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Simultaneously optimizing nonlinear absorption coefficient and modulation depth is a considerable challenge for nonlinear optical materials. Here we present an effective solution through constructing PbS2‐based inorganic‐organic superlattice. PbS2/Cn superlattice particles are synthesized, where n (4, 6, and 8) denotes the number of carbon atoms in the organic component. First‐principles simulations indicate the formation of covalent bonds and van der Waals interaction between PbS2 unit and interlayer organic molecules. All samples exhibit strong nonlinear absorption under femtosecond laser excitation with a wavelength range between 515 nm and 900 nm, and the nonlinear absorption coefficient increases with interlayer distance. The optimized sample, PbS2/C8, demonstrates outstanding nonlinear absorption and substantial modulation depth under 800 nm (the third‐order nonlinear absorption coefficient βeff, 10449 ± 609 cm GW−1; modulation depth, 39.1%) and 900 nm (the fifth‐order nonlinear absorption coefficient γeff, 6465 ± 68 cm3 GW−2; modulation depth, 88.1%), which exhibits saturable absorption under 515 nm (βeff, ‐4932 ± 818 cm GW−1; modulation depth, 48.1%). It exhibits a small optical limiting threshold of 1.23 mJ cm−2. These performances surpass those of typical single‐/few‐layer metal chalcogenides. Structural and spectral analyses elucidate that the remarkable optical nonlinearity can be attributed to quantum confinement in the inorganic layer and the dielectric enhancement of the superlattice. [ABSTRACT FROM AUTHOR]

Achieving a perfectly spherical nanostructures might not be feasible in experiments due to factors like growth kinetics, solvent's nature and surface effects. This numerical investigation examines how the shape of a surrounding shell (prolate, spherical or oblate) in core/shell quantum dots (CSQDs) buried into two commonly used dielectric oxides (SiO2 or HfO2), microscopically influences their electro-optical characteristics. In the context of the effective mass approach (EMA) and the density matrix formalism (DMF), we have reached the stationary eigenstates and their matching wave functions by solving the Schrödinger equation. Our computations revealed that the discrete electronic states can fluctuate with ellipticity parameter as a consequence of different quantum confinement origins along the major and minor axes. The shell anisotropy provided an effective opportunity to finely adjust resonant frequencies and calibrate the magnitude order of the Quadratic electro-optic effects (QEOEs), electro-absorption (EA) process, optical absorption characteristics (OACs) and refractive index changes (RICs) within QD/oxide interfacs. Computed coefficients have experienced red/blue shift contingent upon variations in the inner core radius, ellipticity parameter and the types of capping oxides. [ABSTRACT FROM AUTHOR]

The halide perovskite CsPbBr3 belongs to the Cs‐Pb‐Br material system, which features two additional thermodynamically stable ternary phases, Cs4PbBr6 and CsPb2Br5. The coexistence of these phases and their reportedly similar photoluminescence (PL) have resulted in a debate on the nature of the emission in these systems. Herein, optical and microscopic characterizations are combined with an effective mass, correlated electron–hole model of excitons in confined systems, to investigate the emission properties of the ternary phases in the Cs‐Pb‐Br system. It is found that all Cs‐Pb‐Br phases exhibit green emission and the non‐perovskite phases exhibit PL quantum yields orders of magnitude larger than CsPbBr3. In particular, blue‐ and red‐shifted emission for the Cs‐ and Pb‐rich phases, respectively, are measured, stemming from embedded CsPbBr3 nanocrystals (NCs). This model reveals that the difference in emission shift is caused by the combined effects of NC size and different band mismatch. Furthermore, the importance of including the dielectric mismatch in the calculation of the emission energy for Cs‐Pb‐Br composites is demonstrated. The results explain the reportedly limited blue shift in CsPbBr3@Cs4PbBr6 composites and rationalize some of its differences with CsPb2Br5. [ABSTRACT FROM AUTHOR]

Understanding and controlling exciton properties are important for the design of 2D semiconductors, such as monolayer transition metal dichalcogenides (TMDCs) and 2D halide perovskites (HPs). This paper demonstrates that the widespread strategy used for the exciton engineering of 2D HPs, based on dielectric mismatch, is flawed since dielectric mismatch has very little correlation with exciton properties. For monolayer TMDCs, however, the dielectric mismatch is shown to be more important.

