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International audience; Three-dimensional organic–inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley–Queisser limit for a single‐junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden–Popper phases—layered two-dimensional perovskite films—have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

We present photoluminescence studies of individual semiconducting single-wall carbon nanotubes at room and cryogenic temperatures. From the analysis of spatial and spectral features of nanotube photoluminescence, we identify characteristic signatures of unintentional exciton localization. Moreover, we quantify the energy scale of exciton localization potentials as ranging from a few to a few tens of millielectronvolts and stemming from both environmental disorder and shallow covalent side-wall defects. Our results establish disorder-induced crossover from the diffusive to the localized regime of nanotube excitons at cryogenic temperatures as a ubiquitous phenomenon in micelle-encapsulated and as-grown carbon nanotubes.

International audience; State-of-the-art light emitting diodes (LEDs) are made from high-purity alloys of III-V semiconductors or small molecules, but high fabrication cost and conplicated synthetic process have limited their widespread use for large area solid-state lighting applications. Here we report efficient and stable LEDs processed from solution with tunable color enabled by using phase-pure two-dimensional (2D) Ruddlesden-Popper (RP) layered perovskites with a formula (CH3(CH2)3NH3)2(CH3NH3)n-1PbnI3n+1 (n=3-5 in this report). By using controlled vertically oriented of crystal in the thin-films that facilitate efficient charge injection and transport, we obtain efficient electroluminescence with a radiance of 35 W Sr-1 cm-2 at 744 nm with an ultra-low turn-on voltage of 1V. Finally, operational stability tests suggest that phase purity is strongly correlated to stability. Phase-pure 2D perovskites exhibit >14 hours of stable operation at peak operating conditions with no droop at current-densities of several Amperes/cm2 in comparison to mixtures of 2D/3D mixture or 3D perovskites, which degrade within minutes.

Electronic interactions in low-dimensional nanomaterial heterostructures can lead to novel optical responses arising from exciton delocalization over the constituent materials. Similar phenomena have been suggested to arise between closely interacting semiconducting carbon nanotubes of identical structure. Such behavior in carbon nanotubes has potential to generate new exciton physics, impact exciton transport mechanisms in nanotube networks, and place nanotubes as one-dimensional models for such behaviors in systems of higher dimensionality. Here we use resonance Raman spectroscopy to probe intertube interactions in (6,5) chirality-enriched bundles. Raman excitation profiles for the radial breathing mode and G-mode display a previously unobserved sharp resonance feature. We show the feature is evidence for creation of intertube excitons and is identified as a Fano resonance arising from the interaction between intratube and intertube excitons. The universality of the model suggests that similar Raman excitation profile features may be observed for interlayer exciton resonances in 2D multilayered systems., Bundles of single-wall carbon nanotubes with enriched chirality can be used as model systems for exploring exciton physics in low-dimensional nanostructures. Here, the authors use resonant Raman spectroscopy to probe intertube interactions in bundles of (6,5)-enriched carbon nanotubes, and observe a Fano resonance arising from coupling between intertube and intratube excitons.

The electronic properties of single-walled carbon nanotubes can be altered by surface adsorption of electronic impurities or dopants. However, fully understanding the influence of these impurities is difficult because of the inherent complexity of the solution-based colloidal chemistry of nanotubes, and because of a lack of techniques for directly imaging dynamic processes involving these impurities. Here, we show that photoluminescence microscopy can be used to image exciton quenching in semiconducting single-walled carbon nanotubes during the early stages of chemical doping with two different species. The addition of AuCl3 leads to localized exciton-quenching sites, which are attributed to a mid-gap electronic impurity level, and the adsorbed species are also found sometimes to be mobile on the surface of the nanotubes. The addition of H2O2 leads to delocalized exciton-quenching hole states, which are responsible for long-range photoluminescence blinking, and are also mobile. Photoluminescence microscopy can be used to image exciton quenching in semiconducting single-walled carbon nanotubes during the early stages of chemical doping.

