Electronic Structure of Isolated Graphene Nanoribbons in Solution Revealed by Two-Dimensional Electronic Spectroscopy.

Structurally well-defined graphene nanoribbons (GNRs) are nanostructures with unique optoelectronic properties. In the liquid phase, strong aggregation typically hampers the assessment of their intrinsic properties. Recently we reported a novel type of GNRs, decorated with aliphatic side chains, yielding dispersions consisting mostly of isolated GNRs. Here we employ two-dimensional electronic spectroscopy to unravel the optical properties of isolated GNRs and disentangle the transitions underlying their broad and rather featureless absorption band. We observe that vibronic coupling, typically neglected in modeling, plays a dominant role in the optical properties of GNRs. Moreover, a strong environmental effect is revealed by a large inhomogeneous broadening of the electronic transitions. Finally, we also show that the photoexcited bright state decays, on the 150 fs time scale, to a dark state which is in thermal equilibrium with the bright state, that remains responsible for the emission on nanosecond time scales.

Adjusting the energy of interfacial states in organic photovoltaics for maximum efficiency.

A critical bottleneck for improving the performance of organic solar cells (OSC) is minimising non-radiative losses in the interfacial charge-transfer (CT) state via the formation of hybrid energetic states. This requires small energetic offsets often detrimental for high external quantum efficiency (EQE). Here, we obtain OSC with both non-radiative voltage losses (0.24 V) and photocurrent losses (EQE > 80%) simultaneously minimised. The interfacial CT states separate into free carriers with ≈40-ps time constant. We combine device and spectroscopic data to model the thermodynamics of charge separation and extraction, revealing that the relatively high performance of the devices arises from an optimal adjustment of the CT state energy, which determines how the available overall driving force is efficiently used to maximize both exciton splitting and charge separation. The model proposed is universal for donor:acceptor (D:A) with low driving forces and predicts which D:A will benefit from a morphology optimization for highly efficient OSC.

Visualizing Ultrafast Electron Transfer Processes in Semiconductor-Metal Hybrid Nanoparticles: Toward Excitonic-Plasmonic Light Harvesting.

Recently, it was demonstrated that charge separation in hybrid metal-semiconductor nanoparticles (HNPs) can be obtained following photoexcitation of either the semiconductor or of the localized surface plasmon resonance (LSPR) of the metal. This suggests the intriguing possibility of photocatalytic systems benefiting from both plasmon and exciton excitation, the main challenge being to outcompete other ultrafast relaxation processes. Here we study CdSe-Au HNPs using ultrafast spectroscopy with high temporal resolution. We describe the complete pathways of electron transfer for both semiconductor and LSPR excitation. In the former, we distinguish hot and band gap electron transfer processes in the first few hundred fs. Excitation of the LSPR reveals an ultrafast (<30 fs) electron transfer to CdSe, followed by back-transfer from the semiconductor to the metal within 210 fs. This study establishes the requirements for utilization of the combined excitonic-plasmonic contribution in HNPs for diverse photocatalytic applications.

Dark Subgap States in Metal-Halide Perovskites Revealed by Coherent Multidimensional Spectroscopy.

Metal-halide perovskites show excellent properties for photovoltaic and optoelectronic applications, with power conversion efficiencies of solar cell and LEDs exceeding 20%. Being solution processed, these polycrystalline materials likely contain a large density of defects compared to melt-grown semiconductors. Surprisingly, typical effects from defects (absorption below the bandgap, low fill factor and open circuit voltage in devices, strong nonradiative recombination) are not observed. In this work, we study thin films of metal-halide perovskites CH3NH3PbX3 (X = Br, I) with ultrafast multidimensional optical spectroscopy to resolve the dynamics of band and defect states. We observe a shared ground state between the band-edge transitions and a continuum of sub-bandgap states, which extends at least 350 meV below the band edge). We explain the comparatively large bleaching of the dark sub-bandgap states with oscillator strength borrowing from the band-edge transition. Our results show that upon valence to conduction band excitation, such subgap states are instantaneously bleached for large parts of the carrier lifetime and conversely that most dark sub-bandgap states can be populated by light excitation. This observation helps to unravel the photophysical origin of the unexpected optoelectronic properties of these materials.

Intrinsic Properties of Single Graphene Nanoribbons in Solution: Synthetic and Spectroscopic Studies.

We report a novel type of structurally defined graphene nanoribbons (GNRs) with uniform width of 1.7 nm and average length up to 58 nm. These GNRs are decorated with pending Diels-Alder cycloadducts of anthracenyl units and N- n-hexadecyl maleimide. The resultant bulky side groups on GNRs afford excellent dispersibility with concentrations of up to 5 mg mL-1 in many organic solvents such as tetrahydrofuran (THF), two orders of magnitude higher than the previously reported GNRs. Multiple spectroscopic studies confirm that dilute dispersions in THF (<0.1 mg mL-1) consist mainly of nonaggregated ribbons, exhibiting near-infrared emission with high quantum yield (9.1%) and long lifetime (8.7 ns). This unprecedented dispersibility allows resolving in real-time ultrafast excited-state dynamics of the GNRs, which displays features of small isolated molecules in solution. This study achieves a breakthrough in the dispersion of GNRs, which opens the door for unveiling obstructed GNR-based physical properties and potential applications.

Laser-induced shockwave chromatography: a separation and analysis method for nanometer-sized particles and molecules.

A microscopic chromatography has been developed where nanometer-size molecules or particles are separated according to their size by the laser-induced shockwave in a water-filled capillary. As the shockwave passed through the mixture of molecules/particles in solution, they move to the direction of the propagation of the shockwave. The distance from the point of shockwave generation depends on the particle size or molecular weight. This technique has some advantages compared to conventional chromatography, in terms of quick analysis of molecular weight and applicability to sticky and adsorbing polymers. Experimental results obtained for proteins, their aggregates, and inorganic nanoparticles are presented.