We have studied Single donor transistors with designed nanochannels in which the tunnel barrier height is enhanced due to dielectric confinement. For single electron tunneling effects the charging energy is significantly large. Which is a first limiting factor for shallow dopants? At high temperatures, thermally activated transport became quickly dominant. We have found that at high temperature operation of electron tunneling occurred via a single donor. We have found that the single dopant devices operating at room temperature paving the way for practical applications based on individual dopant atom in silicon nanodevices. We have also found that in nanopatterned channel transistors, single electron tunneling via individual positive donors was observed at elevated temperatures. The obtained results were found in good agreement with previously obtained results. [ABSTRACT FROM AUTHOR]

Colloidal quantum dots exhibit size-dependent optical properties due to quantum and dielectric confinements at the semiconductor/solvent boundary. To consider both confinement effects, we take a natural potential well approach that assumes separate potential wells for electron and hole which are surrounded by dielectric media. The potential well depths for electron and hole are set by the band offsets at the semiconductor/solvent heterojunction. The kinetic energy is calculated using an effective mass approximation and the electron-hole interaction energy is obtained by taking image charges into account. For cadmium chalcogenides, resulting transition energies agree well with size-dependent optical bandgaps from experiments. [ABSTRACT FROM AUTHOR]

Surface plasmon resonance and photonic crystals (PCs) effect are effective methods for improving upconversion luminescence (UCL) for upconversion nanoparticles. In this work, PCs/Ag/Al 2 O 3 /UC hybrid structure is presented to enhance UCL of NaGdF 4 :Er3+/Yb3+/Al3+ nanorods through tuning the thickness of the Al 2 O 3 layer. The optical and luminescence properties were studied and compared with those of UC and PCs/Ag/UC hybrid, it is shown that the thickness of Al 2 O 3 layer has a significant effect on fluorescence intensity, outstanding upconversion luminescence enhancement and the green-to-red intensity ratios have been achieved at 980 nm excitation. The maximum enhancement factors of the red and green emission were obtained for the sample with 10 nm Al 2 O 3 layer, respectively. The mechanism of UCL enhancement for PCs/Ag/Al 2 O 3 /UC hybrid structure was discussed. • A hybrid structure is presented to improve the upconversion emission of NaGdF 4 :Er3+/Yb3+/Al3+ nanorods. • Combining dielectric confinement effect with coupling effect, the UCL and R G/R were obviously improved. • The mechanism of UCL enhancement is attributed to the increase of the emission rate and energy transfer rate. [ABSTRACT FROM AUTHOR]

In the semiconducting perovskite materials family, the cesium-lead-chloride compound (CsPbCl 3 ) supports robust excitons characterized by a blue-shifted transition and the largest binding energy, thus presenting a high potential to achieve demanding solid-state room-temperature photonic or quantum devices. Here we study the fundamental emission properties of cubic-shaped colloidal CsPbCl 3 nanocrystals (NCs), examining in particular individual NC responses using micro-photoluminescence in order to unveil the exciton fine structure (EFS) features. Within this work, NCs with average dimensions ⟨ L α ⟩ ≈ 8 nm (α = x , y , z ) are studied with a level of dispersity in their dimensions that allows disentangling the effects of size and shape anisotropy in the analysis. We find that most of the NCs exhibit an optical response under the form of a doublet with crossed polarized peaks and an average inter-bright-state splitting, Δ BB ≈ 1.53 meV, but triplets are also observed though being a minority. The origin of the EFS patterns is discussed in the frame of the electron-hole exchange model by taking into account the dielectric mismatch at the NC interface. The different features (large dispersity in the Δ BB values and occasional occurrence of triplets) are reconciled by incorporating a moderate degree of shape anisotropy, observed in the structural characterization, by preserving the relatively high degree of the NC lattice symmetry. The energy distance between the optically inactive state and the bright manifold, Δ BD , is also extracted from time-resolved photoluminescence measurements (Δ BD ≈ 10.7 meV), in good agreement with our theoretical predictions.

The realization of semiconductor structures with stable excitons at room temperature is crucial for the development of excitonics and polaritonics. Quantum confinement has commonly been employed for enhancing excitonic effects in semiconductor heterostructures. Dielectric confinement, which gives rises to much stronger enhancement, has proven to be more difficult to achieve because of the rapid nonradiative surface/interface recombination in hybrid dielectric-semiconductor structures. Here, we demonstrate intense excitonic emission from bare GaN nanowires with diameters down to 6 nm. The large dielectric mismatch between the nanowires and vacuum greatly enhances the Coulomb interaction, with the thinnest nanowires showing the strongest dielectric confinement and the highest radiative efficiency at room temperature. In situ monitoring of the fabrication of these structures allows one to accurately control the degree of dielectric enhancement. These ultrathin nanowires may constitute the basis for the fabrication of advanced low-dimensional structures with an unprecedented degree of confinement. [ABSTRACT FROM AUTHOR]

