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1.
J Phys Chem C Nanomater Interfaces ; 127(48): 23312-23322, 2023 Dec 07.
Article in English | MEDLINE | ID: mdl-38090136

ABSTRACT

Quasi-two-dimensional (2D) metal halide perovskites (MHPs) are promising photovoltaic (PV) materials because of their impressive optical and optoelectronic properties and improved stability compared to their 3D counterparts. The presence of domains with varying numbers of inorganic layers between the organic spacers (n-phases), each with different bandgaps, makes the photoinduced carrier dynamics in films of these materials complex and intriguing. Existing interpretations of the ultrafast femto- or picosecond spectroscopy data have been inconsistent, most of them focusing either on exciton/charge transfer from low-n to high-n phases or on hot carrier cooling, but not combined. Here, we present a comprehensive study of the carrier dynamics in the Dion-Jacobson type (PDMA)(MA)(n-1)PbnI(3n+1) (PDMA = 1,4-phenylenedimethylammonium, MA = methylammonium) perovskite, stoichiometrically prepared as ⟨n⟩ = 5. Within the film, a coexistence of various n-phases is observed instead of solely the n = 5 phase, resulting in an interesting energy landscape for the motion of excitons and charge carriers. We disentangle hot carrier cooling from exciton transfer between low-n and high-n phases using ultrafast time-resolved photoluminescence and transient absorption spectroscopy. Photophysical modeling by target analysis shows that carrier cooling occurring on a subpicosecond time scale is followed by exciton transfer from low-n into high-n phases in ca. 35 ps when the film is excited by 532 or 490 nm light. Carriers in the high-n phase are much longer lived and decay in a ns time window. Overall, our results provide a comprehensive understanding of the photophysics of this material, which helps to optimize quasi-2D MHP materials for a new generation of PV devices.

2.
J Phys Chem C Nanomater Interfaces ; 125(29): 16049-16058, 2021 Jul 29.
Article in English | MEDLINE | ID: mdl-34484551

ABSTRACT

Dye-sensitized photoelectrochemical (DSPEC) water splitting is an attractive approach to convert and store solar energy into chemical bonds. However, the solar conversion efficiency of a DSPEC cell is typically low due to a poor performance of the photocathode. Here, we demonstrate that Cu-doping improves the performance of a functionalized NiO-based photocathode significantly. Femtosecond transient absorption experiments show longer-lived photoinduced charge separation for the Cu:NiO-based photocathode relative to the undoped analogue. We present a photophysical model that distinguishes between surface and bulk charge recombination, with the first process (∼10 ps) occurring more than 1 order of magnitude faster than the latter. The longer-lived photoinduced charge separation in the Cu:NiO-based photocathode likely originates from less dominant surface recombination and an increased probability for holes to escape into the bulk and to be transported to the electrical contact of the photocathode. Cu-doping of NiO shows promise to suppress detrimental surface charge recombination and to realize more efficient photocathodes.

3.
Chemphyschem ; 19(22): 3084-3091, 2018 11 19.
Article in English | MEDLINE | ID: mdl-30221834

ABSTRACT

Recent studies on hydrogen-generating supramolecular bimetallic photocatalysts indicate a more important role of the peripheral ligands than expected, motivating us to design a Ru/Pt complex with 4,7-diphenyl-1,10-phenanthroline peripheral ligands. Photoinduced intra- and inter-ligand internal conversion processes have been investigated using transient absorption spectroscopy, spanning the femto- to nanosecond timescale. After photoexcitation and ultrafast intersystem crossing, triplet states localised on either the peripheral ligands or on the bridging ligand/catalytic unit are populated in a non-equilibrated way. Time-resolved photoluminescence demonstrates that the lifetime for the Ru/Pt dinuclear species (795±8 ns) is significantly less than that of the mononuclear analogue (1375±20 ns). The photocatalytic studies show modest hydrogen turnover numbers, which is possibly caused by the absence of an excited state equilibrium. Finally, we identify challenges that must be overcome to further develop this class of photocatalysts and propose directions for future research.

