Improved mid-infrared photoconductors based on colloidal HgTe quantum dots are realized using a hybrid ligand exchange and polar phase transfer. The doping can also be controlled n and p by adjusting ...the HgCl2 concentration in the ligand exchange process. We compare the photoconductive properties with the prior “solid-state ligand exchange” using ethanedithiol, and we find that the new process affords a ∼100-fold increase of the electron and hole mobility, a ∼100-fold increase in responsivity, and a ∼10-fold increase in detectivity. These photodetector improvements are primarily attributed to the increase in mobility (μ) because the optical properties are mostly unchanged. We show that the specific detectivity (D*) of a photoconductive device is expected to scale as μ . The application potential is further verified by long-term device stability.
In this work, we synthesized InP and InAs nanocrystals (NCs) capped with different inorganic ligands, including various molecular metal chalcogenide complexes (MCCs) and chalcogenide ions. We found ...that MCCs and chalcogenide ions can quantitatively displace organic ligands from the surface of III–V NCs and serve as the inorganic capping groups for III–V NC surfaces. These inorganic ligands stabilize colloidal solutions of InP and InAs NCs in polar solvents and greatly facilitate charge transport between individual NCs. Charge transport studies revealed high electron mobility in the films of MCC-capped InP and InAs NCs. For example, we found that bridging InAs NCs with Cu7S4 – MCC ligands can lead to very high electron mobility exceeding 15 cm2/(V s). In addition, we observed unprecedented ambipolar (positive/negative) photoresponse of MCC-capped InAs NC solids that changed sign depending on the ligand chemistry, illumination wavelength, and doping of the NC solid. For example, the sign of photoconductance of InAs NCs capped with Cu7S4 – or Sn2S6 4– ions converted from positive at 0.80 and 0.95 eV to negative at 1.27 and 1.91 eV. We propose an explanation of this unusually complex photoconductivity of InAs NC solids.
Solution processing of photovoltaic semiconducting layers offers the potential for drastic cost reduction through improved materials utilization and high device throughput. One compelling ...solution-based processing strategy utilizes semiconductor layers produced by sintering nanocrystals into large-grain semiconductors at relatively low temperatures. Using n-ZnO/p-CdTe as a model system, we fabricate sintered CdTe nanocrystal solar cells processed at 350 °C with power conversion efficiencies (PCE) as high as 12.3%. J SC of over 25 mA cm–2 are achieved, which are comparable or higher than those achieved using traditional, close-space sublimated CdTe. We find that the V OC can be substantially increased by applying forward bias for short periods of time. Capacitance measurements as well as intensity- and temperature-dependent analysis indicate that the increased V OC is likely due to relaxation of an energetic barrier at the ITO/CdTe interface.
Arrays of ligand-stabilized colloidal nanocrystals with size-tunable electronic structure are promising alternatives to single-crystal semiconductors in electronic, optoelectronic and energy-related ...applications. Hard/soft interfaces in these nanocrystal arrays (NCAs) create a complex and uncharted vibrational landscape for thermal energy transport that will influence their technological feasibility. Here, we present thermal conductivity measurements of NCAs (CdSe, PbS, PbSe, PbTe, Fe3O4 and Au) and reveal that energy transport is mediated by the density and chemistry of the organic/inorganic interfaces, and the volume fractions of nanocrystal cores and surface ligands. NCA thermal conductivities are controllable within the range 0.1-0.3 W m(-1) K(-1), and only weakly depend on the thermal conductivity of the inorganic core material. This range is 1,000 times lower than the thermal conductivity of silicon, presenting challenges for heat dissipation in NCA-based electronics and photonics. It is, however, 10 times smaller than that of Bi2Te3, which is advantageous for NCA-based thermoelectric materials.
All-inorganic nanocrystals (NCs) are of great importance in a range of electronic devices. However, current all-inorganic NCs suffer from limitations in their optical properties, such as low ...fluorescence efficiencies. Here, we develop a general surface treatment strategy to obtain intensely luminescent all-inorganic NCs (ILANs) by using designed metal salts with noncoordinating anions that play a dual role in the surface treatment process: (i) removing the original organic ligands and (ii) binding to unpassivated Lewis basic sites to preserve the photoluminescent (PL) properties of the NCs. The absolute photoluminescence quantum yields (PLQYs) of red-emitting CdSe/ZnS NCs, green-emitting CdSe/CdZnSeS/ZnS NCs and blue-emitting CdZnS/ZnS NCs in polar solvents are 97%, 80% and 72%, respectively. Further study reveals that the passivated Lewis basic sites of ILANs by metal cations boost the efficiency of radiative recombination of electron-hole pairs. While the passivation of Lewis basic sites leads to a high PLQY of ILANs, the exposed Lewis acidic sites provide the possibility for in situ tuning of the functions of NCs, creating opportunities for direct optical patterning of functional NCs with high resolution.
The development of probes for single-molecule imaging has dramatically facilitated the study of individual molecules in cells and other complex environments. Single-molecule probes ideally exhibit ...good brightness, uninterrupted emission, resistance to photobleaching, and minimal spectral overlap with cellular autofluorescence. However, most single-molecule probes are imperfect in several of these aspects, and none have been shown to possess all of these characteristics. Here we show that individual lanthanide-doped upconverting nanoparticles (UCNPs)--specifically, hexagonal phase NaYF₄ (β-NaYF₄) nanocrystals with multiple Yb³⁺ and Er³⁺ dopants--emit bright anti-Stokes visible upconverted luminescence with exceptional photostability when excited by a 980-nm continuous wave laser. Individual UCNPs exhibit no on/off emission behavior, or "blinking," down to the millisecond timescale, and no loss of intensity following an hour of continuous excitation. Amphiphilic polymer coatings permit the transfer of hydrophobic UCNPs into water, resulting in individual water-soluble nanoparticles with undiminished photophysical characteristics. These UCNPs are endocytosed by cells and show strong upconverted luminescence, with no measurable anti-Stokes background autofluorescence, suggesting that UCNPs are ideally suited for single-molecule imaging experiments.
