Vibrationally resolved fluorescence from organic molecules near metal surfaces in a scanning tunneling microscope

Intrinsic molecular fluorescence from porphyrin molecules on Au(100) has been realized by using a nanoscale multimonolayer decoupling approach with nanoprobe excitation in the tunneling regime. The molecular origin of luminescence is established by the observed well-defined vibrationally resolved fluorescence spectra. The molecules fluoresce at low "turn-on" voltages for both bias polarities, suggesting an excitation mechanism via hot electron injection from either tip or substrate. The excited molecules decay radiatively through Franck-Condon pi(*)-pi transitions.     

Radical-recombination luminescence,ion-luminescence and photoluminescence of CaGa2S4:Eu

CaGa₂S₄ based luminophors have recently attracted significant attention due to their high efficiency. Very little is known now about the surface and near surface luminescence of these luminophors. The ion-luminescence of CaGa₂S₄:Eu excited by low energy hydrogen ions (up to 3 keV) and the radical-recombination luminescence excited by neutral hydrogen atoms of thermal energies have been studied. The latter is due to chemical energy released at the surface during heterogeneous recombination of atoms into molecules (∼4 eV per recombination event). The radical-recombination luminescence is likely the most surface kind of luminescence, while the ion-luminescence is the luminescence of near-surface layers. In this regard the photoluminescence is the bulk one of with which the characteristics of the surface luminescence might be compared.     

Evidence for interlayer donor–acceptor recombination in type II GaAs/AlAs superlattices

Steady-state and time-resolved photoluminescence of (GaAs)₇(AlAs)₉type II superlattices grown simultaneously by molecular beam epitaxy on (311)A and (100) GaAs substrates, intentionally undoped or uniformly doped with silicon, has been studied. It is shown that at temperatures T >  30 K, the dominant line in the photoluminescence spectra of superlattices is caused by donor–acceptor recombination between the donors located in the AlAs layers and the acceptors in the GaAs layers. The sum of the binding energies of the donors and acceptors in the pairs has been determined. A spectrally-dependent linear polarization of the donor–acceptor line along the direction of the interface corrugation of the superlattice has been discovered in the spectra of (311)A-oriented superlattices.     

Optical transitions and carrier dynamics in self-organized InAs quantum dots grown on In0.52Al0.48As/InP(0 0 1)

Optical transitions in self-organized InAs quantum dots (QDs) grown on In_0.52Al_0.48As layer lattice matched to InP(0 0 1) substrate, have been studied by continuous wave (cw) photoluminescence (PL) and time-resolved PL. The dependence of the PL transition on excitation power and photoluminescence excitation measurements clearly shows that the multi-component cw-PL spectrum is related to emission coming from ground and related excited states of QDs with heights varying by monolayer fluctuations. While decay times measured by time-resolved PL are in the nanosecond range for the ground states, shorter decay times related to relaxation of carriers down directly to the ground state are determined for the excited states.     

STM tip-enhanced photoluminescence from porphyrin film

Tunneling electrons-induced molecular fluorescence in organic film is enhanced by the surface plasmons. The plasmon enhancement can be expected not only by the plasmons of the substrate but also by the noble metal tip of scanning tunneling microscope (STM). In this report we investigate the tip effect in photoluminescence of meso-tetrakis(3,5-di-tertiarybutyl-phenyl)porphyrin (H₂TBPP) film on indium tin oxide (ITO) combined with a STM. The experimental result shows the PL of molecules is enhanced by an Ag tip. This enhancement factor is evaluated larger than 2000.     

方酸菁染料在电致发光层中的能量传递研究

通过方酸菁与卟啉相互作用的研究证实，方酸菁可以作为很好的能量受体发红光利用这一原理，用方酸菁掺杂于８－羟基喹啉铝作为发光层，获得了红光有机薄膜电致发光器件，为了说明相关的机理，我们考察了方酸菁和８－羟基喹啉铝在固体膜中相互作用的情况，把光致发光光谱和电致发光光光结合起来，证实该器件的发光机制与激发态的８－羟基喹啉铝到掺杂剂方酸菁的能量传递过程有关，在驱动电压的作用下，ＴＰＤ（一种有机材料）传输的空     

Interaction of intense beams of highly vibrationally excited molecules with molecules (clusters) condensed on a cold surface

The interaction of intense beams of SF₆ and CF₃I molecules, excited by powerful IR laser radiation to high vibrational states (0.3 eV ≤ E _vib ≤ 2.0 eV), with molecules (clusters) condensed on a cold surface (T _s ≈ 80–85 K) has been studied. The probability that the excited and unexcited molecules are reflected from the cold metal surface covered by condensed molecules (clusters), as well as the probability that such excited and unexcited molecules are transmitted through a cooled multichannel metal plate and a converging cone oriented at an angle relative to the molecular beam axis, has been determined. Expressions for these probabilities of reflection and transmission as functions of the angle of incidence and the parameters of the exciting laser radiation and the molecular beam are obtained. It is shown that highly vibrationally excited molecules are reflected from the surface and transmitted through the plates and cones with a much higher probability than unexcited molecules. The results suggest that this phenomenon can be used for the separation of molecules in a beam with respect to isotope (or atomic) composition.     