A general challenge in generating functional materials from nanoscale components is integrating them into useful composites that retain or enhance their properties of interest. Development of single walled carbon nanotube (SWNT) materials for optoelectronics and sensing has been especially challenging in that SWNT optical and electronic properties are highly sensitive to environmental interactions, which can be particularly severe in composite matrices. Percolation of SWNTs into aqueous silica gels shows promise as an important route for exploiting their properties, but retention of the aqueous and surfactant environment still impacts and limits optical response, while also limiting the range of conditions in which these materials may be applied. Here, we present for the first time an innovative approach to obtain highly fluorescent solution-free SWNT-silica aerogels, which provides access to novel photophysical properties. Strongly blue-shifted spectral features, revelation of new diameter-dependent gas-phase adsorption phenomena, and significant increase (approximately three times that at room temperature) in photoluminescence intensities at cryogenic temperatures all indicate greatly reduced SWNT-matrix interactions consistent with the SWNTs experiencing a surfactant-free environment. The results demonstrate that this solid-state nanomaterial will play an important role in further revealing the true intrinsic SWNT chemical and photophysical behaviors and represent for the first time a promising new solution- and surfactant-free material for advancing SWNT applications in sensing, photonics, and optoelectronics.

Photoluminescence quantum yields and nonradiative decay of the excitonic S(1) state in length fractionated (6,5) single-wall carbon nanotubes (SWNTs) are studied by continuous wave and time-resolved fluorescence spectroscopy. The experimental data are modeled by diffusion limited contact quenching of excitons at stationary quenching sites including tube ends. A combined analysis of the time-resolved photoluminescence decay and the length dependence of photoluminescence quantum yields (PL QYs) from SWNTs in sodium cholate suspensions allows to determine the exciton diffusion coefficient D = 10.7 ± 0.4 cm(2)s(-1) and lifetime τ(PL) for long tubes of 20 ± 1 ps. PL quantum yields Φ(PL) are found to scale with the inverse diffusion coefficient and the square of the mean quenching site distance, here l(d) = 120 ± 25 nm. The results suggest that low PL QYs of SWNTs are due to the combination of high-diffusive exciton mobility with the presence of only a few quenching sites.

We study excitation energy transfer in small aggregates of chirality enriched carbon nanotubes by transient absorption spectroscopy. Ground state photobleaching is used to monitor exciton population dynamics with sub-10 fs time resolution. Upon resonant excitation of the first exciton transition in (6,5) tubes, we find evidence for energy transfer to (7,5) tubes within our time resolution (

We study the photo-induced transmission change (ΔT/T) upon quasi-continuum laser excitation, for different modulation frequency and excitation intensity in films of (6, 5) enriched CoMoCat single wall nanotubes (SWNTs) embedded in a polymeric matrix. This technique probes long-lived excited species, with lifetime in the 1 ms–1 s domain. The observed line-shape of ΔT/T spectra that can be assigned to a superposition of ground state bleaching and absorption modulation. We speculate that photo-excitation creates charges which get trapped in the sample, acquiring ms lifetime. This causes bleaching of the ground state absorption due to state filling and possibly a tube diameter expansion, with consequent blue shift of the optical transition.

Knowledge of excited-state dynamics in carbon nanotubes is determinant for their prospective use in optoelectronic applications. It is known that primary photoexcitations are quasi-one-dimensional excitons, the electron–hole correlation length (‘exciton size’) of which corresponds to a finite volume in the phase space. This volume can be directly measured by nonlinear spectroscopy provided the time resolution is short enough for probing before population relaxation. Here, we report on the experimental determination of exciton size and mobility in (6, 5) carbon nanotubes. The samples are sodium cholate suspensions of nanotubes (produced by the CoMoCat method) obtained by density-gradient ultracentrifugation. By using sub-15 fs near-infrared pulses to measure the nascent bleach of the lowest exciton resonance, we estimate the exciton size to be 2.0±0.7 nm. Exciton–exciton annihilation in our samples is found to be rather inefficient so that many excitons can coexist on a single nanotube. An accurate determination of the size and diffusion length of excitons generated with single-walled nanotubes supports the Wannier–Mott picture of their behaviour, and improves the outlook for the use of nanotubes in optoelectronics and biosensing applications.