Abstract: Nanoscale pn junctions have been investigated by Kelvin probe force microscopy and several particular features were found. Within the depletion region, a localized noise area is observed, induced by temporal fluctuations of dopant states. Electronic potential landscape is significantly affected by dopants with ground-state energies deeper than in bulk. Finally, the effects of light illumination were studied and it was found that the depletion region shifts its position as a function of light intensity. This is ascribed to charge redistribution within the pn junction as a result of photovoltaic effect and due to the impact of deepened-level dopants. [Copyright &y& Elsevier]

Abstract: Third-order nonlinear optical processes associated with the interlevel transitions in ZnS/CdSe core–shell quantum dots under electric fields are theoretically investigated. Taking into account the dielectric mismatch with the surrounding matrix, the electronic structure of the dots is obtained within the effective mass and parabolic band approximations. It is shown that large applied electric fields break the symmetry of the confinement potential and lead to a significant blue-shift of the peak positions in the nonlinear optical spectrum. The size effect is also discussed and it is proved that large nonlinear susceptibility can be obtained by increasing the thickness of the nanocrystal shell. Our results suggest that external factors such as the applied electric field and orientation of the incident light polarization can be used – in addition to spatial confinement – to improve the performances of the optical devices. [Copyright &y& Elsevier]

Abstract: The effects of the electric field and impurity position on the ground and lowest excited states of a hydrogenic donor in the core–shell CdSe/ZnS quantum dot are studied within the effective mass approximation, taking into account the polarization charges at the nanocrystal boundary. We found a pronounced redshift of the impurity energy under low dielectric constant environment due to the predominance of the effective Coulomb term over the self-interaction potential. For particular donor positions the resonant peak of the photoionization cross-section is strongly enhanced as a result of the dielectric confinement-induced changes in the electronic states. The tuning of the nanodot optical properties can be also achieved by an applied electric field which allows a red- or blue-shift of the threshold energy for the impurity photoionization. [Copyright &y& Elsevier]

Silver nanocluster precipitation in AR Schott glass by subsequently silver ionic exchange and helium bombardment was investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-visible optical absorption. Helium ion bombardment was used to induce local defects in the matrix and to promote the growth of the silver nano-aggregates. The typical implantation depth was estimated at 1 μm by Trim simulation. SEM investigations give us the concentration profile of the exchanged samples and the maximum depth. Optical absorption was performed to visualize the effect of the He+ fluence on the ion exchanged sample spectra and compared to the Drude model varying size and matrix refractive index. TEM was used to evaluate the distribution size of the silver nanoparticles, their structure by diffraction pattern, size, and shape and to correlate it to the experimental and theoretical absorption curves. The TEM observations prove that we are in a confinement regime with a particle size below the mean free path of the silver bulk metal. [ABSTRACT FROM AUTHOR]

We have investigated the exciton–exciton interaction in an inorganic–organic layered semiconductor, (C6H5C2H4NH3)2PbI4, by the pump–probe spectroscopy. The excitonic shift and the induced absorption due to the excitation of the exciton to the excitonic molecule are measured as functions of the delay time in the co-circular and opposite-circular polarization configurations. The contribution of the exciton–exciton interaction to exciton renormalization is distinguished by femtosecond resolution. Based on a rate-equation analysis for exciton-relaxation kinetics, it is found that the contribution of the interaction between excitons with opposite spins is ca. −5% of that of the interaction between excitons with the same spin. In order to explain this result, possible types of interactions, which originate solely from the Coulomb interaction without restriction from the Pauli exclusion principle, are examined. [Copyright &y& Elsevier]

Measurements of the resonantly enhanced, third-order nonlinear optical properties of gold nanostructures exhibiting reduced charge-carrier mobility in three dimensions were performed with a number of ultrafast nonlinear optical techniques. The size of the particles investigated was varied between 5 and 40 nm. The magnitude of the nonlinear susceptibility is of the order of 5·10−16 m2V−2 at resonance and an order of magnitude lower off-resonance. The response time of the nonlinearity is found to be extremely fast and could not be resolved in the experiments undertaken here. The only statement that can be made in this regard is that the phase relaxation time is of the order of or less than 20 fs while the energy relaxation time is of the order of or less than 75 fs. [ABSTRACT FROM AUTHOR]

