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We report on the photoluminescence of pairs of organic color centers in single-wall carbon nanotubes grafted with 3,5-dichlorobenzene. Using various techniques such as intensity correlations, superlocalization microscopy, and luminescence excitation spectroscopy, we distinguish two pairs of color centers grafted on the same nanotube; the distance between the pairs is on the order of several hundreds of nanometers. In contrast, by studying the strong temporal correlations in the spectral diffusion in the framework of the photoinduced Stark effect, we can estimate the distance within each pair to be on the order of a few nanometers. Finally, the electronic population dynamics is investigated using time-resolved luminescence and saturation measurements, showing a biexponential decay with a fast overall recombination (compatible with a fast population transfer between the color centers within a pair) and a weak delayed repopulation of the traps, possibly due to the diffusion of excitons along the tube axis.

Individual single-walled carbon nanotubes with covalent sidewall defects have emerged as a class of photon sources whose photoluminescence spectra can be tailored by the carbon nanotube chirality and the attached functional group/molecule. Here we present electroluminescence spectroscopy data from single-tube devices based on (7, 5) carbon nanotubes, functionalized with dichlorobenzene molecules, and wired to graphene electrodes. We observe electrically generated, defect-induced emissions that are controllable by electrostatic gating and strongly red-shifted compared to emissions from pristine nanotubes. The defect-induced emissions are assigned to excitonic and trionic recombination processes by correlating electroluminescence excitation maps with electrical transport and photoluminescence data. At cryogenic conditions, additional gate-dependent emission lines appear, which are assigned to phonon-assisted hot-exciton electroluminescence from quasi-levels. Similar results were obtained with functionalized (6, 5) nanotubes. We also compare functionalized (7, 5) electroluminescence data with photoluminescence of pristine and functionalized (7, 5) nanotubes redox-doped using gold(III) chloride solution. This work shows that electroluminescence excitation is selective toward neutral defect-state configurations with the lowest transition energy, which in combination with gate-control over neutral versus charged defect-state emission leads to high spectral purity.

Incorporating fluorescent quantum defects in the sidewalls of semiconducting single-wall carbon nanotubes (SWCNTs) through chemical reaction is an emerging route to predictably modify nanotube electronic structures and develop advanced photonic functionality. Applications such as room-temperature single-photon emission and high-contrast bio-imaging have been advanced through aryl-functionalized SWCNTs, in which the binding configurations of the aryl group define the energies of the emitting states. However, the chemistry of binding with atomic precision at the single-bond level and tunable control over the binding configurations are yet to be achieved. Here, we explore recently reported photosynthetic protocol and find that it can control chemical binding configurations of quantum defects, which are often referred to as organic color centers, through the spin multiplicity of photoexcited intermediates. Specifically, photoexcited aromatics react with SWCNT sidewalls to undergo a singlet-state pathway in the presence of dissolved oxygen, leading to ortho binding configurations of the aryl group on the nanotube. In contrast, the oxygen-free photoreaction activates previously inaccessible para configurations through a triplet-state mechanism. These experimental results are corroborated by first principles simulations. Such spin-selective photochemistry diversifies SWCNT emission tunability by controlling the morphology of the emitting sites., (© 2022. The Author(s).)

Solid-state single-photon sources are essential building blocks for quantum photonics and quantum information technologies. This study demonstrates promising single-photon emission from quantum defects generated in single-wall carbon nanotubes (SWCNTs) by covalent reaction with guanine nucleotides in their single-stranded DNA coatings. Low-temperature photoluminescence spectroscopy and photon-correlation measurements on individual guanine-functionalized SWCNTs (GF-SWCNTs) indicate that multiple, closely spaced guanine defect sites within a single ssDNA strand collectively form an exciton trapping potential that supports a localized quantum state capable of room-temperature single-photon emission. In addition, exciton traps from adjacent ssDNA strands are weakly coupled to give cross-correlations between their separate photon emissions. Theoretical modeling identifies coupling mechanism as a capture of band-edge excitons. Because the spatial pattern of nanotube functionalization sites can be readily controlled by selecting ssDNA base sequences, GF-SWCNTs should become a versatile family of quantum light emitters with engineered properties.

Chemical reactions between semiconducting single-wall carbon nanotubes (SWCNTs) and single-stranded DNA (ssDNA) achieve spatially patterned covalent functionalization sites and create coupled fluorescent quantum defects on the nanotube surface, tailoring SWCNT photophysics for applications such as single-photon emitters in quantum information technologies. The evaluation of relaxation dynamics of photoluminescence (PL) from those coupled quantum defects is essential for understanding the nanotube electronic structure and beneficial to the design of quantum light emitters. Here, we measured the PL decay for ssDNA-functionalized SWCNTs as a function of the guanine content of the ssDNA oligo that dictates the red-shifting of their PL emission peaks relative to the band-edge exciton. We then correlate the observed dependence of PL decay dynamics on energy red-shifts to the exciton potential energy landscape, which is modeled using first-principles approaches based upon the morphology of ssDNA-altered SWCNTs obtained by atomic force microscopy (AFM) imaging. Our simulations illustrate that the multiple guanine defects introduced within a single ssDNA strand strongly interact to create a deep exciton trapping well, acting as a single hybrid trap. The emission decay from the distinctive trapping potential landscape is found to be biexponential for ssDNA-modified SWCNTs. We attributed the fast time component of the biexponential PL decay to the redistribution of exciton population among the lowest energy bright states and a manifold of dark states emerging from the coupling of multiple guanine defects. The long lifetime component in the biexponential decay, on the other hand, is attributed to the redistribution of exciton population among different exciton trapping sites that arise from the binding of multiple ssDNA strands along the nanotube axis. AFM measurements indicate that those trapping sites are separated on average by ∼8 nm along the nanotube axis.

