Quantum-confined Semiconductor Research Articles

(Invited) Electronic Doping in Two-Dimensional Semiconductors

Quantum-confined semiconductors provide highly tunable optical and electrical properties for a wide variety of emerging applications. Two-dimensional semiconductors possess tunable bandgaps, high charge carrier mobilities, and strong light-matter interactions that can enable applications in photovoltaics, quantum information processing, and spintronics. Electronic doping, the intentional introduction of controlled charge carrier density and type (electrons or holes) is a fundamental enabler for many emerging applications of two-dimensional semiconductors. While electrostatic doping in transistor geometries is useful for certain applications, it is important to develop additional methods based on e.g. molecular redox doping and substitutional atomic doping that can provide tunable Fermi level control in the absence of an applied bias. In this presentation, I will discuss our efforts to develop such doping strategies for a variety of two-dimensional semiconductors. I will discuss how electronic doping modulates opto-electronic properties, including ground-state absorbance, charge transport, and excited-state dynamics in these 2D semiconductors. These studies provide fundamental insights into the degree to which molecular and substitutional doping strategies can modulate Fermi level, charge transport, and excitonic optical transitions in 2D semiconductors.

(Invited) Exciton Dissociation in Mixed-Dimensionality SWCNT-Based Heterojunctions

Quantum-confined semiconductors provide highly tunable optical and electrical properties for a wide variety of emerging applications. Semiconducting single-walled carbon nanotubes (s-SWCNTs) have shown tremendous potential in applications ranging from digital logic, biological imaging, quantum information processing, photovoltaics, and thermoelectric energy harvesting. Energy harvesting applications rely critically upon the creation of tailored interfaces that enable the movement of energetic species (excitons, electrons, holes) in specified directions. In this talk, I will discuss the use of a variety of rationally designed “mixed-dimensionality” heterojunctions between s-SWCNTs and transition metal dichalcogenide (TMDC) monolayers to harvest visible/near-infrared photons and convert these excitations into long-lived charge-separated states. Type-II heterojunctions between s-SWCNTs and TMDCs enable rapid exciton dissociation and microsecond charge-separated state lifetimes. We have developed new TMDC/SWCNT/TMDC trilayer architectures that enable charge transfer cascades for improving charge separation yield and lifetime. These trilayer architectures allow us to probe out-of-plane carrier diffusion in the nanotube layer and the degree to which bound interfacial excitons impact the photophysics in these mixed-dimensionality heterostructures. I will also discuss the methodology by which we attempt to quantify the photoinduced exciton dissociation quantum yields in these nanoscale heterostructures. Using several heterostructure results, we are attempting to narrow in on appropriate ways to quantify the local dielectric constant and exciton size in both the SWCNT and TMDC components, each of which impact the estimated charge carrier yields. Taken together, these studies provide fundamental insights into the links between ground-state thermodynamics and excited-state dynamics for model nanoscale heterojunctions used to harvest solar energy and produce long-lived charge-separated states.

Measuring the Electronic Bandgap of Carbon Nanotube Networks in Non-Ideal p-n Diodes.

The measurement of the electronic bandgap and exciton binding energy in quasi-one-dimensional materials such as carbon nanotubes is challenging due to many-body effects and strong electron-electron interactions. Unlike bulk semiconductors, where the electronic bandgap is well known, the optical resonance in low-dimensional semiconductors is dominated by excitons, making their electronic bandgap more difficult to measure. In this work, we measure the electronic bandgap of networks of polymer-wrapped semiconducting single-walled carbon nanotubes (s-SWCNTs) using non-ideal p-n diodes. We show that our s-SWCNT networks have a short minority carrier lifetime due to the presence of interface trap states, making the diodes non-ideal. We use the generation and recombination leakage currents from these non-ideal diodes to measure the electronic bandgap and excitonic levels of different polymer-wrapped s-SWCNTs with varying diameters: arc discharge (~1.55 nm), (7,5) (0.83 nm), and (6,5) (0.76 nm). Our values are consistent with theoretical predictions, providing insight into the fundamental properties of networks of s-SWCNTs. The techniques outlined here demonstrate a robust strategy that can be applied to measuring the electronic bandgaps and exciton binding energies of a broad variety of nanoscale and quantum-confined semiconductors, including the most modern nanoscale transistors that rely on nanowire geometries.

