Photosensitivity Enhancement with TiO₂ in Semitransparent Light-Sensitive Skins of Nanocrystal Monolayers

We propose and demonstrate light-sensitive nanocrystal skins that exhibit broadband sensitivity enhancement based on electron transfer to a thin TiO₂ film grown by atomic layer deposition. In these photosensors, which operate with no external bias, photogenerated electrons remain trapped inside the nanocrystals. These electrons generally recombine with the photogenerated holes that accumulate at the top interfacing contact, which leads to lower photovoltage buildup. Because favorable conduction band offset aids in transferring photoelectrons from CdTe nanocrystals to the TiO₂ layer, which decreases the exciton recombination probability, TiO₂ has been utilized as the electron-accepting material in these light-sensitive nanocrystal skins. A controlled interface thickness between the TiO₂ layer and the monolayer of CdTe nanocrystals enables a photovoltage buildup enhancement in the proposed nanostructure platform. With TiO₂ serving as the electron acceptor, we observed broadband sensitivity improvement across 350–475 nm, with an approximately 22% enhancement. Furthermore, time-resolved fluorescence measurements verified the electron transfer from the CdTe nanocrystals to the TiO₂ layer in light-sensitive skins. These results could pave the way for engineering nanocrystal-based light-sensing platforms, such as smart transparent windows, light-sensitive walls, and large-area optical detection systems

Exciton Dynamics in Colloidal Quantum-Dot LEDs under Active Device Operations

Colloidal quantum-dot light-emitting diodes (QLEDs) are lucrative options for color-pure lighting sources. To achieve high-performance QLEDs, besides developing high-efficiency quantum dots (QDs), it is essential to understand their device physics. However, little understanding of the QD emission behavior in active QLEDs is one of the main factors hindering the improvement of device efficiency. In this work, we systematically studied the exciton dynamics of gradient composition CdSe@ZnS QDs during electroluminescence in a working QLED. With time-resolved photoluminescence analyses using fluorescence lifetime imaging microscopy we analyzed a large population of QDs spatially spreading over an extended area inside and outside the device. This allows us to reveal the statistically significant changes in the behavior of QD emission in the device at different levels of applied voltages and injection currents. We find that the QD emission efficiency first drops in device fabrication with Al electrode deposition and that the QD exciton lifetime is then statistically reduced further under the QLED’s working conditions. This implies the nonradiative Auger recombination process is active in charged QDs as a result of imbalanced charge injection in a working QLED. Our results help to understand the exciton behavior during the operation of a QLED and demonstrate a new approach to explore the exciton dynamics statistically with a large QD population

Förster-Type Nonradiative Energy Transfer for Assemblies of Arrayed Nanostructures: Confinement Dimension vs Stacking Dimension

Förster-type nonradiative energy transfer (NRET) provides us with the ability to transfer excitation energy between proximal nanostructures with high efficiency under certain conditions. Nevertheless, the well-known Förster theory was developed for the case of a single donor (e.g., a molecule, a dye) together with single acceptor. There is no complete understanding for the cases when the donors and the acceptors are assembled in nanostructure arrays, though there are special cases previously studied. Thus, a comprehensive theory that models Förster-type NRET for assembled nanostructure arrays is required. Here, we report a theoretical framework of generalized theory for the Förster-type NRET with mixed dimensionality in arrays. These include combinations of arrayed nanostructures made of nanoparticles (NPs) and nanowires (NWs) assemblies in one-dimension (1D), two-dimension (2D), and three-dimension (3D) completing the framework for the transfer rates in all possible combinations of different confinement geometries and assembly architectures, we obtain a unified picture of NRET in assembled nanostructures arrays. We find that the generic NRET distance dependence is modified by arraying the nanostructures. For an acceptor NP the rate distance dependence changes from γ ∝ <i>d</i>^–6 to γ ∝ <i>d</i>^–5 when they are arranged in a 1D stack, and to γ ∝ <i>d</i>^–4 when in a 2D array, and to γ ∝ <i>d</i>^–3 when in a 3D array. Likewise, an acceptor NW changes its distance dependence from γ ∝ <i>d</i>^–5 to γ ∝ <i>d</i>^–4 when they are arranged in a 1D array and to γ ∝ <i>d</i>^–3 when in a 2D array. These finding shows that the numbers of dimensions across which nanostructures are stacked is equally critical as the confinement dimension of the nanostructure in determining the NRET kinetics