ConspectusSingle-walled carbon nanotubes (SWCNTs) show promise as light sources for modern fiber optical communications due to their emission wavelengths tunable via chirality and diameter dependency. However, the emission quantum yields are relatively low owing to the existence of low-lying dark electronic states and fast excitonic diffusion leading to carrier quenching at defects. Covalent functionalization of SWCNTs addresses this problem by brightening their infrared emission. Namely, introduction of sp 3 -hybridized defects makes the lowest energy transitions optically active for some defect geometries and enables further control of their optical properties. Such functionalized SWCNTs are currently the only material exhibiting room-temperature single photon emission at telecom relevant infrared wavelengths. While this fluorescence is strong and has the right wavelength, functionalization introduces a variety of emission peaks resulting in spectrally broad inhomogeneous photoluminescence that prohibits the use of SWCNTs in practical applications. Consequently, there is a strong need to control the emission diversity in order to render these materials useful for applications. Recent experimental and computational work has attributed the emissive diversity to the presence of multiple localized defect geometries each resulting in distinct emission energy. This Account outlines methods by which the morphology of the defect in functionalized SWCNTs can be controlled to reduce emissive diversity and to tune the fluorescence wavelengths. The chirality-dependent trends of emission energies with respect to individual defect morphologies are explored. It is demonstrated that defect geometries originating from functionalization of SWCNT carbon atoms along bonds with strong π-orbital mismatch are favorable. Furthermore, the effect of controlling the defect itself through use of different chemical groups is also discussed. Such tunability is enabled due to the formation of specific defect geometries in close proximity to other existing defects. This takes advantage of the changes in π-orbital mismatch enforced by existing defects and the resulting changes in reactivities toward formation of specific defect morphologies. Furthermore, the trends in emissive energies are highly dependent on the value of mod( n - m ,3) for an ( n , m ) tube chirality. These powerful concepts allow for a targeted formation of defects that emit at desired energies based on SWCNT single chirality enriched samples. Finally, the impact of functionalization with specific types of defects that enforce certain defect geometries due to steric constraints in bond lengths and angles to the SWCNT are discussed. We further relate to a similar effect that is present in systems where high density of surface defects is formed due to high reactant concentration. The outlined strategies suggested by simulations are instrumental in guiding experimental efforts toward the generation of functionalized SWCNTs with tunable emission energies.

A robust and reliable method for enhancing the photoluminescence (PL) of multilayer MoS 2 is demonstrated using an oxygen plasma treatment process followed by laser exposure. Here, the plasma and laser treatments result in an indirect-to-direct band gap transition. The oxygen plasma creates a slight decoupling of the layers and converts some of the MoS 2 to MoO 3 . Subsequent laser irradiation further oxidizes the MoS 2 to MoO 3 , as confirmed via X-ray photoelectron spectroscopy, and results in localized regions of brightly luminescent MoS 2 monolayer triangular islands as seen in high-resolution transmission electron microscopy images. The PL lifetimes are found to decrease from 494 to 190 ps after plasma and laser treatment, reflecting the smaller size of the MoS 2 grains/regions. Atomic force microscopic imaging shows a 2 nm increase in thickness of the laser-irradiated regions, which provides further evidence of the MoS 2 being converted to MoO 3 ., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Organic color-center quantum defects in semiconducting carbon nanotube hosts are rapidly emerging as promising candidates for solid-state quantum information technologies. However, it is unclear whether these defect color-centers could support the spin or pseudospin-dependent excitonic fine structure required for spin manipulation and readout. Here we conducted magneto-photoluminescence spectroscopy on individual organic color-centers and observed the emergence of fine structure states under an 8.5 T magnetic field applied parallel to the nanotube axis. One to five fine structure states emerge depending on the chirality of the nanotube host, nature of chemical functional group, and chemical binding configuration, presenting an exciting opportunity toward developing chemical control of magnetic brightening. We attribute these hidden excitonic fine structure states to field-induced mixing of singlet excitons trapped at sp 3 defects and delocalized band-edge triplet excitons. These findings provide opportunities for using organic color-centers for spintronics, spin-based quantum computing, and quantum sensing.

There are various mechanisms of light emission in carbon nanotubes (CNTs), which give rise to a wide range of spectral characteristics that provide important information. Here we report suppression of incandescence via Auger recombination in suspended carbon nanotube pn-junctions generated from dual-gate CNT field-effect transistor (FET) devices. By applying equal and opposite voltages to the gate electrodes (i.e., V g1 = - V g2 ), we create a pn-junction within the CNT. Under these gating conditions, we observe a sharp peak in the incandescence intensity around zero applied gate voltage, where the intrinsic region has the largest spatial extent. Here, the emission occurs under high electrical power densities of around 0.1 MW/cm 2 (or 6 μW) and arises from thermal emission at elevated temperatures above 800 K (i.e., incandescence). It is somewhat surprising that this thermal emission intensity is so sensitive to the gating conditions, and we observe a 1000-fold suppression of light emission between V g1 = 0 and 15 V, over a range in which the electrical power dissipated in the nanotube is roughly constant. This behavior is understood on the basis of Auger recombination, which suppresses light emission by the excitation of free carriers. Based on the calculated carrier density and band profiles, the length of the intrinsic region drops by a factor of 7-25× over the range from | V g | = 0 to 15 V. We, therefore, conclude that the light emission intensity is significantly dependent on the free carrier density profile and the size of the intrinsic region in these CNT devices.

Indistinguishable single photon generation at telecom wavelengths from solid-state quantum emitters remains a significant challenge to scalable quantum information processing. Here we demonstrate efficient generation of "indistinguishable" single photons directly in the telecom O-band from aryl-functionalized carbon nanotubes by overcoming the emitter quantum decoherence with plasmonic nanocavities. With an unprecedented single-photon spontaneous emission time down to 10 ps (from initially 0.7 ns) generated in the coupling scheme, we show a two-photon interference visibility at 4 K reaching up to 0.79, even without applying post selection. Cavity-enhanced quantum yields up to 74% and Purcell factors up to 415 are achieved with single-photon purities up to 99%. Our results establish the capability to fabricate fiber-based photonic devices for quantum information technology with coherent properties that can enable quantum logic.

Molecularly functionalized single-walled carbon nanotubes (SWCNTs) are potentially useful for fiber optical applications due to their room temperature single-photon emission capacity at telecommunication wavelengths. Several distinct defect geometries are generated upon covalent functionalization. While it has been shown that the defect geometry controls electron localization around the defect site, thereby changing the electronic structure and generating new optically bright red-shifted emission bands, the reasons for such localization remain unexplained. Our joint experimental and computational studies of functionalized SWCNTs with various chiralities show that the value of mod(n-m,3) in an (n,m) chiral nanotube plays a key role in the relative ordering of defect-dependent emission energies. This dependence is linked to the complex nodal characteristics of electronic wave function extending along specific bonds in the tube, which justifies the defect-geometry dependent exciton localization. This insight helps to uncover the essential structural motifs allowing tuning the redshifts of emission energies in functionalized SWCNTs.

