The "energy gap law" for mid-infrared nanocrystals.

Colloidal quantum dots are of increasing interest for mid-infrared detection and emission, but device performances will vastly benefit from reducing the non-radiative recombination. Empirically, the photoluminescence quantum yield decreases exponentially toward the mid-infrared, which appears similar to the energy gap law known for molecular fluorescence in the near-infrared. For molecules, the mechanism is electron-vibration coupling and fast internal vibrational relaxation. Here, we explore the possible mechanisms for inorganic quantum dots. The primary mechanism is assigned to an electric dipole near-field energy transfer from the quantum dot electronic transitions to the infrared absorption of surface organic ligands and then to the multiphonon absorption of the quantum dot inorganic core or the surrounding inorganic matrix. In order to obtain luminescent quantum dots in the 3-10 µm range, we motivate the importance of using inorganic matrices, which have a higher infrared transparency compared to organic materials. At longer wavelengths, inter-quantum dot energy transfer is noted to be much faster than radiative relaxation, indicating that bright mid-infrared colloidal quantum dot films might then benefit from dilution.

Intraband cascade electroluminescence with weakly n-doped HgTe colloidal quantum dots.

Room temperature 6 µm intraband cascade electroluminescence (EL) is demonstrated with lightly n-doped HgTe colloidal quantum dots of ∼8 nm diameter deposited on interdigitated electrodes in a metal-insulator-metal device. With quantum dot films of ∼150 nm thickness made by solid-state-ligand-exchange, the devices emit at 1600 cm-1 (6.25 µm), with a spectral width of 200 cm-1, determined by the overlap of the 1Se-1Pe intraband transition of the quantum dots and the substrate photonic resonance. At the maximum current used of 20 mA, the bias was 30 V, the external quantum efficiency was 2.7%, and the power conversion efficiency was 0.025%. Adding gold nano-antennas between the electrodes broadened the emission and increased the quantum efficiency to 4.4% and the power efficiency to 0.036%. For these films, the doping was about 0.1 electron/dot, the electron mobility was 0.02 cm2 V-1 s-1, and the maximum current density was 0.04 kA cm-2. Higher mobility films made by solution ligand exchange show a 20-fold increase in current density and a 10-fold decrease in EL efficiencies. Electroluminescence with weak doping is interesting for eventually achieving electrically driven stimulated emission, and the requirements for population inversion and lasing are discussed.

Bright Fluorophores in the Second Near-Infrared Window: HgSe/CdSe Quantum Dots.

Fluorophores emitting in the NIR-IIb wavelength range (1.5-1.7 µm) show great potential for bioimaging due to their large tissue penetration. However, current fluorophores suffer from poor emission with quantum yields ∼2% in aqueous solvents. In this work, we report the synthesis of HgSe/CdSe core/shell quantum dots (QDs) emitting at 1.7 µm through the interband transition. Growth of a thick shell led to a drastic increase in the photoluminescence quantum yield, with a value of 63% in nonpolar solvents. The quantum yields of our QDs and other reported QDs are explained well by a model of Forster resonance energy transfer to ligands and solvent molecules. The model predicts a quantum yield >12% when these HgSe/CdSe QDs are solubilized in water. Our work demonstrates the importance of a thick type-I shell to obtain bright emission in the NIR-IIb region.

Multicarrier Dynamics in Quantum Dots.

Multicarrier dynamics play an essential role in quantum dot photophysics and photochemistry, and they are primarily governed by nonradiative Auger processes. Auger recombination affects the performance of lasers, light-emitting diodes, and photodetectors, and it has been implicated in fluorescence intermittency phenomena which are relevant in microscopy and biological tagging. Auger cooling is an important mechanism of rapid electron thermalization. Inverse Auger recombination, known as impact ionization, results in carrier multiplication which can enhance the efficiencies of solar cells. This article first reviews the physical picture, theoretical framework and experimental data for Auger processes in bulk crystalline semiconductors. With this context these aspects are then reexamined for nanocrystal quantum dots, and we first consider fundamental features of Auger recombination in these systems. Methods for the chemical control of Auger recombination and Auger cooling are then discussed in the context of how they illuminate the underlying mechanisms, and we also examine the current understanding of carrier multiplication in quantum dots. Manifestations of Auger recombination in quantum dot devices are finally considered, and we conclude the article with a perspective on remaining unknowns in quantum dot multicarrier physics.

Toward Bright Mid-Infrared Emitters: Thick-Shell n-Type HgSe/CdS Nanocrystals.