4.
Opt Express ; 24(16): 17874-85, 2016 Aug 08.
Article in English | MEDLINE | ID: mdl-27505755

ABSTRACT

Small metal structures sustaining plasmon resonances in the optical regime are of great interest due to their large scattering cross sections and ability to concentrate light to subwavelength volumes. In this paper, we study the dipolar plasmon resonances of optical antennas with a constant volume and a sinusoidal modulation in width. We experimentally show that by changing the phase of the width-modulation, with a small 10 nm modulation amplitude, the resonance shifts over 160 nm. Using simulations we show how this simple design can create resonance shifts greater than 600 nm. The versatility of this design is further shown by creating asymmetric structures with two different modulation amplitudes, which we experimentally and numerically show to give rise to two resonances. Our results on both the symmetric and asymmetric antennas show the capability to control the localization of the fields outside the antenna, while still maintaining the freedom to change the antenna resonance wavelength. The antenna design we tested combines a large spectral tunability with a small footprint: all the antenna dimensions are factor 7 to 13 smaller than the wavelength, and hold potential as a design element in meta-surfaces for beam shaping.

5.
Chem Commun (Camb) ; 52(60): 9371-4, 2016 Aug 04.
Article in English | MEDLINE | ID: mdl-27367442

ABSTRACT

The contrasting early-time photodynamics of two related Ru/Pt photocatalysts with very different photocatalytic H2 generation capabilities are reported. Ultrafast equilibration (535 ± 17 fs) creates an electron reservoir on the peripheral ligands of the ester substituted complex, allowing a dramatic increase in photocatalytic performance. This insight opens the way towards a novel design strategy for H2 generating molecular photocatalysts.

6.
Chemphyschem ; 17(17): 2654-9, 2016 Sep 05.
Article in English | MEDLINE | ID: mdl-27258159

ABSTRACT

The effect of the catalytic moiety on the early-time photodynamics of Ru/M (M=Pt or Pd) bimetallic photocatalysts is studied by ultrafast transient absorption spectroscopy. In comparison to the Ru/Pd photocatalyst described earlier, the Ru/Pt analogue shows complex excited-state dynamics with three distinct kinetic components ranging from sub-ps to 10(2)  ps, requiring a more sophisticated photophysical model than that developed earlier for the Ru/Pd complex. In the Pu/Pt photocatalyst, an additional lower-lying excited state is proposed to quench the hot higher-lying triplet metal-to-ligand charge-transfer states. Furthermore, a strong excitation wavelength dependence on the population of excited states is observed for both the Ru/Pt and Ru/Pd complexes, indicating a non-equilibrated distribution even on the 10(2)  ps timescale. These insights shed light on the significant impact of the catalytic moiety on the fundamental early-time photophysics of Ru-based photocatalysts.

7.
Sci Rep ; 6: 25037, 2016 04 28.
Article in English | MEDLINE | ID: mdl-27121099

ABSTRACT

Surface plasmon polaritons are electromagnetic waves that propagate tightly bound to metal surfaces. The concentration of the electromagnetic field at the surface as well as the short wavelength of surface plasmons enable sensitive detection methods and miniaturization of optics. We present an optical frequency plasmonic analog to the phased antenna array as it is well known in radar technology and radio astronomy. Individual holes in a thick gold film act as dipolar emitters of surface plasmon polaritons whose phase is controlled individually using a digital spatial light modulator. We show experimentally, using a phase sensitive near-field microscope, that this optical system allows accurate directional emission of surface waves. This compact and flexible method allows for dynamically shaping the propagation of plasmons and holds promise for nanophotonic applications employing propagating surface plasmons.

8.
Opt Lett ; 39(20): 5814-7, 2014 Oct 15.
Article in English | MEDLINE | ID: mdl-25361092

ABSTRACT

We demonstrate a system for the phase-resolved epi-detection of coherent anti-Stokes Raman scattering (CARS) signals in highly scattering and/or thick samples. With this setup, we measure the complex vibrational responses of multiple components in a thick, highly-scattering pharmaceutical tablet in real time and verify that the epi- and forward-detected information are in very good agreement.


Subject(s)
Spectrum Analysis, Raman/methods , Vibration , Pharmaceutical Preparations/chemistry
9.
J Biomed Opt ; 18(4): 046009, 2013 Apr.
Article in English | MEDLINE | ID: mdl-23588807

ABSTRACT

Nature has developed many pathways to produce medicinal products of extraordinary potency and specificity with significantly higher efficiencies than current synthetic methods can achieve. Identification of these mechanisms and their precise locations within plants could substantially increase the yield of a number of natural pharmaceutics. We report label-free imaging of Δ9-tetrahydrocannabinolic acid (THCa) in Cannabis sativa L. using coherent anti-Stokes Raman scattering microscopy. In line with previous observations we find high concentrations of THCa in pistillate flowering bodies and relatively low amounts within flowering bracts. Surprisingly, we find differences in the local morphologies of the THCa-containing bodies: organelles within bracts are large, diffuse, and spheroidal, whereas in pistillate flowers they are generally compact, dense, and have heterogeneous structures. We have also identified two distinct vibrational signatures associated with THCa, both in pure crystalline form and within Cannabis plants; at present the exact natures of these spectra remain an open question.


