Visualizing Thermally Activated Conical Intersections Governing Non-Radiative Triplet Decay in a Ni(II) Porphyrin-Nanographene Conjugate with Variable Temperature Transient Absorption Spectroscopy.

Metalloporphyrins based on open-shell transition metals, such as Ni(II), exhibit typically fast excited-state relaxation. In this work, we shed light into the nonradiative relaxation mechanism in a nanographene-Ni(II) porphyrin conjugate. Variable temperature transient absorption and global fit analysis are combined to produce a picture of the relaxation pathways. At room temperature, photoexcitation of the lowest π-π* transition is followed by vibrational cooling in 1.6 ps, setting a short 20 ps temporal window wherein a small fraction of relaxed singlets radiatively decay to the ground state before intersystem crossing proceeds. Following intersystem crossing, triplets relax rapidly to the ground state (S0) in a few tens of picoseconds. By performing measurements at low temperature, we provide evidence for a competition between two terminal relaxation pathways from the lowest (metal-centered) triplet to the ground state: a slow ground state relaxation process proceeding in time scales beyond 1.6 ns and a faster pathway dictated by a sloped conical intersection, which is thermally accessible at room temperature from the triplet state. The overall triplet decay at a given temperature is dictated by the interplay of these two contributions. This observation bears significance in understanding the underlying fast relaxation processes in Ni-based molecules and related transition metal complexes, opening avenues for potential applications for energy harvesting and optoelectronics.

Near-Infrared Plasmon-Induced Hot Electron Extraction Evidence in an Indium Tin Oxide Nanoparticle/Monolayer Molybdenum Disulfide Heterostructure.

In this work, we observe plasmon-induced hot electron extraction in a heterojunction between indium tin oxide nanocrystals and monolayer molybdenum disulfide. We study the sample with ultrafast differential transmission, exciting the sample at 1750 nm where the intense localized plasmon surface resonance of the indium tin oxide nanocrystals is and where the monolayer molybdenum disulfide does not absorb light. With the excitation at 1750 nm, we observe the excitonic features of molybdenum disulfide in the visible range, close to the exciton of molybdenum disulfide. Such a phenomenon can be ascribed to a charge transfer between indium tin oxide nanocrystals and monolayer molybdenum disulfide upon plasmon excitation. These results are a first step toward the implementation of near-infrared plasmonic materials for photoconversion.

Electrically Tunable Nonequilibrium Optical Response of Graphene.

The ability to tune the optical response of a material via electrostatic gating is crucial for optoelectronic applications, such as electro-optic modulators, saturable absorbers, optical limiters, photodetectors, and transparent electrodes. The band structure of single layer graphene (SLG), with zero-gap, linearly dispersive conduction and valence bands, enables an easy control of the Fermi energy, EF, and of the threshold for interband optical absorption. Here, we report the tunability of the SLG nonequilibrium optical response in the near-infrared (1000-1700 nm/0.729-1.240 eV), exploring a range of EF from -650 to 250 meV by ionic liquid gating. As EF increases from the Dirac point to the threshold for Pauli blocking of interband absorption, we observe a slow-down of the photobleaching relaxation dynamics, which we attribute to the quenching of optical phonon emission from photoexcited charge carriers. For EF exceeding the Pauli blocking threshold, photobleaching eventually turns into photoinduced absorption, because the hot electrons' excitation increases the SLG absorption. The ability to control both recovery time and sign of the nonequilibrium optical response by electrostatic gating makes SLG ideal for tunable saturable absorbers with controlled dynamics.

Excited states engineering enables efficient near-infrared lasing in nanographenes.

The spectral overlap between stimulated emission (SE) and absorption from dark states (i.e. charges and triplets) especially in the near-infrared (NIR), represents one of the most effective gain loss channels in organic semiconductors. Recently, bottom-up synthesis of atomically precise graphene nanostructures, or nanographenes (NGs), has opened a new route for the development of environmentally and chemically stable materials with optical gain properties. However, also in this case, the interplay between gain and absorption losses has hindered the attainment of efficient lasing action in the NIR. Here, we demonstrate that the introduction of two fluoranthene imide groups to the NG core leads to a more red-shifted emission than the precursor NG molecule (685 vs. 615 nm) and also with a larger Stokes shift (45 nm vs. 2 nm, 1026 cm-1vs. 53 cm-1, respectively). Photophysical results indicate that, besides the minimisation of ground state absorption losses, such substitution permits to suppress the detrimental excited state absorption in the NIR, which likely arises from a dark state with charge-transfer character and triplets. This has enabled NIR lasing (720 nm) from all-solution processed distributed feedback devices with one order of magnitude lower thresholds than those of previously reported NIR-emitting NGs. This study represents an advance in the field of NGs and, in general, organic semiconductor photonics, towards the development of cheap and stable NIR lasers.