Trions, charged excitons that are reminiscent of hydrogen and positronium ions, have been intensively studied for energy harvesting, light-emitting diodes, lasing, and quantum computing applications because of their inherent connection with electron spin and dark excitons. However, these quasi-particles are typically present as a minority species at room temperature making it difficult for quantitative experimental measurements. Here, we show that by chemically engineering the well depth of sp 3 quantum defects through a series of alkyl functional groups covalently attached to semiconducting carbon nanotube hosts, trions can be efficiently generated and localized at the trapping chemical defects. The exciton-electron binding energy of the trapped trion approaches 119 meV, which more than doubles that of "free" trions in the same host material (54 meV) and other nanoscale systems (2-45 meV). Magnetoluminescence spectroscopy suggests the absence of dark states in the energetic vicinity of trapped trions. Unexpectedly, the trapped trions are approximately 7.3-fold brighter than the brightest previously reported and 16 times as bright as native nanotube excitons, with a photoluminescence lifetime that is more than 100 times larger than that of free trions. These intriguing observations are understood by an efficient conversion of dark excitons to bright trions at the defect sites. This work makes trions synthetically accessible and uncovers the rich photophysics of these tricarrier quasi-particles, which may find broad implications in bioimaging, chemical sensing, energy harvesting, and light emitting in the short-wave infrared., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Graphene quantum dots (GQDs) have attracted significant interest as synthetically tunable optoelectronic and photonic materials that can also serve as model systems for understanding size-dependent behaviors of related graphene structures such as nanoribbons. We present a Raman spectroscopy study of bottom-up synthesized GQDs with lateral dimensions between 0.97 to 1.62 nm, well-defined (armchair) edge type, and fully benzenoid structures. For a better understanding of observed size-dependent trends, the study is extended to larger graphene structures including nano-graphene platelets (>25 nm) and large-area graphene. Raman spectra of GQDs reveal the presence of D and G bands, as well as higher order modes (2D, D + G, and 2G). The D and G band frequencies and intensity were found to increase as GQD size increases, while higher order modes (2D, D + G, and 2G) also increased in intensity and became more well-defined. The integrated intensity ratios of D and G bands (I D /I G ) increase as the size of the GQDs approaches 2 nm and rapidly decrease for larger graphene structures. We present a quantitative comparison of I D /I G ratios for the GQDs and for defects introduced into large area graphenes through ion bombardment, for which inter-defect distances are comparable to the sizes of GQDs studied here. Close agreement suggests the I D /I G ratio as a size diagnostic for other nanographenes. Finally, we show that Raman spectroscopy is also a good diagnostic tool for monitoring the formation of bottom-up synthesized GQDs.

Defect states introduced to single wall carbon nanotubes (SWCNTs) by covalent functionalization give rise to novel photophysics and are showing promise as sources of room-temperature quantum emission of interest for quantum information technologies. Evaluation of their ultimate potential for such needs requires a knowledge of intrinsic dynamic and coherence behaviors. Here we probe population relaxation and dephasing time (T1 and T2, respectively) of defect states following deposition of functionalized SWCNTs on polystyrene substrates that are subjected to an isopropanol rinse to remove surfactant. Low-temperature (4 K) photo-luminescence linewidths (∼100 μeV) following surfactant removal are a factor of ten narrower than those for unrinsed SWCNTs. Measured recombination lifetimes, on the order of 1.5 ns, compare well with those estimated from DFT calculations, indicating that the intrinsic radiatively-limited lifetime is approached following this sample treatment. Dephasing times evaluated directly through an interferometric approach compare closely to those established by photoluminescence linewidths. Dephasing times as high as 12 ps are found; a factor of up to 6 times greater than those evaluated for band-edge exciton states. Such enhancement of dephasing and photoluminescence lifetime behavior is a direct consequence of exciton localization at the SWCNT defect sites.

Recent demonstration of room temperature, telecommunication wavelength single photon generation by sp 3 defects of single wall carbon nanotubes established these defects as a new class of quantum materials. However, their practical utilization in development of quantum light sources calls for a significant improvement in their imperfect quantum yield (QY∼10-30%). PL intensity fluctuations observed with some defects also need to be eliminated. Aiming toward attaining fundamental understanding necessary for addressing these critical issues, we investigate PL intensity fluctuation and PL decay dynamics of aryl sp 3 defects of (6,5), (7,5), and (10,3) single wall carbon nanotubes (SWCNTs) at temperatures ranging from 300 to 4 K. By correlating defect-state PL intensity fluctuations with change (or lack of change) in PL decay dynamics, we identified random variations in the trapping efficiency of E 11 band-edge excitons (likely resulting from the existence of a fluctuating potential barrier in the vicinity of the defect) as the mechanism mainly responsible for the defect PL intensity fluctuations. Furthermore, by analyzing the temperature dependence of PL intensity and decay dynamics of individual defects based on a kinetic model involving the trapping and detrapping of excitons by optically allowed and forbidden (bright and dark) defect states, we estimate the height of the potential barrier to be in the 3-22 meV range. Our analysis also provides further confirmation of recent DFT simulation results that the emissive sp 3 defect state is accompanied by an energetically higher-lying optically forbidden (dark) exciton state.

The electronic structure of a series of bottom-up synthesized graphene quantum dots (GQDs) smaller than 2 nm was investigated by spectroelectrochemistry, yielding insights not previously available from ensemble-level studies. The results show that for the strongly confined GQDs the dependence of the band gap on the GQD size deviates from the prediction of the standard Dirac Fermion model but agrees well with the models explicitly accounting for the electron-electron and electron-hole interactions. The HOMO/LUMO energy levels are found to be distributed nearly symmetrically around the 0 V value versus normal hydrogen electrode (NHE), becoming more positive/negative, respectively, with increasing GQD size. The exciton binding energies are found to follow power dependence on the number of carbon atoms per GQD, with the experimental values falling within the range of ∼0.1 to ∼0.6 eV. Given the broad accessibility of the described experimental tools and methods, our work opens a path to a more systematic examination of quantum confinement effects in GQDs.

