Disclosing Early Excited State Relaxation Events in Prototypical Linear Carbon Chains.

One-dimensional (1D) linear nanostructures comprising sp-hybridized carbon atoms, as derivatives of the prototypical allotrope known as carbyne, are predicted to possess outstanding mechanical, thermal, and electronic properties. Despite recent advances in their synthesis, their chemical and physical properties are still poorly understood. Here, we investigate the photophysics of a prototypical polyyne (i.e., 1D chain with alternating single and triple carbon bonds) as the simplest model of finite carbon wire and as a prototype of sp-carbon-based chains. We perform transient absorption experiments with high temporal resolution (<30 fs) on monodispersed hydrogen-capped hexayne H─(C≡C)6─H synthesized by laser ablation in liquid. With the support of computational studies based on ground state density functional theory (DFT) and excited state time-dependent (TD)-DFT calculations, we provide a comprehensive description of the excited state relaxation processes at early times following photoexcitation. We show that the internal conversion from a bright high-energy singlet excited state to a low-lying singlet dark state is ultrafast and takes place with a 200 fs time constant, followed by thermalization on the picosecond time scale and decay of the low-energy singlet state with hundreds of picoseconds time constant. We also show that the time scale of these processes does not depend on the end groups capping the sp-carbon chain. The understanding of the primary photoinduced events in polyynes is of key importance both for fundamental knowledge and for potential optoelectronic and light-harvesting applications of low-dimensional nanostructured carbon-based materials.

Optical and Magneto-Optical Properties of Donor-Bound Excitons in Vacancy-Engineered Colloidal Nanocrystals.

Controlled insertion of electronic states within the band gap of semiconductor nanocrystals (NCs) is a powerful tool for tuning their physical properties. One compelling example is II-VI NCs incorporating heterovalent coinage metals in which hole capture produces acceptor-bound excitons. To date, the opposite donor-bound exciton scheme has not been realized because of the unavailability of suitable donor dopants. Here, we produce a model system for donor-bound excitons in CdSeS NCs engineered with sulfur vacancies (VS) that introduce a donor state below the conduction band (CB), resulting in long-lived intragap luminescence. VS-localized electrons are almost unaffected by trapping, and suppression of thermal quenching boosts the emission efficiency to 85%. Magneto-optical measurements indicate that the VS are not magnetically coupled to the NC bands and that the polarization properties are determined by the spin of the valence-band photohole, whose spin flip is massively slowed down due to suppressed exchange interaction with the donor-localized electron.

Quantized Electronic Doping towards Atomically Controlled "Charge-Engineered" Semiconductor Nanocrystals.

"Charge engineering" of semiconductor nanocrystals (NCs) through so-called electronic impurity doping is a long-standing challenge in colloidal chemistry and holds promise for ground-breaking advancements in many optoelectronic, photonic, and spin-based nanotechnologies. To date, our knowledge is limited to a few paradigmatic studies on a small number of model compounds and doping conditions, with important electronic dopants still unexplored in nanoscale systems. Equally importantly, fine-tuning of charge engineered NCs is hampered by the statistical limitations of traditional approaches. The resulting intrinsic doping inhomogeneity restricts fundamental studies to statistically averaged behaviors and complicates the realization of advanced device concepts based on their advantageous functionalities. Here we aim to address these issues by realizing the first example of II-VI NCs electronically doped with an exact number of heterovalent gold atoms, a known p-type acceptor impurity in bulk chalcogenides. Single-dopant accuracy across entire NC ensembles is obtained through a novel non-injection synthesis employing ligand-exchanged gold clusters as "quantized" dopant sources to seed the nucleation of CdSe NCs in organic media. Structural, spectroscopic, and magneto-optical investigations trace a comprehensive picture of the physical processes resulting from the exact doping level of the NCs. Gold atoms, doped here for the first time into II-VI NCs, are found to incorporate as nonmagnetic Au+ species activating intense size-tunable intragap photoluminescence and artificially offsetting the hole occupancy of valence band states. Fundamentally, the transient conversion of Au+ to paramagnetic Au2+ (5d9 configuration) under optical excitation results in strong photoinduced magnetism and diluted magnetic semiconductor behavior revealing the contribution of individual paramagnetic impurities to the macroscopic magnetism of the NCs. Altogether, our results demonstrate a new chemical approach toward NCs with physical functionalities tailored to the single impurity level and offer a versatile platform for future investigations and device exploitation of individual and collective impurity processes in quantum confined structures.