Amplified Spontaneous Emission and Lasing in Colloidal Nanoplatelets

Colloidal nanoplatelets (NPLs) have recently emerged as favorable light-emitting materials, which also show great potential as optical gain media due to their remarkable optical properties. In this work, we systematically investigate the optical gain performance of CdSe core and CdSe/CdS core/crown NPLs having different CdS crown size with one- and two-photon absorption pumping. The core/crown NPLs exhibit enhanced gain performance as compared to the core-only NPLs due to increased absorption cross section and the efficient interexciton funneling, which is from the CdS crown to the CdSe core. One- and two-photon absorption pumped amplified spontaneous emission thresholds are found as low as 41 μJ/cm² and 4.48 mJ/cm², respectively. These thresholds surpass the best reported optical gain performance of the state-of-the-art colloidal nanocrystals (<i>i.e.</i>, quantum dots, nanorods, <i>etc.</i>) emitting in the same spectral range as the NPLs. Moreover, gain coefficient of the NPLs is measured as high as 650 cm^–1, which is 4-fold larger than the best reported gain coefficient of the colloidal quantum dots. Finally, we demonstrate a two-photon absorption pumped vertical cavity surface emitting laser of the NPLs with a lasing threshold as low as 2.49 mJ/cm². These excellent results are attributed to the superior properties of the NPLs as optical gain media

Temperature-Dependent Emission Kinetics of Colloidal Semiconductor Nanoplatelets Strongly Modified by Stacking

We systematically studied temperature-dependent emission kinetics in solid films of solution-processed CdSe nanoplatelets (NPLs) that are either intentionally stacked or nonstacked. We observed that the steady-state photoluminescence (PL) intensity of nonstacked NPLs considerably increases with decreasing temperature, whereas there is only a slight increase in stacked NPLs. Furthermore, PL decay time of the stacked NPL ensemble is comparatively much shorter than that of the nonstacked NPLs, and this result is consistent at all temperatures. To account for these observations, we developed a probabilistic model that describes excitonic processes in a stack using Markov chains, and we found excellent agreement between the model and experimental results. These findings develop the insight that the competition between the radiative channels and energy transfer-assisted hole trapping leads to weakly temperature-dependent PL intensity in the case of the stacked NPL ensembles as compared to the nonstacked NPLs lacking strong energy transfer. This study shows that it is essential to account for the effect of NPL stacking to understand their resulting PL emission properties

Stacking in Colloidal Nanoplatelets: Tuning Excitonic Properties

Colloidal semiconductor quantum wells, also commonly known as nanoplatelets (NPLs), have arisen among the most promising materials for light generation and harvesting applications. Recently, NPLs have been found to assemble in stacks. However, their emerging characteristics essential to these applications have not been previously controlled or understood. In this report, we systematically investigate and present excitonic properties of controlled column-like NPL assemblies. Here, by a controlled gradual process, we show that stacking in colloidal quantum wells substantially increases exciton transfer and trapping. As NPLs form into stacks, surprisingly we find an order of magnitude decrease in their photoluminescence quantum yield, while the transient fluorescence decay is considerably accelerated. These observations are corroborated by ultraefficient Förster resonance energy transfer (FRET) in the stacked NPLs, in which exciton migration is estimated to be in the ultralong range (>100 nm). Homo-FRET (<i>i</i>.<i>e</i>., FRET among the same emitters) is found to be ultraefficient, reaching levels as high as 99.9% at room temperature owing to the close-packed collinear orientation of the NPLs along with their large extinction coefficient and small Stokes shift, resulting in a large Förster radius of ∼13.5 nm. Consequently, the strong and long-range homo-FRET boosts exciton trapping in nonemissive NPLs, acting as exciton sink centers, quenching photoluminescence from the stacked NPLs due to rapid nonradiative recombination of the trapped excitons. The rate-equation-based model, which considers the exciton transfer and the radiative and nonradiative recombination within the stacks, shows an excellent match with the experimental data. These results show the critical significance of stacking control in NPL solids, which exhibit completely different signatures of homo-FRET as compared to that in colloidal nanocrystals due to the absence of inhomogeneous broadening

