Dielectric Confinement Research Articles

Reducing Dielectric Confinement Effect Enhances Carrier Separation in Two-Dimensional Hybrid Perovskite Photocatalysts.

Two-dimensional organic-inorganic hybrid perovskites (OIHPs) with alternating structure of the organic and inorganic layers have a natural quantum well structure. The difference of dielectric constants between organic and inorganic layers in this structure results in the enhancement of dielectric confinement effect, which exhibits a large exciton binding energy and hinders the separation of electron-hole pairs. Herein, a strategy to reduce the dielectric confinement effect by narrowing the dielectric difference between organic amine molecule and [PbBr6]4- octahedron is put forward. The Ethanolamine (EOA) contains hydroxyl groups, resulting in the positive and negative charge centers of O and H non-overlapping, which generated a larger polarity and dielectric constant. The reduced dielectric constant produces a smaller exciton binding energy (71.03 meV) of (C2H7NO)2PbBr4 ((EOA)2PbBr4) than (C8H11N)2PbBr4 ((PEA)2PbBr4 (156.07 meV), and promotes the dissociation of electrons and holes. The increasing of lifetime of photogenerated carrier in (EOA)2PbBr4 are proved by femtosecond transient absorption spectra. Density functional theory (DFT) calculations have also indicated that the small energy shift of the total density of states (DOS) between the C/H/N and the Pb/Br in (EOA)2PbBr4 favors the separation of electrons and holes. In addition, this work demonstrates the application of (PEA)2PbBr4 and (EOA)2PbBr4 in the field of photocatalytic CO2 reduction.

Visible-Light Photodetection by Zero-Dimensional Hybrid Indium-Halide with Minimal Structural Distortion and Reduced Band Gap.

Perovskite-inspired zero-dimensional (0D) hybrid halides exhibit impressive light emission properties; however, their potential in photovoltaics is hindered by the absence of interconnection between the inorganic polyhedra, leading to acute radiative recombination and insufficient charge separation. We demonstrate that incorporating closely-spaced dissimilar polyhedral units with minimal structural distortion leads to a remarkable enhancement in visible-light photodetection capability. We designed 0D C24H72N8In2Br14 (HIB) with a tetragonal crystal system, replacing the Cs+ of Cs2InBr5.H2O (CIB) with 1,6-hexanediammonium (HDA) cation. HIB comprises [InBr6]3- octahedra, and [InBr4]- tetrahedra units spaced 3.9 Å apart by the HDA linker. The [InBr4]- unit is additionally linked to HDA via intercalated bromine through hydrogen and halogen bonding interactions, respectively. This structural arrangement lowers the dielectric confinement, thereby enhancing carrier density and mobility, and increasing the diffusion coefficient compared to CIB. With 3.6 % bromine vacancy within the [InBr4]- block, mid-gap states are created, reducing the direct band gap to 2.19 eV. HIB demonstrates an unprecedently high responsivity of 9975.9±201.6 mA W-1 under 3 V potential bias at 485 nm wavelength, among low-dimensional hybrid halides. In the absence of potential bias, the self-powered photodetection parameters are 81.2±3.0 mA W-1 and (6.98±0.21)×109 Jones.

Visible‐Light Photodetection by Zero‐Dimensional Hybrid Indium‐Halide with Minimal Structural Distortion and Reduced Band Gap

