Confined Quantum Dots Research Articles

Parity-independent Kondo effect of correlated electrons in electrostatically defined ZnO quantum dots

Quantum devices such as spin qubits have been extensively investigated in electrostatically confined quantum dots using high-quality semiconductor heterostructures like GaAs and Si. Here, we present a demonstration of electrostatically forming the quantum dots in ZnO heterostructures. Through the transport measurement, we uncover the distinctive signature of the Kondo effect independent of the even-odd electron number parity, which contrasts with the typical behavior of the Kondo effect in GaAs. By analyzing temperature and magnetic field dependences, we find that the absence of the even-odd parity in the Kondo effect is not straightforwardly interpreted by the considerations developed for conventional semiconductors. We propose that, based on the unique parameters of ZnO, electron correlation likely plays a fundamental role in this observation. Our study not only clarifies the physics of correlated electrons in the quantum dot but also holds promise for applications in quantum devices, leveraging the unique features of ZnO.

Vertical Electric-Field-Induced Switching from Strong to Asymmetric Strong-Weak Confinement in GaAs Cone-Shell Quantum Dots Using Transparent Al-Doped ZnO Gates.

The first part of this work evaluates Al-doped ZnO (AZO) as an optically transparent top-gate material for studies on semiconductor quantum dots. In comparison with conventional Ti gates, samples with AZO gates demonstrate a more than three times higher intensity in the quantum dot emission under comparable excitation conditions. On the other hand, charges inside a process-induced oxide layer at the interface to the semiconductor cause artifacts at gate voltages above U≈ 1 V. The second part describes an optical and simulation study of a vertical electric-field (F)-induced switching from a strong to an asymmetric strong-weak confinement in GaAs cone-shell quantum dots (CSQDs), where the charge carrier probability densities are localized on the surface of a cone. These experiments are performed at low U and show no indications of an influence of interface charges. For a large F, the measured radiative lifetimes are substantially shorter compared with simulation results. We attribute this discrepancy to an F-induced transformation of the shape of the hole probability density. In detail, an increasing F pushes the hole into the wing part of a CSQD, where it forms a quantum ring. Accordingly, the confinement of the hole is changed from strong, which is assumed in the simulations, to weak, where the local radius is larger than the bulk exciton Bohr radius. In contrast to the hole, an increasing F pushes the electron into the CSQD tip, where it remains in a strong confinement. This means the radiative lifetime for large F is given by an asymmetric confinement with a strongly confined electron and a hole in a weak confinement. To our knowledge, this asymmetric strong-weak confinement represents a novel kind of quantum mechanical confinement and has not been observed so far. Furthermore, the observed weak confinement for the hole represents a confirmation of the theoretically predicted transformation of the hole probability density from a quantum dot into a quantum ring. For such quantum rings, application as storage for photo-excited charge carriers is predicted, which can be interesting for future quantum photonic integrated circuits.

Thermal transport in metal halide perovskites and other third-generation photovoltaic materials

Third-generation photovoltaic materials, including metal halide perovskites (MHPs), colloidal quantum dots (QDs), copper zinc tin sulfide (CZTS), and organic semiconductors, among others, have become attractive in the past two decades. Unlike their first- and second-generation counterparts, these advanced materials boast properties beyond mere photovoltaic performance, such as mechanical flexibility, light weight, and cost-effectiveness. Meanwhile, these materials possess more intricate crystalline structures that aid in understanding and predicting their transport properties. In particular, the distinctive phonon dispersions in MHPs, the layered architecture in quasi-two-dimensional (2D) perovskites, the strong quantum confinement in QDs, and the complex crystal structures interspersed with abundant disorders in quaternary CZTS result in unique and sometimes anomalous thermal transport behaviors. Concurrently, the criticality of thermal management in applications such as photovoltaics, thermoelectrics, light emitting diodes, and photodetection devices has received increased recognition, considering that many of these third-generation photovoltaic materials are not good thermal conductors. Effective thermal management necessitates precise measurement, advanced modeling, and a profound understanding and interpretation of thermal transport properties in these novel materials. In this review, we provide a comprehensive summary of various techniques for measuring thermal transport properties of these materials and discuss the ultralow thermal conductivities of three-dimensional (3D) MHPs, superlattice-like thermal transport in 2D perovskites, and novel thermal transport characteristics inherent in QDs and CZTS. By collecting and comparing the literature-reported results, we offer a thorough discussion on the thermal transport phenomenon in these materials. The collective understanding from the literature in this area, as reviewed in this article, can provide guidance for improving thermal management across a wide spectrum of applications extending beyond photovoltaics.

