Long-lived Single Excitons,Trions, and Biexcitons in CdSe/CdTe Type-Ⅱ Colloidal Quantum Wells

Light-harvesters with long-lived excited states are desired for efficient solar energy conversion systems. Many solar-to-fuel conversion reactions, such as H₂ evolution and CO₂ reduction, require multiple sequential electron transfer processes, which leads to a complicated situation that excited states involves not only excitons (electron-hole pairs) but also multi-excitons and charged excitons. While long-lived excitons can be obtained in various systems (e.g., semiconductor nanocrystals), multi-excitons and charged excitons are typically shorted-lived due to nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the third carrier on a few to hundreds of picoseconds timescale. In this work, we report a study of excitons, trions (an exciton plus an additional charge), and biexcitons in CdSe/CdTe colloidal quantum wells or nanoplatelets. The typeⅡ band alignment effectively separates electrons and holes in space, leading to a single exciton lifetime of 340 ns which is ~2 order of magnitudes longer than that in plane CdSe nanoplatelets. More importantly, the electron-hole separation also dramatically slows down Auger decay, giving rise to a trion lifetime of 70 ns and a biexciton lifetime of 11 ns, among the longest values ever reported for colloidal nanocrystals. The long-lived exciton, trion, and biexciton states, combined with the intrinsically strong light-absorption capability of two-dimensional systems, enable the CdSe/CdTe type-Ⅱ nanoplatelets as promising light harvesters for efficient solar-to-fuel conversion reactions.     

Excitons in semiconducting carbon nanotubes: diameter-dependent photoluminescence spectra

Semiconducting single-walled carbon nanotubes are one-dimensional (1D) quantum nanostructures and their unique optical responses arise from stable 1D excitons with huge binding energies. Here we review recent studies on optical properties of semiconducting carbon nanotubes. The diameter dependence of luminescence spectra and dynamics are revealed by single-nanotube spectroscopy and time-resolved optical spectroscopy. Short-range Coulomb interactions play a crucial role in energy structures of dark, triplet, and charged excitons. Enhanced exciton-exciton interactions in 1D semiconductor nanostructures determine nonlinear optical responses. We present generic configurations of neutral and charged excitons and discuss exciton optics of single-walled carbon nanotubes.     

Aqueous dispersion, surface thiolation, and direct self-assembly of carbon nanotubes on gold

We report the efficient aqueous dispersion of pristine HiPco single-walled carbon nanotubes (SWNTs) with ionic liquid (IL)-based surfactants 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), the thiolation of nanotube sidewalls with 2, and the controlled self-assembly of positively charged SWNT-1,2 composites on gold. Optical absorption spectra and resonance Raman (RR) data of obtained aqueous SWNT-1,2 dispersions are consistent with debundled and noncovalently functionalized nanotubes whose electronic properties have not been disturbed. Additionally, the dispersion of pristine nanotube material with surfactants 1 and 2 leads to a high degree of purification from carbonaceous particles. The chiralities of the 14 smallest semiconducting HiPco SWNTs in resonance with Raman excitation at 1064 nm (1.165 eV) were determined in SWNT-2 aqueous dispersion using UV-vis-NIR and RR spectra. X-ray photoelectron spectroscopy (XPS) and surface-enhanced resonance Raman scattering (SERRS) spectroscopy of SWNT-2 submonolayers on gold verified the encapsulation of individualized SWNTs with IL surfactants, the cleavage of S-S disulfide bonds formed in aqueous SWNT-2 suspensions, and the direct chemisorption of the SWNT-2 composite on bare gold via the Au-S bond. Aqueous dispersions of SWNTs with IL-based surfactants add biofunctionality to carbon nanotubes by imparting the positive surface charge necessary for interactions with cell membranes. Our technique, which purifies pristine nanotube material and produces water-soluble, positively charged nanotubes with pendent surface-active thiol groups, may also be translated to other carbon nanotubes and carbon nanostructures. Self-assembled, positively charged submonolayers of SWNTs can be further used for applications in cell biology and sensor technology.     