Self-assembly of two sizes of nearly spherical colloidal nanocrystals (NCs) capped with hydrocarbon surface ligands has been shown to produce more than 20 distinct phases of binary nanocrystal ...superlattices (BNSLs). Such structural diversity, in striking contrast to binary systems of micron-sized colloidal beads, cannot be rationalized by models assuming entropy-driven crystallization of simple spheres. In this work, we show that the PbS ligand binding equilibrium controls the relative stability of two closely related BNSL structures featuring alternating layers of PbS and Au NCs. At an intermediate size ratio, as-prepared PbS NCs assemble with Au NCs into CuAu BNSLs featuring orientational coherence of PbS NCs across the lattice. Measurement of interparticle separations within CuAu and modeling of the structure reveal that PbS inorganic cores are nearly in contact through (100) NC surfaces in the square tiling of the CuAu basal plane. On the other hand, AlB2 BNSLs with PbS NCs packed in random orientations were found to be the dominant self-assembly product when the same binary NC solution was evaporated in the presence of added oleic acid (OAH). Solution nuclear magnetic resonance titration experiments confirmed that added OAH binds to PbS NCs, implicating ligand surface coverage as an important factor influencing the relative stability of CuAu and AlB2 BNSLs at the experimental size ratio. From these results, we conclude that as-prepared PbS NCs feature sparsely covered (100) surfaces and thus effectively flat patches along NC x-, y-, and z-directions. Such anisotropic PbS–PbS interactions can be efficiently screened by restoring effectively spherical NC shape via addition of OAH to the binary assembly solution. Our findings underscore the important contribution of NC surfaces to superlattice phase stability and offer a strategy for targeted BNSL assembly.
Spatially patterned dielectric materials are ubiquitous in electronic, photonic, and optoelectronic devices. These patterns are typically made by subtractive or additive approaches utilizing ...vapor-phase reagents. On the other hand, recent advances in solution-phase synthesis of oxide nanomaterials have unlocked a materials library with greater compositional, microstructural, and interfacial tunability. However, methods to pattern and integrate these nanomaterials in real-world devices are less established. In this work, we directly optically pattern oxide nanoparticles (NPs) by mixing them with photosensitive diazo-2-naphthol-4-sulfonic acid and irradiating with widely available 405 nm light. We demonstrate the direct optical lithography of ZrO2, TiO2, HfO2, and ITO NPs and investigate the chemical and physical changes responsible for this photoinduced decrease in solubility. Micron-thick layers of amorphous ZrO2 NPs were patterned with micron resolution and shown to allow 2π phase control of visible light. We also show multilayer patterning and use it to fabricate features with different thicknesses and distinct structural colors. Upon annealing at 400 °C, the deposited ZrO2 structures have excellent optical transparency across a wide wavelength range (0.3–10 μm), a high refractive index (n = 1.84 at 633 nm), and are optically smooth. We then fabricate diffractive optical elements, such as binary phase diffraction gratings, that show efficient diffractive behavior and good thermal stability. Different oxide NPs can also be mixed prior to patterning, providing a high level of material tunability. This work demonstrates a general patterning approach that harnesses the processability and diversity of colloidal oxide nanomaterials for use in photonic applications.
Colloidal nanocrystals of metals, semiconductors, and other functional materials can self-assemble into long-range ordered crystalline and quasicrystalline phases, but insulating organic surface ...ligands prevent the development of collective electronic states in ordered nanocrystal assemblies. We reversibly self-assembled colloidal nanocrystals of gold, platinum, nickel, lead sulfide, and lead selenide with conductive inorganic ligands into supercrystals exhibiting optical and electronic properties consistent with strong electronic coupling between the constituent nanocrystals. The phase behavior of charge-stabilized nanocrystals can be rationalized and navigated with phase diagrams computed for particles interacting through short-range attractive potentials. By finely tuning interparticle interactions, the assembly was directed either through one-step nucleation or nonclassical two-step nucleation pathways. In the latter case, the nucleation was preceded by the formation of two metastable colloidal fluids.
We studied the effect of temperature on self-assembly of monodisperse colloidal nanocrystals into single-component and binary superlattices. Temperature, which serves as a weighting factor for the ...internal energy (U) and entropy (S) contributions to the Helmholtz free energy F = U − TS, allows tailoring relative weights of the interparticle interactions and free-volume entropy during the formation of nanocrystal superlattices. Temperature also provides a convenient tool for directing self-assembly of nanocrystals toward desired superlattice structures. We found that temperature strongly affects the structures of binary superlattices self-assembled from the mixtures of CdSe + PbS nanocrystals and PbSe + Pd nanocrystals. In the former case, small Hamaker constants for CdSe and PbS nanocrystals led to a relatively simple phase diagram, including only high-density NaZn13-, AlB2-, and NaCl-type binary superlattices. In contrast, binary superlattices self-assembled at different temperatures from PbSe and Pd nanocrystals showed a number of low-density complex phases stabilized by strong local van der Waals interactions between Pd nanocrystals. The structural diversity of nanoparticle superlattices is shown to be a result of the cooperative effect of the entropy-driven crystallization and the interparticle interactions. Both ΔU and TΔS terms associated with the superlattice formation should be of the same order of magnitude, with |ΔU| < |TΔS| for the assembly of CdSe and PbS nanocrystals and |ΔU| > |TΔS| for the PbSe and Pd nanocrystals.
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