoretically quantified. Herein, we show that there exist two distinct spin-coupling-induced improper polarizations in the R3c BFO on the basis of the Landau-Lifshitz-Ginzburg theory: ΔP LF arising from the Lifshitz gradient coupling in a cycloidal spin-density wave, and ΔP ms originating from the biquadratic magnetostrictive interaction. With the help of ab initio calculations, we have numerically evaluated magnitudes of these improper polarizations, in addition to the estimate of all three relevant coupling constants. We further predict that the magnetic susceptibility increases substantially upon the transition from the bulk R3c BFO to the homogeneous canted spin state in a constrained epitaxial film, which satisfactorily accounts for the experimental observation. The present study will help us understand the magnetoelectric coupling and shed light on design of BFO-based materials with improved multiferroic properties.

Enhanced Switchable Ferroelectric Photovoltaic Effects in Hexagonal Ferrite Thin Films via Strain Engineering.

Ferroelectric photovoltaics (FPVs) are being extensively investigated by virtue of switchable photovoltaic responses and anomalously high photovoltages of ∼104 V. However, FPVs suffer from extremely low photocurrents due to their wide band gaps (Eg). Here, we present a promising FPV based on hexagonal YbFeO3 (h-YbFO) thin-film heterostructure by exploiting its narrow Eg. More importantly, we demonstrate enhanced FPV effects by suitably exploiting the substrate-induced film strain in these h-YbFO-based photovoltaics. A compressive-strained h-YbFO/Pt/MgO heterojunction device shows ∼3 times enhanced photovoltaic efficiency than that of a tensile-strained h-YbFO/Pt/Al2O3 device. We have shown that the enhanced photovoltaic efficiency mainly stems from the enhanced photon absorption over a wide range of the photon energy, coupled with the enhanced polarization under a compressive strain. Density functional theory studies indicate that the compressive strain reduces Eg substantially and enhances the strength of d-d transitions. This study will set a new standard for determining substrates toward thin-film photovoltaics and optoelectronic devices.

Low-Temperature Solid-State Synthesis of High-Purity BiFeO3 Ceramic for Ferroic Thin-Film Deposition.

The synthesis of high-purity BiFeO3 (BFO) ceramic by solid-state reaction is known to be very difficult due to inevitable formation of the secondary phases, mostly mullite-type Bi2Fe4O9 and sillenite-type Bi25FeO39. In particular, it is very difficult to completely remove the Bi-deficient Bi2Fe4O9 phase from sintered ceramic BFO targets. This problem consequently leads to the difficulty of fabricating high-quality BFO thin films using these sintered targets. Herein, we introduce a simple but effective low-temperature processing scheme for removing impurity phases in which optimized processing conditions are obtained by chemically correlating the first calcination step with the subsequent leaching and sintering steps. More specifically, we suitably avoid the formation of the high-temperature-stable Bi2Fe4O9 phase by performing the calcination at significantly low temperatures (between 650 and 675 °C) with Bi-excess starting powders. We have then fabricated epitaxially grown BFO thin films using these phase-pure ceramic targets and consequently achieved high-quality ferroelectricity and switchable photovoltaic responses. On the basis of the present experimental observations, we suggest that a low impurity concentration in the sintered BFO ceramic target, even with a low relative density, is advantageous for high-quality thin-film fabrication.

Influence of tensile-strain-induced oxygen deficiency on metal-insulator transitions in NdNiO3-δ epitaxial thin films.

We report direct evidence that oxygen vacancies affect the structural and electrical parameters in tensile-strained NdNiO3-δ epitaxial thin films by elaborately adjusting the amount of oxygen deficiency (δ) with changing growth temperature T D. The modulation in tensile strain and T D tended to increase oxygen deficiency (δ) in NdNiO3-δ thin films; this process relieves tensile strain of the thin film by oxygen vacancy incorporation. The oxygen deficiency is directly correlated with unit-cell volume and the metal-insulator transition temperature (T MI), i.e., resulting in the increase of both unit-cell volume and metal-insulator transition temperature as oxygen vacancies are incorporated. Our study suggests that the intrinsic defect sensitively influences both structural and electronic properties, and provides useful knobs for tailoring correlation-induced properties in complex oxides.