Controlling the electrophoretic mobility of single-walled carbon nanotubes: a comparison of theory and experiment

The electrophoretic mobilities of single-walled carbon nanotubes (SWNTs) in agarose gels subjected to negatively charged covalent functionalization and noncovalent anionic surfactant adsorption are compared using a simplified hydrodynamic model. Net charges are calculated on the basis of estimated friction coefficients for cylindrical rodlike particles. The effects of functionalization with negatively charged 4-hydroxybenzene diazonium and anionic sodium cholate are quantified and compared with model predictions. The adsorption of Na+ counterions into the nonionic surfactant layer adsorbed on SWNTs (Triton-X-405) is shown to induce a positive charge and reverse the mobility under select conditions. This effect has not been identified or quantified for nanoparticle systems and may be important in the processing of these systems.     

Exciton energy transfer-assisted photoluminescence brightening from freestanding single-walled carbon nanotube bundles

Photoluminescence (PL) brightening is clearly observed through the direct morphology transition from isolated to thin bundled vertically- and individually freestanding single-walled carbon nanotubes (SWNTs). On the basis of the precise spectra analysis and equation-based estimation of the PL time trace, the origin of the PL brightening is consistently explained in terms of the exciton energy transfer through the tube bundles. The PL brightening is also revealed to obviously depend on SWNT diameters. Only the small-diameter rich sample can realize the PL brightening, which can be explained by the different concentrations of metallic SWNTs causing a PL quenching. Since it can be possible to fabricate brightly illuminating nanotubes on various kinds of substrates, the bundle engineering with freestanding nanotubes is expected to be a potential candidate for realizing the nanotube-based PL device fabrication.     

Nanostructured biosensors built by layer-by-layer electrostatic assembly of enzyme-coated single-walled carbon nanotubes and redox polymers

In this study, we describe the construction of glucose biosensors based on an electrostatic layer-by-layer (LBL) technique. Gold electrodes were initially functionalized with negatively charged 11-mercaptoundecanoic acid followed by alternate immersion in solutions of a positively charged redox polymer, poly[(vinylpyridine)Os(bipyridyl)2Cl(2+/3+)], and a negatively charged enzyme, glucose oxidase (GOX), or a GOX solution containing single-walled carbon nanotubes (SWNTs). The LBL assembly of the multilayer films were characterized by UV-vis spectroscopy, ellipsometry, and cyclic voltammetry, while characterization of the single-walled nanotubes was performed with transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. When the GOX solution contained single-walled carbon nanotubes (GOX-SWNTs), the oxidation peak currents during cyclic voltammetry increased 1.4-4.0 times, as compared to films without SWNTs. Similarly the glucose electro-oxidation current also increased (6-17 times) when SWNTs were present. By varying the number of multilayers, the sensitivity of the sensors could be controlled.     

Distribution patterns and controllable transport of water inside and outside charged single-walled carbon nanotubes

The density distribution patterns of water inside and outside neutral and charged single-walled carbon nanotubes (SWNTs) soaked in water have been studied using molecular dynamics simulations based on TIP3P potential and Lennard-Jones parameters of CHARMM force field, in conjunction with ab initio calculations to provide the electron density distributions of the systems. Water molecules show different electropism near positively and negatively charged SWNTs. Different density distribution patterns of water, depending on the diameter and chirality of the SWNTs, are observed inside and outside the tube wall. These special distribution patterns formed can be explained in terms of the van der Waals and electrostatic interactions between the water molecules and the carbon atoms on the hexagonal network of carbon nanotubes. The electric field produced by the highly charged SWNTs leads to high filling speed of water molecules, while it prevents them from flowing out of the nanotube. Water molecules enter the neutral SWNTs slowly and can flow out of the nanotube in a fluctuating manner. It indicates that by adjusting the electric charge on the SWNTs, one can control the adsorption and transport behavior of polar molecules in SWNTs to be used as stable storage medium with template effect or transport channels. The transport rate can be tailored by changing the charge on the SWNTs.     