Plasmon-Enhanced Energy Transfer in Photosensitive Nanocrystal Device

Förster resonance energy transfer (FRET) interacted with localized surface plasmon (LSP) gives us the ability to overcome inadequate transfer of energy between donor and acceptor nanocrystals (NCs). In this paper, we show LSP-enhanced FRET in colloidal photosensors of NCs in operation, resulting in substantially enhanced photosensitivity. The proposed photosensitive device is a layered self-assembled colloidal platform consisting of separated monolayers of the donor and the acceptor colloidal NCs with an intermediate metal nanoparticle (MNP) layer made of gold interspaced by polyelectrolyte layers. Using LBL assembly, we fabricated and comparatively studied seven types of such NC-monolayer devices (containing only donor, only acceptor, Au MNP–donor, Au MNP–acceptor, donor–acceptor bilayer, donor–Au MNP–acceptor trilayer, and acceptor–Au MNP–donor reverse trilayer). In these structures, we revealed the effect of LSP-enhanced FRET and exciton interactions from the donor NCs layer to the acceptor NCs layer. Compared to a single acceptor NC device, we observed a significant extension in operating wavelength range and a substantial photosensitivity enhancement (2.91-fold) around the LSP resonance peak of Au MNPs in the LSP-enhanced FRET trilayer structure. Moreover, we present a theoretical model for the intercoupled donor–Au MNP–acceptor structure subject to the plasmon-mediated nonradiative energy transfer. The obtained numerical results are in excellent agreement with the systematic experimental studies done in our work. The potential to modify the energy transfer through mastering the exciton–plasmon interactions and its implication in devices make them attractive for applications in nanophotonic devices and sensors

Tunable White-Light-Emitting Mn-Doped ZnSe Nanocrystals

We report white-light-emitting Mn-doped ZnSe nanocrystals (NCs) that are synthesized using modified nucleation doping strategy. Tailoring three distinct emission mechanisms in these NCs, which are MnSe-related blue emission (410 and 435 nm), Zn-related defect state green emission (520 nm), and Mn-dopant related orange emission (580 nm), allowed us to achieve excitation wavelength tailorable white-light generation as studied by steady state and time-resolved fluorescence spectroscopy. These NCs will be promising as single component white-light engines for solid-state lighting

Solvent-Assisted Surface Engineering for High-Performance All-Inorganic Perovskite Nanocrystal Light-Emitting Diodes

All-inorganic cesium halide perovskite nanocrystals have attracted much interest in optoelectronic applications for the sake of the readily adjustable band gaps, high photoluminescence quantum yield, pure color emission, and affordable cost. However, because of the ineluctable utilization of organic surfactants during the synthesis, the structural and optical properties of CsPbBr₃ nanocrystals degrade upon transforming from colloidal solutions to solid thin films, which plagues the device operation. Here, we develop a novel solvent-assisted surface engineering strategy, producing high-quality CsPbBr₃ thin films for device applications. A good solvent is first introduced as an assembly trigger to conduct assembly in a one-dimensional direction, which is then interrupted by adding a nonsolvent. The nonsolvent drives the adjacent nanoparticles connecting in a two-dimensional direction. Assembled CsPbBr₃ nanocrystal thin films are densely packed and very smooth with a surface roughness of ∼4.8 nm, which is highly desirable for carrier transport in a light-emitting diode (LED) device. Meanwhile, the film stability is apparently improved. Benefiting from this facile and reliable strategy, we have achieved remarkably improved performance of CsPbBr₃ nanocrystal-based LEDs. Our results not only enrich the methods of nanocrystal surface engineering but also shed light on developing high-performance LEDs

Phonon-Assisted Exciton Transfer into Silicon Using Nanoemitters: The Role of Phonons and Temperature Effects in Förster Resonance Energy Transfer

We study phonon-assisted Förster resonance energy transfer (FRET) into an indirect band-gap semiconductor using nanoemitters. The unusual temperature dependence of this energy transfer, which is measured using the donor nanoemitters of quantum dot (QD) layers integrated on the acceptor monocrystalline bulk silicon as a model system, is predicted by a phonon-assisted exciton transfer model proposed here. The model includes the phonon-mediated optical properties of silicon, while considering the contribution from the multimonolayer-equivalent QD film to the nonradiative energy transfer, which is derived with a <i>d</i>^–3 distance dependence. The FRET efficiencies are experimentally observed to decrease at cryogenic temperatures, which are well explained by the model considering the phonon depopulation in the indirect band-gap acceptor together with the changes in the quantum yield of the donor. These understandings will be crucial for designing FRET-enabled sensitization of silicon based high-efficiency excitonic systems using nanoemitters