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.
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