Douglas R. Pernik

Stimulated Raman scattering (SRS) microscopy is a newly developed label-free chemical imaging technique that overcomes the speed limitation of confocal Raman microscopy while avoiding the nonresonant background problem of coherent anti-Stokes Raman scattering (CARS) microscopy. Previous demonstrations have been limited to single Raman band measurements. We present a novel modulation multiplexing approach that allows real-time detection of multiple species using the fast Fourier transform. We demonstrate the quantitative determination of chemical concentrations in a ternary mixture. Furthermore, two imaging applications are pursued: (1) quantitative determination of oil content as well as pigment and protein concentration in microalgae cultures; and (2) 3D high-resolution imaging of blood, lipids, and protein distribution in ex vivo mouse skin tissue. We believe that quantitative multiplex SRS uniquely combines the advantage of fast label-free imaging with the fingerprinting capability of Raman spectroscopy and enables numerous applications in lipid biology as well as biomedical imaging.

Understanding CdSe quantum dot (QD) adsorption phenomena on mesoscopic TiO2 films is important for improving the performance of quantum dot sensitized solar cells (QDSSCs). A kinetic adsorption model has been developed to elucidate both Langmuir-like submonolayer adsorption and QD aggregation processes. Removal of surface-bound trioctylphosphine oxide as well as the use of 3-mercaptopropionic acid (MPA) as a molecular linker improved the adsorption of toluene-suspended QDs onto TiO2 films. The adsorption constant Kad for submonolayer coverage was (6.7 ± 2.7) × 103 M–1 for direct adsorption and (4.2 ± 2.0) × 104 M–1 for MPA-linked assemblies. Prolonged exposure of a TiO2 film to a CdSe QD suspension resulted in the assembly of aggregated particles regardless of the method of adsorption. A greater coverage of TiO2 was achieved with smaller QDs due to reduced size constraints. Ultrafast transient absorption spectroscopy demonstrated faster electron injection into TiO2 from directly adsorbed QDs (kET = 7.2 × 109 s–1) compared with MPA-linked QDs (kET = 2.3 × 109 s–1). The adsorption kinetic details presented in this study are useful for controlling CdSe QD adsorption on TiO2 and designing efficient photoanodes for QDSSCs.

Peak external quantum efficiencies (EQEs) of just over 120% were observed in photovoltaic (PV) devices of CuInSe2 nanocrystals prepared with a photonic curing process. The extraction of more than one electron/hole pair as a result of the absorption of a single photon can occur if multiple excitons are generated and extracted. Multiexciton generation (MEG) in the nanocrystal films was substantiated by transient absorption spectroscopy. We propose that photonic curing leads to sufficient electronic coupling between nanocrystals to enable multiexciton extraction under typical solar illumination conditions. Under low light conditions, however, the EQE drops significantly, indicating that photonic curing-induced ligand desorption creates a significant amount of traps in the film that limit the overall power conversion efficiency of the device.

The power conversion efficiency of photovoltaic devices made with ink-deposited Cu(InxGa1-x)Se2 (CIGS) nanocrystal layers can be enhanced by sintering the nanocrystals with a high temperature selenization process. This process, however, can be challenging to control. Here, we report that ink deposition followed by annealing under inert gas and then selenization can provide better control over CIGS nanocrystal sintering and yield generally improved device efficiency. Annealing under argon at 525 °C removes organic ligands and diffuses sodium from the underlying soda lime glass into the Mo back contact to improve the rate and quality of nanocrystal sintering during selenization at 500 °C. Shorter selenization time alleviates excessive MoSe2 formation at the Mo back contact that leads to film delamination, which in turn enables multiple cycles of nanocrystal deposition and selenization to create thicker, more uniform absorber films. Devices with power conversion efficiency greater than 7% are fabricated using the multiple step nanocrystal deposition and sintering process.

Copper indium diselenide (CuInSe2) is a prototype ternary compound and group I–III–VI semiconductor with useful optoelectronic properties. CuInSe2 nanocrystals have been of significant interest because of their size-tunable optical properties and lack of toxic heavy metals. Because of the particular vacancy and antisite substitutional point defects in CuInSe2, large stoichiometric deviations can be tolerated, sometimes leading to the so-called ordered vacancy compounds (OVCs). Here, we use Raman spectroscopy of oleylamine-capped CuInSe2 nanocrystals and ab initio lattice dynamics modeling to study the concentration and arrangements of (2vCu– + InCu2+) defect pairs in the nanocrystals. The nanocrystals have randomly distributed defect pairs that become mobile under light excitation and accumulate, as in OVCs, along the [100] direction. Because the high concentration of vacancies in CuInSe2 nanocrystals is compensated by InCu2+ antisite defects, these nanocrystals do not exhibit an optical plasmon resonance like many other copper chalcogenide nanocrystals. Annealing the nanocrystals at a high temperature (600 °C) was found to significantly reduce the defect concentration.