Bright band gap photoluminescence from unprocessed single-walled carbon nanotubes

Unprocessed single-walled carbon nanotubes suspended in air at room temperature emit bright, sharply peaked band gap photoluminescence. This is in contrast with measurements taken from nanotubes lying on the flat surface for which no luminescence was detected. Each individual nanotube has a luminescence peak of similar linewidth ( approximately 13 meV), with different species emitting at various different wavelengths spanning at least 1.0 to 1.6 microm. A strong enhancement of photoluminescence intensity is observed when the excitation wavelength is resonant with the second Van Hove singularity, unambiguously confirming the origin of the photoluminescence.     

Femtosecond luminescence decay due to exciton energy transfer in single-walled carbon nanotube bundles

We investigated luminescence decay kinetics in single-walled carbon nanotubes in large bundles excited by femtosecond pulses. The time constant of luminescence decay becomes longer with decrease in photon energy: 40 fs at 1.2 eV and 380 fs at 0.6 eV. This behavior is explained by exciton energy transfer from an excited to neighboring tubes.     

Photon antibunching in the photoluminescence spectra of a single carbon nanotube

We report the first observation of photon antibunching in the photoluminescence from single carbon nanotubes. The emergence of a fast luminescence decay component under strong optical excitation indicates that Auger processes are partially responsible for inhibiting two-photon generation. Additionally, the presence of exciton localization at low temperatures ensures that nanotubes emit photons predominantly one by one. The fact that multiphoton emission probability can be smaller than 5% suggests that carbon nanotubes could be used as a source of single photons for applications in quantum cryptography.     

Diameter-dependent relaxation dynamics of 1D excitons in single-walled carbon nanotubes

We have studied 1D exciton relaxation dynamics in semiconducting single-walled carbon nanotubes (SWNTs) by femtosecond pump–probe experiments. The time evolution of change in transmittance ΔT/T induced by photo-excitation varies depending on the tube diameter. The decay time decreases with a decrease in the tube diameter. Pressure measurements have been conducted to explore the relaxation mechanism. The deformation potential estimated from the pressure dependence of photoluminescence spectra increases with decreasing tube diameter. This means that the exciton–phonon interaction becomes stronger in the smaller diameter tubes. The diameter dependences of decay time and deformation potential suggest that the exciton–phonon interaction plays an important role in exciton nonradiative relaxation process in semiconducting SWNTs.     

Luminescence decay and the absorption cross section of individual single-walled carbon nanotubes

The absorption cross section of highly luminescent individual single-walled carbon nanotubes is determined using time-resolved and cw luminescence spectroscopy. A mean value of approximately 1 x 10(-17) cm2 per carbon atom is obtained for (6,5) tubes excited at their second optical transition, and corroborated by single tube photothermal absorption measurements. Biexponential luminescence decays are systematically observed, with short and long lifetimes around 45 and 250 ps. This behavior is attributed to the band edge exciton fine structure with a dark level lying a few meV below a bright one.     

Synthesis of CdS nanostructures using template-assisted ammonia-free chemical bath deposition

CdS micro- and nano-structures (micro/nanotubes and nanostructured films) were obtained by ammonia-free chemical bath deposition using polymer templates (ion track-etched polycarbonate membranes and poly(styrene-hydroxyethyl methacrylate) nanosphere arrays). The semiconductor structures were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), optical absorption, photoluminescence and electrical measurements. The diameters of CdS tubes are between 300 nm and few microns and the lengths are up to tens of micrometers. The SEM images prove that the CdS films are nanostructured due to the deposition on the polymer nanosphere arrays. For both CdS structures (tubes and films) the XRD patterns show a hexagonal phase. The optical studies reveal a band gap value of about 2.5?2.6 eV and a red luminescence at ～1.77 eV. A higher increase of conductivity is observed for illuminating the CdS nanostructured film when compared to the simple semiconductor film. This is a consequence of the periodic patterning induced by the polymer nanosphere array.     

多壁纳米碳管的频率上转换效应研究

实验上测量了多壁纳米碳管的吸收光谱和光致发光谱,观察到了多壁纳米碳管的光频率上转换效应,激发波长为1064 nm,发射光谱为带状光谱,峰值波长为780 nm.由吸收光谱上观察到了纳米碳管的态密度分布的范霍夫奇点,这些奇点对应的吸收峰位置为685nm,719nm和894nm.上转换过程是纳米碳管的电子经双光子吸收,再经无辐射跃迁布居在范霍夫奇点,最后经辐射跃迁而产生荧光.     

Chirality distribution and transition energies of carbon nanotubes

From resonant Raman scattering on isolated nanotubes we obtained the optical transition energies, the radial breathing mode frequency, and the Raman intensity of both metallic and semiconducting tubes. We unambiguously assigned the chiral index (n(1),n(2)) of approximately 50 nanotubes based solely on a third-neighbor tight-binding Kataura plot and find omega(RBM)=(214.4+/-2) cm(-1) nm/d+(18.7+/-2) cm(-1). In contrast to luminescence experiments we observe all chiralities including zigzag tubes. The Raman intensities have a systematic chiral-angle dependence confirming recent ab initio calculations.     