We have studied intersubband decay of E22 excitons in semiconducting carbon nanotubes experimentally and theoretically. Photoluminescence excitation line widths of semiconducting nanotubes with chiral indicess (n, m) can be mapped onto a connectivity grid with curves of constant (n-m) and (2n+m). Moreover, the global behavior of E22 linewidths is best characterized by a strong increase with energy irrespective of their (n-m) mod(3)= \pm 1 family affiliation. Solution of the Bethe-Salpeter equations shows that the E22 linewidths are dominated by phonon assisted coupling to higher momentum states of the E11 and E12 exciton bands. The calculations also suggest that the branching ratio for decay into exciton bands vs free carrier bands, respectively is about 10:1., Comment: 4 pages, 4 figures

Using density gradient ultracentrifugation and isopycnic fractionation we structurally sort traditionally prepared single-wall carbon nanotube suspensions, and show that fractions with photoluminescence (PL) quantum yields of over 1% can be isolated. Moreover, we find that traditionally prepared suspensions appear to be composed of a significant fraction of small nanotube aggregates which reduce the quantum yield of the ensembles by a factor of 5 with respect to the most photoluminescent fractions. In order to better understand the nature of the nonradiative decay processes that lead to lower ensemble PL quantum yields, nanotube ropes of diameter enriched tubes are made and compared with the aforementioned ensemble measurements. Changes in the optical properties are discussed in terms of energy transfer to metallic tubes, carbonaceous particles, and smaller band gap tubes.

We investigate exciton dynamics in isopycnically enriched (6,5) nanotube-DNA suspensions using femtosecond time-resolved pump−probe spectroscopy. The ground state recovery is characterized by a t-0.45 ± 0.03 power law behavior, indicative of a one-dimensional diffusion-limited reaction that is tentatively attributed to subdiffusive trapping of dark excitons. Spectral transients of bright singlet excitons within the E11 and E22 manifolds exhibit a photobleach (PB) and a photoabsorption (PA) signal of similar strength. The PA is blue-shifted with respect to the PB-signal by 7.5 meV and is attributed to a transition from the dark singlet exciton to a + state within the two exciton E11 manifold.

Shallow hole doping in small-diameter semiconducting carbon nanotubes with a valley degeneracy is predicted to result in the resonant ionization of excitons into free electron-hole pairs. This mechanism, which relies on the chirality of the electronic states, causes excitons to decay with high efficiencies where the rate scales as the square of the dopant density. Moreover, multiparticle exciton ionization can account for delocalized fluorescence quenching when a few holes per micrometer of tube length are present.

We report on a pump-probe study of CoMoCAT nanotube suspensions with narrow chirality distribution. Visible pump pulses and a white light continuum are used for resonant excitation of the strongest dipole allowed E 22 subband exciton in the semiconducting (6, 5) tube and for broadband probe of the resulting spectral transients between 1300 nm and 480 nm, respectively. Transient spectra show signatures of both photobleaching (PB) and photoabsorption (PA) with practically identical decay- but slightly different rise-times. The experiments reveal that apparent variations of decay rates at different wavelengths do not reflect dynamics of different relaxation processes but are a consequence of the superposition of PB and blue-shifted PA response.

International audience; While addition of electrolyte to sodium dodecyl sulfate suspensions of single-wall carbon nanotubes has been demonstrated to result in significant brightening of the nanotube photoluminescence (PL), the brightening mechanism has remained unresolved. Here, we probe this mechanism using time-resolved PL decay measurements. We find that PL decay times increase by a factor of 2 on addition of CsCl as the electrolyte. Such an increase directly parallels an observed near-doubling of PL intensity, indicating the brightening results primarily from changes in nonradiative decay rates associated with exciton diffusion to quenching sites. Our findings indicate that a reduced number of these sites results from electrolyte-induced reorientation of the surfactant surface structure that partially removes pockets of water from the tube surface where excitons can dissociate, and thus underscores the contribution of interfacial water in exciton recombination processes.

International audience; We present measurements of S1 exciton transport in (6,5) carbon nanotubes at room temperature in a colloidal environment. Exciton diffusion lengths associated with end quenching paired with photoluminescence lifetimes provide a direct basis for determining a median dif- fusion constant of approximately 7.5 cm2s-1. Our experimental results are compared to model diffusion constants calculated using a realistic exciton dispersion accounting for a logarithmic correction due to the exchange self-energy and a non-equilibrium distribution between bright and dark excitons. The intrinsic diffusion constant associated with acoustic phonon scattering is too large to explain the observed diffusion length, and as such, we attribute the observedtransport to disorder-limited diffusional transport associated with the dynamics of the colloidal interface. In this model an effective surface potential limits the exciton mean free path to the same size as that of the exciton wavefunction, defined by the strength of the electron-hole Coulomb interaction.