Light-emitting sources and devices permeate every aspect of our lives and are used in lighting, communications, transportation, computing, and medicine. Advances in multifunctional and "smart lighting" would require revolutionary concepts in the control of emission spectra and directionality. Such control might be possible with new schemes and regimes of light-matter interaction paired with developments in light-emitting materials. Here we show that all-dielectric metasurfaces made from III-V semiconductors with embedded emitters have the potential to provide revolutionary lighting concepts and devices, with new functionality that goes far beyond what is available in existing technologies. Specifically, we use Mie-resonant metasurfaces made from semiconductor heterostructures containing epitaxial quantum dots. By controlling the symmetry of the resonant modes, their overlap with the emission spectra, and other structural parameters, we can enhance the brightness by 2 orders of magnitude, as well as reduce its far-field divergence significantly.

The introduction of sp 3 defects into single-walled carbon nanotubes through covalent functionalization can generate new light-emitting states and thus dramatically expand their optical functionality. This may open up routes to enhanced imaging, photon upconversion, and room-temperature single-photon emission at telecom wavelengths. However, a significant challenge in harnessing this potential is that the nominally simple reaction chemistry of nanotube functionalization introduces a broad diversity of emitting states. Precisely defining a narrow band of emission energies necessitates constraining these states, which requires extreme selectivity in molecular binding configuration on the nanotube surface. We show here that such selectivity can be obtained through aryl functionalization of so-called 'zigzag' nanotube structures to achieve a threefold narrowing in emission bandwidth. Accompanying density functional theory modelling reveals that, because of the associated structural symmetry, the defect states become degenerate, thus limiting emission energies to a single narrow band. We show that this behaviour can only result from a predominant selectivity for ortho binding configurations of the aryl groups on the nanotube lattice.

In the version of this Perspective originally published, the x-axis label of Fig. 1d was missing; it should have read 'Wavelength (nm)'. The units of the y axis of Fig. 3b were incorrect; they should have been meV. And the citation of Fig. 3c in the main text was incorrect; it should have been to Fig. 3b. These issues have now been corrected.

Photoluminescent sp 3 defect states introduced to single wall carbon nanotubes (SWCNTs) through low-level covalent functionalization create new photophysical behaviors and functionality as a result of defect sites acting as exciton traps. Evaluation of relaxation dynamics in varying dielectric environments can aid in advancing a more complete description of defect-state relaxation pathways and electronic structure. Here, we exploit helical wrapping polymers as a route to suspending (6,5) SWCNTs covalently functionalized with 4-methoxybenzene in solvent systems including H 2 O, D 2 O, methanol, dimethylformamide, tetrahydrofuran, and toluene, spanning a range of dielectric constants from 80 to 3. Defect-state photoluminescence decays were measured as a function of emission wavelength and solvent environment. Emission decays are biexponential, with short lifetime components on the order of 65 ps and long components ranging from around 100 to 350 ps. Both short and long decay components increase as emission wavelength increases, while only the long lifetime component shows a solvent dependence. We demonstrate that the wavelength dependence is a consequence of thermal detrapping of defect-state excitons to produce mobile E 11 excitons, providing an important mechanism for loss of defect-state population. Deeper trap states (i.e., those emitting at longer wavelengths) result in a decreased rate for thermal loss. The solvent-independent behavior of the short lifetime component is consistent with its assignment as the characteristic time for redistribution of exciton population between bright and dark defect states. The solvent dependence of the long lifetime component is shown to be consistent with relaxation via an electronic to vibrational energy transfer mechanism, in which energy is resonantly lost to solvent vibrations in a complementary mechanism to multiphonon decay processes.

Progress in quantum computing and quantum cryptography requires efficient, electrically triggered, single-photon sources at room temperature in the telecom wavelengths. It has been long known that semiconducting single-wall carbon nanotubes (SWCNTs) display strong excitonic binding and emit light over a broad range of wavelengths, but their use has been hampered by a low quantum yield and a high sensitivity to spectral diffusion and blinking. In this Perspective, we discuss recent advances in the mastering of SWCNT optical properties by chemistry, electrical contacting and resonator coupling towards advancing their use as quantum light sources. We describe the latest results in terms of single-photon purity, generation efficiency and indistinguishability. Finally, we consider the main fundamental challenges stemming from the unique properties of SWCNTs and the most promising roads for SWCNT-based chip integrated quantum photonic sources.

Covalent functionalization of single-walled carbon nanotubes (SWCNTs) is a promising route to enhance the quantum yield of exciton emission and can lead to single-photon emission at room temperature. However, the spectral linewidth of the defect-related E11* emission remains rather broad. Here, we systematically investigate the low-temperature exciton emission of individual SWCNTs that have been dispersed with sodium-deoxycholate (DOC) and polyfluorene (PFO-BPy), are grown by laser vaporization (LV) or by CoMoCat techniques and are functionalized with oxygen as well as 3,5-dichlorobenzene groups. The E11 excitons in oxygen-functionalized SWCNTs remain rather broad with up to 10 meV linewidth while exciton emission from 3,5-dichlorobenzene functionalized SWCNTs is found to be about one order of magnitude narrower. In all cases, wrapping with PFO-BPy provides significantly better protection against pump induced dephasing compared to DOC. To further study the influence of exciton localization on pump-induced dephasing, we have embedded the functionalized SWCNTs into metallo-dielectric antenna cavities to maximize light collection. We show that 0D excitons attributed to the E11* emission of 3,5-dichlorobenzene quantum defects of LV-grown SWCNTs can display near resolution-limited linewidths down to 35 μeV. Interestingly, these 0D excitons give rise to a 3-fold suppressed pump-induced exciton dephasing compared to the E11 excitons in the same SWCNT. These findings provide a foundation to build a unified description of the emergence of novel optical behavior from the interplay of covalently introduced defects, dispersants, and exciton confinement in SWCNTs and might further lead to the realization of indistinguishable photons from carbon nanotubes.

The intrinsic near-infrared photoluminescence observed in long single-walled carbon nanotubes is known to be quenched in ultrashort nanotubes due to their tiny size as compared to the exciton diffusion length in these materials (>100 nm). Here, we show that intense photoluminescence can be created in ultrashort nanotubes (∼40 nm length) upon incorporation of exciton-trapping sp 3 defect sites. Using super-resolution photoluminescence imaging at <25 nm resolution, we directly show the preferential localization of excitons at the nanotube ends, which separate by less than 40 nm and behave as independent emitters. This unexpected observation opens the possibility to synthesize fluorescent ultrashort nanotubes-a goal that has been long thought impossible-for bioimaging applications, where bright near-infrared photoluminescence and small size are highly desirable, and for quantum information science, where high quality and well-controlled near-infrared single photon emitters are needed.

