Phonons and their interactions with other phonons, electrons or photons drive energy gain, loss and transport in materials. Although the phonon density of states has been measured and calculated in bulk crystalline semiconductors, phonons remain poorly understood in nanomaterials, despite the increasing prevalence of bottom-up fabrication of semiconductors from nanomaterials and the integration of nanometre-sized components into devices. Here we quantify the phononic properties of bottom-up fabricated semiconductors as a function of crystallite size using inelastic neutron scattering measurements and ab initio molecular dynamics simulations. We show that, unlike in microcrystalline semiconductors, the phonon modes of semiconductors with nanocrystalline domains exhibit both reduced symmetry and low energy owing to mechanical softness at the surface of those domains. These properties become important when phonons couple to electrons in semiconductor devices. Although it was initially believed that the coupling between electrons and phonons is suppressed in nanocrystalline materials owing to the scarcity of electronic states and their large energy separation, it has since been shown that the electron-phonon coupling is large and allows high energy-dissipation rates exceeding one electronvolt per picosecond (refs 10-13). Despite detailed investigations into the role of phonons in exciton dynamics, leading to a variety of suggestions as to the origins of these fast transition rates and including attempts to numerically calculate them, fundamental questions surrounding electron-phonon interactions in nanomaterials remain unresolved. By combining the microscopic and thermodynamic theories of phonons and our findings on the phononic properties of nanomaterials, we are able to explain and then experimentally confirm the strong electron-phonon coupling and fast multi-phonon transition rates of charge carriers to trap states. This improved understanding of phonon processes permits the rational selection of nanomaterials, their surface treatments, and the design of devices incorporating them.
Among the advantages of multicomponent nanocrystals is the possibility to adjust their electronic and optical properties with composition as well as size. However, the synthesis of multicomponent nanocrystals is challenging due to the presence of several metal precursors in the reaction mixture. This review takes I−III−VI semiconductor materials as an example class of multicomponent nanocrystals to highlight the underestimated importance of composition, which can affect the electronic and optical properties of nanocrystals as much as size. We discuss synthetic strategies, which enable the composition control, and show that the ability to separately choose nanocrystal size and nanocrystal composition can be beneficial for many optoelectronic and biomedical applications.
We report a simple, high-yield colloidal synthesis of copper indium selenide nanocrystals (CISe NCs) based on a silylamide-promoted approach. The silylamide anions increase the nucleation rate, which results in small-sized NCs exhibiting high luminescence and constant NC stoichiometry and crystal structure regardless of the NC size and shape. In particular, by systematically varying synthesis time and temperature, we show that the size of the CISe NCs can be precisely controlled to be between 2.7 and 7.9 nm with size distributions down to 9–10%. By introducing a specific concentration of silylamide-anions in the reaction mixture, the shape of CISe NCs can be preselected to be either spherical or tetrahedral. Optical properties of these CISe NCs span from the visible to near-infrared region with peak luminescence wavelengths of 700 to 1200 nm. The luminescence efficiency improves from 10 to 15% to record values of 50–60% by overcoating as-prepared CISe NCs with ZnSe or ZnS shells, highlighting their potential for applications such as biolabeling and solid state lighting.
We implement three complementary techniques to quantify the number, energy, and electronic properties of trap states in nanocrystal (NC)-based devices. We demonstrate that, for a given technique, the ability to observe traps depends on the Fermi level position, highlighting the importance of a multitechnique approach that probes trap coupling to both the conduction and the valence bands. We then apply our protocol for characterizing traps to quantitatively explain the measured performances of PbS NC-based solar cells.
Improving devices incorporating solution-processed nanocrystal-based semiconductors requires a better understanding of charge transport in these complex, inorganic–organic materials. Here we perform a systematic study on PbS nanocrystal-based diodes using temperature-dependent current–voltage characterization and thermal admittance spectroscopy to develop a model for charge transport that is applicable to different nanocrystal-solids and device architectures. Our analysis confirms that charge transport occurs in states that derive from the quantum-confined electronic levels of the individual nanocrystals and is governed by diffusion-controlled trap-assisted recombination. The current is limited not by the Schottky effect, but by Fermi-level pinning because of trap states that is independent of the electrode–nanocrystal interface. Our model successfully explains the non-trivial trends in charge transport as a function of nanocrystal size and the origins of the trade-offs facing the optimization of nanocrystal-based solar cells. We use the insights from our charge transport model to formulate design guidelines for engineering higher-performance nanocrystal-based devices.
The promise for next generation light‐emitting device (LED) technologies is a major driver for research on nanocrystal quantum dots (QDs). The low efficiencies of current QD‐LEDs are often attributed to luminescence quenching of charged QDs through Auger‐processes. Although new QD chemistries successfully suppress Auger recombination, high performance QD‐LEDs with these materials have yet to be demonstrated. Here, QD‐LED performance is shown to be significantly limited by the electric field. Experimental field‐dependent photoluminescence decay studies and tight‐binding simulations are used to show that independent of charging, the electric field can strongly quench the luminescence of QD solids by reducing the electron and hole wavefunction overlap, thereby lowering the radiative recombination rate. Quantifying this effect for a series of CdSe/CdS QD solids reveals a strong dependence on the QD band structure, which enables the outline of clear design strategies for QD materials and device architectures to improve QD‐LED performance.
The potential of semiconductors assembled from nanocrystals has been demonstrated for a broad array of electronic and optoelectronic devices, including transistors, light emitting diodes, solar cells, photodetectors, thermoelectrics, and phase change memory cells. Despite the commercial success of nanocrystal quantum dots as optical absorbers and emitters, applications involving charge transport through nanocrystal semiconductors have eluded exploitation due to the inability to predictively control their electronic properties. Here, we perform large-scale, ab initio simulations to understand carrier transport, generation, and trapping in strongly confined nanocrystal quantum dot-based semiconductors from first principles. We use these findings to build a predictive model for charge transport in these materials, which we validate experimentally. Our insights provide a path for systematic engineering of these semiconductors, which in fact offer previously unexplored opportunities for tunability not achievable in other semiconductor systems.
Ternary I-III-VI nanocrystals, such as silver indium selenide (AISe), are candidates to replace cadmium- and lead-based chalcogenide nanocrystals as efficient emitters in the visible and near IR, but, due to challenges in controlling the reactivities of the group I and III cations during synthesis, full compositional and size-dependent behavior of I-III-VI nanocrystals is not yet explored. We report an amide-promoted synthesis of AISe nanocrystals that enables independent control over nanocrystal size and composition. By systematically varying reaction time, amide concentration, and Ag- and In-precursor concentrations, we develop a predictive model for the synthesis and show that AISe sizes can be tuned from 2.4 to 6.8 nm across a broad range of indium-rich compositions from AgIn11Se17 to AgInSe2. We perform structural and optical characterization for representative AISe compositions (Ag0.85In1.05Se2, Ag3In5Se9, AgIn3Se5, and AgIn11Se17) and relate the peaks in quantum yield to stoichiometries exhibiting defect ordering in the bulk. We optimize luminescence properties to achieve a record quantum yield of 73%. Finally, time-resolved photoluminescence measurements enable us to better understand the physics of donor-acceptor emission and the role of structure and composition in luminescence.
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