Green luminescence from triphenylphosphine functionalized single-wall carbon nanotubes

In a simple wet chemical process, purified single-wall carbon nanotubes (SWCNTs) are treated with triphenylphosphine (Ph₃P) at room temperature. The functionalized material is characterized by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. HRTEM micrograph clearly reveals that triphenylphosphine nanocrystals of nearly uniform size are attached to the surfaces of SWCNTs. The hybrid structure shows remarkable green luminescence with peak emission at around 500 nm, under UV excitation. The photoluminescence may be attributed to charge transfer from the electron-donating phosphorous atoms to the carbon nanotubes.     

Eu3+离子掺杂钛酸盐纳米管的直接水热合成与发光性能

 采用纳米管制备和离子掺杂同步进行的直接水热合成方法，合成了纯钛酸盐纳米管（TNT）和Eu³⁺离子掺杂的纳米管（TNT-Eu）；并利用X射线衍射（XRD）、透射电子显微镜（TEM）、光致发光谱仪研究了纳米管的形貌特征、物相组成、热稳定性和发光性能。结果显示：这种方法简便易行、稳定性好、产率高。钛酸盐纳米管物相可近似表示为(H,Na)₂Ti₃O₇或(H,Na)₂(Ti,Eu)₃O₇。高温处理对钛酸盐纳米管的结构产生很大的影响，450 ℃下纳米管的层状结构被破坏，晶体结构转化为锐钛矿型的TiO₂。TNT-Eu样品的发光性能较强，出现的393.5 nm、593 nm、614 nm的谱带归属于⁵D₀-⁷F₁和⁵D₀-⁷F₂电子的跃迁。     

Role of bright and dark excitons in the temperature-dependent photoluminescence of carbon nanotubes

We report studies of the temperature dependence of the photoluminescence efficiency of single walled carbon nanotubes which demonstrate the role of bright and dark excitons. This is determined by the energy splitting of the excitons combined with 1-D excitonic properties. The splitting of the bright and dark singlet exciton states is found to be only a few meV and is very strongly diameter dependent for diameters in the range 0.8-1.2 nm. The luminescence intensities are also found to be strongly enhanced by magnetic fields at low temperatures due to mixing of the exciton states.     

SiOx纳米管的制备及其发光特性

以液态金属镓为媒介,利用热蒸发法合成大量非晶SiOx纳米管,这些纳米管管径均匀分布,平均约80 nm,长度大于10μm,且管内外径比例较小．分析发现,在实验过程中,熔入金属镓液滴中的硅元素和氧元素结合并从液滴的表面饱和析出,形成以镓为中心的非晶SiOx纳米管状结构．在室温中,利用260 nm的激发光源激发SiOx纳米管,发现在蓝光波段附近发出强而稳定的PL谱线,这可能与样品中的氧缺陷和空位有关．     

Photophysics of polymer-wrapped single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) are successfully dispersed in two conjugated polymer poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) and poly[2-methoxy-5- (2’-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEHPPV) solutions. Steady-state and time-resolved photoluminescence spectroscopy in the near-infrared and visible spectral regions are used to study the interaction of the dispersed carbon nanotube and the wrapped polymer in the nano-hybrids. The SWNTs infrared emission is the signatures of the separation of single semiconducting tubes, the lifetime of the photoluminescence of these tubes is bi-exponential with the first component varying from 6 ps (in MEHPPV wrapped SWNTs) to 14 ps (in PFO wrapped SWNTs), while the second component of the decay for all samples is in the range of 30-40 ps, revealing the intrinsic lifetime of the SWNTs. The study of the photoluminescence of the nano-hybrids in the visible spectral range shows, in the case of the PFO, a relatively strong quenching, the photoluminescence lifetime for the hybrid is more than 100 ps shorter than the one of the pristine polyfluorene solution. For the MEHPPV-SWNT hybrid an opposite behavior is revealed with the photoluminescence lifetime surprisingly longer than the polymer solution. The possible mechanism for the interaction of the two conjugated polymers and the SWNTs is discussed in terms of their electronic band structure.     

Exponential decay lifetimes of excitons in individual single-walled carbon nanotubes

The dynamics of excitons in individual semiconducting single-walled carbon nanotubes was studied using time-resolved photoluminescence (PL) spectroscopy. The PL decay from tubes of the same (n,m) type was found to be monoexponential, however, with lifetimes varying between less than 20 and 200 ps from tube to tube. Competition of nonradiative decay of excitons is facilitated by a thermally activated process, most likely a transition to a low-lying optically inactive trap state that is promoted by a low-frequency phonon mode.     

Field-induced lifetime enhancement and ionization of excitons in GaAs/AlGaAs quantum wells

Picosecond and nanosecond luminescence studies of GaAs/AlGaAs quantum wells exposed to electric fields perpendicular to the layers are reported. The drastic red-shift of the photoluminescence with the electric field strength is accompanied by a strong increase of the electron-hole recombination lifetime. These features are most dominant for the wider wells due to the stronger polarization of the confined electron-hole pairs. Our observations are consistent with the model of the Quantum-Confined Stark Effect. In contrast, for high fields in the regime of ∼100 kV/cm field ionization limits the confinement of electrons and holes and leads to a strong decrease of the photoluminescence yield and lifetime with increasing field strength.     