Single-walled carbon nanotubes are a promising material as quantum light sources at room temperature and as nanoscale light sources for integrated photonic circuits on silicon. Here, we show that the integration of dopant states in carbon nanotubes and silicon microcavities can provide bright and high-purity single-photon emitters on a silicon photonics platform at room temperature. We perform photoluminescence spectroscopy and observe the enhancement of emission from the dopant states by a factor of ∼50, and cavity-enhanced radiative decay is confirmed using time-resolved measurements, in which a ∼30% decrease of emission lifetime is observed. The statistics of photons emitted from the cavity-coupled dopant states are investigated by photon-correlation measurements, and high-purity single photon generation is observed. The excitation power dependence of photon emission statistics shows that the degree of photon antibunching can be kept high even when the excitation power increases, while the single-photon emission rate can be increased to ∼1.7 × 10 7 Hz.

Covalent functionalization of single-walled carbon nanotubes (SWCNTs) introduces red-shifted emission features in the near-infrared spectral range due to exciton localization around the defect site. Such chemical modifications increase their potential use as near-infrared emitters and single-photon sources in telecommunications applications. Density functional theory (DFT) studies using finite-length tube models have been used to calculate their optical transition energies. Predicted energies are typically blue-shifted compared to experiment due to methodology errors including imprecise self-interaction corrections in the density functional and finite-size basis sets. Furthermore, artificial quantum confinement in finite models cannot be corrected by a constant-energy shift since they depend on the degree of exciton localization. Herein, we present a method that corrects the emission energies predicted by time-dependent DFT. Confinement and methodology errors are separately estimated using experimental data for unmodified tubes. Corrected emission energies are in remarkable agreement with experiment, suggesting the value of this straightforward method toward predicting and interpreting the optical features of functionalized SWCNTs.

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.

Aiming to unravel the relationship between chemical configuration and electronic structure of sp 3 defects of aryl-functionalized (6,5) single-walled carbon nanotubes (SWCNTs), we perform low-temperature single nanotube photoluminescence (PL) spectroscopy studies and correlate our observations with quantum chemistry simulations. We observe sharp emission peaks from individual defect sites that are spread over an extremely broad, 1000-1350 nm, spectral range. Our simulations allow us to attribute this spectral diversity to the occurrence of six chemically and energetically distinct defect states resulting from topological variation in the chemical binding configuration of the monovalent aryl groups. Both PL emission efficiency and spectral line width of the defect states are strongly influenced by the local dielectric environment. Wrapping the SWCNT with a polyfluorene polymer provides the best isolation from the environment and yields the brightest emission with near-resolution limited spectral line width of 270 μeV, as well as spectrally resolved emission wings associated with localized acoustic phonons. Pump-dependent studies further revealed that the defect states are capable of emitting single, sharp, isolated PL peaks over 3 orders of magnitude increase in pump power, a key characteristic of two-level systems and an important prerequisite for single-photon emission with high purity. These findings point to the tremendous potential of sp 3 defects in development of room temperature quantum light sources capable of operating at telecommunication wavelengths as the emission of the defect states can readily be extended to this range via use of larger diameter SWCNTs.

Cycloparaphenylenes represent the smallest possible fragments of armchair carbon nanotubes. Due to their cyclic and curved conjugation, these nanohoops own unique photophysical properties. Herein, the internal conversion processes of cycloparaphenylenes of sizes 9 through 16 are simulated using Non-Adiabatic Excited States Molecular Dynamics. In order to analyze effects of increased conformational disorder, simulations are done at both low temperature (10 K) and room temperature (300 K). We found the photoexcitation and subsequent electronic energy relaxation and redistribution lead to different structural and electronic signatures such as planarization of the chain, electron-phonon couplings, wavefunction localization, and intra-ring migration of excitons. During excited state dynamics on a picosecond time-scale, an electronic excitation becomes partially localized on a portion of the ring (about 3-5 phenyl rings), which is not a mere static contraction of the wavefunction. In a process of non-radiative relaxation involving non-adiabatic transitions, the latter exhibits significant dynamical mobility by sampling uniformly the entire molecular structure. Such randomized migration involving all phenyl rings, occurs in a wave-like fashion coupled to vibrational degrees of freedom. These results can be connected to unpolarized emission observed in single-molecule fluorescence experiments. Observed intra-ring energy transfer is subdued for lower temperatures and adiabatic dynamics involving low-energy photoexcitation to the first excited state. Overall our analysis provides a detailed description of photo excited dynamics in molecular systems with circular geometry, outlines size-dependent trends and connotes specific spectroscopic signatures appearing in time-resolved experimental probes.

By separating the photons from slow and fast decays of single and multi-exciton states in a time gated 2 nd order photon correlation experiment, we show that solitary oxygen dopant states of single-walled carbon nanotubes (SWCNTs) allow emission of photon pairs with efficiencies as high as 44% of single exciton emission. Our pump dependent time resolved photoluminescence (PL) studies further reveal diffusion-limited exciton-exciton annihilation as the key process that limits the emission of multi-excitons at high pump fluences. We further postulate that creation of additional permanent exciton quenching sites occurring under intense laser irradiation leads to permanent PL quenching. With this work, we bring out multi-excitonic processes of solitary dopant states as a new area to be explored for potential applications in lasing and entangled photon generation.

All-dielectric metasurfaces made from arrays of high index nanoresonators supporting strong magnetic dipole modes have emerged as a low-loss alternative to plasmonic metasurfaces. Here we use oxygen-doped single-walled carbon nanotubes (SWCNTs) as quantum emitters and couple them to silicon metasurfaces to study effects of the magnetic dipole modes of the constituent nanoresonators on the photoluminescence (PL) of individual SWCNTs. We find that when in resonance, the magnetic mode of the silicon nanoresonators can lead to a moderate average PL enhancement of 0.8-4.0 of the SWCNTs, accompanied by an average increase in the radiative decay rate by a factor of 1.5-3.0. More interestingly, single dopant polarization experiments show an anomalous photoluminescence polarization rotation by coupling individual SWCNTs to silicon nanoresonators. Numerical simulations indicate that this is caused by modification of near-field polarization distribution at certain areas in the proximity of the silicon nanoresonators at the excitation wavelength, thus presenting an approach to control emission polarization. These findings indicate silicon nanoresonators as potential building blocks of quantum photonic circuits capable of manipulating PL intensity and polarization of single photon sources.

