Photoluminescence phenomena normally obey Stokes' law of luminescence according to which the emitted photon energy is typically lower than its excitation counterparts. Here we show that carbon nanotubes break this rule under one-photon excitation conditions. We found that the carbon nanotubes exhibit efficient near-infrared photoluminescence upon photoexcitation even at an energy lying >100–200 meV below that of the emission at room temperature. This apparently anomalous phenomenon is attributed to efficient one-phonon-assisted up-conversion processes resulting from unique excited-state dynamics emerging in an individual carbon nanotube with accidentally or intentionally embedded localized states. These findings may open new doors for energy harvesting, optoelectronics and deep-tissue photoluminescence imaging in the near-infrared optical range.

We report distinctive nonlinear behavior of photoluminescence (PL) intensities from localized exciton states embedded in single-walled carbon nanotubes (SWNTs) at room temperature. We found that PL from the local states exhibits strong nonlinear behavior with increasing continuous-wave excitation power density, whereas free exciton PL shows only weak sublinear behavior. The strong nonlinear behavior was observed regardless of the origin of the local states and found to be nearly independent of the local state density. These results indicate that the strong PL nonlinearity arises from a universal mechanism to SWNTs with sparse local states. The significant nonlinear PL is attributed to rapid ground-state depletion of the local states caused by an efficient accumulation of photogenerated free excitons into the sparse local states through one-dimensional diffusional migration of excitons along the nanotube axis; this mechanism is verified by Monte Carlo simulations of exciton diffusion dynamics.

Single-walled carbon nanotubes doped with a limited amount of oxygen (O-doped SWNTs) are expected to be novel materials due to the appearance of red-shifted new emission and enhancement of the luminescence quantum yields compared to those of pristine SWNTs, which are of importance for the development of high performance biosensors, imaging materials, and optical devices. The appearance of the new optical properties is due to the change in the electronic states induced by the oxygen doping (Odoping) of the SWNTs, thus quantitative analysis of the electronic states of the O-doped SWNTs is crucial. In this study, we have successfully determined the precise electronic states of the O-doped SWNTs based on the in situ photoluminescence (PL) electrochemical method. The measurements revealed the presence of at least two distinct O-doping sites with unique optical and electrochemical properties for all four studied chiralities. The electrochemical measurements also showed that shifts in the valence and conduction band resulting from the O doping are on the order of 0.02−0.03 eV, which is much lower than the red shift of the photoluminescence peak. This behavior agrees with the theoretical simulations using the density functional based tight binding (DFTB) method. This study suggests that the doped sites on the SWNTs act as a neutral quantum dot trapping exciton generated on the tubes.

In this study, high-purity single-chirality (5,4) and (6,4) single-wall carbon nanotubes (SWCNTs) were efficiently extracted using gel chromatography, and their optical properties were investigated. In the photoluminescence spectrum, the (5,4) SWCNTs exhibited multiple emission peaks, such as E11 * at 968 and E11 *− at 1096 nm, in addition to the original E11 peak at 829 nm for the E22 excitation. Although the (6,4) SWCNTs also exhibited similar emission peaks, the intensity of the additional peaks relative to the E11 peak was approximately four times lower than that of (5,4) SWCNTs, even though the same separation procedure was used for both species. The results from density functional theory calculations indicated that both the E11 * and E11 *− emissions originated as emissions from the oxide states. Because no oxidation treatments were performed on the samples, these oxides were most likely spontaneously produced during the sample preparation process. Theoretical results indicated that the (5,4) SWCNT possesses a more stable ether-a-O structure that could cause the E11 * emission. The difference in the stability of the oxide states for (5,4) SWCNT and (6,4) SWCNT strongly suggests that the (5,4) SWCNT is more likely to be oxidized by weak stimulation. These results indicate that the (5,4) SWCNT remained near the outside of the robust structure due to its strong curvature effects.

We studied the excitation density dependence of photoluminescence (PL) spectra of excitons and trions (charged excitons) in hole-doped single-walled carbon nanotubes.We found that the PL intensity of trions exhibited a strong nonlinear saturation behavior as the excitation density increased, whereas that of excitons exhibited a weak sublinear behavior. The strong PL saturation of trions is attributed to depletion of doped holes that are captured by excitons in the formation processes. Moreover, the effective radiative lifetime of a trion was evaluated to be approximately 20 ns.