A procedure is developed for the growth of thick, conformal CdS shells that preserve the optical properties of 5 nm HgSe cores. The n-doping of the HgSe/CdS core/shell particles is quantitatively tuned through a simple postsynthetic Cd treatment, while the doping is monitored via the intraband optical absorption at 5 µm wavelength. Photoluminescence lifetime and quantum yield measurements show that the CdS shell greatly increases the intraband emission intensity. This indicates that decoupling the excitation from the environment reduces the nonradiative recombination. We find that weakly n-type HgSe/CdS are the brightest solution-phase mid-infrared chromophores reported to date at room temperature, achieving intraband photoluminescence quantum yields of 2%. Such photoluminescence corresponds to intraband lifetimes in excess of 10 ns, raising important questions about the fundamental limits to achievable slow intraband relaxation in quantum dots.

Quantum dot solids showing state-resolved band-like transport.

Improving charge mobility in quantum dot (QD) films is important for the performance of photodetectors, solar cells and light-emitting diodes. However, these applications also require preservation of well defined QD electronic states and optical transitions. Here, we present HgTe QD films that show high mobility for charges transported through discrete QD states. A hybrid surface passivation process efficiently eliminates surface states, provides tunable air-stable n and p doping and enables hysteresis-free filling of QD states evidenced by strong conductance modulation. QD films dried at room temperature without any post-treatments exhibit mobility up to µ ~ 8 cm2 V-1 s-1 at a low carrier density of less than one electron per QD, band-like behaviour down to 77 K, and similar drift and Hall mobilities at all temperatures. This unprecedented set of electronic properties raises important questions about the delocalization and hopping mechanisms for transport in QD solids, and introduces opportunities for improving QD technologies.

Towards Infrared Electronic Eyes: Flexible Colloidal Quantum Dot Photovoltaic Detectors Enhanced by Resonant Cavity.

Electronic eye cameras are receiving increasing interest due to their unique advantages such as wide field of view, low aberrations, and simple imaging optics compared to conventional planar focal plane arrays. However, the spectral sensing ranges of most electronic eyes are confined to the visible, which is limited by the energy gaps of the sensing materials and by fabrication obstacles. Here, a potential route leading to infrared electronic eyes is demonstrated by exploring flexible colloidal quantum dot (CQD) photovoltaic detectors. Benefitting from their tunable optical response and the ease of fabrication as solution processable materials, mercury telluride (HgTe) CQD detectors with mechanical flexibility, wide spectral sensing range, fast response, and high detectivity are demonstrated. A strategy is provided to further enhance the light absorption in flexible detectors by integrating a Fabry-Perot resonant cavity. Integrated short-wave IR detectors on flexible substrates have peak D* of 7.5 × 1010 Jones at 2.2 µm at room temperature and promise the development of infrared electronic eyes with high-resolution imaging capability. Finally, infrared images are captured with the flexible CQD detectors at varying bending conditions, showing a practical approach to sensitive infrared electronic eyes beyond the visible range.

Uncooled High Detectivity Mid-Infrared Photoconductor Using HgTe Quantum Dots and Nanoantennas.

Using a metal/insulator/metal (MIM) structure with a gold nanoantenna array made by electron beam lithography, the responsivity of a HgTe colloidal quantum dot film is enhanced in the mid-infrared. Simulations indicate that the spatially averaged peak spectral absorption of an 80 nm film is 60%, enhanced 23-fold compared to that of the same film on a bare sapphire substrate. The field intensity enhancement is focused near the antenna tips, being 20-fold 100 nm away, which represents only 1% of the total area and up to 1000-fold at the tips. The simulated polarized absorption spectra are in good agreement with the experiments, with a strong resonance around 4 µm. A responsivity of 0.6 A/W is obtained at a 1 V bias. Noise measurements separate the 1/f noise from the generation-recombination white noise and give a spatially averaged photoconductive gain of 0.3 at 1 V bias. The spatially averaged peak detectivity is improved 15-fold compared to the same film on a sapphire substrate without an MIM structure. The experimental peak detectivity reaches 9 × 109 Jones at 2650 cm-1 and 80 kHz, decreasing at lower frequencies. The MIM structure also enhances the spatially averaged peak photoluminescence of the CQD film by 16-fold, which is a potential Purcell enhancement. The good agreement between simulations and measurements confirms the viability of lithographically designed nanoantenna structures for vastly improving the performance of mid-IR colloidal quantum dot photoconductors. Further improvements will be possible by matching the optically enhanced and current collection areas.

Viscoelastic flows in simple liquids generated by vibrating nanostructures.

Newtonian fluid mechanics, in which the shear stress is proportional to the strain rate, is synonymous with the flow of simple liquids such as water. We report the measurement and theoretical verification of non-Newtonian, viscoelastic flow phenomena produced by the high-frequency (20 GHz) vibration of gold nanoparticles immersed in water-glycerol mixtures. The observed viscoelasticity is not due to molecular confinement, but is a bulk continuum effect arising from the short time scale of vibration. This represents the first direct mechanical measurement of the intrinsic viscoelastic properties of simple bulk liquids, and opens a new paradigm for understanding extremely high frequency fluid mechanics, nanoscale sensing technologies, and biophysical processes.

