Mark C. Weidman

Monodisperse, Air-Stable PbS Nanocrystals via Precursor Stoichiometry Control

Despite their technological importance, lead sulfide (PbS) nanocrystals have lagged behind nanocrystals of cadmium selenide (CdSe) and lead selenide (PbSe) in terms of size and energy homogeneity. Here, we show that the ratio of lead to sulfur precursor available during nucleation is a critical parameter affecting subsequent growth and monodispersity of PbS nanocrystal ensembles. Applying this knowledge, we synthesize highly monodisperse (size dispersity <5%) PbS nanocrystals over a wide range of sizes (exciton energies from 0.70 to 1.25 eV, or 1000-1800 nm) without the use of size-selective precipitations. This degree of monodispersity results in absorption peak half width at half max (HWHM) values as small as 20 meV, indicating an ensemble that is close to the homogeneous limit. Photoluminescence emission is correspondingly narrow and exhibits small Stokes shifts and quantum efficiencies of 30-60%. The nanocrystals readily self-assemble into ordered superlattices and exhibit exceptional air stability over several months.

Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition

Colloidal perovskite nanoplatelets are a promising class of semiconductor nanomaterials-exhibiting bright luminescence, tunable and spectrally narrow absorption and emission features, strongly confined excitonic states, and facile colloidal synthesis. Here, we demonstrate the high degree of spectral tunability achievable through variation of the cation, metal, and halide composition as well as nanoplatelet thickness. We synthesize nanoplatelets of the form L2[ABX3]n-1BX4, where L is an organic ligand (octylammonium, butylammonium), A is a monovalent metal or organic molecular cation (cesium, methylammonium, formamidinium), B is a divalent metal cation (lead, tin), X is a halide anion (chloride, bromide, iodide), and n-1 is the number of unit cells in thickness. We show that variation of n, B, and X leads to large changes in the absorption and emission energy, while variation of the A cation leads to only subtle changes but can significantly impact the nanoplatelet stability and photoluminescence quantum yield (with values over 20%). Furthermore, mixed halide nanoplatelets exhibit continuous spectral tunability over a 1.5 eV spectral range, from 2.2 to 3.7 eV. The nanoplatelets have relatively large lateral dimensions (100 nm to 1 μm), which promote self-assembly into stacked superlattice structures-the periodicity of which can be adjusted based on the nanoplatelet surface ligand length. These results demonstrate the versatility of colloidal perovskite nanoplatelets as a material platform, with tunability extending from the deep-UV, across the visible, into the near-IR. In particular, the tin-containing nanoplatelets represent a significant addition to the small but increasingly important family of lead- and cadmium-free colloidal semiconductors.

Subdiffusive Exciton Transport in Quantum Dot Solids

Colloidal quantum dots (QDs) are promising materials for use in solar cells, light-emitting diodes, lasers, and photodetectors, but the mechanism and length of exciton transport in QD materials is not well understood. We use time-resolved optical microscopy to spatially visualize exciton transport in CdSe/ZnCdS core/shell QD assemblies. We find that the exciton diffusion length, which exceeds 30 nm in some cases, can be tuned by adjusting the inorganic shell thickness and organic ligand length, offering a powerful strategy for controlling exciton movement. Moreover, we show experimentally and through kinetic Monte Carlo simulations that exciton diffusion in QD solids does not occur by a random-walk process; instead, energetic disorder within the inhomogeneously broadened ensemble causes the exciton diffusivity to decrease over time. These findings reveal new insights into exciton dynamics in disordered systems and demonstrate the flexibility of QD materials for photonic and optoelectronic applications.

Kinetics of the self-assembly of nanocrystal superlattices measured by real-time in situ X-ray scattering

On solvent evaporation, non-interacting monodisperse colloidal particles self-assemble into a close-packed superlattice. Although the initial and final states can be readily characterized, little is known about the dynamic transformation from colloid to superlattice. Here, by using in situ grazing-incidence X-ray scattering, we tracked the self-assembly of lead sulfide nanocrystals in real time. Following the first appearance of an ordered arrangement, the superlattice underwent uniaxial contraction and collective rotation as it approached its final body-centred cubic structure. The nanocrystals became crystallographically aligned early in the overall self-assembly process, showing that nanocrystal ordering occurs on a faster timescale than superlattice densification. Our findings demonstrate that synchrotron X-ray scattering is a viable method for studying self-assembly in its native environment, with ample time resolution to extract kinetic rates and observe intermediate configurations. The method could be used for real-time direction of self-assembly processes and to better understand the forces governing self-organization of soft materials.