Needles and clusters of zinc porphyrin molecules on mica

Molecular monolayers of zinc porphyrins deposited from a liquid solution on mica substrates have been characterised using atomic force microscopy (AFM). At room temperature, needle-shaped single layer porphyrin islands are formed due to an anisotropic growth rate. The average island size depends on the concentration of the porphyrin solution, but the length to width aspect ratio is rather independent of the island size. Annealing the porphyrin monolayers to 450 K leads to the reduction of the size of the monolayer islands in two different ways depending on the heating rate. With slow heating rate, the island size was found to shrink by losing molecules from the edge of the island. With high heating rate, nanoscale molecular clusters were found to form.     

Stacking of multilayer InAs quantum dots with combination capping of InAlGaAs and high temperature grown GaAs

We are reporting the growth of multilayer stacks of quantum dots (10 periods) with a combination capping of In_0.21Al_0.21Ga_0.58As (30 Å) and GaAs (70–180 Å) grown by solid source molecular beam epitaxy (MBE). Reflection high energy electron diffraction (RHEED) has been used for the insitu monitoring of quantum dot (QD) formation in heterostructure samples. The samples were also characterized by other exsitu techniques like cross sectional transmission electron microscopy (XTEM) and photoluminescence measurements (PL). For a heterostructure sample with thin barrier thickness (<100 Å), an XTEM image showed the stacking of QDs only up to the 5th layer and in the upper layers there was hardly any formation of dots. We presume the stoppage of dot formation is due to the uneven surface of the InAlGaAs alloy overgrown on the InAs QDs, as a result of the local compositional deviations of the Group-III atoms. Samples grown with thicker barriers (>100 Å of GaAs) showed good stacking of islands until the tenth layer. The thick GaAs layer overgrown on the InAlGaAs at 590 ^°C is believed to remove the surface modifications of the quaternary layer thereby creating a smoother surface front for the growth of subsequent QD layers.     

Synthesis and optical spectroscopy of ZnO nanowires

Single crystal ZnO nanowires with lengths and diameters ranging from 2 to 30 μm and 100 to 300 nm, respectively, have been grown by the vapor transport method on SiO₂/Si substrates using Au as catalyst. Their Raman and emission properties under different excitation wavelengths have been studied at the nanoscale. Whereas Raman measurements on nanowires corroborate the well-known ZnO phonon characteristics, their photoluminescence spectra exhibit a very broad emission band, mainly in the visible region from 450 to 800 nm, which corresponds to different defect-related recombination processes. Spectrally resolved scanning near-field optical microscopy, SNOM, of single ZnO nanowires have also been performed for a direct imaging of the photoluminescence emission with high spatial resolution below 100 nm, establishing a relationship with the simultaneously acquired topography.     

一种新型卟啉侧链聚合物的飞秒荧光动力学

研究了一种新型的卟啉侧链聚合物丙烯腈丙烯酸卟啉酯共聚物{poly[porphyrin acrylate-acrylonitrile](p[(por)A-AN]}的链间和链内的卟啉分子的相互作用对聚合物薄膜发光性质的影响。通过采用飞秒荧光光谱技术测量了p[(por)A-AN]薄膜的荧光动力学过程。测量结果表明:纯p[(por)A-AN]薄膜(~450ps)显示出了比混合物薄膜p[(por)A-AN]/polystyrene(PSE)(~1.3 ns)快得多的荧光弛豫过程。而p[(por)A-AN]/PSE混合物薄膜显示出较纯p[(por)A-AN]薄膜增强的荧光效率。增加p[(por)A-AN]分子内卟啉侧链基团的浓度导致纯p[(por)A-AN]薄膜和p[(por)A-AN]/PSE混合物薄膜的荧光效率的增强和寿命(由近26~36 ps)的增加。分子间和分子内卟啉侧链基团之间的无辐射能量转移和分子内卟啉侧链基团的旋转运动在p[(por)A-AN]的荧光动力学过程中起着重要的作用。     