A theoretical exploration of the electronic structure and single photoionization of the many-electron system confined in Gaussian potential

This manuscript investigates the electronic structures, spectral properties, and photoionization processes of the confined atomic system. For this purpose, a relativistic methodology employing the Dirac–Coulomb Hamiltonian within the context of relativistic configuration interaction is suggested, utilizing independent particle basis wavefunctions. The key idea of this approach is to place the atom inside a Gaussian potential, which gives a realistic description of the spatial confinement in quantum dots due to a smooth change at the quantum dot boundaries and has a finite range and depth for the spatial confinement. As a result, the local central potential is modified, which is determined by a self-consistent process. The solutions to the Dirac equation, incorporating the aforementioned central potential, yield both the continuous and bound state wave functions. The photoionization process is determined through the application of the distorted wave approach within the context of relativistic Dirac theory. As an application, the electronic structures of the confined Li atom, including energies, ionization potentials, transition rates, and photoionization dynamical properties such as wave functions, cross sections, and photoelectron angular distributions, are systematically investigated within the dipole approximation for a wide range of potential depths and confining radii. A systematic comparison of the present outcomes is made with other available results. The present study is not only meaningful for fundamental research in atomic and molecular physics, but also has implications for a range of disciplines, such as nanochemistry, materials science, and other related fields.

Correlation of Thermo-Magnetic Properties of Non-Interacting Two-Electron Parabolic Confined Quantum Dots under External Parameters

Correlation of Thermo-Magnetic Properties of Non-Interacting Two-Electron Parabolic Confined Quantum Dots under External Parameters

Interfacial negative biexcitons in a monolayer WS2/InGaN quantum dots heterostructure

In this work, we fabricated a Van der Waals heterostructure of monolayer (ML) WS2 and InGaN quantum dots (QDs). This heterostructure is divided into coupled and uncoupled regions based on the thickness of the inserted hBN layer. Upon measuring its PL spectra, we identified an interfacial negative biexciton, which consists of a trion in ML WS2 and an exciton in QDs, in the coupled region. This interfacial negative biexciton features the negative charge of the trion and the quantum confinement of QDs, with its relative intensity showing a strong dependence on the excitation photon energy and featuring a significant threshold. Our work highlights the effective coupling within the mixed-dimensional heterostructure, offering new prospects for the study of many-body physics.

A comparative study of broadband PbS quantum dots/graphene photodetectors with monolayer and bilayer graphene

Colloidal quantum dots (QDs)/graphene nanohybrids provide a unique platform to design photodetectors of high performance. These photodetectors are quantum sensors due to the strong quantum confinement in QDs for spectral tunability, and in graphene for high charge mobility. Quantitatively, the high carrier mobility of graphene plays a critical role to enable high photoconductive gain and understanding its impact on the photodetector performance is imperative. Herein, we report a comparative study of PbS QDs/graphene nanohybrids with monolayer and bilayer graphene for broadband photodetection ranging from ultraviolet, visible, near-infrared to short-wave infrared spectra (wavelength: 400 nm–1750 nm) to determine if a specific advantage exists for one over the other. This study has revealed that both the monolayer and bilayer graphene grown in chemical vapor deposition can provide a highly efficient charge transfer channel for photo-generated carriers for high broadband photoresponse.

Confinement of excited states in two-dimensional, in-plane, quantum heterostructures

Two-dimensional (2D) semiconductors are promising candidates for optoelectronic application and quantum information processes due to their inherent out-of-plane 2D confinement. In addition, they offer the possibility of achieving low-dimensional in-plane exciton confinement, similar to zero-dimensional quantum dots, with intriguing optical and electronic properties via strain or composition engineering. However, realizing such laterally confined 2D monolayers and systematically controlling size-dependent optical properties remain significant challenges. Here, we report the observation of lateral confinement of excitons in epitaxially grown in-plane MoSe2 quantum dots (~15-60 nm wide) inside a continuous matrix of WSe2 monolayer film via a sequential epitaxial growth process. Various optical spectroscopy techniques reveal the size-dependent exciton confinement in the MoSe2 monolayer quantum dots with exciton blue shift (12-40 meV) at a low temperature as compared to continuous monolayer MoSe2. Finally, single-photon emission (g2(0) ~ 0.4) was also observed from the smallest dots at 1.6 K. Our study opens the door to compositionally engineered, tunable, in-plane quantum light sources in 2D semiconductors.

Host-Guest Interaction Mediated Perovskite@Metal-Organic Framework Z-Scheme Heterojunction Enabled Paper-Based Photoelectrochemical Sensing.