Subject(s)
Cannabis/chemistry , Dronabinol/chemistry , Spectrum Analysis, Raman/methods , Dronabinol/analysis , Flowers/chemistry , Nonlinear Dynamics , Plant Leaves/chemistry , Signal Processing, Computer-Assisted
10.
Phys Rev Lett ; 107(25): 253902, 2011 Dec 16.
Article in English | MEDLINE | ID: mdl-22243075

ABSTRACT

We demonstrate a method for performing nonlinear microspectroscopy that provides an intuitive and unified description of the various signal contributions, and allows the direct extraction of the vibrational response. Three optical fields create a pair of Stokes Raman pathways that interfere in the same vibrational state. Frequency modulating one of the fields leads to amplitude modulations on all of the fields. This vibrational molecular interferometry technique allows imaging at high speed free of nonresonant background, and is able to distinguish between electronic and vibrational contributions to the total signal.


Subject(s)
Interferometry/methods , Molecular Probe Techniques , Spectrum Analysis/methods , Nonlinear Dynamics , Vibration
11.
Anal Chem ; 82(18): 7656-9, 2010 Sep 15.
Article in English | MEDLINE | ID: mdl-20731373

ABSTRACT

In coherent anti-Stokes Raman scattering (CARS), the emitted signal carries both amplitude and phase information of the molecules in the focal volume. Most CARS experiments ignore the phase component, but its detection allows for two advantages over intensity-only CARS. First, the pure resonant response can be determined, and the nonresonant background rejected, by extracting the imaginary component of the complex response, enhancing the sensitivity of CARS measurements. Second, selectivity is increased via determination of the phase and amplitude, allowing separation of individual molecular components of a sample even when their vibrational bands overlap. Here, using vibrational phase contrast CARS (VPC-CARS), we demonstrate enhanced sensitivity in quantitative measurements of ethanol/methanol mixtures and increased selectivity in a heterogeneous mixture of plastics and water. This powerful technique opens a wide range of possibilities for studies of complicated systems where overlapping resonances limit standard methodologies.


Subject(s)
Computer Graphics , Spectrum Analysis, Raman/methods , Vibration , Ethanol/chemistry , Methanol/chemistry , Water/chemistry
12.
Chemphyschem ; 8(10): 1473-80, 2007 Jul 16.
Article in English | MEDLINE | ID: mdl-17577901

ABSTRACT

DC-SIGN, a C-type lectin exclusively expressed on dendritic cells (DCs), plays an important role in pathogen recognition by binding with high affinity to a large variety of microorganisms. Recent experimental evidence points to a direct relation between the function of DC-SIGN as a viral receptor and its spatial arrangement on the plasma membrane. We have investigated the nanoscale organization of fluorescently labeled DC-SIGN on intact isolated DCs by means of near-field scanning optical microscopy (NSOM) combined with single-molecule detection. Fluorescence spots of different intensity and size have been directly visualized by optical means with a spatial resolution of less than 100 nm. Intensity- and size-distribution histograms of the DC-SIGN fluorescent spots confirm that approximately 80 % of the receptors are organized in nanosized domains randomly distributed on the cell membrane. Intensity-size correlation analysis revealed remarkable heterogeneity in the molecular packing density of the domains. Furthermore, we have mapped the intermolecular organization within a dense cluster by means of sequential NSOM imaging combined with discrete single-molecule photobleaching. In this way we have determined the spatial coordinates of 13 different individual dyes, with a localization accuracy of 6 nm. Our experimental observations are all consistent with an arrangement of DC-SIGN designed to maximize its chances of binding to a wide range of microorganisms. Our data also illustrate the potential of NSOM as an ultrasensitive, high-resolution technique to probe nanometer-scale organization of molecules on the cell membrane.


Subject(s)
Cell Adhesion Molecules/metabolism , Lectins, C-Type/metabolism , Receptors, Cell Surface/metabolism , Cell Membrane/metabolism , Chemical Phenomena , Chemistry, Physical , Dendritic Cells/immunology , Dendritic Cells/metabolism , Humans , Microscopy, Fluorescence/methods , Nanotechnology
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