AbstractPerovskite‐inspired zero‐dimensional (0D) hybrid halides exhibit impressive light emission properties; however, their potential in photovoltaics is hindered by the absence of interconnection between the inorganic polyhedra, leading to acute radiative recombination and insufficient charge separation. We demonstrate that incorporating closely‐spaced dissimilar polyhedral units with minimal structural distortion leads to a remarkable enhancement in visible‐light photodetection capability. We designed 0D C24H72N8In2Br14 (HIB) with a tetragonal crystal system, replacing the Cs+ of Cs2InBr5.H2O (CIB) with 1,6‐hexanediammonium (HDA) cation. HIB comprises [InBr6]3− octahedra, and [InBr4]− tetrahedra units spaced 3.9 Å apart by the HDA linker. The [InBr4]− unit is additionally linked to HDA via intercalated bromine through hydrogen and halogen bonding interactions, respectively. This structural arrangement lowers the dielectric confinement, thereby enhancing carrier density and mobility, and increasing the diffusion coefficient compared to CIB. With 3.6 % bromine vacancy within the [InBr4]− block, mid‐gap states are created, reducing the direct band gap to 2.19 eV. HIB demonstrates an unprecedently high responsivity of 9975.9±201.6 mA W−1 under 3 V potential bias at 485 nm wavelength, among low‐dimensional hybrid halides. In the absence of potential bias, the self‐powered photodetection parameters are 81.2±3.0 mA W−1 and (6.98±0.21)×109 Jones.

Two-Dimensional Lead Iodide Perovskites with Extremely Reduced Dielectric Confinement: Embedded Self-Erasing Second-Harmonic Generation Switching, Thermochromism, and Photoluminescence

Two-Dimensional Lead Iodide Perovskites with Extremely Reduced Dielectric Confinement: Embedded Self-Erasing Second-Harmonic Generation Switching, Thermochromism, and Photoluminescence

Anomalous Behavior in Dark-Bright Splitting Impacts the Biexciton Binding Energy in (BA)2(MA)n-1PbnBr3n+1 (n = 1-3).

Two-dimensional Ruddlesden-Popper series are an excellent system for tuning physical properties of the perovskite by controlling the layer number (n). For instance, bandgap and exciton binding energies of the series gradually increase upon reducing n via enhanced quantum and dielectric confinements. Here, we present findings that challenge the anticipated trend in electron-hole exchange interaction within (BA)2MAn-1PbnBr3n+1 (n = 1-3), which causes spin-dependent exciton level splitting into bright and dark states, where the latter is partially visible near the surface of the Br-based two-dimensional Ruddlesden-Popper series. Contrary to expectations, the smallest gap between bright and dark exciton levels is observed from n = 2 at 10 K. This anomaly results in the strongest biexciton binding between two dark excitons occurring at n = 2, rather than at n = 1 as initially hypothesized. The observed anomaly arises from a phase transition induced by octahedral tilting occurring only for n = 2 near 100 K as confirmed by temperature-dependent optical and X-ray diffraction measurements. Our results show that Coulomb interaction need not vary gradually with n, which can impact the optoelectronic properties of the Ruddlesden-Popper series.

Interfacial and Defective Construction from Diverse CuxSy Quantum Dots toward Broadband Carbon-Based Microwave Absorber.

In this study, highly monodisperse copper sulfide (CuxSy) quantum dots (QDs) have been successfully obtained using a ligand-chemistry strategy, and then a variety of S-deficient CuxSy/nitrogen-doped carbon (NC) heterointerfaces are constructed by compositional fine-tuning (Cu9S5 → Cu1.96S → Cu). First-principles calculations show that the S-deficient domains of CuxSy QDs and N-doped domains of carbon synergistically enhance the electron transfer from CuxSy to NC. In addition, the finite element simulations demonstrate that the diverse CuxSy QDs exhibit their intrinsic size and dielectric confinement effects to precisely manipulate the electric field distortion and improve the relaxation polarization. Consequently, CuxSy@NC achieves excellent impedance matching and a strong loss mode dominated by dielectric polarization. Among them, CuxSy@NC-650 has a maximum effective absorption bandwidth of 7.7 GHz at 2.5 mm, while CuxSy@NC-700 features a minimum reflection loss of -66.7 dB at 13.7 GHz, respectively. Furthermore, the simulations of radar cross-sections have confirmed that the CuxSy@NC series is promising in the field of radar stealth.

Nonlinear Absorption in 2D Ruddlesden-Popper Perovskites: Pathways to Ultrafast Optical Applications.

