Bright and durable scintillation from colloidal quantum shells.

Efficient, fast, and robust scintillators for ionizing radiation detection are crucial in various fields, including medical diagnostics, defense, and particle physics. However, traditional scintillator technologies face challenges in simultaneously achieving optimal performance and high-speed operation. Herein we introduce colloidal quantum shell heterostructures as X-ray and electron scintillators, combining efficiency, speed, and durability. Quantum shells exhibit light yields up to 70,000 photons MeV-1 at room temperature, enabled by their high multiexciton radiative efficiency thanks to long Auger-Meitner lifetimes (>10 ns). Radioluminescence is fast, with lifetimes of 2.5 ns and sub-100 ps rise times. Additionally, quantum shells do not exhibit afterglow and maintain stable scintillation even under high X-ray doses (>109 Gy). Furthermore, we showcase quantum shells for X-ray imaging achieving a spatial resolution as high as 28 line pairs per millimeter. Overall, efficient, fast, and durable scintillation make quantum shells appealing in applications ranging from ultrafast radiation detection to high-resolution imaging.

Two-Dimensional Electron-Hole Plasma in Colloidal Quantum Shells Enables Integrated Lasing Continuously Tunable in the Red Spectrum.

Combining integrated optical platforms with solution-processable materials offers a clear path toward miniaturized and robust light sources, including lasers. A limiting aspect for red-emitting materials remains the drop in efficiency at high excitation density due to non-radiative quenching pathways, such as Auger recombination. Next to this, lasers based on such materials remain ill characterized, leaving questions about their ultimate performance. Here, we show that colloidal quantum shells (QSs) offer a viable solution for a processable material platform to circumvent these issues. We first show that optical gain in QSs is mediated by a 2D plasma state of unbound electron-hole pairs, opposed to bound excitons, which gives rise to broad-band and sizable gain across the full red spectrum with record gain lifetimes and a low threshold. Moreover, at high excitation density, the emission efficiency of the plasma state does not quench, a feat we can attribute to an increased radiative recombination rate. Finally, QSs are integrated on a silicon nitride platform, enabling high spectral contrast, surface emitting, and TE-polarized lasers with ultranarrow beam divergence across the entire red spectrum from a small surface area. Our results indicate QS materials are an excellent materials platform to realize highly performant and compact on-chip light sources.

Green Light from Red-Emitting Nanocrystals: Broadband, Low-Threshold Lasing from Colloidal Quantum Shells in Optical Nanocavities.

Spherical semiconductor nanoplatelets, known as quantum shells (QSs), have captured significant interest for their strong suppression of Auger recombination, which leads to long multiexciton lifetimes and wide optical gain bandwidth. Yet, the realization of benefits associated with the multiexciton lasing regime using a suitably designed photonic cavity remains elusive. Here, we demonstrate broadly tunable lasing from close-packed films of CdS/CdSe/CdS QSs deposited over nanopillar arrays on Si substrates. Wide spectral tuning of the stimulated emission in QSs with a fixed bandgap value was achieved by engaging single exciton (λX ∼ 634 nm), biexciton (λBX ∼ 627 nm), and multiple exciton (λMX ∼ 615-565 nm) transitions. The ensemble-averaged gain threshold of ∼ 2.6 electron-hole pairs per QS particle and the low photonic cavity fluence threshold of ∼4 µJ/cm2 were attributed to Auger suppression. The tuning of the lasing emission closely aligns with our model predictions achieved by varying the array period while preserving mode confinement and quality (Q) factors. These results mark a notable step toward the development of colloidal nanocrystal lasers.

Large two-photon cross sections and low-threshold multiphoton lasing of CdS/CdSe/CdS quantum shells.

Colloidal quantum shells are spherical semiconductor quantum wells, which have shown strong promise as optical materials, particularly in classes of experiments requiring multiple excitons. The two-photon properties of CdS/CdSe/CdS quantum shell samples are studied here to demonstrate large non-linear absorption cross-sections while retaining advantageous multiexciton physics conferred by the geometrical structure. The quantum shells have large two-phonon cross sections (0.4-7.9 × 106 GM), which highlights their potential use in upconversion imaging in which large per particle two-photon absorption is critical. Time-resolved measurements confirmed that the quantum shells have long biexciton lifetime (>10 ns in the largest core samples reported here) and large gain bandwidth (>300 meV). The combination of these attributes with large two-photon cross sections makes the CdS/CdSe/CdS quantum shells excellent gain media for two-photon excitation. With a broad gain bandwidth and long gain lifetime, quantum shell solids support multimodal amplified spontaneous emission from excitons, biexcitons, and higher excited states. Thresholds for amplified spontaneous emission and lasing, which are as low as 1 mJ cm-2, are comparable to, or lower than, the thresholds reported for other colloidal materials.