Exploring the high-performance photoelectronic properties of perovskite quantum dots (QDs) is desirable for paper-based photoelectrochemical (PEC) sensing;however, challenges remain in improving their stability and fundamental performance. Herein, a novel Z-scheme heterostructure with host-guest interaction by the confinement of CH3NH3PbBr3 QDs within Cu3(BTC)2 metal-organic framework (MOF) crystal (MAPbBr3@Cu3(BTC)2) is successfully constructed on the paper-based PEC device for ultrasensitive detection of Ochratoxin A (OTA), with the assistance of the exciton-plasmon interaction (EPI) effect. The host-guest interaction is estabilished by encapsulating MAPbBr3 QDs as guests within Cu3(BTC)2 MOF as a host, which prevents MAPbBr3 QDs from being damaged in the polar system, offering access to long-term stability with high-performance PEC properties. Benefiting from the precise alignment of energy levels, the photogenerated charge carriers can migrate according to the Z-scheme charge-transfer pathway under the driving force of the internal electric field, achieving a high photoelectric conversion efficiency. Upon OTA recognition, the EPI effect is activated to modulate the exciton response in MAPbBr3 QDs by accelerating radiative decay, finally achieving sensitive OTA sensing with a detection limit of 0.017 pg mL-1. We believe this work renders new insight into designing host-guest Z-scheme heterojunctions in constructing the paper-based PEC sensing platforms for environmental monitoring.

InGaAs quantum dot chains grown by twofold selective area molecular beam epitaxy

Increasing quantum confinement in semiconductor quantum dot (QD) systems is essential to perform robust simulations of many-body physics. By combining molecular beam epitaxy and lithographic techniques, we developed an approach consisting of a twofold selective area growth to build QD chains. Starting from 15 nm-thick and 65 nm-wide in-plane In0.53Ga0.47As nanowires on InP substrates, linear arrays of In0.53Ga0.47As QDs were grown on top, with tunable lengths and separations. Kelvin probe force microscopy performed at room temperature revealed a change of quantum confinement in chains with decreasing QD sizes, which was further emphasized by the spectral shift of quantum levels resolved in the conduction band with low temperature scanning tunneling spectroscopy. This approach, which allows the controlled formation of 25 nm-thick QDs with a minimum length and separation of 30 nm and 22 nm respectively, is suitable for the construction of scalable fermionic quantum lattices.

Slow Hot-Exciton Cooling and Enhanced Interparticle Excitonic Coupling in HgTe Quantum Dots.

Rapid hot-carrier/exciton cooling constitutes a major loss channel for photovoltaic efficiency. How to decelerate the hot-carrier/exciton relaxation remains a crux for achieving high-performance photovoltaic devices. Here, we demonstrate slow hot-exciton cooling that can be extended to hundreds of picoseconds in colloidal HgTe quantum dots (QDs). The energy loss rate is 1 order of magnitude smaller than bulk inorganic semiconductors, mediated by phonon bottleneck and interband biexciton Auger recombination (BAR) effects, which are both augmented at reduced QD sizes. The two effects are competitive with the emergence of multiple exciton generation. Intriguingly, BAR dominates even under low excitation fluences with a decrease in interparticle distance. Both experimental evidence and numerical evidence reveal that such efficient BAR derives from the tunneling-mediated interparticle excitonic coupling induced by wave function overlap between neighboring HgTe QDs in films. Thus, our study unveils the potential for realizing efficient hot-carrier/exciton solar cells based on HgTe QDs. Fundamentally, we reveal that the delocalized nature of quantum-confined wave function intensifies BAR. The interparticle excitonic coupling may cast light on the development of next-generation photoelectronic materials, which can retain the size-tunable confinement of colloidal semiconductor QDs while simultaneously maintaining high mobilities and conductivities typical for bulk semiconductor materials.

3D‐cavity‐confined CsPbBr3 quantum dots for visible‐light‐driven photocatalytic C(sp3)–H bond activation

AbstractMetal halide perovskite (MHP) quantum dots (QDs) offer immense potential for several areas of photonics research due to their easy and low‐cost fabrication and excellent optoelectronic properties. However, practical applications of MHP QDs are limited by their poor stability and, in particular, their tendency to aggregate. Here, we develop a two‐step double‐solvent strategy to grow and confine CsPbBr3 QDs within the three‐dimensional (3D) cavities of a mesoporous SBA‐16 silica scaffold (CsPbBr3@SBA‐16). Strong confinement and separation of the MHP QDs lead to a relatively uniform size distribution, narrow luminescence, and good ambient stability over 2 months. In addition, the CsPbBr3@SBA‐16 presents a high activity and stability for visible‐light‐driven photocatalytic toluene C(sp3)–H bond activation to produce benzaldehyde with ∼730 µmol g−1 h−1 yield rate and near‐unity selectivity. Similarly, the structural stability of CsPbBr3@SBA‐16 QDs is superior to that of both pure CsPbBr3 QDs and those confined in MCM‐41 with 1D channels.