Tunable Light-Emitting Diodes Utilizing Quantum-Confined Layered Perovskite Emitters

Organic–inorganic perovskites have been shown to have excellent optoelectronic properties. Further, layered perovskites have been demonstrated, utilizing quantum confinement to achieve emission blue-shifted from the bulk band gap. Here, we tune this blue-shift to build LEDs that span the visible spectrum. We demonstrate that electroluminescence from red-shifted layers dominates emission from mixed-thickness devices and that the addition of excess ligand is necessary to drive emission toward blue-shifted layers. By tuning the thickness of the layers, we build LEDs with blue emission utilizing the lead bromide system and orange emission utilizing the lead iodide system. Finally, we demonstrate that these materials suffer reversible degradation under an applied electric field. The spectrally narrow emission, combined with the favorable electronic properties of perovskite materials and access to shorter emission wavelengths through quantum confinement, demonstrates the promise of these materials as a new plat...

CdSe Nanoplatelet Films with Controlled Orientation of their Transition Dipole Moment

Using liquid-liquid interfacial assembly, we control the deposition of CdSe nanoplatelets into face-down or edge-up configurations. Controlled assembly, combined with back focal plane imaging, enabled unambiguous determination of the transition dipole orientation. The transition dipole moment of the emissive band-edge exciton in CdSe nanoplatelets was found to be isotropically oriented within the plane of the nanoplatelet with no measurable out-of-plane component and no preference for the long- or short-axis of the nanoplatelet. Importantly, CdSe nanoplatelet films in the face-down configuration exhibited unity dipole orientation within the plane of the film, which could improve the external efficiency of nanoplatelet LEDs, lasers, photodetectors, and photovoltaic cells beyond that which is possible with isotropic emitters. We also show that the two self-assembled configurations have different Förster energy transfer rates, as a result of different dipole orientation and internanoplatelet distance.

Charge Carrier Hopping Dynamics in Homogeneously Broadened PbS Quantum Dot Solids

Energetic disorder in quantum dot solids adversely impacts charge carrier transport in quantum dot solar cells and electronic devices. Here, we use ultrafast transient absorption spectroscopy to show that homogeneously broadened PbS quantum dot arrays (σhom2:σinh2 > 19:1, σinh/kBT < 0.4) can be realized if quantum dot batches are sufficiently monodisperse (δ ≲ 3.3%). The homogeneous line width is found to be an inverse function of quantum dot size, monotonically increasing from ∼25 meV for the largest quantum dots (5.8 nm diameter/0.92 eV energy) to ∼55 meV for the smallest (4.1 nm/1.3 eV energy). Furthermore, we show that intrinsic charge carrier hopping rates are faster for smaller quantum dots. This finding is the opposite of the mobility trend commonly observed in device measurements but is consistent with theoretical predictions. Fitting our data to a kinetic Monte Carlo model, we extract charge carrier hopping times ranging from 80 ps for the smallest quantum dots to over 1 ns for the largest, with the same ethanethiol ligand treatment. Additionally, we make the surprising observation that, in slightly polydisperse (δ ≲ 4%) quantum dot solids, structural disorder has a greater impact than energetic disorder in inhibiting charge carrier transport. These findings emphasize how small improvements in batch size dispersity can have a dramatic impact on intrinsic charge carrier hopping behavior and will stimulate further improvements in quantum dot device performance.

Spatially resolved energy transfer in patterned colloidal quantum dot heterostructures.

Spatial uniformity is a key consideration in high-resolution displays and light-emitting structures fabricated from colloidal quantum dots (QDs). We report spatially and spectrally resolved transient photoluminescence measurements of laterally patterned QD heterostructures. We show, using a microcontact printing technique, that spatially uniform energy transfer can be achieved in a QD donor-acceptor bilayer system, highlighting the promising potential of colloidal QDs as flexible photonic components in next-generation optoelectronic technologies.

Tunable light emitting diodes utilizing quantum-confined layered perovskite emitters (Conference Presentation)

Organic-inorganic perovskites have revolutionized the optoelectronics field, providing materials with a wide range of properties for solving numerous applications. Indeed, much recent work has been focused on nanostructured perovskites, with quantum dots, nanowires, and nanoplatelets showing tremendous potential. Here, we utilize the unique tunability of 2D perovskite nanoplatelets to build LEDs that span the visible spectrum. Quantum confinement in the z direction drives a significant blueshift, allowing for blue devices utilizing the bromide system and orange devices utilizing the iodide system. We demonstrate that excess ligand addition is crucial to achieving this blueshift in thin films that otherwise suffer from energy funneling. We build devices that show electroluminescence from 440 nm to 650 nm, although they still suffer from low efficiencies due to low photoluminescence quantum yields. We finally demonstrate that these materials suffer from reversible degradation with an applied electric field, further limiting the efficiency. The favorable optoelectronic properties of perovskite materials, combined with the blueshift due to quantum confinement, shows the promise of these materials as a new class of low cost emitters.