Colloidal Synthesis of Bipolar Off-Stoichiometric Gallium Iron Oxide Spinel-Type Nanocrystals with Near-IR Plasmon Resonance.

We report the colloidal synthesis of ∼5.5 nm inverse spinel-type oxide Ga2FeO4 (GFO) nanocrystals (NCs) with control over the gallium and iron content. As recently theoretically predicted, some classes of spinel-type oxide materials can be intrinsically doped by means of structural disorder and/or change in stoichiometry. Here we show that, indeed, while stoichiometric Ga2FeO4 NCs are intrinsic small bandgap semiconductors, off-stoichiometric GFO NCs, produced under either Fe-rich or Ga-rich conditions, behave as degenerately doped semiconductors. As a consequence of the generation of free carriers, both Fe-rich and Ga-rich GFO NCs exhibit a localized surface plasmon resonance in the near-infrared at ∼1000 nm, as confirmed by our pump-probe absorption measurements. Noteworthy, the photoelectrochemical characterization of our GFO NCs reveal that the majority carriers are holes in Fe-rich samples, and electrons in Ga-rich ones, highlighting the bipolar nature of this material. The behavior of such off-stoichiometric NCs was explained by our density functional theory calculations as follows: the substitution of Ga3+ by Fe2+ ions, occurring in Fe-rich conditions, can generate free holes (p-type doping), while the replacement of Fe2+ by Ga3+ cations, taking place in Ga-rich samples, produces free electrons (n-type doping). These findings underscore the potential relevance of spinel-type oxides as p-type transparent conductive oxides and as plasmonic semiconductors.

Towards compact laser-driven accelerators: exploring the potential of advanced double-layer targets.

The interest in compact, cost-effective, and versatile accelerators is increasing for many applications of great societal relevance, ranging from nuclear medicine to agriculture, pollution control, and cultural heritage conservation. For instance, Particle Induced X-ray Emission (PIXE) is a non-destructive material characterization technique applied to environmental analysis that requires MeV-energy ions. In this context, superintense laser-driven ion sources represent a promising alternative to conventional accelerators. In particular, the optimization of the laser-target coupling by acting on target properties results in an enhancement of ion current and energy with reduced requirements on the laser system. Among the advanced target concepts that have been explored, one appealing option is given by double-layer targets (DLTs), where a very low-density layer, which acts as an enhanced laser absorber, is grown to a thin solid foil. Here we present some of the most recent results concerning the production with deposition techniques of advanced DLTs for laser-driven particle acceleration. We assess the potential of these targets for laser-driven ion acceleration with particle-in-cell simulations, as well as their application to PIXE analysis of aerosol samples with Monte Carlo simulations. Our investigation reports that MeV protons, accelerated with a ∼20 TW compact laser and optimized DLTs, can allow performing PIXE with comparable performances to conventional sources. We conclude that compact DLT-based laser-driven accelerators can be relevant for environmental monitoring.

Band-edge ultrafast pump-probe spectroscopy of core/shell CdSe/CdS rods: assessing electron delocalization by effective mass calculations.

CdSe/CdS dot/rods nanocrystals show interesting physical properties related to the band-alignment at the hetero-interface, which controls the band-edge electron delocalization over the rods. Here the differential transmission spectra of CdSe/CdS nanorod samples with different core sizes have been measured using excitation resonant to the core transition. The photo bleaching ratio between dot and rod transitions increases with the dot size, indicating a trend towards electron localization. This trend has been further quantified by performing effective mass calculations in which the conduction band misalignment was varied in order to reproduce the observed bleaching feature ratio. The best agreement was found for negligible conduction band misalignment for small dots of around 2.3 nm in diameter, and about -0.1 eV misalignment was estimated for the larger dots, above 3.5 nm in diameter. This shows that the band misalignment might be dependent on the geometry of the system, and we argue that this might be related to different strain developed at the hetero-interface.