Hydrogen-doped Brookite TiO2 Nanobullets Array as a Novel Photoanode for Efficient Solar Water Splitting.

As a representative photocatalyst for photoelectrochemical solar water splitting, TiO2 has been intensively studied but most researches have focused on the rutile and anatsase phases because brookite, another important crystalline polymorph of TiO2, rarely exists in nature and is difficult to synthesize. In this work, hydrogen doped brookite (H:brookite) nanobullet arrays were synthesized via a well-designed solution reaction for the first time. H:brookite shows highly improved PEC properties with excellent stability, enhanced photocurrent, and significantly high Faradaic efficiency for overall solar water splitting. To support the experimental data, ab initio density functional theory calculations were also conducted. At the interstitial doping site that has minimum formation energy, the hydrogen atoms act as shallow donors and exist as H+. which has the minimum formation energy among three states of hydrogen (H+. H0, and H-). The calculated density of states of H:brookite shows a narrowed bandgap and an increased electron density compared to the pristine brookite. The combined experimental and theoretical results provide frameworks for the exploration of the PEC properties of doped brookite and extend our knowledge regarding the undiscovered properties of brookite of TiO2.

Implementing Room-Temperature Multiferroism by Exploiting Hexagonal-Orthorhombic Morphotropic Phase Coexistence in LuFeO3 Thin Films.

Room-temperature multiferroism in LuFeO3 (LFO) films is demonstrated by exploiting the orthorhombic-hexagonal (o-h) morphotrophic phase coexistence. The LFO film further reveals a magnetoelectric coupling effect that is not shown in single-phase (h- or o-) LFO. The observed multiferroism is attributed to the combination of sufficient polarization from h-LFO and net magnetization from o-LFO.

Anomalous domain periodicity observed in ferroelectric PbTiO3 nanodots having 180° stripe domains.

Nanometer-scale ferroelectric dots and tubes have received a great deal of attention owing to their potential applications to nonvolatile memories and multi-functional devices. As for the size effect of 180° stripe domains in ferroelectric thin films, there have been numerous reports on the thickness-dependent domain periodicity. All these studies have revealed that the domain periodicity (w) of 180° stripe domains scales with the film thickness (d) according to the classical Landau-Lifshitz-Kittel (LLK) scaling law (w ∝ d(1/2)) down to the thickness of ~2 nm. In the case of PbTiO3 nanodots, however, we obtained a striking correlation that for the thickness less than a certain critical value, dc (~35 nm), the domain width even increases with decreasing thickness of the nanodot, which surprisingly indicates a negative value in the LLK scaling-law exponent. On the basis of theoretical considerations of dc, we attributed this anomalous domain periodicity to the finite lateral-size effect of a ferroelectric nanodot with an additional effect possibly coming from the existence of a thin non-ferroelectric surface layer.

Modulation of metal-insulator transitions by field-controlled strain in NdNiO3/SrTiO3/PMN-PT (001) heterostructures.

The band width control through external stress has been demonstrated as a useful knob to modulate metal-insulator transition (MIT) in RNiO3 as a prototype correlated materials. In particular, lattice mismatch strain using different substrates have been widely utilized to investigate the effect of strain on transition temperature so far but the results were inconsistent in the previous literatures. Here, we demonstrate dynamic modulation of MIT based on electric field-controlled pure strain in high-quality NdNiO3 (NNO) thin films utilizing converse-piezoelectric effect of (001)-cut Pb(Mg(1/3)Nb(2/3)O3-(PbTiO3) (PMN-PT) single crystal substrates. Despite the difficulty in the NNO growth on rough PMN-PT substrates, the structural quality of NNO thin films has been significantly improved by inserting SrTiO3 (STO) buffer layers. Interestingly, the MIT temperature in NNO is downward shifted by ~3.3 K in response of 0.25% in-plane compressive strain, which indicates less effective TMI modulation of field-induced strain than substrate-induced strain. This study provides not only scientific insights on band-width control of correlated materials using pure strain but also potentials for energy-efficient electronic devices.

The nature of hydrogen-bonding interaction in the prototypic hybrid halide perovskite, tetragonal CH3NH3PbI3.