Charge Transfer from Quantum-Confined 0D, 1D, and 2D Nanocrystals.

The properties of colloidal quantum-confined semiconductor nanocrystals (NCs), including zero-dimensional (0D) quantum dots, 1D nanorods, 2D nanoplatelets, and their heterostructures, can be tuned through their size, dimensionality, and material composition. In their photovoltaic and photocatalytic applications, a key step is to generate spatially separated and long-lived electrons and holes by interfacial charge transfer. These charge transfer properties have been extensively studied recently, which is the subject of this Review. The Review starts with a summary of the electronic structure and optical properties of 0D-2D nanocrystals, followed by the advances in wave function engineering, a novel way to control the spatial distribution of electrons and holes, through their size, dimension, and composition. It discusses the dependence of NC charge transfer on various parameters and the development of the Auger-assisted charge transfer model. Recent advances in understanding multiple exciton generation, decay, and dissociation are also discussed, with an emphasis on multiple carrier transfer. Finally, the applications of nanocrystal-based systems for photocatalysis are reviewed, focusing on the photodriven charge separation and recombination processes that dictate the function and performance of these materials. The Review ends with a summary and outlook of key remaining challenges and promising future directions in the field.

Recent advances of colloidal quantum dots in a physical perspective

In quantum-confined semiconductor nanostructures, electrons show unique behaviors compared to bulk solids, which endows materials with tunable physicochemical and photoelectric properties. Zero-dimensional semiconductor quantum dots (QDs) provide intense light absorption and strong narrowband emission at visible and infrared bands, and have been employed to exhibit optical gain and lasing. These properties are beneficial for different application. Here, we provide a review in the synthesis and understanding of unique properties of colloidal QDs, and discuss their applications in display, lasers, sensing and solar energy conversion.

Physical origins of optical anisotropy in quantum-confined semiconductors: The roles of valence band mixing, transition broadening, and state filling

We investigate experimentally and theoretically the impact of valence band mixing and spectrum of confined states on the polarization of light emitted from or absorbed by GaAs/AlGaAs semiconductor quantum dots and quantum wires with tailored heterostructure potential. In particular, such nanostructures with parabolic-profile confinement potentials, realized by organometallic vapor phase epitaxy inside pyramidal pits, served as model systems for the study. Different degrees of linear polarization (DOLP) of emitted light, depending on the confinement potential profile, the specific excitonic transition, and the level of excitation, are observed. A theoretical model shows that, besides the impact of valence band mixing, the overlap of conduction and valence band wavefunctions as well as state occupation probability and broadening of transitions determine the DOLP. The conclusions are useful for the design of quantum light emitters with controlled polarization properties.

Mesoscale Quantum-Confined Semiconductor Nanoplatelets through Seeded Growth

Mesoscale Quantum-Confined Semiconductor Nanoplatelets through Seeded Growth

The Fine-Structure Constant as a Ruler for the Band-Edge Light Absorption Strength of Bulk and Quantum-Confined Semiconductors.

Low-dimensional semiconductors have found numerous applications in optoelectronics. However, a quantitative comparison of the absorption strength of low-dimensional versus bulk semiconductors has remained elusive. Here, we report generality in the band-edge light absorptance of semiconductors, independent of their dimensions. First, we provide atomistic tight-binding calculations that show that the absorptance of semiconductor quantum wells equals mπα (m = 1 or 2 with α as the fine-structure constant), in agreement with reported experimental results. Then, we show experimentally that a monolayer (superlattice) of quantum dots has similar absorptance, suggesting an absorptance quantum of mπα per (confined) exciton diameter. Extending this idea to bulk semiconductors, we experimentally demonstrate that an absorptance quantum equal to mπα per exciton Bohr diameter explains their widely varying absorption coefficients. We thus provided compelling evidence that the absorptance quantum πα per exciton diameter rules the band-edge absorption of all direct semiconductors, regardless of their dimension.