Plasmon dynamics in colloidal Cu2-xSe nanocrystals.

The optical response of metallic nanostructures after intense excitation with femtosecond-laser pulses has recently attracted increasing attention: such response is dominated by ultrafast electron-phonon coupling and offers the possibility to achieve optical modulation with unprecedented terahertz bandwidth. In addition to noble metal nanoparticles, efforts have been made in recent years to synthesize heavily doped semiconductor nanocrystals so as to achieve a plasmonic behavior with spectrally tunable features. In this work, we studied the dynamics of the localized plasmon resonance exhibited by colloidal Cu(2-x)Se nanocrystals of 13 nm in diameter and with x around 0.15, upon excitation by ultrafast laser pulses via pump-probe experiments in the near-infrared, with ∼200 fs resolution time. The experimental results were interpreted according to the two-temperature model and revealed the existence of strong nonlinearities in the plasmonic absorption due to the much lower carrier density of Cu(2-x)Se compared to noble metals, which led to ultrafast control of the probe signal with modulation depth exceeding 40% in transmission.

Tunable physics through coordination chemistry: formation on oxide surface of Ti and Al chelates with 3-hydroxyflavone capable of electron injection and light emission.

The optoelectronic features of 3-hydroxyflavone (3HF) self-assembled on the surface of an n-type semiconducting metal oxide (TiO2) and an insulator (Al2O3) are herein investigated. 3HF molecules use the coordinatively unsaturated metal ions present on the oxide surface to form metal complexes, which exhibit different behaviors upon light irradiation, depending on the nature of the metal ion. Specifically, we show that the photoluminescence of the surface species can be modulated according to the chemical properties of the complex (i.e. the binding metal ion), resulting in solid-state emitters in a high quantum yield (about 15%). Furthermore, photoinduced charge injection can be promoted or inhibited, providing a multifunctional hybrid system.

Steady-state photoinduced absorption of CdSe/CdS octapod shaped nanocrystals.

Colloidal branched nanocrystals have been attracting increasing attention due to evidence of an interesting relationship between their complex shape and charge carrier dynamics. Herein, continuous wave photoinduced absorption (CW PIA) measurements of CdSe/CdS octapod-shaped nanocrystals are reported. CW PIA spectra show strong bleaching due to the one-dimensional (1D) CdS pod states (480 nm) and the zero-dimensional (0D) CdSe core states (690 nm). The agreement with previously reported ultrafast pump-probe experiments indicates that this strong bleaching signal may be assigned to state filling. Additional bleaching features at 520 and 560 nm are characterized by a longer lifetime and are thus ascribed to defect states, localized at the pod-core interface of the octapod, showing that some of the initially photogenerated carriers get quickly trapped into these long-lived defect states. However, we remark that a relevant part of electrons remain untrapped: this opens up the opportunity to exploit octapod shaped nanocrystals in photovoltaics applications, as electron acceptor materials, considering that several efficient hole extracting materials are already available for the realization of a composite bulk heterojunction.

Suppression of biexciton auger recombination in CdSe/CdS dot/rods: role of the electronic structure in the carrier dynamics.

We studied carrier dynamics in semiconductor nanocrystals consisting of a small CdSe dot embedded in an elongated, rod-shaped CdS shell, using the ultrafast pump-probe technique. We found clear evidence of a substantial suppression of the Auger nonradiative recombination in the biexciton regime. Moreover, a simple model of the dynamics in which biexcitons show no Auger recombination, and only holes are localized in the dot, fits well the differential transmission observed at all pump densities. The long biexciton lifetime results into an observed long-living gain having a peak that is red shifted with respect to the lowest energy absorption peak. We argue that the origin of the large relative gain observed at large fillings is related to the peculiar structure of the electronic levels, and in particular, to delocalization of electrons in the rod.