Owing to their distinctive photophysical properties resulting from their larger exciton binding energy and the influence of dielectric and quantum confinement effects, considerable research interest has been directed toward two-dimensional Ruddlesden-Popper halide perovskites (2D RP-HPs). Particularly, 2D RP-HPs exhibit exceptional multiphoton absorption (MPA) effects that reveal versatile applications. In this work, two-photon absorption (2PA) and three-photon absorption (3PA) in 2D RP-HPs, specifically (PEA)2PbBr4 and (BA)2PbBr4 platelets, have been demonstrated through their photoluminescence spectra under multiphoton excitation, revealing a power law relationship with excitation energy. On the other hand, polarization-dependent MPA measurements are also conducted to obtain their anisotropy properties. The excellent 2PA and 3PA effects of 2D RP-HPs have found applications in ultrafast optics to construct fringe-resolved autocorrelation traces, enabling the retrieval of pulse duration not only passively mode-locked Ti:sapphire at 800 nm but also Yb-doped fiber lasers at 1030 nm.

Reducing Dielectric Confinement Effect Enhances Carrier Separation in Two‐Dimensional Hybrid Perovskite Photocatalysts

AbstractTwo‐dimensional organic–inorganic hybrid perovskites (OIHPs) with alternating structure of the organic and inorganic layers have a natural quantum well structure. The difference of dielectric constants between organic and inorganic layers in this structure results in the enhancement of dielectric confinement effect, which exhibits a large exciton binding energy and hinders the separation of electron‐hole pairs. Herein, a strategy to reduce the dielectric confinement effect by narrowing the dielectric difference between organic amine molecule and [PbBr6]4− octahedron is put forward. The Ethanolamine (EOA) contains hydroxyl groups, resulting in the positive and negative charge centers of O and H non‐overlapping, which generated a larger polarity and dielectric constant. The reduced dielectric constant produces a smaller exciton binding energy (71.03 meV) of (C2H7NO)2PbBr4 ((EOA)2PbBr4) than (C8H11N)2PbBr4 ((PEA)2PbBr4 (156.07 meV), and promotes the dissociation of electrons and holes. The increasing of lifetime of photogenerated carrier in (EOA)2PbBr4 are proved by femtosecond transient absorption spectra. Density functional theory (DFT) calculations have also indicated that the small energy shift of the total density of states (DOS) between the C/H/N and the Pb/Br in (EOA)2PbBr4 favors the separation of electrons and holes. In addition, this work demonstrates the application of (PEA)2PbBr4 and (EOA)2PbBr4 in the field of photocatalytic CO2 reduction.

Fluorinated Organic Cations Derived Chiral 2D Perovskite Enabling Enhanced Spin-Dependent Oxygen Evolution Reaction.

Chirality-induced spin selectivity observed in chiral 2D organic-inorganic hybrid perovskite holds promise to achieve spin-dependent electrochemistry. However, conventional chiral 2D perovskites suffer from low conductivity and hygroscopicity, limiting electrochemical performance and operational stability. Here, a cutting-edge material design is introduced to develop a stable and efficient chiral perovskite-based spin polarizer by employing fluorinated chiral cation. The fluorination approach effectively promotes the charge carrier transport along the out-of-plane direction by mitigating the dielectric confinement effect within the multi-quantum well-structured 2D perovskite. Integrating the fluorinated cation incorporated spin polarizer with BiVO4 photoanode considerably boosts the photocurrent density while reducing overpotential through a spin-dependent oxygen evolution reaction. Furthermore, the hydrophobic nature of fluorine in spin polarizer endows operational stability to the photoanode, extending the durability by 280% as compared to the device with non-fluorinated spin polarizer.

Electronic Structure of Biexcitons in Metal Halide Perovskite Nanoplatelets.