Marcus inverted region of charge transfer from low-dimensional semiconductor materials

A key process underlying the application of low-dimensional, quantum-confined semiconductors in energy conversion is charge transfer from these materials, which, however, has not been fully understood yet. Extensive studies of charge transfer from colloidal quantum dots reported rates increasing monotonically with driving forces, never displaying an inverted region predicted by the Marcus theory. The inverted region is likely bypassed by an Auger-like process whereby the excessive driving force is used to excite another Coulomb-coupled charge. Herein, instead of measuring charge transfer from excitonic states (coupled electron-hole pairs), we build a unique model system using zero-dimensional quantum dots or two-dimensional nanoplatelets and surface-adsorbed molecules that allows for measuring charge transfer from transiently-populated, single-charge states. The Marcus inverted region is clearly revealed in these systems. Thus, charge transfer from excitonic and single-charge states follows the Auger-assisted and conventional Marcus charge transfer models, respectively. This knowledge should enable rational design of energetics for efficient charge extraction from low-dimensional semiconductor materials as well as suppression of the associated energy-wasting charge recombination.

Prospects and challenges of colloidal quantum dot laser diodes

Colloidal quantum dots (QDs) combine the superior light-emission characteristics of quantum-confined semiconductors with the chemical flexibility of molecular systems. These properties could, in principle, enable solution-processable laser diodes with an ultrawide range of accessible colours. However, the realization of such devices has been hampered by fast optical gain decay due to non-radiative Auger recombination and poor stability of QD solids at the high current densities required for the lasing regime. Recently, these problems have been resolved, which resulted in the development of electrically pumped optical gain devices operating at ultrahigh current densities of around 1,000 A cm−2. The next step is the realization of a QD laser diode (QLD). Here we assess the status of the QD lasing field, examine the remaining challenges on the path to a QLD and discuss practical strategies for attaining electrically pumped QD lasing. Colloidal quantum dots may offer solution-processable lasers, with a wide range of colours available. Technical hurdles and progress towards realization of useful quantum dot laser diodes is reviewed.

Semiconductor quantum dots: Technological progress and future challenges.

In quantum-confined semiconductor nanostructures, electrons exhibit distinctive behavior compared with that in bulk solids. This enables the design of materials with tunable chemical, physical, electrical, and optical properties. Zero-dimensional semiconductor quantum dots (QDs) offer strong light absorption and bright narrowband emission across the visible and infrared wavelengths and have been engineered to exhibit optical gain and lasing. These properties are of interest for imaging, solar energy harvesting, displays, and communications. Here, we offer an overview of advances in the synthesis and understanding of QD nanomaterials, with a focus on colloidal QDs, and discuss their prospects in technologies such as displays and lighting, lasers, sensing, electronics, solar energy conversion, photocatalysis, and quantum information.

Ultra-Confined Visible-Light-Emitting Colloidal Indium Arsenide Quantum Dots.

Indium arsenide quantum dots, which typically emit in the near-infrared, have been utilized in various optoelectronics and biomedical applications, such as covert illumination, optical communication, and deep-tissue imaging. While theory predicts that further quantum confinement through size reduction could enable visible light emission, systems with larger optical bandgaps have not been realized. Here, we report a method of preparing highly luminescent, visible-light-emitting In(Zn)As/ZnSe/ZnS QD, using a low-temperature nanocluster synthesis approach. Each QD contains an ultraconfined In(Zn)As nanocluster and fluoresces at tunable wavelengths between 538 and 640 nm with a high photoluminescence quantum efficiency of 58%. We confirm, through DFT and spectroscopic analysis, that the strong confinement effects in the few-atom-wide In(Zn)As nanoclusters are responsible for the significant spectral shift from the near-infrared to the visible region. These findings suggest that broader-than-expected optical tuning may now be achievable in other quantum-confined semiconductor systems, which could lead to a wider scope of functional applications in optoelectronics.

Highly uniform GaSb quantum dots with indirect–direct bandgap crossover at telecom range

We demonstrate a new quantum-confined semiconductor material based on GaSb quantum dots (QDs) embedded in a single-crystalline AlGaSb matrix by filling droplet-etched nanoholes. The droplet-mediated growth mechanism allows formation of low QD densities required for non-classical single-QD light sources. The photoluminescence (PL) experiments reveal that the GaSb QDs have an indirect–direct bandgap crossover at telecom wavelengths. This is due to the alignment of the Γ and L valleys in the conduction band as a result of the quantum confinement controlled by the dimensions of the nanostructure. We show that in the direct bandgap regime close to 1.5 µm wavelength, the GaSb QDs have a type I band alignment and exhibit excitonic emission with narrow spectral lines and very low inhomogeneous broadening of PL emission owing to the high material quality and dimensional uniformity. These properties are extremely promising in terms of applications in infrared quantum optics and quantum photonic integration.