Layered Ruddlesden–Popper (RP) hybrid perovskite semiconductors have recently emerged as promising materials for photovoltaics application. However, the strong quantum and dielectric confinement of RP perovskite compounds increases their optical bandgap and binding energy of exciton, which limit their application in solar cells. Herein, the doping of RP‐based (BA)2(MA)3Pb4I13 perovskite materials by means of Li+ is reported for the first time, which can significantly help to reduce dielectric confinement and thus the exciton‐binding energy via reducing the dielectric constant difference between organic spacer cation and inorganic framework. Furthermore, the Li+ doping boosts the carrier mobility, reduces the trap density states, and thus allows to achieve power conversion efficiency of ≈15% via Li+‐(BA)2(MA)3Pb4I13‐based perovskite solar cell, which is the highest efficiency for layered perovskites (n = 4) so far. This work highlights the promising ionic doping engineering for further improvement of the layered perovskite materials. [ABSTRACT FROM AUTHOR]

Recently, considerable researches have reported that the incorporation of potassium cation (K+) in lead halide perovskites obviously improves the performance of perovskite solar cells. The recent finding indicates that the interstitial occupancy position of K+ in perovskite lattice can increase ion‐migration barrier, which dramatically suppresses the hysteresis of the device. However, the enhancement of photoluminescence (PL) as well as bandgap variation cannot be interpreted by K+ interstitial state in perovskite. Considering this discrepancy, it has been found out that potassium‐rich phase grows in three dimensional (3D) perovskite crystal grain boundary through both experiments and theoretical simulations, which can efficiently passivate the grain boundaries on the 3D crystal surface and decrease trap states. Meanwhile, the dielectric confinement effect between potassium‐rich phase and 3D perovskite crystal, contributing to improvement of radiative recombination in perovskite absorber, can further support the enhancement and red‐shift of photoluminescence (PL) spectrum. Therefore, a power conversion efficiency of 20.4% has been achieved in K+ doped halide perovskite solar cell, and still maintains 90% initial efficiency after stored in 30% humidity at room temperature for 1000 h. These findings offer a new path for the structural manipulation by incorporating multi cations in perovskite materials. [ABSTRACT FROM AUTHOR]

Hot carrier (HC) cooling is a critical photophysical process that significantly influences the optoelectronic performance of hybrid perovskite-based devices. The hot carrier extraction at the device interface is very challenging because of its ultrashort lifetime. Here, ultrafast transient reflectance spectroscopy measurements and time-domain ab initio calculations show how the dielectric constant of the organic spacers can control and slow the HC cooling dynamics in single-crystal 2D Ruddlesden-Popper hybrid perovskites. We find that (EA) 2 PbI 4 (EA = HOC 2 H 4 NH 3 + ) that correspond to a high dielectric constant organic spacer has a longer HC cooling time compared to that of (AP) 2 PbI 4 (AP = HOC 3 H 6 NH 3 + ) and (PEA) 2 PbI 4 (PEA = C 6 H 5 C 2 ). The slow HC relaxation process in the former case can be ascribed to a stronger screening of the Coulomb interactions, a small nonradiative internal conversion within the conduction bands, as well as a weak electron-phonon coupling. Our findings provide a strategy to prolong the hot carrier cooling time in low-dimensional hybrid perovskite materials by using organic spacers with reduced dielectric confinement.4 NH 3 + ). The slow HC relaxation process in the former case can be ascribed to a stronger screening of the Coulomb interactions, a small nonradiative internal conversion within the conduction bands, as well as a weak electron-phonon coupling. Our findings provide a strategy to prolong the hot carrier cooling time in low-dimensional hybrid perovskite materials by using organic spacers with reduced dielectric confinement.

Two-dimensional (2D) lead halide perovskites with long-chain ammonium halides display high photoluminescence quantum yields (PLQYs), because of their size and dielectric confinement, which hold promise for a high-efficiency and low-cost light-emitting diode (LED). However, the presence of an insulating organic long-chain spacer cation (L) dramatically deteriorates the charge transport properties along the out-of-plane nanoplatelet direction or adjacent nanocrystals, which would limit the device performance of the LED. To overcome this issue, we successfully incorporate small alkaline ions such as sodium (Na + ) to replace the long organic molecule. Grazing incidence X-ray diffraction measurements verify 2D layer formation with a preferred crystallite orientation. In addition, the incorporated sodium salt also generates amorphous sodium lead bromide (NaPbBr 3 ) in perovskite as spacers to form a nanocrystal-like halide perovskite film. The PLQY is dramatically improved in the sodium-incorporated film because of its enhanced photoluminescence lifetime. Upon incorporation of a low concentration of an organic additive, this two-dimensional-three-dimensional (2D-3D) perovskite can achieve a compact and uniform film. Therefore, a 2D-3D perovskite achieves a high external quantum efficiency of 15.9% with good operational stability. We develop a type of 2D-3D halide perovskite with various inorganic ions as spacers for promising high-performance optoelectronic devices.