Molecules confined inside single-walled carbon nanotubes (SWCNTs) behave quite differently from their bulk analogues. In this Letter we present temperature-dependent (4.2 K up to room temperature) photoluminescence (PL) spectra of water-filled and empty single-chirality (6,5) SWCNTs. Superimposed on a linear temperature-dependent PL spectral shift of the empty SWCNTs, an additional stepwise PL spectral shift of the water-filled SWCNTs is observed at ∼150  K. With the empty SWCNTs serving as an ideal reference system, we assign this shift to temperature-induced changes occurring in the single-file chain of water molecules encapsulated in the tubes. Our molecular dynamics simulations further support the occurrence of a quasiphase transition of the orientational order of the water dipoles in the single-file chain.

A prerequisite for carbon nanotube-based optoelectronic devices is the ability to sort them into a pure semiconductor phase. One of the most common sorting routes is enabled through using specific wrapping polymers. Here we show that subtle changes in the polymer structure can have a dramatic influence on the figures of merit of a carbon nanotube-based photovoltaic device. By comparing two commonly used polyfluorenes (PFO and PFO-BPy) for wrapping (7,5) and (6,5) chirality SWCNTs, we demonstrate that they have contrasting effects on the device efficiency. We attribute this to the differences in their ability to efficiently transfer charge. Although PFO may act as an efficient interfacial layer at the anode, PFO-BPy, having the additional pyridine side groups, forms a high resistance layer degrading the device efficiency. By comparing PFO|C 60 and C 60 -only devices, we found that presence of a PFO layer at low optical densities resulted in the increase of all three solar cell parameters, giving nearly an order of magnitude higher efficiency over that of C 60 -only devices. In addition, with a relatively higher contribution to photocurrent from the PFO-C 60 interface, an open circuit voltage of 0.55 V was obtained for PFO-(7,5)-C 60 devices. On the other hand, PFO-BPy does not affect the open circuit voltage but drastically reduces the short circuit current density. These results indicate that the charge transport properties and energy levels of the sorting polymers have to be taken into account to fully understand their effect on carbon nanotube-based solar cells.

Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. Here, we present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. Pump-probe measurements suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. The open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.

Photoluminescent defect states introduced by sp(3) functionalization of semiconducting carbon nanotubes are rapidly emerging as important routes for boosting emission quantum yields and introducing new functionality. Knowledge of the relaxation dynamics of these states is required for understanding how functionalizing agents (molecular dopants) may be designed to access specific behaviors. We measure photoluminescence (PL) decay dynamics of sp(3) defect states introduced by aryl functionalization of the carbon nanotube surface. Results are given for five different nanotube chiralities, each doped with a range of aryl functionality. We find that the PL decays of these sp(3) defect states are biexponential, with both components relaxing on time scales of ∼100 ps. Exciton trapping at defects is found to increases PL lifetimes by a factor of 5-10, in comparison to those for the free exciton. A significant chirality dependence is observed in the decay times, ranging from 77 ps for (7,5) nanotubes to >600 ps for (5,4) structures. The strong correlation of time constants with emission energy indicates relaxation occurs via multiphonon decay processes, with close agreement to theoretical expectations. Variation of the aryl dopant further modulates decay times by 10-15%. The aryl defects also affect PL lifetimes of the free E11 exciton. Shortening of the E11 bright state lifetime as defect density increases provides further confirmation that defects act as exciton traps. A similar shortening of the E11 dark exciton lifetime is found as defect density increases, providing strong experimental evidence that dark excitons are also trapped at such defect sites.

The one-dimensional character of electrons, phonons and excitons in individual single-walled carbon nanotubes leads to extremely anisotropic electronic, thermal and optical properties. However, despite significant efforts to develop ways to produce large-scale architectures of aligned nanotubes, macroscopic manifestations of such properties remain limited. Here, we show that large (>cm(2)) monodomain films of aligned single-walled carbon nanotubes can be prepared using slow vacuum filtration. The produced films are globally aligned within ±1.5° (a nematic order parameter of ∼1) and are highly packed, containing 1 × 10(6) nanotubes in a cross-sectional area of 1 μm(2). The method works for nanotubes synthesized by various methods, and film thickness is controllable from a few nanometres to ∼100 nm. We use the approach to create ideal polarizers in the terahertz frequency range and, by combining the method with recently developed sorting techniques, highly aligned and chirality-enriched nanotube thin-film devices. Semiconductor-enriched devices exhibit polarized light emission and polarization-dependent photocurrent, as well as anisotropic conductivities and transistor action with high on/off ratios.

Covalent dopants in semiconducting single wall carbon nanotubes (SWCNTs) are becoming important as routes for introducing new photoluminescent emitting states with potential for enhanced quantum yields, new functionality, and as species capable of near-IR room-temperature single photon emission. The origin and behavior of the dopant-induced emission is thus important to understand as a key requirement for successful room-T photonics and optoelectronics applications. Here, we use direct correlated two-color photoluminescence imaging to probe how the interplay between the SWCNT bright E(11) exciton and solitary dopant sites yields the dopant-induced emission for three different dopant species: oxygen, 4-methoxybenzene, and 4-bromobenzene. We introduce a route to control dopant functionalization to a low level as a means for introducing spatially well-separated solitary dopant sites. Resolution of emission from solitary dopant sites and correlation to their impact on E(11) emission allows confirmation of dopants as trapping sites for localization of E(11) excitons following their diffusive transport to the dopant site. Imaging of the dopant emission also reveals photoluminescence intermittency (blinking), with blinking dynamics being dependent on the specific dopant. Density functional theory calculations were performed to evaluate the stability of dopants and delineate the possible mechanisms of blinking. Theoretical modeling suggests that the trapping of free charges in the potential well created by permanent dipoles introduced by dopant atoms/groups is likely responsible for the blinking, with the strongest effects being predicted and observed for oxygen-doped SWCNTs.