Adsorption of spillover hydrogen atoms on single-wall carbon nanotubes

Spillover of hydrogen on nanostructured carbons is a phenomenon that is critical to understand in order to produce efficient hydrogen storage adsorbents for fuel cell applications. The spillover and interaction of atomic hydrogen with single-walled carbon nanotubes (SWNTs) is the focus of this combined theoretical and experimental work. To understand the spillover mechanism, very low occupancies (i.e., 1 and 2 H atoms adsorbed) on (5,0), (7,0), (9,0) zigzag (semiconducting) SWNTs and a (5,5) armchair (metallic) SWNT, with corresponding diameters of 3.9, 5.5, 7.0, and 6.8 A, were investigated. The adsorption binding energy of H atoms depends on H occupancy, tube diameter, and helicity (or chirality), as well as endohedral (interior) vs exohedral (exterior) binding. Exohedral binding energies are substantially higher than endohedral binding energies due to easier sp(2)-sp(3) transition in hybridization of carbon on exterior walls upon binding. A binding energy as low as -8.9 kcal/mol is obtained for 2H atoms on the exterior wall of a (5, 0) SWNT. The binding energies of H atoms on the metallic SWNT are significantly weaker (about 23 kcal/mol weaker) than that on the semiconductor SWNT, for both endohedral and exohedral adsorption. The binding energy is generally higher on SWNTs of larger diameters, while its dependence on H occupancy is relatively weak except at very low occupancies. Experimental results at 298 K and for pressures up to 10 MPa with a carbon-bridged composite material containing SWNTs demonstrate the presence of multiple adsorption sites based on desorption hysteresis for the spiltover H on SWNTs, and the experimental results were in qualitative agreement with the molecular orbital calculation results.     

Stability of supershort single-walled carbon nanotubes

How short can single-walled carbon nanotubes (SWNTs) be? How stable are such supershort SWNTs (ss-SWNTs)? This work is the first to address these questions. On the basis of binding energy (E(B)), standard heats of formation , and strain energy (E(S)), we found that SWNTs with only one benzene ring in the axial direction, which we refer to as supershort SWNTs (ss-SWNTs), can be thermodynamically stable. On the basis of the data of E(B), , and E(S), the relative stabilities of ss-SWNTs, fullerenes, polycyclic aromatic hydrocarbons, and butadiyne are discussed. This study has laid a theoretical foundation for the possible synthesis of ss-SWNTs.     

Interactions of hydrogen with Pd and Pd/Ni alloy chain-functionalized single walled carbon nanotubes from density functional theory

Density functional theory is employed to study Pd and Pd/Ni alloy monatomic chain-functionalized metallic single walled carbon nanotubes (SWNT(6,6)) and semiconducting SWNT(10,0), and their interactions with hydrogen molecules. The stable geometries and binding energies have been determined for both isolated chains and chains on SWNT surfaces. We found that continuous Pd and Pd/Ni chains form on SWNTs with geometries close to stable geometries in the isolated chains. Ni alloying improves stability of the chains owing to a higher binding energy to both Pd and C atoms. The physical properties of SWNTs are significantly modified by chain functionalization. SWNT(10,0) is transformed to metal by either Pd or alloy chains, or to a smaller band gap semiconductor, depending on the Pd binding site. From calculations for H(2) interactions with the optimized chain-SWNT systems, the adsorption energy per H atom is found to be about 2.6 times larger for Pd/Ni chain-functionalized SWNTs than for pure Pd chain-functionalized SWNTs. Band structure calculations show that the SWNT(10,0) reverts back to semiconductor and SWNT(6,6) has reduced density of states at the Fermi level upon H(2) adsorption. This result is consistent with the experimentally observed increase of electrical resistance when Pd-coated SWNTs are used as H(2) sensing materials. Finally, our results suggest that Pd/Ni-SWNT materials are potentially good H(2)-sensing materials.     

Single electron emission from the closed-tips of single-walled carbon nanotubes

The single electron emission behaviors and characteristics from the well-defined quantized energy levels, corresponding to localized electronic states at the dome-structure tips, in single-walled carbon nanotubes (SWNTs) are investigated and illuminated by use of the energy level emission model in combination with the first-principles calculations on the electronic structures. Under the external electric field, the confined electrons are emitted simultaneously from each quantized energy level by virtue of the resonant tunneling effects. With increasing applied voltage, the emission current increases monotonically and exponentially up to the first peak value, and then steps into the increasing and decreasing "sawtoothlike" variations in sequence. The negative differential resistance or conductivity and the maximum current for SWNTs are simulated. The influences of localized electronic states and curvatures of the different closed tips on the single electron emission behaviors of SWNTs are evaluated and discussed. Also a few issues and applications relevant to electron emission of carbon nanotubes are addressed.     