Spin blockade and phonon bottleneck for hot electron relaxation observed in n-doped colloidal quantum dots

Understanding and manipulating hot electron dynamics in semiconductors may enable disruptive energy conversion schemes. Hot electrons in bulk semiconductors usually relax via electron-phonon scattering on a sub-picosecond timescale. Quantum-confined semiconductors such as quantum dots offer a unique platform to prolong hot electron lifetime through their size-tunable electronic structures. Here, we study hot electron relaxation in electron-doped (n-doped) colloidal CdSe quantum dots. For lightly-doped dots we observe a slow 1Pe hot electron relaxation (~10 picosecond) resulting from a Pauli spin blockade of the preoccupying 1Se electron. For heavily-doped dots, a large number of electrons residing in the surface states introduce picosecond Auger recombination which annihilates the valance band hole, allowing us to observe 300-picosecond-long hot electrons as a manifestation of a phonon bottleneck effect. This brings the hot electron energy loss rate to a level of sub-meV per picosecond from a usual level of 1 eV per picosecond. These results offer exciting opportunities of hot electron harvesting by exploiting carrier-carrier, carrier-phonon and spin-spin interactions in doped quantum dots.

Charge and energy transfer in the context of colloidal nanocrystals

As the number of hybrid systems comprising quantum-confined semiconductor nanocrystals and molecules continues to grow, so does the need to accurately describe interfacial energy and charge transfer in these systems. The earliest work often successfully captured at least qualitative trends in the rates of these processes using well-known results from Forster, Dexter, and Marcus theories, but recent studies have showcased how unique properties of nanocrystals drive interfacial energy transfer (EnT) and charge transfer (CT) to diverge from familiar trends. This review first describes how the nanocrystal-ligand system fits, at least superficially, into conventional models for EnT and CT, and then gradually introduces individual properties of nanocrystals that complicate our understanding of EnT and CT mechanisms. The review then explores instances in which features of nanocrystals that seem detrimental, such as trap states that introduce non-radiative recombination pathways and strong spin–orbit coupling, can be controlled or used synergistically to produce a wider range of functionality than available in all-molecular donor-acceptor systems.

Thermodynamic Control in the Synthesis of Quantum-Confined Blue-Emitting CsPbBr3 Perovskite Nanostrips.

Size control is critical in the synthesis of quantum-confined semiconductor nanocrystals, otherwise known as quantum dots. The achievement of size-uniformity and narrow spectral line-width in quantum dots conventionally relies on a very precise kinetic control of the reactions, where reaction time plays a significant role in defining the final crystal sizes and distribution. Here, we show that synthesis of quantum-confined perovskite nanostrips could be achieved through a thermodynamically controlled reaction, using a low-temperature and ligand-rich approach. The nanostrip growth proceeds through an initial one-dimensional (1D) nanorod stage, followed by the lateral widening of the rod to form a two-dimensional (2D) nanostrip. The spectral characteristics of the final product remain unchanged after prolonged reaction, indicating no signs of crystal ripening and confirming the thermodynamic nature of this reaction. The CsPbBr3 perovskite nanostrips were highly uniform and emit at a deep-blue wavelength of 462 nm with a remarkably narrow line-width of 13 nm. This corresponds to color coordinates of (0.136, 0.049) on the CIE 1931 color space, which fulfils the stringent Rec. 2020 standard for next-generation color displays. The well-passivated nanostrips also possess negligible defects and provide a near-unity photoluminescence quantum yield at 94%. Crucially, the achievement of blue emission through a pure-halide perovskite circumvents the problems of spectral instability that are frequently experienced in mixed-halide perovskite systems. The convenience and scalability of our thermodynamic approach, coupled with the excellent optical attributes, would likely enable these quantum-confined perovskite systems to be the preferred method toward color control in trichromatic display applications.