A theoretical description of biexcitons in metal halide perovskite nanoplatelets is presented. The description is based on a variational effective mass model, including polaronic effects by means of a Haken potential. The strong quantum and dielectric confinements are shown to squeeze the biexciton under the polaronic radius, which greatly enhances Coulomb attractions and (to a lesser extent) repulsions. This explains the need for effective dielectric constants approaching the high-frequency limit in previous simulations, and the binding energies exceeding 40 meV observed in single-monolayer nanoplatelets. Biexcitons are formed by a pair of weakly interacting excitons, with a roughly rectangular geometry. This translates into a constant ratio between biexciton and exciton binding energies (2D Haynes rule) well below the ideal value of ΔBX/ΔX = 0.228 proposed for squared biexcitons. The ratio is independent of the number of monolayers in the platelet, but it does depend on the lateral and dielectric confinement.

Broken symmetries in quasi-2D charged systems via negative dielectric confinement

We report spontaneous symmetry breaking (SSB) phenomena in symmetrically charged binary particle systems under planar nanoconfinement with negative dielectric constants. The SSB is triggered solely via the dielectric confinement effect, without any external fields. The mechanism of SSB is found to be caused by the strong polarization field enhanced by nanoconfinement, giving rise to charge/field oscillations in the transverse directions. Interestingly, dielectric contrast can even determine the degree of SSB in transverse and longitudinal dimensions, forming charge-separated interfacial liquids and clusters on square lattices. Furthermore, we analytically show that the formed lattice constant is determined by the dielectric mismatch and the length scale of confinement, which is validated via molecular dynamics simulations. The novel broken symmetry mechanism may provide new insights into the study of quasi-2D systems and the design of future nanodevices.

Theoretical insights into size and dielectric confinement: Unraveling real and imaginary parts of the effective complex dielectric function in spherical multilayered quantum dots with oxide interfaces

A quantitative numerical exploration is conducted to scrutinize the combined effects of size and dielectric confinement consequences on the electronic and optical characteristics of spherical multilayered quantum dot CdSe/ZnS/CdSe/ZnS (SMLQD) and its inverted configuration ZnS/CdSe/ZnS/CdSe (ISMLQD) buried into two oxides: HfO2 and SiO2. By employing the effective mass approximation (EMA) and the density matrix approach (DMA), the derived quantized electron energy states and their associated wave functions were obtained by solving the Schrödinger equation in a spherical coordinates. The dipole transition element, both real and imaginary parts of the effective complex dielectric function (ECDF) as well as its linear, nonlinear and total counterparts are brought out for various values of inner core radii, number density of QDs and incident photon intensity. In addition, a specific analysis of electron probability distributions is provided to gain a clearer understanding of the underlying physical factors. Our findings point to a notable influence of these mentionned factors on the computed coefficients. The study unveils that the dielectric mismatch occurring at the system/oxide interfaces plays a crucial role in modifying the electronic structure and a substantial impact on both linear and third-order nonlinear components is witnessed.

Structural and photophysical properties of two-dimensional lead bromide hybrid perovskite (C8H17NH3)2PbBr4

The structural versatility of organic compounds imparts manifold properties to hybrid organic−inorganic perovskites, where two-dimensional (2D) halide perovskites are potential future platforms for light-emitting devices because of their unique quantum well configuration and dielectric confinement. Notwithstanding the numerous studies on the organic−inorganic perovskites carried out to date, precisely charactering the structure and photoluminescence mechanism remain considerable challenges. Herein, by applying Rietveld refinement, we have obtained crystal structure and atomic sites of 2D layered OA2PbBr4 perovskite, which undergoes a phase transition at 190 K with activation energies of 29.6 and 3.8 meV for the two phases, respectively. The theoretical analysis based on the crystal structure were performed to understand the nature of vibrations and band structure. Steady-state PL shows a narrow emission and a broad emission located at 409 and 487 nm, respectively. With temperature cooling down to 118 K, narrow emission gradually narrowed and enhanced. Meanwhile, intensity of broad emission first weakens and then increases. The turning point occurs near 198 K. By applying time-resolved PL (TRPL) and transient absorption (TA) spectra experiment, we observed a rapid carrier transfer from the FE to the STE state, and demonstrated the narrow and broad bands originate from free exciton and self-trapped exciton emission, respectively. And the self-trapping depth is proved to be 26.3 meV by low-temperature PL. Our findings indicate the synthesized 2D perovskite has potential applications in optoelectronic and display devices.