Selective interaction between nanotubes and perylene‐based surfactant

We recently reported a significant deviation in the photoluminescence intensities of HiPco nanotubes solubilized with a perylene‐based surfactant, C16 , compared to bile salt surfactants. For C16 , the photoluminescence emission of chiralities (9,5), (10,3), and (11,1) is enhanced by up to 430%. Resonant Raman spectroscopy is less sensitive to bundling state and also yields disparate chirality intensity ratios: The (11,0) zigzag tube signal increases by 100% compared to (8,6), (9,4), and (10,2) after suspension with C16 . We also report the change in photoluminescence intensity distribution after the swelling of bile salt suspended nanotubes with a series of small organic chromophores in DCM. These changes are attributed to chromophore‐induced surfactant reorganization, resulting in better nanotube individualization. The chirality for which the PL intensity is most enhanced is (11,1) for all chromophores, a chirality also increased by 300% in the C16 ‐solubilized sample. Conjointly, these measurements indicate that both preferential solubilization and enhanced debundling contribute to the PL intensity distribution in the C16 ‐solubilized nanotube sample. This has wide ranging implications for the design of chirally selective surfactants and the demonstration of their selectivity, which is typically only shown through luminescence measurements. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

稀土掺杂氧化物纳米发光材料研究

综述了稀土掺杂纳米发光材料方面的研究进展;主要介绍稀土掺杂氧化物纳米晶与体相材料相比所具有的一些特有的光谱学性质,包括光谱的移动与谱线的展宽、4fN电子的跃迁与弛豫过程、表面局域环境和格位对称性、电子-声子耦合、能量传递、浓度猝灭、温度猝灭以及光诱导发光强度变化等光谱现象,同时也探寻了其中的物理实质。主要对上转换纳米发光材料和一维纳米线/管的发光性质进行了介绍。     

The photoluminescence of ZnSe bulk single crystals excited by femtosecond pulse

This paper reports on the photoluminescence spectra of ZnSe single crystal with trace chlorine excited by the femtosecond laser pulse. Three emission bands, including second-harmonic-generation, two-photon-excited peak and a broad band at 500--700nm, were detected. The thermal strain induced by femtosecond pulse strongly influences the photoluminescence of ZnSe crystal. The corresponding strain \va in ZnSe crystal is estimated to be about 8.8 \ti10^-3 at room temperature. The zinc-vacancy, as the main point defect induced by femtosecond pulse, is successfully used to interpret the broad emission at 500--700nm. The research shows that self-activated luminescence possesses the recombination mechanism of donor--vacancy pair, and it is also influenced by a few selenium defects and the temperature. The rapid decrease in photoluminescence intensity of two-photon-excited fluorescence and second-harmonic generation emission at lower temperature is attributed to the fact that more point defects result in the thermal activation of the two-photo-absorption energy converting to the stronger recombination emission of chlorine--zinc vacancy in 500--700nm. The experimental results indicate that the femtosecond exciting photoluminescence shows a completely different emission mechanism to that of He--Cd exciting luminescence in ZnSe single crystal. The femtosecond laser exhibits a higher sensitive to the impurity in crystal materials, which can be recommended as an efficient way to estimate the trace impurity in high quality crystals.     

Photoluminescence of multiwalled carbon nanotubes excited at different wavelengths

In this paper the multiwalled carbon nanotubes (MWNTs) were synthesized by a chemical vapour deposition and the SEM graph shows that the sample has good construction. The micro-Raman spectrum shows the characteristic line of the MWNTs and an additional line produced by the defects on the outer surface of MWNTs. The photoluminescence (PL) spectra observed experimentally are variable under different excitation wavelengths and the strong excitation wavelength dependence of luminescence indicates a distribution of emitters which include electron $\pi$ in excited states and the Van Hove singularities. The absorption spectra confirm the transition channels which are consistent with the PL emission.     

Enhancement of single-walled nanotubes luminescence intensity upon dithiothreitol doping

In the present work the influence of reducing agent dithiothreitol doping on photoluminescence spectra of nanotubes with adsorbed biopolymers (single-stranded DNA and polyC) in aqueous suspensions and films was studied. It is revealed that greater intensity enhancement at 10^?3 mol/L dithiothreitol concentration is observed for (7,5) and (6,5) nanotubes in suspension with single-stranded DNA (by more than 150% of initial intensity) comparing to polyC suspension (less than 60%) while for (6,4) and (9,1) nanotubes enhancement is less than 50% for both suspensions. Photoluminescence intensity increasing for nanotube film with DNA is less than 50% without noticeable dependence on nanotube chirality. It is assumed, that different influence of biopolymers on nanotube luminescence intensity enhancement is due to their different coverage of nanotube surface.