Self-assembled monolayers of double-chain disulfides of adenine on Au: an IR-UV sum-frequency generation spectroscopic study.

We have synthesized double-chain disulfides of adenine with different chain lengths (n = 2, 4, 5, 9, and 10) and studied their self-assembled monolayers (SAM) on gold surface by IR-UV doubly resonant sum frequency generation spectroscopy with the help of DFT calculation. A versatile way to investigate the orientation angle of functional groups of SAMs and their surface coverage has been demonstrated. It was revealed that the IR dipoles of the band at around 1630 cm(-1), which were almost parallel to the long molecular axis of the adenine ring, were less tilted with respect to the substrate surface in the SAMs with longer chains (n = 9 and 10) in comparison to those with shorter chains (n = 2, 4, and 5).

Chiral sum frequency spectroscopy of thin films of porphyrin J-aggregates.

Thin films of chiral porphyrin J-aggregates have been studied by vibrationally and electronically doubly resonant sum frequency generation (SFG) spectroscopy. It was revealed that the chiral supramolecular structures of porphyrin aggregates in solutions were retained in the thin film samples, and their chirality was determined by using chiral vibrational SFG spectroscopy. Electronic resonance profiles of some vibrational bands in achiral and chiral SFG were different from each other, and both were distinct from electronic absorption spectra. To account for these peculiar profiles, we have proposed interference effects of Raman tensor components in achiral and chiral SFG susceptibilities, which is analogous to that of resonance Raman scattering.

Pulse compression based on coherent molecular motion induced by transient stimulated Raman scattering.

A novel method for compressing a laser pulse, using a combination of transient stimulated Raman scattering and a pump-probe technique, is proposed. The approach does not require a short laser pulse, in contrast to a reported method based on impulsive stimulated Raman scattering. The observed spectrum was sufficiently broad to generate a sub-10 fs pulse. In fact, a 100-fs pulse in the near-ultraviolet region was compressed to the sub-30 fs. Further compression of the laser pulse would be achieved by compensating for phase distortion, as suggested from the observed data of the spectral phase.

Near-field optical imaging of plasmon modes in gold nanorods.

We have investigated optical properties of single gold nanorods by using an apertured-type scanning near-field optical microscope. Near-field transmission spectrum of single gold nanorod shows several longitudinal surface plasmon resonances. Transmission images observed at these resonance wavelengths show oscillating pattern along the long axis of the nanorod. The number of oscillation increases with decrement of observing wavelength. These spatial characteristics were well reproduced by calculated local density-of-states maps and were attributed to spatial characteristics of plasmon modes inside the nanorods. Dispersion relation for plasmons in gold nanorods was obtained by plotting the resonance frequencies of the plasmon modes versus the wave vectors obtained from the transmission images.

Near-field two-photon-induced photoluminescence from single gold nanorods and imaging of plasmon modes.

We investigated the two-photon-induced photoluminescence properties of single gold nanorods by scanning near-field spectroscopy. The process was found to be initiated by a sequential one-photon absorption for creating a pair of an electron and a hole in the sp and d bands. Photoluminescence is then radiated when the electron near the Fermi surface recombines with the hole near the X and L symmetry points. The polarization characteristics of emitted photons from the X and L regions were found to be different. These characteristics can be understood by the crystalline structure and the band structure of the gold nanorod. We found characteristic spatial oscillatory features along the long axis of the nanorods in photoluminescence excitation images. The images were well reproduced by density-of-states maps of the nanorods calculated with Green's dyadic method and were attributed to the spatial characteristics of the wave functions of the plasmon modes inside the nanorods.

Morphological and spectroscopic properties of thin films of self-assembling amphiphilic porphyrins on a hydrophilic surface as revealed by scanning near-field optical microscopy.

We fabricated porphyrin thin films on mica surfaces from acidic aqueous solutions of the preorganized H-aggregates of amphiphilic porphyrins by the simple spin-coating method. The morphological and spectroscopic properties of the film were investigated by scanning near-field optical microscopy. The results obtained in this study demonstrate that the preorganized structure in solution can be transferred as a thin film with a thickness of the monolayer level without losing their substantial structure and photophysical properties.

Near-field spectroscopy of water-soluble and water-insoluble porphyrin J-aggregates.

Mesoscopic properties of J-aggregates of water-soluble [tetrakis(4-sulfonatophenyl)porphyrin] and water-insoluble [tetrakis(4-methoxyphenyl)porphyrin and tetraphenylporphyrin] tetraphenylporphyrin derivatives in thin films have been investigated by scanning near-field optical microscopy. From surface topography, the sample films were found to be composed of planar J-aggregate microcrystallines. The transmittance spectra of the water-insoluble samples are site specific, while those of the water-soluble samples are not. This observation might reflect the spatial inhomogeneity of the thin films in mesoscopic scales and is related to the broad J-bands of water-insoluble samples. Excited state lifetimes, obtained from time-resolved, pump-probe measurements in small domains, were in the 30-70 ps range for 4-methoxy substituted and in the 40-100 ps range for unsubstituted tetraphenylporphyrin, which are of the same order as the reported far-field results for 4-sulfonated compound in water.

Plasmon mode imaging of single gold nanorods.

We have investigated two-photon-induced photoluminescence images and spectra of single gold nanorods by using an apertured scanning near-field optical microscope. The observed PL spectrum of single gold nanorod can be explained by the radiative recombination of the electron-hole pair near the X and L symmetry points. PL images reveal characteristic features reflecting an eigenfunction of a specific plasmon mode as well as electric field distributions around the nanorod.