In spite of the key role of hydrogen bonding in the structural stabilization of the prototypic hybrid halide perovskite, CH3NH3PbI3 (MAPbI3), little progress has been made in our in-depth understanding of the hydrogen-bonding interaction between the MA(+)-ion and the iodide ions in the PbI6-octahedron network. Herein, we show that there exist two distinct types of the hydrogen-bonding interaction, naming α- and ß-modes, in the tetragonal MAPbI3 on the basis of symmetry argument and density-functional theory calculations. The computed Kohn-Sham (K-S) energy difference between these two interaction modes is 45.14 meV per MA-site with the α-interaction mode being responsible for the stable hydrogen-bonding network. The computed bandgap (Eg) is also affected by the hydrogen-bonding mode, with Eg of the α-interaction mode (1.73 eV) being significantly narrower than that of the ß-interaction mode (2.03 eV). We have further estimated the individual bonding strength for the ten relevant hydrogen bonds having a bond critical point.

SnS4(4-), SbS4(3-), and AsS3(3-) Metal Chalcogenide Surface Ligands: Couplings to Quantum Dots, Electron Transfers, and All-Inorganic Multilayered Quantum Dot Sensitized Solar Cells.

Three inorganic capping ligands (ICLs) for quantum dots (QDs), SnS4(4-), SbS4(3-) and AsS3(3-), were synthesized and the energy levels determined. Proximity between the ICL LUMO and QD conduction level governed the electronic couplings such as absorption shift upon ligand exchange, and electron transfer rate to TiO2. QD-sensitized solar cells were fabricated, using the ICL-QDs and also using QD multilayers layer-by-layer assembled by bridging coordinations, and studied as a function of the ICL ligand and the number of QD layers.

Atomic-scale origin of piezoelectricity in wurtzite ZnO.

ZnO has been extensively studied by virtue of its remarkably high piezoelectric responses, especially in nanowire forms. Currently, the high piezoelectricity of wurtzite ZnO is understood in terms of the covalent-bonding interaction between Zn 3d and O 2p orbitals. However, the Zn 3d orbitals are not capable of forming hybridized orbitals with the O 2pz orbitals since the Zn ion is characterized by fully filled non-interacting 3d orbitals. To resolve this puzzling problem, we have investigated the atomic-scale origin of piezoelectricity by exploiting density-functional theory calculations. On the basis of the computed orbital-resolved density of states and the band structure over the Γ-M first Brillouin zone, we propose an intriguing bonding mechanism that accounts for the observed high piezoelectricity - intra-atomic 3dz(2)-4pz orbital self-mixing of Zn, followed by asymmetric hybridization between the Zn 3dz(2)-4pz self-mixed orbital and the O 2pz orbital along the polar c-axis of the wurtzite ZnO.

Bandgap tuning with thermal residual stresses induced in a quantum dot.

Lattice distortion induced by residual stresses can alter electronic and mechanical properties of materials significantly. Herein, a novel way of the bandgap tuning in a quantum dot (QD) by lattice distortion is presented using 4-nm-sized CdS QDs grown on a TiO2 particle as an application example. The bandgap tuning (from 2.74 eV to 2.49 eV) of a CdS QD is achieved by suitably adjusting the degree of lattice distortion in a QD via the tensile residual stresses which arise from the difference in thermal expansion coefficients between CdS and TiO2. The idea of bandgap tuning is then applied to QD-sensitized solar cells, achieving ≈60% increase in the power conversion efficiency by controlling the degree of thermal residual stress. Since the present methodology is not limited to a specific QD system, it will potentially pave a way to unexplored quantum effects in various QD-based applications.

Confinement of ferroelectric domain-wall motion at artificially formed conducting-nanofilaments in epitaxial BiFeO3 thin films.

We report confinement of ferroelectric domain-wall motion at conducting-nanofilament wall in epitaxial BiFeO3 thin film on Nb-doped SrTiO3 substrate. The BiFeO3 film exhibited well-defined ferroelectric response and unipolar resistive switching behavior. We artificially formed conducting-nanofilaments in the BiFeO3 via conducting atomic force microscope techniques. The conducting-nanofilament wall, which does not possess any ferroelectric polarization, is then able to block domain propagation. Consequently, we demonstrate that the domain-wall motion is effectively confined within the conducting-nanofilament wall during polarization switching. This significant new insight potentially gives an opportunity for the artificial manipulation of nanoscale ferroelectric domain.