Large scale indium tin oxide (ITO) one dimensional gratings for ultrafast signal modulation in the visible spectral region.

Indium tin oxide (ITO) is a heavily doped semiconductor with a plasmonic response in the near infrared region. When exposed to light, the distribution of conduction band electron induces a change in the real and imaginary parts of the dielectric permittivity. The coupling of the electromagnetic waves with the electrons in the conduction band of metallic nanostructures with ultrashort light pulses results in a nonlinear plasmonic response. Such optical modulation occurring on ultrafast time scales, e.g. picosecond response times, can be exploited and used to create integrated optical components with terahertz modulation speed. Here, we present a photophysical study on a one dimensional ITO grating, realized using a femtosecond micromachining process, a very industrially accessible technology. The geometries, dimensions and pitch of the various gratings analyzed are obtained by means of direct ablation in a controlled atmosphere of a homogeneous thin layer of ITO deposited on a glass substrate. The pitch has been selected in order to obtain a higher order of the photonic band gap in the visible spectral region. Femtosecond micromachining technology guarantees precision, repeatability and extreme manufacturing flexibility. By means of ultrafast pump-probe spectroscopy, we characterize both the plasmon and inter-band temporal dynamics. We observe a large optical nonlinearity of the ITO grating in the visible range, where the photonic band gap occurs, when pumped at the surface plasmon resonance in the near infrared (1500 nm) region. All together, we show the possibility of all-optical signal modulation with heavily doped semiconductors in their transparency window with a picosecond response time through the formation of ITO grating structures.

Colloidal Bi-Doped Cs2Ag1-x Na x InCl6 Nanocrystals: Undercoordinated Surface Cl Ions Limit their Light Emission Efficiency.

Understanding and tuning the ligand shell composition in colloidal halide perovskite nanocrystals (NCs) has been done systematically only for Pb-based perovskites, while much less is known on the surface of Pb-free perovskite systems. Here, we reveal the ligand shell architecture of Bi-doped Cs2Ag1-x Na x InCl6NCs via nuclear magnetic resonance analysis. This material, in its bulk form, was found to have a photoluminescence quantum yield (PLQY) as high as 86%, a record value for halide double perovskites. Our results show that both amines and carboxylic acids are present and homogeneously distributed over the surface of the NCs. Notably, even for an optimized surface ligand coating, achieved by combining dodecanoic acid and decylamine, a maximum PLQY value of only 37% is reached, with no further improvements observed when exploiting post-synthesis ligand exchange procedures (involving Cs-oleate, different ammonium halides, thiocyanates and sulfonic acids). Our density functional theory calculations indicate that, even with the best ligands combination, a small fraction of unpassivated surface sites, namely undercoordinated Cl ions, is sufficient to create deep trap states, opposite to the case of Pb-based perovskites that exhibit much higher defect tolerance. This was corroborated by our transient absorption measurements, which showed that an ultrafast trapping of holes (most likely mediated by surface Cl-trap states) competes with their localization at the AgCl6 octahedra, from where, instead, they can undergo an optically active recombination yielding the observed PL emission. Our results highlight that alternative surface passivation strategies should be devised to further optimize the PLQY of double perovskite NCs, which might include their incorporation inside inorganic shells.

π-Extended Pyrene-Fused Double [7]Carbohelicene as a Chiral Polycyclic Aromatic Hydrocarbon.

A π-extended double [7]carbohelicene 2 with fused pyrene units was synthesized, revealing considerable intra- and intermolecular π-π interactions as confirmed with X-ray crystallography. As compared to the previous double [7]carbohelicene 1, the π-extended homologue 2 demonstrated considerably red-shifted absorption with an onset at 645 nm (1: 550 nm) corresponding to a smaller optical gap of 1.90 eV (1: 2.25 eV). A broad near-infrared emission from 600 to 900 nm with a large Stokes shift of ∼100 nm (2.3 × 103 cm-1) was recorded for 2, implying formation of an intramolecular excimer upon excitation, which was corroborated with femtosecond transient absorption spectroscopy. Moreover, 2 revealed remarkable chiral stability with a fairly high isomerization barrier of 46 kcal mol-1, according to density functional theory calculations, which allowed optical resolution by chiral HPLC and suggests potential applications in chiroptical devices.

Regioselective Hydrogenation of a 60-Carbon Nanographene Molecule toward a Circumbiphenyl Core.

Regioselective peripheral hydrogenation of a nanographene molecule with 60 contiguous sp2 carbons provides unprecedented access to peralkylated circumbiphenyl (1). Conversion to the circumbiphenyl core structure was unambiguously validated by MALDI-TOF mass spectrometry, NMR, FT-IR, and Raman spectroscopy. UV-vis absorption spectra and DFT calculations demonstrated the significant change of the optoelectronic properties upon peripheral hydrogenation. Stimulated emission from 1, observed via ultrafast transient absorption measurements, indicates potential as an optical gain material.