Photosensitivity Enhancement with TiO₂ in Semitransparent Light-Sensitive Skins of Nanocrystal Monolayers

We propose and demonstrate light-sensitive nanocrystal skins that exhibit broadband sensitivity enhancement based on electron transfer to a thin TiO₂ film grown by atomic layer deposition. In these photosensors, which operate with no external bias, photogenerated electrons remain trapped inside the nanocrystals. These electrons generally recombine with the photogenerated holes that accumulate at the top interfacing contact, which leads to lower photovoltage buildup. Because favorable conduction band offset aids in transferring photoelectrons from CdTe nanocrystals to the TiO₂ layer, which decreases the exciton recombination probability, TiO₂ has been utilized as the electron-accepting material in these light-sensitive nanocrystal skins. A controlled interface thickness between the TiO₂ layer and the monolayer of CdTe nanocrystals enables a photovoltage buildup enhancement in the proposed nanostructure platform. With TiO₂ serving as the electron acceptor, we observed broadband sensitivity improvement across 350–475 nm, with an approximately 22% enhancement. Furthermore, time-resolved fluorescence measurements verified the electron transfer from the CdTe nanocrystals to the TiO₂ layer in light-sensitive skins. These results could pave the way for engineering nanocrystal-based light-sensing platforms, such as smart transparent windows, light-sensitive walls, and large-area optical detection systems

Phonon-Assisted Exciton Transfer into Silicon Using Nanoemitters: The Role of Phonons and Temperature Effects in Förster Resonance Energy Transfer

We study phonon-assisted Förster resonance energy transfer (FRET) into an indirect band-gap semiconductor using nanoemitters. The unusual temperature dependence of this energy transfer, which is measured using the donor nanoemitters of quantum dot (QD) layers integrated on the acceptor monocrystalline bulk silicon as a model system, is predicted by a phonon-assisted exciton transfer model proposed here. The model includes the phonon-mediated optical properties of silicon, while considering the contribution from the multimonolayer-equivalent QD film to the nonradiative energy transfer, which is derived with a <i>d</i>^–3 distance dependence. The FRET efficiencies are experimentally observed to decrease at cryogenic temperatures, which are well explained by the model considering the phonon depopulation in the indirect band-gap acceptor together with the changes in the quantum yield of the donor. These understandings will be crucial for designing FRET-enabled sensitization of silicon based high-efficiency excitonic systems using nanoemitters

Understanding the Journey of Dopant Copper Ions in Atomically Flat Colloidal Nanocrystals of CdSe Nanoplatelets Using Partial Cation Exchange Reactions

Unique electronic and optical properties of doped semiconductor nanocrystals (NCs) have widely stimulated a great deal of interest to explore new effective synthesis routes to achieve controlled doping for highly efficient materials. In this work, we show copper doping via postsynthesis partial cation exchange (CE) in atomically flat colloidal semiconductor nanoplatelets (NPLs). Here chemical reactivity of different dopant precursors, reaction kinetics, and shape of seed NPLs were extensively elaborated for successful doping and efficient emission. Dopant-induced Stokes-shifted and tunable photoluminescence emission (640 to 830 nm) was observed in these Cu-doped CdSe NPLs using different thicknesses and heterostructures. High quantum yields (reaching 63%) accompanied by high absorption cross sections (>2.5 times) were obtained in such NPLs compared to those of Cu-doped CdSe colloidal quantum dots (CQDs). Systematic tuning of the doping level in these two-dimensional NPLs provides an insightful understanding of the chemical dopant based orbital hybridization in NCs. The unique combination of doping via the partial CE method and precise control of quantum confinement in such atomically flat NPLs originating from their magic-sized vertical thickness exhibits an excellent model platform for studying photophysics of doped quantum confined systems

Chiral Ceramic Nanoparticles and Peptide Catalysis

The chirality of nanoparticles (NPs) and their assemblies has been investigated predominantly for noble metals and II–VI semiconductors. However, ceramic NPs represent the majority of nanoscale materials in nature. The robustness and other innate properties of ceramics offer technological opportunities in catalysis, biomedical sciences, and optics. Here we report the preparation of chiral ceramic NPs, as represented by tungsten oxide hydrate, WO_3–<i>x</i>·H₂O, dispersed in ethanol. The chirality of the metal oxide core, with an average size of ca. 1.6 nm, is imparted by proline (Pro) and aspartic acid (Asp) ligands via bio-to-nano chirality transfer. The amino acids are attached to the NP surface through C–O–W linkages formed from dissociated carboxyl groups and through amino groups weakly coordinated to the NP surface. Surprisingly, the dominant circular dichroism bands for NPs coated by Pro and Asp are different despite the similarity in the geometry of the NPs; they are positioned at 400–700 nm and 500–1100 nm for Pro- and Asp-modified NPs, respectively. The differences in the spectral positions of the main chiroptical band for the two types of NPs are associated with the molecular binding of the two amino acids to the NP surface; Asp has one additional C–O–W linkage compared to Pro, resulting in stronger distortion of the inorganic crystal lattice and greater intensity of CD bands associated with the chirality of the inorganic core. The chirality of WO_3–<i>x</i>·H₂O atomic structure is confirmed by atomistic molecular dynamics simulations. The proximity of the amino acids to the mineral surface is associated with the catalytic abilities of WO_3–<i>x</i>·H₂O NPs. We found that NPs facilitate formation of peptide bonds, leading to Asp-Asp and Asp-Pro dipeptides. The chiroptical activity, chemical reactivity, and biocompatibility of tungsten oxide create a unique combination of properties relevant to chiral optics, chemical technologies, and biomedicine