Quantum shells versus quantum dots: suppressing Auger recombination in colloidal semiconductors.

Colloidal semiconductor nanocrystals (NCs) have attracted a great deal of attention in recent decades. The quantum efficiency of many optoelectronic processes based on these nanomaterials, however, declines with increasing optical or electrical excitation intensity. This issue is caused by Auger recombination of multiple excitons, which converts the NC energy into excess heat, whereby reducing the efficiency and lifespan of NC-based devices, including lasers, photodetectors, X-ray scintillators, and high-brightness LEDs. Recently, semiconductor quantum shells (QSs) have emerged as a viable nanoscale architecture for the suppression of Auger decay. The spherical-shell geometry of these nanostructures leads to a significant reduction of Auger decay rates, while exhibiting a near unity photoluminescence quantum yield. Here, we compare the optoelectronic properties of quantum shells against other low-dimensional semiconductors and discuss their emerging opportunities in solid-state lighting and energy-harvesting applications.

Quantum Shell in a Shell: Engineering Colloidal Nanocrystals for a High-Intensity Excitation Regime.

Many optoelectronic processes in colloidal semiconductor nanocrystals (NCs) suffer an efficiency decline under high-intensity excitation. This issue is caused by Auger recombination of multiple excitons, which converts the NC energy into excess heat, reducing the efficiency and life span of NC-based devices, including photodetectors, X-ray scintillators, lasers, and high-brightness light-emitting diodes (LEDs). Recently, semiconductor quantum shells (QSs) have emerged as a promising NC geometry for the suppression of Auger decay; however, their optoelectronic performance has been hindered by surface-related carrier losses. Here, we address this issue by introducing quantum shells with a CdS-CdSe-CdS-ZnS core-shell-shell-shell multilayer structure. The ZnS barrier inhibits the surface carrier decay, which increases the photoluminescence (PL) quantum yield (QY) to 90% while retaining a high biexciton emission QY of 79%. The improved QS morphology allows demonstrating one of the longest Auger lifetimes reported for colloidal NCs to date. The reduction of nonradiative losses in QSs also leads to suppressed blinking in single nanoparticles and low-threshold amplified spontaneous emission. We expect that ZnS-encapsulated quantum shells will benefit many applications exploiting high-power optical or electrical excitation regimes.

Colloidal Nanoribbons: From Infrared to Visible.

Using the cation-exchange method, colloidal PbS nanoribbons are converted completely into CdS nanoribbons. This process expands the emission spectrum of the nanoribbons from infrared to visible. The morphology of nanoribbons remains the same after cation exchange, but the crystal structure changes from rock salt to zincblende. CdS nanoribbons exhibit blue band-edge photoluminescence under ultraviolet-light excitation. Cathodoluminescence spectroscopy of the CdS nanoribbons shows multicolor (blue, green, and red) emissions. Further time-resolved photoluminescence spectroscopy studies show that the lifetime of the midgap states is more than 2 orders of magnitude longer than that of the band-edge states.

Quantum Shells Boost the Optical Gain of Lasing Media.

Auger decay of multiple excitons represents a significant obstacle to photonic applications of semiconductor quantum dots (QDs). This nonradiative process is particularly detrimental to the performance of QD-based electroluminescent and lasing devices. Here, we demonstrate that semiconductor quantum shells with an "inverted" QD geometry inhibit Auger recombination, allowing substantial improvements to their multiexciton characteristics. By promoting a spatial separation between multiple excitons, the quantum shell geometry leads to ultralong biexciton lifetimes (>10 ns) and a large biexciton quantum yield. Furthermore, the architecture of quantum shells induces an exciton-exciton repulsion, which splits exciton and biexciton optical transitions, giving rise to an Auger-inactive single-exciton gain mode. In this regime, quantum shells exhibit the longest optical gain lifetime reported for colloidal QDs to date (>6 ns), which makes this geometry an attractive candidate for the development of optically and electrically pumped gain media.