The spatial extent of charged electronic states in semiconducting carbon nanotubes with indices (6,5) and (7,6) was evaluated using density functional theory. It was observed that electrons and holes self-trap along the nanotube axis on length scales of about 4 and 8 nm, respectively, which localize cations and anions on comparable length scales. Self-trapping is accompanied by local structural distortions showing periodic bond-length alternation. The average lengthening (shortening) of the bonds for anions (cations) is expected to shift the G-mode frequency to lower (higher) values. The smaller-diameter nanotube has reduced structural relaxation due to higher carbon-carbon bond strain. The reorganization energy due to charge-induced deformations in both nanotubes is found to be in the 30-60 meV range. Our results represent the first theoretical simulation of self-trapping of charge carriers in semiconducting nanotubes, and agree with available experimental data.

On-demand single-photon sources capable of operating at room temperature and the telecom wavelength range of 1,300-1,500 nm hold the key to the realization of novel technologies that span from sub-diffraction imaging to quantum key distribution and photonic quantum information processing. Here, we show that incorporation of undoped (6,5) single-walled carbon nanotubes into a SiO2 matrix can lead to the creation of solitary oxygen dopant states capable of fluctuation-free, room-temperature single-photon emission in the 1,100-1,300 nm wavelength range. We investigated the effects of temperature on photoluminescence emission efficiencies, fluctuations and decay dynamics of the dopant states and determined the conditions most suitable for the observation of single-photon emission. This emission can in principle be extended to 1,500 nm by doping of smaller-bandgap single-walled carbon nanotubes. This easy tunability presents a distinct advantage over existing defect centre single-photon emitters (for example, diamond defect centres). Our SiO2-encapsulated sample also presents exciting opportunities to apply Si/SiO2-based micro/nano-device fabrication techniques in the development of electrically driven single-photon sources and integration of these sources into quantum photonic devices and networks.

Pump-dependent photoluminescence imaging and second-order photon correlation studies have been performed on individual single-walled carbon nanotubes (SWCNTs) at room temperature. These studies enable the extraction of both the exciton diffusion constant and the Auger recombination coefficient. A linear correlation between these parameters is attributed to the effect of environmental disorder in setting the exciton mean free path and capture-limited Auger recombination at this length scale. A suppression of photon antibunching is attributed to the creation of multiple spatially nonoverlapping excitons in SWCNTs, whose diffusion length is shorter than the laser spot size. We conclude that complete antibunching at room temperature requires an enhancement of the exciton-exciton annihilation rate that may become realizable in SWCNTs allowing for strong exciton localization.

The conformational structure and the electronic properties of various electronic excitations in cycloparaphenylenes (CPPs) are calculated using hybrid density functional theory (DFT). The results demonstrate that wavefunctions of singlet and triplet excitons as well as the positive and negative polarons remain fully delocalized in CPPs. In contrast, these excitations in larger CPP molecules become localized on several phenyl rings, which are locally planarized, while the undeformed ground state geometry is preserved on the rest of the hoop. As evidenced by the measurements of bond-length alternation and dihedral angles, localized regions show stronger hybridization between neighboring bonds and thus enhanced electronic communication. This effect is even more significant in the smaller hoops, where phenyl rings have strong quinoid character in the ground state. Thus, upon excitation, electron-phonon coupling leads to the self-trapping of the electronic wavefunction and release of energy from fractions of an eV up to two eVs, depending on the type of excitation and the size of the hoop. The impact of such localization on electronic and optical properties of CPPs is systematically investigated and compared with the available experimental measurements.

In this contribution we demonstrate the effective separation of single-wall carbon nanotube (SWCNT) species with diameters larger than 1 nm through multistage aqueous two-phase extraction (ATPE), including isolation at the near-monochiral species level up to at least the diameter range of SWCNTs synthesized by electric arc synthesis (1.3-1.6 nm). We also demonstrate that refined species are readily obtained from both the metallic and semiconducting subpopulations of SWCNTs and that this methodology is effective for multiple SWCNT raw materials. Using these data, we report an empirical function for the necessary surfactant concentrations in the ATPE method for separating different SWCNTs into either the lower or upper phase as a function of SWCNT diameter. This empirical correlation enables predictive separation design and identifies a subset of SWCNTs that behave unusually as compared to other species. These results not only dramatically increase the range of SWCNT diameters to which species selective separation can be achieved but also demonstrate that aqueous two-phase separations can be designed across experimentally accessible ranges of surfactant concentrations to controllably separate SWCNT populations of very small (∼0.62 nm) to very large diameters (>1.7 nm). Together, the results reported here indicate that total separation of all SWCNT species is likely feasible by the ATPE method, especially given future development of multistage automated extraction techniques.

Polyclic aromatic hydrocarbons also called Graphene Molecules (GMs), with chemical composition C132H36(COOH)2 were synthesized in situ on the surface of transparent nanocrystalline indium tin oxide (nc-ITO) electrodes and their electronic structure was studied electrochemically and spectro-electrochemically. Variations in the potential applied onto the nc-ITO/GM electrodes induce only small changes in the observed current, but they produce dramatic changes in the absorption of the GMs, which are associated with their oxidation and reduction. Analysis of the absorption changes using a modified Nernst equation is used to determine standard potentials associated with the individual charge transfer processes. For the GMs prepared here, these were found to be E1,ox(0) = 0.77 ± 0.01 V and E2,ox(0) = 1.24 ± 0.02 V vs NHE for the first and second oxidation and E1,red(0) = -1.50 ± 0.04 V for the first reduction. The charge transfer processes are found to be nonideal. The nonideality factors associated with the oxidation and reduction processes are attributed to strong interactions between the GM redox centers. Under the conditions of potential cycling, GMs show rapid (seconds) color change with high contrast and stability. An electrochromic application is demonstrated wherein the GMs are used as the optically active component.