Regulation of the quantum barrier and carrier transport toward high-efficiency quasi-2D Dion-Jacobson tin perovskite solar cells

Quasi-2D Dion-Jacobson (DJ) tin halide perovskite has attracted much attention due to its elimination of Van der Waals gap and enhanced environmental stability. However, the bulky organic spacers usually form a natural quantum well structure, which brings a large quantum barrier and poor film quality, further limiting the carrier transport and device performance. Here, we designed three organic spacers with different chain lengths (ethylenediamine (EDA), 1,3-propanediamine (PDA), and 1,4-butanediamine (BDA)) to investigate the quantum barrier dependence. Theoretical and experimental characterizations indicate that EDA with short chain can reduce the lattice distortion and dielectric confinement effect, which is beneficial to the effective dissociation of excitons and the inhibition of trap-free non-radiative relaxation. In addition, EDA cation shows strong interaction with the inorganic octahedron, realizing large aggregates in precursor solution and high-quality films with improved structural stability. Furthermore, femtosecond transient absorption proves that EDA cations can also weaken the formation of small n-phases with large quantum barrier to achieve effective carrier transport between different n-phases. Finally, the quasi-2D DJ (EDA)FA9Sn10I31 solar cells achieves a 7.07% power conversion efficiency with good environment stability. Therefore, this work sheds light on the regulation of the quantum barrier and carrier transport through the chain length of organic spacer for quasi-2D DJ lead-free perovskites.

Direct Observation of Circularly Polarized Nonlinear Optical Activities in Chiral Hybrid Lead Halides.

Circularly polarized light emission is a crucial application in imaging, sensing, and photonics. However, utilizing low-energy photons to excite materials, as opposed to high-energy light excitation, can facilitate deep-tissue imaging and sensing applications. The challenge lies in finding materials capable of directly generating circularly polarized nonlinear optical effects. In this study, we introduce a chiral hybrid lead halide (CHLH) material system, R/S-DPEDPb3Br8·H2O (DPED = 1,2-diphenylethylenediammonium), which can directly produce circularly polarized second harmonic generation (CP-SHG) through linearly polarized infrared light excitation, exhibiting a polarization efficiency as high as 37% at room temperature. To understand the spin relaxation mechanisms behind the high polarization efficiency, we utilized two models, so-called D'yakonov-Perel' (DP) and Bir-Aronov-Pikus (BAP) mechanisms. The unique zigzag inorganic frameworks within the hybrid structure are believed to reduce the dielectric confinement and exciton binding energy, thus enhancing spin polarization, especially in regions with a high excitation pump fluence based on the DP mechanism. In the case of low excitation pump fluence, the BAP mechanism dominates, as evidenced by the observed decrease in the polarization ratio from CP-SHG measurement. Using density functional theory analysis, we elucidate how the distinctive 8-coordination environment of lead bromide building blocks effectively suppresses spin-orbit coupling at the conduction band minimum. This suppression significantly diminishes spin-splitting, thereby slowing the spin relaxation rate.