Tuning the Dimensionality of Excitons in Colloidal Quantum Dot Molecules.

Electrically coupled quantum dots (QDs) can support unique optoelectronic properties arising from the superposition of single-particle excited states. Experimental methods for integrating colloidal QDs within the same nano-object, however, have remained elusive to the rational design. Here, we demonstrate a chemical strategy that allows for the assembling of colloidal QDs into coupled composites, where proximal interactions give rise to unique optoelectronic behavior. The assembly method employing "adhesive" surfactants was used to fabricate both homogeneous (e.g., CdS-CdS, PbS-PbS, CdSe-CdSe) and heterogeneous (e.g., PbS-CdS, CdS-CdSe) nanoparticle assemblies, exhibiting quasi-one-dimensional exciton fine structure. In addition, tunable mixing of single-particle exciton states was achieved for dimer-like assemblies of CdSe/CdS core-shell nanocrystals. The nanoparticle assembly mechanism was explained within the viscoelastic interaction theory adapted for molten-surface colloids. We expect that the present work will provide the synthetic and theoretical foundation needed for building assemblies of many inorganic nanocrystals.

Photoinduced Rotation of Colloidal Semiconductor Nanocrystals in an Electric Field.

We demonstrate that solution-phase semiconductor nanocrystals (NCs) undergo photoinduced rotation in an external electric field. Present measurements backed by theoretical calculations show that the rotation of colloidal NCs is driven by the excited-state dipole moment, which is counterbalanced by the solvent viscosity drag. Corresponding angular velocities range from 0.5°/ns for cubic CsPbBr3 NCs to 3°/ns for nanoparticles with a large photoinduced charge separation (CdSe/CdS core-shell and dot-in-a-rod NCs). Because of photoinduced rotation, solution-phase semiconductor NCs exhibited an order-of-magnitude increase in the spectral changes caused by the quantum confined Stark effect (QCSE), compared to solid NC assemblies. The enhanced QCSE of colloidal NCs reflected their global alignment in solution, which could be retained in a solid environment by slow crystallization. Overall, we expect that the demonstrated phenomenon of the colloidal nanocrystal rotation in an electric field will open up new avenues for developing electro-optical and voltage-sensitive applications.

Influence of QD photosensitizers in the photocatalytic production of hydrogen with biomimetic [FeFe]-hydrogenase. Comparative performance of CdSe and CdTe.

Photocatalytic systems comprising a hydrogenase-type catalyst and CdX (X = S, Se, Te) chalcogenide quantum dot (QD) photosensitizers show extraordinary hydrogen production rates under visible light excitation. What remains unknown is the mechanism of energy conversion in these systems. Here, we have explored this question by comparing the performance of two QD sensitizers, CdSe and CdTe, in photocatalytic systems featuring aqueous suspensions of a [Fe2 (µ-1,2-benzenedithiolate) CO6] catalyst and an ascorbic acid sacrificial agent. Overall, the hydrogen production yield for CdSe-sensitized reactions QDs was found to be 13 times greater than that of CdTe counterparts. According to emission quenching experiments, an enhanced performance of CdSe sensitizers reflected a greater rate of electron transfer from the ascorbic acid (kAsc). The observed difference in the QD-ascorbic acid charge transfer rates between the two QD materials was consistent with respective driving forces for these systems.

Low-threshold laser medium utilizing semiconductor nanoshell quantum dots.

Colloidal semiconductor nanocrystals (NCs) represent a promising class of nanomaterials for lasing applications. Currently, one of the key challenges facing the development of high-performance NC optical gain media lies in enhancing the lifetime of biexciton populations. This usually requires the employment of charge-delocalizing particle architectures, such as core/shell NCs, nanorods, and nanoplatelets. Here, we report on a two-dimensional nanoshell quantum dot (QD) morphology that enables a strong delocalization of photoinduced charges, leading to enhanced biexciton lifetimes and low lasing thresholds. A unique combination of a large exciton volume and a smoothed potential gradient across interfaces of the reported CdSbulk/CdSe/CdSshell (core/shell/shell) nanoshell QDs results in strong suppression of Auger processes, which was manifested in this work though the observation of stable amplified stimulated emission (ASE) at low pump fluences. An extensive charge delocalization in nanoshell QDs was confirmed by transient absorption measurements, showing that the presence of a bulk-size core in CdSbulk/CdSe/CdSshell QDs reduces exciton-exciton interactions. Overall, present findings demonstrate unique advantages of the nanoshell QD architecture as a promising optical gain medium in solid-state lighting and lasing applications.

