Olesya Yarema

Quantification of deep traps in nanocrystal solids, their electronic properties, and their influence on device behavior.

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.

A quantitative model for charge carrier transport, trapping and recombination in nanocrystal-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.

Highly Luminescent, Size- and Shape-Tunable Copper Indium Selenide Based Colloidal Nanocrystals

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.

From Highly Monodisperse Indium and Indium Tin Colloidal Nanocrystals to Self-Assembled Indium Tin Oxide Nanoelectrodes

Indium tin oxide (ITO) nanopatterned electrodes are prepared from colloidal solutions as a material saving alternative to the industrial vapor phase deposition and top down processing. For that purpose highly monodisperse In(1-x)Sn(x) (x < 0.1) colloidal nanocrystals (NCs) are synthesized with accurate size and composition control. The outstanding monodispersity of the NCs is evidenced by their self-assembly properties into highly ordered superlattices. Deposition on structured substrates and subsequent treatment in oxygen plasma converts the NC assemblies into transparent electrode patterns with feature sizes down to the diameter of single NCs. The conductivity in these ITO electrodes competes with the best values reported for electrodes from ITO nanoparticle inks.

Soft surfaces of nanomaterials enable strong phonon interactions

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, 11, 12, 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.

Deep Level Transient Spectroscopy (DLTS) on Colloidal-Synthesized Nanocrystal Solids

We demonstrate current-based, deep level transient spectroscopy (DLTS) on semiconductor nanocrystal solids to obtain quantitative information on deep-lying trap states, which play an important role in the electronic transport properties of these novel solids and impact optoelectronic device performance. Here, we apply this purely electrical measurement to an ethanedithiol-treated, PbS nanocrystal solid and find a deep trap with an activation energy of 0.40 eV and a density of NT = 1.7 × 10(17) cm(-3). We use these findings to draw and interpret band structure models to gain insight into charge transport in PbS nanocrystal solids and the operation of PbS nanocrystal-based solar cells.

Hole Mobility in Nanocrystal Solids as a Function of Constituent Nanocrystal Size

Solids of semiconductor nanocrystals (NCs) are semiconductors in which the band gap can be controlled by changing the size of the constituent NCs. To date, nontrivial dependencies of the carrier mobility on the NC size have been reported. We use the time-of-flight (TOF) technique to measure the carrier mobility as a function of the NC size and find that the hole mobility of the NC solid increases dramatically with decreasing NC radius. We show that this result is in agreement with an analytic model for carrier mobility in NC solids. We further implement Monte Carlo simulations to aid in understanding the transient measurements in the context of models of dispersive transport. This work highlights that changing NC size in a device has important implications for charge transport.

Independent Composition and Size Control for Highly Luminescent Indium-Rich Silver Indium Selenide Nanocrystals

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.

Research Update: Comparison of salt- and molecular-based iodine treatments of PbS nanocrystal solids for solar cells

Molecular- and salt-based chemical treatments are believed to passivate electronic trap states in nanocrystal-based semiconductors, which are considered promising for solar cells but suffer from high carrier recombination. Here, we compare the chemical, optical, and electronic properties of PbS nanocrystal-based solids treated with molecular iodine and tetrabutylammonium iodide. Surprisingly, both treatments increase—rather than decrease—the number density of trap states; however, the increase does not directly influence solar cell performance. We explain the origins of the observed impact on solar cell performance and the potential in using different chemical treatments to tune charge carrier dynamics in nanocrystal-solids.

Rapid, microwave-assisted synthesis of battery-grade lithium titanate (LTO)

We report a fast, scalable, and low energy approach to synthesize battery-grade Li4Ti5O12 (LTO). Low-temperature, microwave-assisted solvothermal synthesis yields nanoplatelets that self-assemble into microspheres. Following calcination, these microspheres exhibit capacities of 170 mAh g−1 and a capacity retention of 99% over 100 cycles.