We present evidence for the generation of free carriers in aggregated single-wall carbon nanotubes by photoexcitation in the energetic range of the π→π(*) transition associated with the M saddle point of the graphene lattice. The underlying broad absorption culminating at 4.3 eV can be fit well with a Fano line shape that describes strong coupling of a saddle-point exciton to an underlying free electron-hole pair continuum. Moreover, it is demonstrated that transitions in this energetic region autoionize into the continuum by detecting features unique to the presence of free charges in the transient transmission spectra of the continuum-embedded second sub-band exciton, S(2).

The optical properties of selectively aggregated, nearly single chirality single-wall carbon nanotubes were investigated by both continuous-wave and time-resolved spectroscopies. With reduced sample heterogeneities, we have resolved aggregation-dependent reductions of the excitation energy of the S(1) exciton and enhanced electron-hole pair absorption. Photoluminescence spectra revealed a spectral splitting of S(1) and simultaneous reductions of the emission efficiencies and nonradiative decay rates. The observed strong deviations from isolated tube behavior are accounted for by enhanced screening of the intratube Coulomb interactions, intertube exciton tunneling, and diffusion-driven exciton quenching. We also provide evidence that density gradient ultracentrifugation can be used to structurally sort single-wall carbon nanotubes by aggregate size as evident by a monotonic dependence of the aforementioned optical properties on buoyant density.

We study excitation energy and charge transfer in small aggregates of chirality enriched carbon nanotubes by transient absorption spectroscopy. Ground state photobleaching is used to monitor exciton population dynamics with sub-10 fs time resolution. Upon resonant excitation of the first exciton transition in (6,5) tubes, we find evidence for energy transfer to (7,5) tubes within our time resolution (< 10 fs). After pumping at high pump energies, free charge carriers are produced via exciton scattering into the underlying continuum bands. We obtain clearly distinguished photoinduced features in the visible spectral range, that allow for real-time tracing of charge carrier dynamics in carbon nanotubes on a sub-picosecond time scale.

Complex multichromophoric systems that display ultrafast excitation transfer between their constituents are of great fundamental interest in technologies such as organic photovoltaics. In this study we focus on diameter enriched single-wall carbon nanotubes (CNTs) networks with a majority being of the (6,5) chirality. It has been recently found that excitation of the first excitonic transition triggers energy transfer (ET) between the (6,5) and the (7,5) CNTs, with ≈10 fs time constant [1]. The aim of this study is to further analyze the transfer processes occurring between the CNTs, with the surprising observation of an ultrafast charge transfer (CT) process.

Transient polarized pump/probe transmission changes upon pulse photoexcitation at 1.6 eV were measured in chiral enriched carbon nanotubes ensembles of both metallic and semiconductor characters, in a very broad probe spectral range from mid-IR to visible, combining several ultrafast laser systems. We identify a photoinduced absorption band at $\ensuremath{\sim}0.7\text{ }\text{eV}$ as due to hot Dirac fermions in the metallic tubes and measure its dynamics. The hot carriers equilibrate within the electronic system in $\ensuremath{\sim}400\text{ }\text{fs}$ and with the lattice within $\ensuremath{\sim}2\text{ }\text{ps}$; in agreement with hot Dirac fermions thermalization in graphene. We also assign excitonic transitions in the semiconducting tubes, mainly of (6,5) chirality; in particular, an intraexciton transition at $\ensuremath{\sim}0.4\text{ }\text{eV}$ represents a lower limit for the exciton binding energy.

Pump-probe spectroscopy with 10 fs time resolution is performed on (6,5) carbon nanotubes. We decompose the spectra into contributions from the first and second exciton,demonstrating their electronic correlation.

We excite and detect coherent phonons in semiconducting (6,5) carbon nanotubes via a sub-10-fs pump-probe technique. Simulation of the amplitude and phase profile via time-dependent wave packet theory yields excellent agreement with experimental results under the assumption of molecular excitonic states and allows determining the electron-phonon coupling strength for the two dominant vibrational modes.