Nanoshell quantum dots: Quantum confinement beyond the exciton Bohr radius.

Nanoshell quantum dots (QDs) represent a novel class of colloidal semiconductor nanocrystals (NCs), which supports tunable optoelectronic properties over the extended range of particle sizes. Traditionally, the ability to control the bandgap of colloidal semiconductor NCs is limited to small-size nanostructures, where photoinduced charges are confined by Coulomb interactions. A notorious drawback of such a restricted size range concerns the fact that assemblies of smaller nanoparticles tend to exhibit a greater density of interfacial and surface defects. This presents a potential problem for device applications of semiconductor NCs where the charge transport across nanoparticle films is important, as in the case of solar cells, field-effect transistors, and photoelectrochemical devices. The morphology of nanoshell QDs addresses this issue by enabling the quantum-confinement in the shell layer, where two-dimensional excitons can exist, regardless of the total particle size. Such a geometry exhibits one of the lowest surface-to-volume ratios among existing QD architectures and, therefore, could potentially lead to improved charge-transport and multi-exciton characteristics. The expected benefits of the nanoshell architecture were recently demonstrated by a number of reports on the CdSbulk/CdSe nanoshell model system, showing an improved photoconductivity of solids and increased lifetime of multi-exciton populations. Along these lines, this perspective will summarize the recent work on CdSbulk/CdSe nanoshell colloids and discuss the possibility of employing other nanoshell semiconductor combinations in light-harvesting and lasing applications.

Delayed Photoluminescence in Metal-Conjugated Fluorophores.

Assemblies of metal nanostructures and fluorescent molecules represent a promising platform for the development of biosensing and near-field imaging applications. Typically, the interaction of molecular fluorophores with surface plasmons in metals results in either quenching or enhancement of the dye excitation energy. Here, we demonstrate that fluorescent molecules can also engage in a reversible energy transfer (ET) with proximal metal surfaces, during which quenching of the dye emission via the energy transfer to localized surface plasmons can trigger delayed ET from metal back to the fluorescent molecule. The resulting two-step process leads to the sustained delayed photoluminescence (PL) in metal-conjugated fluorophores, as was demonstrated here through the observation of increased PL lifetime in assemblies of Au nanoparticles and organic dyes (Alexa 488, Cy3.5, and Cy5). The observed enhancement of the PL lifetime in metal-conjugated fluorophores was corroborated by theoretical calculations based on the reverse ET model, suggesting that these processes could be ubiquitous in many other dye-metal assemblies.

Colloidal semiconductor nanocrystals in energy transfer reactions.

Excitonic energy transfer is a versatile mechanism by which colloidal semiconductor nanocrystals can interact with a variety of nanoscale species. While this process is analogous to dipole-dipole coupling in molecular systems, the corresponding energy transfer dynamics can deviate from that of molecular assemblies due to manifestations of bulk-like features in semiconductor colloids. In particular, weak exciton binding, small singlet-triplet exciton splitting, and the energy disorder across nanocrystal ensembles can all play distinctive roles in the ensuing energy conversion processes. To characterize the variety of energy transfer schemes involving nanocrystals, this feature article will discuss the latest research by both our group and other groups on the key scenarios under which nanocrystals can engage in energy transfer with other nanoparticles, organic fluorophores, and plasmonic nanostructures, highlighting potential technological benefits to be gained from such processes. We will also shed light on experimental strategies for probing the energy transfer in nanocrystal-based assemblies, with a particular emphasis on novel characterization techniques.

Challenges and Prospects of Photocatalytic Applications Utilizing Semiconductor Nanocrystals.