Distributed feedback lasing from a composite poly(phenylene vinylene)-nanoparticle one-dimensional photonic crystal.

Nanoparticle one-dimensional photonic crystals exhibit intense, broadband reflectivity coupled with a unique mesoporosity. The latter property allows for infiltration of the one-dimensional photonic crystal with functional materials, such as emitting polymers, which in turn can lead to the fabrication of composites whereby the emitter's emission can be modulated by the photon density of states of the photonic crystal. We exploit this interaction in order to produce efficient distributed feedback lasing from a composite poly(phenylene vinylene)-infiltrated nanoparticle one-dimensional photonic crystal.

Excitonic pathway to photoinduced magnetism in colloidal nanocrystals with nonmagnetic dopants.

Electronic doping of colloidal semiconductor nanostructures holds promise for future device concepts in optoelectronic and spin-based technologies. Ag+ is an emerging electronic dopant in III-V and II-VI nanostructures, introducing intragap electronic states optically coupled to the host conduction band. With its full 4d shell Ag+ is nonmagnetic, and the dopant-related luminescence is ascribed to decay of the conduction-band electron following transfer of the photoexcited hole to Ag+. This optical activation process and the associated modification of the electronic configuration of Ag+ remain unclear. Here, we trace a comprehensive picture of the excitonic process in Ag-doped CdSe nanocrystals and demonstrate that, in contrast to expectations, capture of the photohole leads to conversion of Ag+ to paramagnetic Ag2+. The process of exciton recombination is thus inextricably tied to photoinduced magnetism. Accordingly, we observe strong optically activated magnetism and diluted magnetic semiconductor behaviour, demonstrating that optically switchable magnetic nanomaterials can be obtained by exploiting excitonic processes involving nonmagnetic impurities.

Dual emission in asymmetric "giant" PbS/CdS/CdS core/shell/shell quantum dots.

Semiconducting nanocrystals optically active in the infrared region of the electromagnetic spectrum enable exciting avenues in fundamental research and novel applications compatible with the infrared transparency windows of biosystems such as chemical and biological optical sensing, including nanoscale thermometry. In this context, quantum dots (QDs) with double color emission may represent ultra-accurate and self-calibrating nanosystems. We present the synthesis of giant core/shell/shell asymmetric QDs having a PbS/CdS zinc blende (Zb)/CdS wurtzite (Wz) structure with double color emission close to the near-infrared (NIR) region. We show that the double emission depends on the excitation condition and analyze the electron-hole distribution responsible for the independent and simultaneous radiative exciton recombination in the PbS core and in the CdS Wz shell, respectively. These results highlight the importance of the driving force leading to preferential crystal growth in asymmetric QDs, and provide a pathway for the rational control of the synthesis of double color emitting giant QDs, leading to the effective exploitation of visible/NIR transparency windows.

Effect of Core/Shell Interface on Carrier Dynamics and Optical Gain Properties of Dual-Color Emitting CdSe/CdS Nanocrystals.

Two-color emitting colloidal semiconductor nanocrystals (NCs) are of interest for applications in multimodal imaging, sensing, lighting, and integrated photonics. Dual color emission from core- and shell-related optical transitions has been recently obtained using so-called dot-in-bulk (DiB) CdSe/CdS NCs comprising a quantum-confined CdSe core embedded into an ultrathick (∼7-9 nm) CdS shell. The physical mechanism underlying this behavior is still under debate. While a large shell volume appears to be a necessary condition for dual emission, comparison between various types of thick-shell CdSe/CdS NCs indicates a critical role of the interface "sharpness" and the presence of potential barriers. To elucidate the effect of the interface morphology on the dual emission, we perform side-by-side studies of CdSe/CdS DiB-NCs with nominally identical core and shell dimensions but different structural properties of the core/shell interface arising from the crystal structure of the starting CdSe cores (zincblende vs wurtzite). While both structures exhibit dual emission under comparable pump intensities, NCs with a zincblende core show a faster growth of shell luminescence with excitation fluence and a more readily realized regime of amplified spontaneous emission (ASE) even under "slow" nanosecond excitation. These distinctions can be linked to the structure of the core/shell interface: NCs grown from the zincblende cores contain a ∼3.5 nm thick zincblende CdS interlayer, which separates the core from the wurtzite CdS shell and creates a potential barrier for photoexcited shell holes inhibiting their relaxation into the core. This helps maintain a higher population of shell states and simplifies the realization of dual emission and ASE involving shell-based optical transitions.