On the specific behavior of the work function and surface potential of an asymmetric metal-dielectric nanosandwich

We examine thin film on a dielectric substrate (vacuum/Al/SiO2) in the stabilized jellium model and the Kohn–Sham method. We investigate surface and size effects on the effective potential and the electron work function, and analyze the spatial distributions of electrons and potentials. It is found that a dielectric environment generally leads to a decrease in the work function. The effect of dielectric confinement for the electron work function of the asymmetric metal-dielectric nanosandwiches is reduced only by the surface area weighted average value of the dielectric constants. This conclusion follows from the application of the Gauss theorem for a conducting sphere with an inhomogeneous dielectric coating. The flow of electrons from the dielectric face to the vacuum one due to the contact potential difference manifests itself in the appearance of an additional dipole between the left and right face within the spatial distributions of ions. This leads to the fact that in a vacuum the electrostatic and effective potentials change sign twice, as a result of which a potential barrier appears above the vacuum level. We introduced the position of an electron conduction band in the dielectric as the input parameter in the self-consistency procedure for one of the sandwich approximations. As it turned out, the barrier height depends only on the used local or non-local approximation of the exchange-correlation energy. The nontrivial origin and behavior of the calculated effective potential on the vacuum side of the film, as well as the reasons for it, are discussed.

Tuning exciton dynamics by the dielectric confinement effect in quasi-two-dimensional perovskites

The dielectric confinement effect plays an essential role in optoelectronic devices. Existing studies on the relationship between the dielectric confinement and the photoelectric properties are inadequate. Herein, three organic spacers with different dielectric constants are employed to tune the exciton dynamics of quasi-two-dimensional (quasi-2D) Ruddlesden–Popper perovskite films. Femtosecond transient absorption spectroscopy reveals that the small dielectric constant ligand enables a weak dynamic disorder and a large modulation depth of the coherent phonons, resulting in a more complete energy transfer and the inhibition of a trap-mediated nonradiative recombination. Additionally, the increase in the bulk-ligand dielectric constant reduces the corresponding exciton binding energy and then suppresses the Auger recombination, which is beneficial for high-luminance light-emitting diodes. This work emphasizes the importance of dielectric confinement for regulating the exciton dynamics of layered perovskites.

Direct linearly polarized electroluminescence from perovskite nanoplatelet superlattices

Polarized light is critical for a wide range of applications, but is usually generated by filtering unpolarized light, which leads to substantial energy losses and requires additional optics. Here we demonstrate the direct emission of linearly polarized light from light-emitting diodes made of CsPbI3 perovskite nanoplatelet superlattices. The use of solvents with different vapour pressures enables the self-assembly of the nanoplatelets with fine control over their orientation (either face-up or edge-up) and therefore their transition dipole moment. As a result of the highly uniform alignment of the nanoplatelets, as well as their strong quantum and dielectric confinement, large exciton fine-structure splitting is achieved at the film level, leading to pure red light-emitting diodes with linearly polarized electroluminescence exhibiting a high degree of polarization of 74.4% without any photonic structures. This work demonstrates the potential of perovskite nanoplatelets as a promising source of linearly polarized light, opening up the development of next-generation three-dimensional displays and optical communications from a highly versatile, solution-processable system.

Development of Quasi-Two-Dimensional Perovskites and Their Application in Light-Emitting Diodes.

Quasi-two-dimensional (quasi-2D) perovskites have attracted much attention due to their outstanding properties, such as inherent quantum-well structure, strong dielectric and quantum confinement, large exciton binding energy, and high photoluminescence quantum yield. By virtue of these superior merits, quasi-2D perovskites have shown great potential for next-generation light-emitting diodes (LEDs). Herein, this review presents an overview of the basic properties of quasi-2D perovskites and their photoluminescence modulations by large organic cation engineering, monovalent cation engineering, halogen engineering, defect passivation engineering, and dimensionality engineering. Furthermore, the strategies of charge-transport layer optimization, interfacial engineering, light-outcoupling efficiency improvement, and operating stability improvement are summarized for fabricating high-performance quasi-2D perovskite LEDs (PeLEDs). Finally, the challenges and outlook for the future development of quasi-2D PeLEDs are unambiguously proposed.

Effect of Dielectric Confinement on Energetics of Quantum Metal Films: Analysis of Calculation Results

Effect of Dielectric Confinement on Energetics of Quantum Metal Films: Analysis of Calculation Results