Studies of bromine modified single-walled carbon nanotubes using photoelectron spectroscopy and density-functional theory

Many applications based on single-walled carbon nanotubes (SWNTs) require chemical modification of carbon nanotube to optimize the functionalities of the device. In this contribution we discuss the properties of SWNTs immersed in a hydrobromic acid (HBr) solution. Changes of atomic and electronic structures of bromine modified SWNTs were investigated using photoelectron spectroscopy (PES). Spectra of SWNTs before and after immersion in the HBr solution exhibit different features. To understand the mechanism of interaction between SWNTs and bromine, we performed density-functional theory calculations to reveal the structural changes, adsorption energy and chemical bonding information of SWNTs interacting with bromine. In addition, based on the Gelius model, from the molecular orbitals (MOs), we calculated ultraviolet photoelectron spectra (UPS) of SWNTs with and without functionalizing and compared them with the experiment. The present study is a first step in the understanding of the functionalization mechanism of carbon nanotubes.     

Mercury telluride crystals encapsulated within single walled carbon nanotubes: A density functional study

The structure and binding energies of mercury telluride crystals encapsulated within single walled carbon nanotubes (SWNTs) have been studied using density functional theory. The energies of three different pseudo one‐dimensional crystals of HgTe with 4:4, 3:3, and 2:2 coordination are compared. The initial structure for the 4:4 crystal was a 2 × 2 cubic motif derived from rock salt bulk structure, the 3:3 crystal corresponds to a novel structure found when HgTe was intercalated within SWNTs, and the 2:2 crystal is a chain motif derived from cinnabar (HgS) bulk structure. The isolated 3:3 crystal was found to be the most thermodynamically stable of the three structures. Calculations were performed on the 3:3 crystal inserted into three different SWNTs, (15, 0), (9, 9), and (17, 0), in order to investigate the perturbations on the molecular and electronic structure of the crystal and the SWNT, and the energy of formation of the HgTe@SWNT composites. The calculated structures are in good agreement with the experimental high resolution transmission electron microscopy images of the HgTe@SWNT composite. The calculated binding energies and density of states show that the interaction between nanotubes and the HgTe crystals is noncovalent. Since the energy difference of the “free” 4:4 and 3:3 structures is small and of the order of magnitude of the binding energies with the nanotubes, we carried out calculations on 4:4 HgTe structure inserted in to two different SWNTs, (15, 0) and (17, 0). The calculated binding energies show that, when the 4:4 structure is inserted into the smallest tube, the resultant composite has an energy comparable to the 3:3 structure, suggesting that this polymporph may also be found experimentally. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Length-dependent optical effects in single walled carbon nanotubes

Recently, Heller et al. reported length-dependent effects on the relative photoluminescence (PL) quantum yield of single walled carbon nanotubes (SWNTs) [Heller et al J. Am. Chem. Soc. 2004, 126, 14567-14573]. We propose a simple model involving thermal diffusion of excitons along the nanotube axis and quenching at the ends, to explain the observed trend in their data. By fitting to our model, we extract a diffusion coefficient of 6 cm(2)/s for excitons in SWNTs. Assuming a mono exponential decay of exciton PL, we also predict that effective length-dependent PL lifetimes for these excitons lie in the range of 1-27 ps. Experimental observations are shown to be consistent with stochastic rather than wavepacket-like exciton migration, which is in agreement with ultrafast excitonic dephasing. Edge effects seem to limit the use of short SWNTs in imaging and optical sensing applications.     

Antibacterial effects of carbon nanotubes: size does matter!

We provide the first evidence that the size (diameter) of carbon nanotubes (CNTs) is a key factor governing their antibacterial effects and that the likely main CNT-cytotoxicity mechanism is cell membrane damage by direct contact with CNTs. Experiments with well-characterized single-walled carbon nanotubes (SWNTs) and multiwalled carbon nanotubes (MWNTs) demonstrate that SWNTs are much more toxic to bacteria than MWNTs. Gene expression data show that in the presence of both MWNTs and SWNTs, Escherichia coli expresses high levels of stress-related gene products, with the quantity and magnitude of expression being much higher in the presence of SWNTs.     