Modulating Exciton Dynamics in Composite Nanocrystals for Excitonic Solar Cells.

Quantum dots (QDs) represent one of the most promising materials for third-generation solar cells due to their potential to boost the photoconversion efficiency beyond the Shockley-Queisser limit. Composite nanocrystals can challenge the current scenario by combining broad spectral response and tailored energy levels to favor charge extraction and reduce energy and charge recombination. We synthesized PbS/CdS QDs with different compositions at the surface of TiO2 nanoparticles assembled in a mesoporous film. The ultrafast photoinduced dynamics and the charge injection processes were investigated by pump-probe spectroscopy. We demonstrated good injection of photogenerated electrons from QDs to TiO2 in the PbS/CdS blend and used the QDs to fabricate solar cells. The fine-tuning of chemical composition and size of lead and cadmium chalcogenide QDs led to highly efficient PV devices (3% maximum photoconversion efficiency). This combined study paves the way to the full exploitation of QDs in next-generation photovoltaic (PV) devices.

Lasing in self-assembled microcavities of CdSe/CdS core/shell colloidal quantum rods.

Colloidal semiconductor quantum rods have demonstrated many advantageous properties as light emitters such as high quantum yield, tunable emission wavelength, and polarized emission. This makes them an interesting optical gain material for laser applications. We report room-temperature gain lifetimes in core/shell CdSe/CdS quantum rods exceeding 300 ps, and show that the long gain lifetimes result from the significant reduction of Auger recombination in our quantum rods, even though the electrons are delocalized over the rod volume. We also fabricate devices by deposition of small droplets of quantum rod solution onto flat substrates. The evaporation dynamics of the droplets are governed by the coffee stain effect which leads to the formation of well defined micron-size stripes. These stripes consist of densely packed, laterally aligned quantum rods and provide optical feedback originating from the abrupt changes of refractive index at the stripe borders. We exploit the optical gain and the coffee stain mediated self-assembly and show that we can fabricate novel microlasers solely by deposition of droplets of quantum rod solutions on flat substrates.

Hollow-pyramid based scanning near-field optical microscope coupled to femtosecond pulses: a tool for nonlinear optics at the nanoscale.

We describe an aperture scanning near-field optical microscope (SNOM) using cantilevered hollow pyramid probes coupled to femtosecond laser pulses. Such probes, with respect to tapered optical fibers, present higher throughput and laser power damage threshold, as well as greater mechanical robustness. In addition, they preserve pulse duration and polarization in the near field. The instrument can operate in two configurations: illumination mode, in which the SNOM probe is used to excite the nonlinear response in the near field, and collection mode, where it collects the nonlinear emission following far-field excitation. We present application examples highlighting the capability of the system to observe the nonlinear optical response of nanostructured metal surfaces (gold projection patterns and gold nanorods) with sub-100-nm spatial resolution.

Ultrafast electron-hole dynamics in core/shell CdSe/CdS dot/rod nanocrystals.

We investigated the transient bleaching and absorption of the asymmetric core/shell CdSe/CdS nanorods using the pump-probe technique. We observed ultrafast carrier relaxation and identified hole localization dynamics with 650 +/- 80 fs time constant. Upon pumping the CdSe core, we found an intense bleaching signal in the CdS spectral region, which we assigned to the delocalization of the electronic wave function on the basis of envelope-function theoretical calculations.