Synthesis and characterization of graphene quantum dots

AbstractConventional inorganic semiconductor quantum dots (QDs) have numerous applications ranging from energy harvesting to optoelectronic and bio-sensing devices primarily due to their unique size and shape tunable band-gap and also surface functionalization capability and consequently, have received significant interest in the last few decades. However, the high market cost of these QDs, on the order of thousands of USD/g and toxicity limit their practical utility in many industrial applications. In this context, graphene quantum dot (GQD), a nanocarbon material and a new entrant in the quantum-confined semiconductors could be a promising alternative to the conventional toxic QDs due to its potential tunability in optical and electronic properties and film processing capability for realizing many of the applications. Variation in optical as well as electronic properties as a function of size, shape, doping and functionalization would be discussed with relevant theoretical backgrounds along with available experimental results and limitations. The review deals with various methods available so far towards the synthesis of GQDs along with special emphasis on characterization techniques starting from spectroscopic, optical and microscopic techniques along with their the working principles, and advantages and limitations. Finally, we will comment on the environmental impact and toxicity limitations of these GQDs and their hybrid nanomaterials to facilitate their future prospects.Graphical Abstract:Structure of doped, functionalized and hybrid GQDs

Mechanisms to enhance the capacitance beyond the classical limits in capacitors with free-electron-like electrodes

The so-called negative electron compressibility refers to the lowering of the chemical potential of a metallic system when the carrier density increases. This effect has often been invoked in the past to explain the enhancement of the capacitance beyond the classical limits in capacitors with two-dimensional electron gases as electrodes. Based on experiments on strongly confined semiconductor quantum wells (QWs), it has been traditionally ascribed to the electron exchange energy as the main driving force. Recent research, however, has revealed that analogous effects can occur in other classes of materials systems, such as polar oxide interfaces, whose characteristics drastically depart from those of the previously considered cases. To rationalize these new results, it is necessary to revisit the established theory of confined electron gases, and test whether its conclusions are valid beyond the specifics of semiconductor-based QWs. Here we find, based on first-principles calculations of jellium slabs, that one must indeed be very careful when extrapolating existing results to other realistic physical systems. In particular, we identify a number of additional, previously overlooked mechanisms (e.g., related to the displacement of the electronic cloud and to the multiband structure of the delocalized gas), that enter into play and become new sources of negative capacitance in the weak-confinement regime. Our detailed analysis of these emerging contributions, supported by analytic models and multiple test cases, will provide a useful guidance in the ongoing quest for nanometric capacitors with enhanced performance.

All-Electric Laser Beam Control Based on a Quantum-Confined Heterostructure with an Integrated Distributed Bragg Grating

The characteristics of semiconductor chip modulators providing the angular deflection of a laser beam due to all-electric modulation of the optical characteristics of a semiconductor heterostructure are theoretically studied. Designs for quantum-confined semiconductor waveguide heterostructures with a distributed Bragg reflector integrated on the heterostructure surface are developed. The design of a waveguide structure including 20 periods of coupled asymmetric quantum wells, which provide an optical confinement factor of the waveguide mode of 20%, and an optimized doping profile allowing a uniform electric-field distribution to be maintained in the quantum-well region in the entire range of operating voltages are proposed. In this waveguide structure, the change in the refractive index due to the quantum-confined Stark effect reaches 0.086 when the control signal changes from 0 to 6 V. It is shown that the spatial (angular) scanning of the laser beam emitted from the surface of a distributed Bragg mirror with a divergence of less than 0.1° in the range of 1°–2° is feasible for the proposed waveguide structure design.

Photosensitization of Single-Crystal Oxide Substrates with Quantum Confined Semiconductors

Dye-sensitized solar cells have been studied for many years as a potential inexpensive and scalable alternative to silicon solar cells. They have recently expanded their list of photosensitizers to include quantum dots. In recent years, there has been substantial progress in the field of quantum dot solar cells, with certified efficiencies now reaching 13.4%. Fundamental studies on nanomaterial/semiconductor electrode coupling have led to a deeper understanding of photoinduced electron-transfer processes that are important for both of these devices. This Feature Article will highlight the use of a model system, nanomaterials sensitizing single-crystal oxide substrates, that is useful for investigating how changes in nanomaterial shape, dimensionality, size, and local environment affect the photoinduced charge separation efficiency.