Room-Temperature 15% Efficient Mid-Infrared HgTe Colloidal Quantum Dot Photodiodes.

Mid-infrared HgTe colloidal quantum dot photovoltaic devices previously achieved background-limited infrared photodetection at cryogenic temperatures but also decreased from 20 to 1% efficiency from 150 to 300 K. The reduced quantum efficiency was tentatively attributed to the carrier diffusion length being much shorter than the device thickness of ∼400 nm at room temperature. Here, the carrier diffusion length is measured and is found to peak at 215 nm at 200 K and decrease only to 180 nm at 295 K. It is therefore not the cause of the much larger reduced quantum efficiency. Instead, it is shown that the efficiency drops due to the series resistance. With the device size reduced to 50 by 50 µm, the room-temperature quantum efficiency reaches 10 and 15% for HgTe colloidal quantum dot devices with 2400 cm-1 (4.2 µm) and 2675 cm-1 (3.7 µm) cutoff, respectively. These small-area devices achieve background-limited photodetection at 150 K and a detectivity above 109 Jones at room temperature with a cutoff at 2675 cm-1 (3.7 µm).

Intraband Transition of HgTe Nanocrystals for Long-Wave Infrared Detection at 12 µm.

The synthesis of n-doped HgTe colloidal quantum dots was optimized to produce samples with a 1Se-1Pe intraband transition in the long-wave infrared (8-12 µm). The spin-orbit splitting of 1Pe states places the 1Se-1Pe1/2 transition around 10 µm. The narrow line width of 130 cm-1 at 300 K is limited by the size distribution. This narrowing leads to an absorption coefficient about 5 times stronger than is possible with the HgTe CQD interband transition at similar energies. From 300 to 80 K, the intraband transition blueshifts by 90 cm-1, while the interband transition redshifts by 350 cm-1. These shifts are assigned to the temperature dependence of the band structure. With ∼2 electrons/dot doping at 80 K, a photoconductive film of 80 nm thickness on a quarter wave reflector substrate showed a detectivity (D*) of ∼107 Jones at 500 Hz in the 8-12 µm range.

Optical properties of HgTe colloidal quantum dots.

Room temperature photodetection with HgTe colloidal quantum films is reported between 2 and 5 µm for particles of sizes between ~5 and ~12 nm diameter, and photodetection extends to 7 µm at 80 K. The size-tuning of the absorption of HgTe colloidal quantum dots, their optical cross section and the infrared absorption depth of films are measured. The tuning with radius is empirically given by [see formula in text] where R is in nm. The optical cross section of the colloidal dots at 415 nm is approximately proportional to their volume and given by σ(Hg)(415) = 2.6 ± 0.4 10(-17) cm(2)/mercury atom. The size-dependent optical cross section at the band edge ~1.5 10(-15) cm(2) is consistent with the expected oscillator strength of the quantum dots. The absorption depth of HgTe colloidal dot films is short, about 1-2 µm, which is an advantage for thin film devices. These properties agree rather well with the expectation from the k · p model. HgTe colloidal quantum dot thin films show a strong tuning with temperature with a large positive thermal shift between 0.4 and 0.2 meV K(-1), decreasing with decreasing size within the size range studied and this is attributed primarily to electron-phonon effects.

A mirage study of CdSe colloidal quantum dot films, Urbach tail, and surface states.

Thermal deflection spectroscopy allows to measure very small absorption and uncovers absorption tails extending well below the bulk bandgap energy for CdSe quantum dots films after ligand exchange by sulfide. In this monodispersed system, the redshift, the broadening, and the absorption tails cannot be solely attributed to electronic coupling between the dots. Instead, mixing of hole states from the quantum dot and surface is proposed to dominate the changes of the interband spectra at the absorption edge.

Mid-infrared HgTe Colloidal Quantum Dot LEDs.

Mid-infrared HgTe colloidal quantum dot electroluminescent devices are demonstrated. With emission at 4 µm, devices achieved an external quantum efficiency of ∼10-3 and power conversion efficiency of ∼10-4 under biases of a few volts. The power conversion efficiency benefited from lowering the transparent electrode resistance through the incorporation of a metal conductive grid. The average power emitted was about 16 µW at 2 V bias with 50% duty cycle and a 1 mm2 device. The room-temperature electroluminescence efficiency at low current was limited by the photoluminescence efficiency of the quantum dots, while the diode structure provided efficient electron-hole recombination.