Plasma Processing Based Synthesis of Functional Nanocarbons

Our recent research has shown that plasma processing techniques, which allow versatile control of both chemical and physical aspects, have considerable potential for the innovative synthesis and functionalization of three varieties of low-dimensional nanocarbons, which show great promise in the development of nanoscience and its applications. In the case of 0-D fullerenes, the mission is the high-yield production of atom (X) encapsulated fullerenes (X@C₆₀). The formation of macro-quantities of charge-exploited Li@C₆₀ and overwhelmingly-high purity spin-exploited N@C₆₀ are realized for the first time by the control of alkali-fullerene and nitrogen double plasmas, respectively. In the case of 1-D carbon nanotubes the challenge is precise structure control, i.e., chirality control of single-walled carbon nanotubes (SWNTs). The extremely narrow-chirality distributed growth of SWNTs is realized with time-programmed and nonmagnetic-catalyzed plasma CVD. As for functionalization of SWNTs, the enhanced p-type C₆₀@SWNTs created under the substrate-bias control in collisionless plasmas are found to be effective for harvesting solar energy in the infrared wavelength range and adapted to the use for multiple exciton generation in solar cells. Concerning 2-D graphene, our aim is to overcome two serious issues for electronics applications. One is the realization of the direct growth of graphene on an insulating (SiO₂) substrate by adjusting the growth parameters using non-equilibrium diffusion plasma CVD. The other is the direct fabrication of field-effect transistor device of a narrow-width (≥20 nm) graphene nanoribbon using a new, simple, and scalable method based on rapid heating plasma CVD, which shows a clear transport gap and a high on/off ratio. Finally the prospects for the above-mentioned results are discussed together with ripple effects of the nanocarbon research on the progress of nanoscience and its applications.     

Immobilizing shortened single-walled carbon nanotubes (SWNTs) on gold using a surface condensation method

We propose a surface condensation method for assembling single-walled carbon nanotubes (SWNTs) on gold. The as-prepared long and randomly tangled SWNTs were cut into short pipes by chemical oxidation, allowing the nanotubes to be terminated by carboxyl functionalities. A surface condensation reaction was then performed by immersing an amino self-assembled monolayer (SAM)-modified gold substrate into the dimethylformamide suspension of carboxylic nanotubes with the aid of dicyclohexylcarbodiimide condensation agent. Raman spectroscopy and atomic force microscopy (AFM) results show that a highly aligned assembly of SWNTs has been formed on gold, with the nanotubes standing on the surface stable enough for a long ultrasonication. In combination with the microcontact printing (muCP) technique, we have fabricated patterned nanotube assemblies using this surface condensation method. Moreover, we found that the "giant" carbon nanotubes tend to form bundles on an amino-terminating surface, likely following a nucleation-growth model.     

Ultrafast energy transfer of one-dimensional excitons between carbon nanotubes: a femtosecond time-resolved luminescence study

Excitation energy transfer has long been an intriguing subject in the fields of photoscience and materials science. Along with the recent progress of photovoltaics, photocatalysis, and photosensors using nanoscale materials, excitation energy transfer between a donor and an acceptor at a short distance (≤1-10 nm) is of growing importance in both fundamental research and technological applications. This Perspective highlights our recent studies on exciton energy transfer between carbon nanotubes with interwall (surface-to-surface) distances of less than ～1 nm, which are equivalent to or shorter than the size of one-dimensional excitons in carbon nanotubes. We show exciton energy transfer in bundles of single-walled carbon nanotubes with the interwall distances of ～0.34 and 0.9 nm (center-to-center distances ～1.3-1.4 and 1.9 nm). For the interwall distance of ～0.34 nm (center-to-center distance ～1.3-1.4 nm), the transfer rate per tube from a semiconducting tube to adjacent semiconducting tubes is (1.8-1.9) × 10(12) s(-1), and that to adjacent metallic tubes is 1.1 × 10(12) s(-1). For the interwall distance of ～0.9 nm (center-to-center distance ～1.9 nm), the transfer rate per tube from a semiconducting tube to adjacent semiconducting tubes is 2.7 × 10(11) s(-1). These transfer rates are much lower than those predicted by the F?rster model calculation based on a point dipole approximation, indicating the failure of the conventional F?rster model calculations. In double-walled carbon nanotubes, which are equivalent to ideal nanoscale coaxial cylinders, we show exciton energy transfer from the inner to the outer tubes. The transfer rate between the inner and the outer tubes with an interwall distance of ～0.38 nm is 6.6 × 10(12) s(-1). Our findings provide an insight into the energy transfer mechanisms of one-dimensional excitons.