Enhanced Multiple Exciton Generation in PbS|CdS Janus-like Heterostructured Nanocrystals.

Generating multiple excitons by a single high-energy photon is a promising third-generation solar energy conversion strategy. We demonstrate that multiple exciton generation (MEG) in PbS|CdS Janus-like heteronanostructures is enhanced over that of single-component and core/shell nanocrystal architectures, with an onset close to two times the PbS band gap. We attribute the enhanced MEG to the asymmetric nature of the heteronanostructure that results in an increase in the effective Coulomb interaction that drives MEG and a reduction of the competing hot exciton cooling rate. Slowed cooling occurs through effective trapping of hot-holes by a manifold of valence band interfacial states having both PbS and CdS character, as evidenced by photoluminescence studies and ab initio calculations. Using transient photocurrent spectroscopy, we find that the MEG characteristics of the individual nanostructures are maintained in conductive arrays and demonstrate that these quasi-spherical PbS|CdS nanocrystals can be incorporated as the main absorber layer in functional solid-state solar cell architectures. Finally, based upon our analysis, we provide design rules for the next generation of engineered nanocrystals to further improve the MEG characteristics.

Synthesis and Spectroscopy of Silver-Doped PbSe Quantum Dots.

Electronic impurity doping of bulk semiconductors is an essential component of semiconductor science and technology. Yet there are only a handful of studies demonstrating control of electronic impurities in semiconductor nanocrystals. Here, we studied electronic impurity doping of colloidal PbSe quantum dots (QDs) using a postsynthetic cation exchange reaction in which Pb is exchanged for Ag. We found that varying the concentration of dopants exposed to the as-synthesized PbSe QDs controls the extent of exchange. The electronic impurity doped QDs exhibit the fundamental spectroscopic signatures associated with injecting a free charge carrier into a QD under equilibrium conditions, including a bleach of the first exciton transition and the appearance of a quantum-confined, low-energy intraband absorption feature. Photoelectron spectroscopy confirms that Ag acts as a p-type dopant for PbSe QDs and infrared spectroscopy is consistent with k·p calculations of the size-dependent intraband transition energy. We find that to bleach the first exciton transition by an average of 1 carrier per QD requires that approximately 10% of the Pb be replaced by Ag. We hypothesize that the majority of incorporated Ag remains at the QD surface and does not interact with the core electronic states of the QD. Instead, the excess Ag at the surface promotes the incorporation of <1% Ag into the QD core where it causes p-type doping behavior.

Quantum dot-induced phase stabilization of α-CsPbI3 perovskite for high-efficiency photovoltaics.

We show nanoscale phase stabilization of CsPbI3 quantum dots (QDs) to low temperatures that can be used as the active component of efficient optoelectronic devices. CsPbI3 is an all-inorganic analog to the hybrid organic cation halide perovskites, but the cubic phase of bulk CsPbI3 (α-CsPbI3)-the variant with desirable band gap-is only stable at high temperatures. We describe the formation of α-CsPbI3 QD films that are phase-stable for months in ambient air. The films exhibit long-range electronic transport and were used to fabricate colloidal perovskite QD photovoltaic cells with an open-circuit voltage of 1.23 volts and efficiency of 10.77%. These devices also function as light-emitting diodes with low turn-on voltage and tunable emission.

All-Inorganic Germanium Nanocrystal Films by Cationic Ligand Exchange.

We introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and (1)H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport in germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.

Preparation of Cd/Pb Chalcogenide Heterostructured Janus Particles via Controllable Cation Exchange.

We developed a strategy for producing quasi-spherical nanocrystals of anisotropic heterostructures of Cd/Pb chalcogenides. The nanostructures are fabricated via a controlled cation exchange reaction where the Cd(2+) cation is exchanged for the Pb(2+) cation. The cation exchange reaction is thermally activated and can be controlled by adjusting the reaction temperature or time. We characterized the particles using TEM, XPS, PL, and absorption spectroscopy. With complete exchange, high quality Pb-chalcogenide quantum dots are produced. In addition to Cd(2+), we also find suitable conditions for the exchange of Zn(2+) cations for Pb(2+) cations. The cation exchange is anisotropic starting at one edge of the nanocrystals and proceeds along the ⟨111⟩ direction producing a sharp interface at a (111) crystallographic plane. Instead of spherical core/shell structures, we produced and studied quasi-spherical CdS/PbS and CdSe/PbSe Janus-type heterostructures. Nontrivial PL behavior was observed from the CdS(e)/PbS(e) heterostructures as the Pb:Cd ratio is increased.

Cu(2)ZnSnS(4) nanocrystal dispersions in polar liquids.

Cu(2)ZnSnS(4) (CZTS) nanocrystals sterically stabilized with oleic acid and oleylamine ligands and dispersed in nonpolar organic liquids have been extracted into, and electrostatically stabilized in, polar liquids by covering their surfaces with S(2-).

Photoelectrochemical activity of as-grown, α-Fe2O3 nanowire array electrodes for water splitting.

Undoped hematite nanowire arrays grown using plasma oxidation of iron foils show significant photoactivity (~0.38 mA cm(-2) at 1.5 V versus reversible hydrogen electrode in 1 M KOH). In contrast, thermally oxidized nanowire arrays grown on iron exhibit no photoactivity due to the formation of a thick (>7 µm Fe(1-x)O) interfacial layer. An atmospheric plasma oxidation process required only a few minutes to synthesize hematite nanowire arrays with a 1­5 µm interfacial layer of magnetite between the nanowire arrays and the iron substrate. An amorphous oxide surface layer on hematite nanowires, if present, is shown to decrease the resulting photoactivity of as-synthesized, plasma grown nanowire arrays. The photocurrent onset potential is improved after removing the amorphous surface on the nanowires using an acid etch. A two-step method involving high temperature nucleation followed by growth at low temperature is shown to produce a highly dense and uniform coverage of nanowire arrays.