Photocatalytic systems based on colloidal semiconductor nanocrystals have gained considerable attention owing to potential benefits that include a visible-range light extinction and a low spatial overlap of photoinduced charges. When coupled to metal catalysts, nanocrystal sensitizers have demonstrated a compelling performance in homogenous photoreduction reactions, including the degradation of organic dyes and hydrogen generation. Going beyond half-cycle reactions, however, the progress in the field of nanocrystal photocatalysis has been rather limited. Here, we review some of the challenges associated with photocatalytic applications of colloidal semiconductor nanocrystals and highlight possible directions aimed toward their resolution. A particular emphasis was made on new paradigms in this field, including the possibility of harvesting triplet excitons and utilizing nanocrystal assemblies to accumulate multiple charges at the reaction site.

Competition of Charge and Energy Transfer Processes in Donor-Acceptor Fluorescence Pairs: Calibrating the Spectroscopic Ruler.

Sensing strategies utilizing Förster resonance energy transfer (FRET) are widely used for probing biological phenomena. FRET sensitivity to the donor-acceptor distance makes it ideal for measuring the concentration of a known analyte or determining the spatial separation between fluorescent labels in a macromolecular assembly. The difficulty lies in extracting the FRET efficiency from the acceptor-induced quenching of the donor emission, which may contain a significant non-FRET contribution. Here, we demonstrate a general spectroscopic approach for differentiating between charge transfer and energy transfer (ET) processes in donor-acceptor assemblies and apply the developed method for unravelling the FRET/non-FRET contributions in cyanine dye-semiconductor quantum dot (QD) constructs. The present method relies on correlating the amplitude of the acceptor emission to specific changes in the donor excitation profile in order to extract ET-only transfer efficiencies. Quenching of the donor emission is then utilized to determine the non-ET component, tentatively attributed to the charge transfer. We observe that the latter accounts for 50-99% of donor emission quenching in QD-Cy5 and QD-Cy7 systems, stressing the importance of determining the non-FRET efficiency in a spectroscopic ruler and other FRET-based sensing applications.

Thermally activated delayed photoluminescence from pyrenyl-functionalized CdSe quantum dots.

The generation and transfer of triplet excitons across semiconductor nanomaterial-molecular interfaces will play an important role in emerging photonic and optoelectronic technologies, and understanding the rules that govern such phenomena is essential. The ability to cooperatively merge the photophysical properties of semiconductor quantum dots with those of well-understood and inexpensive molecular chromophores is therefore paramount. Here we show that 1-pyrenecarboxylic acid-functionalized CdSe quantum dots undergo thermally activated delayed photoluminescence. This phenomenon results from a near quantitative triplet-triplet energy transfer from the nanocrystals to 1-pyrenecarboxylic acid, producing a molecular triplet-state 'reservoir' that thermally repopulates the photoluminescent state of CdSe through endothermic reverse triplet-triplet energy transfer. The photoluminescence properties are systematically and predictably tuned through variation of the quantum dot-molecule energy gap, temperature and the triplet-excited-state lifetime of the molecular adsorbate. The concepts developed are likely to be applicable to semiconductor nanocrystals interfaced with molecular chromophores, enabling potential applications of their combined excited states.

One-Dimensional Carrier Confinement in "Giant" CdS/CdSe Excitonic Nanoshells.

The emerging generation of quantum dot optoelectronic devices offers an appealing prospect of a size-tunable band gap. The confinement-enabled control over electronic properties, however, requires nanoparticles to be sufficiently small, which leads to a large area of interparticle boundaries in a film. Such interfaces lead to a high density of surface traps which ultimately increase the electrical resistance of a solid. To address this issue, we have developed an inverse energy-gradient core/shell architecture supporting the quantum confinement in nanoparticles larger than the exciton Bohr radius. The assembly of such nanostructures exhibits a relatively low surface-to-volume ratio, which was manifested in this work through the enhanced conductance of solution-processed films. The reported core/shell geometry was realized by growing a narrow gap semiconductor layer (CdSe) on the surface of a wide-gap core material (CdS) promoting the localization of excitons in the shell domain, as was confirmed by ultrafast transient absorption and emission lifetime measurements. The band gap emission of fabricated nanoshells, ranging from 15 to 30 nm in diameter, has revealed a characteristic size-dependent behavior tunable via the shell thickness with associated quantum yields in the 4.4-16.0% range.