Graphene oxide (GO) has emerged as a multifunctional material that can be synthesized in bulk quantities and can be solution processed to form large-area atomic layered photoactive, flexible thin films for optoelectronic devices. This is largely due to the potential ability to tune electrical and optical properties of GO using functional groups. For the successful application of GO, it is key to understand the evolution of its optoelectronic properties as the GO undergoes a phase transition from its insulating and optically active state to the electrically conducting state with progressive reduction. In this paper, we use a combination of electrostatic force microscopy (EFM) and optical spectroscopy to monitor the emergence of the optoelectronic properties of GO with progressive reduction. EFM measurements enable, for the first time, direct visualization of charge propagation along the conducting pathways that emerge on progressively reduced graphene oxide (rGO) and demonstrate that with the increasing degree of reduction, injected charges can rapidly migrate over a distance of several micrometers, irrespective of their polarities. Direct imaging reveals the presence of an insurmountable potential barrier between reduced GO (rGO) and GO, which plays the decisive role in the charge transport. We complement charge imaging with theoretical modeling using quantum chemistry calculations that further demonstrate that the role of barrier in regulating the charge transport. Furthermore, by correlating the EFM measurements with photoluminescence imaging and electrical conductivity studies, we identify a bifunctional state in GO, where the optical properties are preserved along with good electrical conductivity, providing design principles for the development of GO-based, low-cost, thin-film optoelectronic applications.

Understanding behavior of rare-earth ions (REI) in crowded environments is crucial for several nano- and bio-technological applications. Evolution of REI photoluminescence (PL) in small compartments inside a silica hydrogel, mimic to a soft matter bio-environment, has been studied and explained within a solvation model. The model uncovered the origin of high PL efficiency to be the formation of REI complexes, surrounded by bile salt (DOC) molecules. Comparative study of these REI-DOC complexes in bulk water solution and those enclosed inside the hydrogel revealed a strong correlation between an up to 5×-longer lifetime of REIs and appearance of the DOC ordered phase, further confirmed by dynamics of REI solvation shells, REI diffusion experiments and morphological characterization of microstructure of the hydrogel.

We present a method for preparation of graphene molecules (GMs), whereby a polyphenylene precursor functionalized with surface anchoring groups, preadsorbed on surface of TiO2, is oxidatively dehydrogenated in situ via a Scholl reaction. The reaction, performed at ambient conditions, yields surface adsorbed GMs structurally and electronically equivalent to those synthesized in solution. The new synthetic approach reduces the challenges associated with the tendency of GMs to aggregate and provides a convenient path for integration of GMs into optoelectronic applications. The surface synthesized GMs can be effectively reduced or oxidized via an interfacial charge transfer and can also function as sensitizers for metal oxides in light harvesting applications. Sensitized solar cells (SSCs) prepared from mesoscopic TiO2/GM films and an iodide-based liquid electrolyte show photocurrents of ∼2.5 mA/cm2, an open circuit voltage of ∼0.55 V and fill factor of ∼0.65 under AM 1.5 illumination. The observed power conversion efficiency of η=0.87% is the highest reported efficiency for the GM sensitized solar cell. The performance of the devices was reproducible and stable for a period of at least 3 weeks. We also report first external and internal quantum efficiency measurements for GM SSCs, which point to possible paths for further performance improvements.

Cycloparaphenylenes, the simplest structural unit of armchair carbon nanotubes, have unique optoelectronic properties counterintuitive in the class of conjugated organic materials. Our time-dependent density functional theory study and excited state dynamics simulations of cycloparaphenylene chromophores provide a simple and conceptually appealing physical picture explaining experimentally observed trends in optical properties in this family of molecules. Fully delocalized degenerate second and third excitonic states define linear absorption spectra. Self-trapping of the lowest excitonic state due to electron-phonon coupling leads to the formation of spatially localized excitation in large cycloparaphenylenes within 100 fs. This invalidates the commonly used Condon approximation and breaks optical selection rules, making these materials superior fluorophores. This process does not occur in the small molecules, which remain inefficient emitters. A complex interplay of symmetry, π-conjugation, conformational distortion and bending strain controls all photophysics of cycloparaphenylenes.

We study temporal evolution of photoluminescence (PL) spectra from individual single-walled carbon nanotubes (SWCNTs) at cryogenic and room temperatures. Sublinear and superlinear correlations between fluctuating PL spectral positions and line widths are observed at cryogenic and room temperatures, respectively. We develop a simple model to explain these two different spectral diffusion behaviors in the framework of quantum-confined Stark effect (QCSE) caused by surface charges trapped in the vicinity of SWCNTs. We show that the wave function properties of excitons, namely, localization at cryogenic temperature and delocalization at room temperature, play a critical role in defining sub- and superlinear correlations. Room temperature PL spectral positions and line widths of SWCNTs coupled to gold dimer nanoantennas on the other hand exhibit sublinear correlations, indicating that excitonic emission mainly originates from nanometer range regions and excitons appear to be localized. Our numerical simulations show that such apparent localization of excitons results from plasmonic confinement of excitation and an enhancement of decay rates in the gap of the dimer nanoantennas.

We performed low temperature photoluminescence (PL) studies on individual oxygen-doped single-walled carbon nanotubes (SWCNTs) and correlated our observations to electronic structure simulations. Our experiment reveals multiple sharp asymmetric emission peaks at energies 50-300 meV red-shifted from that of the E11 bright exciton peak. Our simulation suggests an association of these peaks with deep trap states tied to different specific chemical adducts. In addition, oxygen doping is also observed to split the E11 exciton into two or more states with an energy splitting <40 meV. We attribute these states to dark states that are brightened through defect-induced symmetry breaking. While the wave functions of these brightened states are delocalized, those of the deep-trap states are strongly localized and pinned to the dopants. These findings are consistent with our experimental observation of asymmetric broadening of the deep trap emission peaks, which can result from interaction between pinned excitons and one-dimensional phonons. Exciton pinning also increases the sensitivity of the deep traps to the local dielectric environment, leading to a large inhomogeneous broadening. Observations of multiple spectral features on single nanotubes indicate the possibility of different chemical adducts coexisting on a given nanotube.

Using a macroscopic ensemble of highly enriched (6,5) single-wall carbon nanotubes, combined with high signal-to-noise ratio and time-dependent differential transmission spectroscopy, we have generated vibrational modes in an ultrawide spectral range (10-3000 cm(-1)). A total of 14 modes were clearly resolved and identified, including fundamental modes of A, E1, and E2 symmetries and their combinational modes involving two and three phonons. Through comparison with continuous wave Raman spectra as well as calculations based on an extended tight-binding model, we were able to identify all the observed peaks and determine the frequencies of the individual and combined modes. We provide a full summary of phonon frequencies for (6,5) nanotubes that can serve as a basic reference with which to refine our understanding of nanotube phonon spectra as well as a testbed for new theoretical models.