Aqueous suspensions of single-wall carbon nanotubes (SWNTs) prepared by traditional methods from the supernatant of ultracentrifuged micellar SWNT mixtures are shown to be strongly heterogeneous with respect to the quantum yield of their constituents. The heterogeneities are isolated using preparative ultracentrifugation in iodixanol density gradients and are optically characterized by photoluminescence and linear absorption spectroscopy. We find that the most buoyant fractions with a density of 1.055 ± 0.005 g·cm-3 have the highest photoluminescence quantum yield η of 1.1%, a factor of 5 higher than that of the supernatant. Denser fractions with lower η make up for about 2/3 of these samples and contain mostly small ropes in which the quantum yield is reduced by nonradiative decay through coupling to metallic tubes.

Selective photothermal interaction using dye enhancement has proven to be effective in minimizing surrounding tissue damage and delivering energy to target tissue. During laser irradiation, the process of photon absorption and thermal energy diffusion in the target tissue and its surrounding tissue are crucial. Such information allows the selection of proper operating parameters such as dye concentrations, laser power, and exposure time for optimal therapeutic effect. Combining the Monte Carlo method for energy absorption and the finite difference method for heat diffusion, the temperature distributions in target tissue and surrounding tissue in dye enhanced laser photothermal interaction are obtained. Different tissue configurations and dye enhancement are used in the simulation, and different incident beam sizes are also used to determine optimum beam sizes for various tissue configurations. Our results show that the algorithm developed in this study could predict the thermal outcome of laser irradiation. Our simulation indicates that with appropriate absorption enhancement of the target tissue, the temperature in the target tissue and in the surrounding tissue can be effectively controlled. This method can be used for optimization of lesion treatment using laser photothermal interactions. It may also provide guidance for laser immunotherapy in cancer treatment, since the immunological responses are believed to be related to tissue temperature changes.

We present a pump-probe study of exciton dynamics in semiconducting (6,5) single-wall carbon nanotubes (SWNTs). Optical transients from individual tubes and small bundles (n

The precise and selective destruction of tumor tissue through hyperthermia, when combined with immunoadjuvant applications, has shown promise in the treatment of cancer. The combination of an 805-nm laser and indocyanine green (ICG) has been shown to be highly effective in laboratory experiments in satisfying both the precision and selectivity requirements of such a procedure. A systematic study was conducted to further understand the interaction of the laser and the dye, using both Monte Carlo simulation and direct temperature measurement in gel phantom and chicken tissue. A phantom system, with a spherical, dye-enhanced target in the center, was constructed to simulate a tumor buried in deep tissue. The temperature increase in the target tissue under the irradiation of the 805-nm laser was significantly higher than the surrounding tissue. The same tumor-tissue configuration was also used in the theoretical simulation. The theoretical and experimental results for the temperature distributions and the treatment parameters can be used to provide the optimal thermal effect in cancer treatment.

The search for environmentally clean energy sources has spawned a wave of research into the use of carbon nanomaterials for photovoltaic applications. In particular, research using semiconducting single-walled carbon nanotubes has undergone dramatic transformations due to the availability of high quality samples through colloidal separation techniques. This has led to breakthrough discoveries on how energy and charge transport occurs in these materials and points to applications in energy harvesting. We present a review of the relevant photophysics of carbon nanotubes that dictate processes important for integration as active and passive material elements in thin film photovoltaics. Fundamental processes ranging from light absorption and internal conversion to exciton transport and dissociation are discussed in detail from both a spectroscopic and a device perspective. We also give a perspective on the future of these fascinating materials to be used as active and passive material elements in photovoltaics.

Ultrafast inter-tube exciton transfer in small aggregates of carbon nanotubes is studied by femtosecond spectroscopy with degenerate broadband pulses. After separation of population dynamics from coherent effects, transfer times below 10 fs are obtained.

Using femtosecond pump probe spectroscopy with sub-20 fs resolution, we probe fundamental properties of the E11 exciton in (6,5) single walled carbon nanotubes, prepared by density gradient ultracentrifugation [1]. From the initial photobleaching (PB) signal, measured faster than any relaxation process, we obtain the onedimensional electron-hole correlation length (“exciton size”) of the excitonic wavefunction along the nanotube. Anisotropy measurements in highly purified samples show that there is virtually no depolarisation of the E11 bleach over 40 ps. A photoinduced absorption (PA) band, blueshifted against the E11 bleach, shows only weak anisotropy. We discuss the origin of this PA band.

We observed an ultrafast charge generation and transfer in a carbon nanotube network by a novel pump-probe spectroscopy that makes use of a broadband and positively chirped pump and transform-limited probe pulses.