Layered hybrid organic-inorganic perovskites (HOPs) have re-emerged as potential technological solutions for next-generation photovoltaic and optoelectronic applications. Their two-dimensional (2D) nature confers them a significant flexibility and results in the appearance of quantum and dielectric confinements. Such confinements are at the origin of their fascinating properties, and understanding them from a fundamental level is of paramount importance for optimization. Here, we provide an in-depth investigation of band alignments of 2D HOP allowing access to carriers' confinement potentials. 2D HOPs are conceptualized as composite materials in which pseudoinorganic and -organic components are defined. In this way, computational modeling of band alignments becomes affordable using first-principles methods. First, we show that the composite approach is suitable to study the position-dependent dielectric profiles and enables clear differentiation of the respective contributions of inorganic and organic components. Then we apply the composite approach to a variety of 2D HOPs, assessing the impact on the confinement potentials of well and barrier thickness, of the nature of the inorganic well, and of structural transitions. Using the deduced potentials, we further discuss the limitations of the effective mass approximation, scrutinizing the electronic properties of this family of composite materials. Our simulations demonstrate type-I dominant band alignment in 2D HOPs. Finally, we outline design principles on band alignment toward achieving specific optoelectronic properties. Thus, we present alternative theoretical methods to inspect the properties of 2D hybrid perovskites and expect that the composite approach will be applicable to other classes of layered materials.

Doping, as a central strategy to control free carrier type and concentration in semiconductor materials, suffers from low efficiency at the nanoscale, especially in systems having high permittivity (ϵ) and large Bohr radii, such as lead chalcogenide nanocrystals (NCs) and nanowires (NWs). Here, we study dielectric confinement effects on the doping efficiency of lead chalcogenides nanostructures by integrating PbSe NWs in the platform of field effect transistors (FETs). Elemental Pb or In or elemental Se is deposited by thermal evaporation to remotely n- or p-dope the NWs. Polymeric and oxide materials of varying ϵ are subsequently deposited to control the dielectric environment surrounding the NWs. Analyzing the device characteristics, we extract the change of carrier concentration introduced by tailoring the dielectric environment. The calculated doping efficiency for n-type (Pb/In) and p-type (Se) dopants increases as the ϵ of the surrounding medium increases. Using a high-ϵ material, such as HfO 2 for encapsulation, the doping efficiency can be enhanced by >10-fold. A theoretical model is built to describe the doping efficiency in PbSe NWs embedded in different dielectric environments, which agrees with our experimental data for both NW array and single NW devices. As dielectric confinement affects all low-dimensional materials, engineering the dielectric environment is a promising general approach to enhance doping concentrations, without introducing excess impurities that may scatter carriers, and is suitable for various device applications.

We have investigated the nonlinear conductance in diffusion-doped Si:GaAs nanowires contacted by patterned metal films in a wide range of temperatures <i>T</i>. The wire resistance R<sub>W</sub> and the zero bias resistance R<sub>C</sub>, dominated by the contacts, exhibit very different responses to temperature changes. While R<sub>W</sub> shows almost no dependence on <i>T</i>, R<sub>C</sub> varies by several orders of magnitude as the devices are cooled from room temperature to T= 5 K. We develop a model that employs a sharp donor level very low in the GaAs conduction band and show that our observations are consistent with the model predictions. We then demonstrate that such measurements can be used to estimate carrier properties in nanostructured semiconductors and obtain an estimate for N<sub>D</sub>, the doping density in our samples. We also discuss the effects of surface states and dielectric confinement on carrier density in semiconductor nanowires., (© 2018 IOP Publishing Ltd.)

Layered halide hybrid organic-inorganic perovskites (HOP) have been the subject of intense investigation before the rise of three-dimensional (3D) HOP and their impressive performance in solar cells. Recently, layered HOP have also been proposed as attractive alternatives for photostable solar cells and revisited for light-emitting devices. In this review, we combine classical solid-state physics concepts with simulation tools based on density functional theory to overview the main features of the optoelectronic properties of layered HOP. A detailed comparison between layered and 3D HOP is performed to highlight differences and similarities. In the same way as the cubic phase was established for 3D HOP, here we introduce the tetragonal phase with D 4h symmetry as the reference phase for 2D monolayered HOP. It allows for detailed analysis of the spin-orbit coupling effects and structural transitions with corresponding electronic band folding. We further investigate the effects of octahedral tilting on the band gap, loss of inversion symmetry and possible Rashba effect, quantum confinement, and dielectric confinement related to the organic barrier, up to excitonic properties. Altogether, this paper aims to provide an interpretive and predictive framework for 3D and 2D layered HOP optoelectronic properties.