Thresholds and Delimitations of Quantum Confinement in Spherical Gallium Nitride and Gallium Arsenide Quantum Dots

Thresholds and Delimitations of Quantum Confinement in Spherical Gallium Nitride and Gallium Arsenide Quantum Dots

High-Efficiency Pure-Red CsPbI3 Quantum Dot Light-Emitting Diodes Enabled by Strongly Electrostatic Potential Solvent and Sequential Ligand Post-treatment Process.

Efficient pure-red emission light-emitting diodes (LEDs) are essential for high-definition displays, yet achieving pure-red emission is hindered by challenges like phase segregation and spectral instability when using halide mixing. Additionally, strongly confined quantum dots (QDs) produced through traditional hot-injection methods face byproduct contamination due to poor solubility of metal halide salts in the solvent octadecene (ODE) at low temperatures. Herein, we introduced a novel method using a benzene-series strongly electrostatic potential solvent instead of ODE to prevent PbI2 intermediates and promote their dissolution into [PbI3]-. Increasing methyl groups on benzene yields precisely sized (4.4 ± 0.1 nm) CsPbI3 QDs with exceptional properties: a narrow 630 nm PL peak with photoluminescence quantum yield (PLQY) of 97%. Sequential ligand post-treatment optimizes optical and electrical performance of QDs. PeLEDs based on optimized QDs achieve pure-red EL (CIE: 0.700, 0.290) approaching Rec. 2020 standards, with an EQE of 25.2% and T50 of 120 min at initial luminance of 107 cd/m2.

Pixel Geometry Effect on PbS Quantum Dot/Graphene Nanohybrid Broadband Photodetectors

AbstractPhotodetectors based on colloidal quantum dots (QD)/graphene nanohybrids are quantum sensors due to strong quantum confinement in both QD and graphene. The optoelectronic properties of QD/graphene nanohybrids are affected by the quantum physics that predicts a high photoconductive gain and hence photoresponsivity (R*) depending on the pixel length (L) as R*∝L−2. Experimental confirmation of the effect of the pixel geometric parameters on the optoelectronic properties of the QD/graphene photodetector is therefore important to elucidate the underlying quantum physics. Motivated by this, an array of PbS QDs/graphene nanohybrid photodetectors are designed with variable QD/graphene pixel length L and width (W) in the range of 10–150 µm for a study of R*, noise, and specific detectivity (D*) in a broad spectrum of 400–1500 nm. Intriguingly, R* exhibits a monotonic decreasing trend of 1/L2 while being independent of W, confirming experimentally the theoretical prediction. Interestingly, this geometric effect on the photoresponsivity seems to be partially compensated by that in noise, leading to D* independent of L and W at wavelengths in the ultraviolet‐visible‐near infrared range. This result sheds light on the quantum physics underlying the optoelectronic process in QD/graphene nanohybrids, which is important to the design of high‐quality QD/graphene photodetectors and imaging systems.

Optical gain and entanglement through dielectric confinement and electric field in InP quantum dots.

Quantum dots are widely recognized for their advantageous light-emitting properties. Their excitonic fine structure along with the high quantum yields offers a wide range of possibilities for technological applications. However, especially for the case of colloidal QDs, there are still characteristics and properties which are not adequately controlled and downgrade their performance for applications which go far beyond the simple light emission. Such a challenging task is the ability to manipulate the energetic ordering of exciton and biexciton emission and subsequently control phenomena such as Auger recombination, optical gain and photon entanglement. In the present work we attempt to engineer this ordering for the case of InP QDs embedded in polymer matrix, by means of their size, the dielectric confinement and external electric fields. We employ well tested, state of the art theoretical methods, in order to explore the conditions under which the exciton-biexciton configuration creates the desired conditions either for optical gain or photon entanglement. Indeed, this appears to be feasible for QDs with small diameters (1 nm, 1.5 nm) embedded in a host material with high dielectric constant and additional external electric fields. These findings offer a new design principle which might be complementary to the well-established type II core-shell QDs approach for achieving electron-hole separation.

Hot Excitons Cool in Metal Halide Perovskite Nanocrystals as Fast as CdSe Nanocrystals.