Synthesis of colloidal HgTe quantum dots for narrow mid-IR emission and detection.

HgTe colloidal quantum dots are prepared via a simple two-step injection method. Absorption and photodetection with sharp edges, as well as narrow photoluminescence, are tunable across the near and mid-IR between 1.3 and 5 µm.

Shape-Controlled HgTe Colloidal Quantum Dots and Reduced Spin-Orbit Splitting in the Tetrahedral Shape.

Spherical and tetrahedral HgTe colloidal quantum dots (CQDs) are synthesized, and their doping is tuned electrochemically. Compared to spherical dots of a similar volume, the tetrahedral CQDs show a decrease in confinement energy as well as a sharper band edge absorption. The intraband spectra of the tetrahedral CQDs also display a smaller splitting from spin-orbit coupling. The shape-controlled synthesis with an improved size distribution and sharper optical features could find applications in optoelectronic devices.

State-Resolved Mobility of 1 cm2/(Vs) with HgSe Quantum Dot Films.

HgSe colloidal quantum dot films are made by using a hybrid ligand exchange (HgSe/hybrid) in polar inks and compared with the solid-state ligand exchange using ethanedithiol (HgSe/EDT). In both systems, the conductance shows a peak at one-electron filling of the 1Se state and a dip at 2 electrons before filling the 1Pe state. The HgSe/hybrid films show a ∼100-fold increased mobility, reaching up to ∼1 cm2/Vs for 7.5 nm diameter particles. While field effect transistor and Hall measurements give similar carrier density and mobility, the temperature dependence of the mobility is consistent with hopping transport.

Direct Imprinting of Quasi-3D Nanophotonic Structures into Colloidal Quantum-Dot Devices.

Three-dimensional (3D) subwavelength nanostructures have emerged and triggered tremendous excitement because of their advantages over the two-dimensional (2D) counterparts in fields of plasmonics, photonic crystals, and metamaterials. However, the fabrication and integration of 3D nanophotonic structures with colloidal quantum dots (CQDs) faces several technological obstacles, as conventional lithographic and etching techniques may affect the surface chemistry of colloidal nanomaterials. Here, the direct fabrication of functional quasi-3D nanophotonic structures into CQD films is demonstrated by one-step imprinting with well-controlled precision in both vertical and lateral directions. To showcase the potential of this technique, diffraction gratings, bilayer wire-grid polarizers, and resonant metal mesh long-pass filters are imprinted on CQD films without degrading the optical and electrical properties of CQD. Furthermore, a dual-diode CQD detector into an unprecedented mid-wave infrared two-channel polarization detector is functionalized by embedding an imprinted bilayer wire-grid polarizer within the CQDs. The results show that this approach offers a feasible pathway to combine quasi-3D nanostructures with colloidal materials-based optoelectronics and access a new level of light manipulation.

Auger Suppression in n-Type HgSe Colloidal Quantum Dots.

Transient infrared photoluminescence upconversion is used to study the exciton dynamics in small-gap HgSe colloidal quantum dots in the 2000-6500 cm-1 (0.25-0.80 eV) range. The intraband mid-infrared photoluminescence decays show absent or greatly reduced Auger relaxation of biexcitons, proposed as a generic feature of weakly n-type quantum dots due to the sparse density of states in the conduction band. The nonradiative relaxation of the intraband carriers is instead consistent with near-field energy transfer to molecular vibrations of the surface ligands. In contrast, the interband near-infrared photoluminescence decays exhibit the typical distinct exciton and biexciton lifetimes with Auger coefficients comparable to other similarly sized quantum dots. Also observed are spectral and dynamical evidence of fine structure in the intraband transitions consistent with spin-orbit splitting of the electron P levels, and the emergence of plasmonic resonances in large particles.

Polarized near-infrared intersubband absorptions in CdSe colloidal quantum wells.

Colloidal quantum wells are two-dimensional materials grown with atomically-precise thickness that dictates their electronic structure. Although intersubband absorption in epitaxial quantum wells is well-known, analogous observations in non-epitaxial two-dimensional materials are sparse. Here we show that CdSe nanoplatelet quantum wells have narrow (30-200 meV), polarized intersubband absorption features when photoexcited or under applied bias, which can be tuned by thickness across the near-infrared (NIR) spectral window (900-1600 nm) inclusive of important telecommunications wavelengths. By examination of the optical absorption and polarization-resolved measurements, the NIR absorptions are assigned to electron intersubband transitions. Under photoexcitation, the intersubband features display hot carrier and Auger recombination effects similar to excitonic absorptions. Sequenced two-color photoexcitation permits the sub-picosecond modulation of the carrier temperature in such colloidal quantum wells. This work suggests that colloidal quantum wells may be promising building blocks for NIR technologies.