The idea of phonon bottlenecks has long been pursued in nanoscale materials for their application in hot exciton devices, such as photovoltaics. Decades ago, it was shown that there is no quantum phonon bottleneck in strongly confined quantum dots due to their physics of quantum confinement. More recently, it was proposed that there are hot phonon bottlenecks in metal halide perovskites due to their physics. Recent work has called into question these bottlenecks in metal halide perovskites. Here, we compare hot exciton cooling in a range of sizes of CsPbBr3 nanocrystals from weakly to strongly confined. These results are compared to strongly confined CdSe quantum dots of two sizes and degrees of quantum confinement. CdSe is a model system as a ruler for measuring hot exciton cooling being fast, by virtue of its efficient Auger-assisted processes. By virtue of 3 ps time resolution, the hot exciton photoluminescence can now be directly observed, which is the most direct measure of the presence of hot excitons and their lifetimes. The hot exciton photoluminescence decays on nearly the same 2 ps time scale on both the weakly confined perovskite and the larger CdSe quantum dots, much faster than the 10 ps cooling predicted by transient absorption experiments. The smaller CdSe quantum dot has still faster cooling, as expected from quantum size effects. The quantum dots of perovskites show extremely fast hot exciton cooling, decaying faster than detection limits of <1 ps, even faster than the CdSe system, suggesting the efficiency of Auger processes in these metal halide perovskite nanocrystals and especially in their quantum dot form. These results across a range of sizes of nanocrystals reveal extremely fast hot exciton cooling at high exciton density, independent of composition, but dependent upon size. Hence these metal halide perovskite nanocrystals seem to cool heavily following quantum dot physics.

Enhancing Multiexcitonic Emission in Metal-Halide Perovskites by Quantum Confinement.

Semiconductor metal halide perovskite nanocrystals have been under intense investigation for their promise in a variety of optoelectronic applications, which arises from their remarkable properties of defect tolerance and efficient light emission. Recently, quantum dot versions of perovskite nanocrystals have been available, enabling investigation of how quantum size effects control optical function and performance in these quantum dots (QD), past their well-known covalent II-VI analogues. We perform time-resolved photoluminescence (t-PL) experiments on CsPbBr3 perovskite nanocrystals spanning in diameter from 5.8 nm strongly confined quantum dots to 18 nm weakly confined quantum dots. Experiments are performed with sufficient time resolution of 3 ps to observe the interaction energies and recombination kinetics from excitons to multiexcitons. Comparing the same sized QD reveals that perovskite QD have a larger radiative rate constant for emission from X than CdSe QD due to a larger oscillator strength. The multiexciton (MX) regime reveals that perovskite QD emit brightly and with more focused bandwidth than equivalent sized CdSe QD enabling more spectrally pure brightness. The MX kinetics reveals that the perovskite QD maintain efficient radiative decay, effectively competing with Auger recombination. These experiments reveal that the strongly confined QD of perovskites can be efficient multiexcitonic emitters, such as in high brightness light emitting diodes, especially in the blue.

Tuning Confined States and Valley G‐Factors by Quantum Dot Design in Bilayer Graphene

Electrostatically confined quantum dots in bilayer graphene have shown potential as building blocks for quantum technologies. To operate the dots, e.g., as qubits, a precise understanding and control of the confined states and their properties is required. Herein, a large‐scale numerical characterization of confined quantum states in bilayer graphene dots is performed over an extensive range of gate‐tunable parameters such as the dot size, depth, shape, and the bilayer graphene gap. The dot states’ orbital degeneracy, wave function distribution, and valley g‐factor are established and the parametric dependencies to achieve different regimes are provided. It is found that the dot states are highly susceptible to gate‐dependent confinement and material parameters, enabling efficient tuning of confined states and valley g‐factor modulation by quantum dot design.

Tunable p–n junction barriers in few-electron bilayer graphene quantum dots

Graphene quantum dots provide promising platforms for hosting spin, valley, or spin-valley qubits. Taking advantage of their electrically generated bandgap and their ambipolar nature, high-quality quantum dots can be defined in bilayer graphene using natural p–n junctions as tunnel barriers. In these devices, demonstrating the electrical tunability of the p–n junction barriers and understanding its physical mechanism, especially in the few-electron regime, are essential for further manipulating electrons' quantum degrees of freedom to encode qubits. Here, we show the electrostatic confinement of single quantum dots in bilayer graphene using natural p–n junctions. When the device is operated in the few-electron regime, the electron tunneling rate is found to be monotonically tuned by varying gate voltages, which can be well understood from the view of manipulating the p–n junction barriers. Our results provide an insightful understanding of electrostatic confinement using natural p–n junctions in bilayer graphene, which is beneficial for realizing graphene-based qubits.