Study of the Initial Stage of Fluorinated C<Subscript>60</Subscript>F<Subscript>18</Subscript> Fullerene Adsorption on the Cu(001) Surface

The dynamics of the adsorption and evolution of fluorinated C₆₀F₁₈ fullerene molecules on the Cu(001) surface are studied by real-time ultra-high vacuum scanning tunneling microscopy. Fluorinated fullerene molecules are shown to decompose with time on the Cu(001) surface transforming to C₆₀ molecules. The decay rate depends on the initial molecular coverage. The rapid decay of fluorinated fullerene molecules is observed when the coverage is no higher than 0.2 single layers. As a result, two-dimensional islands consisting of pure C₆₀ molecules are formed on the Cu(001) surface. 2D islands consisting of fluorinated fullerene molecules are formed when the initial molecular coverage is higher than 0.5 single layers. The molecules inside these islands also tend to decompose with time. It is found experimentally that fluorine atoms are removed completely from the initial C₆₀F₁₈ molecules adsorbed on the Cu(001) surface after 250 h when the initial molecular coverage is 0.6 single layers.     

Molecular orientation of thiol-derivatized tetraphenylporphyrin on gold studied by XPS and NEXAFS

Tetraphenylporphyrins bearing four linkers consisting of thioacetyl-functionalized carbon chains were immobilized on a gold surface via thiolate-gold bonds using two different preparation routes. The structure of these molecular layers was characterized in detail with synchrotron radiation based core-level spectroscopy, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results show that the geometry of the molecular layers and the number of linkers that bind to the gold surface depends on the preparation schemes. The deprotection of the linkers through removal of the terminal acetyl group before the molecular adsorption (deprotected systems) resulted in porphyrins bound to the gold surface with on the average three linkers, their normal axis being tilted ∼38° with respect to the surface normal. On the other hand, porphyrin layers prepared directly with the acetyl group still in place on the linkers (protected systems) are made of molecules bound to the gold surface via two linkers on the average. The resulting orientation is more upright, with the normal axis of the porphyrin plane tilted ∼50° with respect to the surface normal. Moreover, NEXAFS measurements revealed that the acetyl deprotected porphyrin layers have a higher degree of ordering than the protected systems.     

Optical properties of 1.3 μm room temperature emitting InAs quantum dots covered by In0.4Ga0.6As/GaAs hetero-capping layer

Room temperature 1.3 μm emitting InAs quantum dots (QDs) covered by an In_0.4Ga_0.6As/GaAs strain reducing layer (SRL) have been fabricated by solid source molecular beam epitaxy (SSMBE) using the Stranski–Krastanov growth mode. The sample used has been investigated by temperature and excitation power dependent photoluminescence (PL), photoluminescence excitation (PLE), and time resolved photoluminescence (TRPL) experiments. Three emission peaks are apparent in the low temperature PL spectrum. We have found, through PLE measurement, a single quantum dot ground state and the corresponding first excited state with relatively large energy spacing. This attribute has been confirmed by TRPL measurements which allow comparison of the dynamics of the ground state with that of the excited states. Optical transitions related to the InGaAs quantum well have been also identified. Over the whole temperature range, the PL intensity is found to exhibit an anomalous increase with increasing temperatures up to 100 K and then followed by a drop by three orders of magnitude. Carrier’s activation energy out of the quantum dots is found to be close to the energy difference between each two subsequent transition energies. PACS 68.65.Ac; 68.65.Hb; 78.67.Hc     

Interaction between the end groups and the main chain of conjugated polymers by time-resolved EPR and fluorescence spectroscopy

ABSTRACT

Interaction between a zinc porphyrin (ZnPor) as the end-group and poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) as the main chain in a porphyrin end-modified fluorescent conjugated polymer, ZnPFV, was studied by time-resolved electron paramagnetic resonance (EPR) and fluorescence spectroscopy. While fluorescence from the PFV part of ZnPFV showed a spectral profile almost identical to that of a PFV oligomer without end-modification, the emission spectrum of the ZnPor part exhibited a much broader profile compared to that of the reference zinc porphyrin monomer. Based on the analysis of lifetimes and quantum yields, it was found that radiative rate constant of the ZnPor part was enhanced by nearly three times. The observed unusual enhancement in the radiative rate constant was rationalised in terms of a partial π-conjugation between the end group and the main chain, as a result of co-planarisation in fluid solution. On the other hand, the time-resolved EPR spectrum of ZnPFV at 100?K basically showed a similar spectral pattern to that of the reference zinc porphyrin, but with significant differences in zero-field spitting parameters and initial population ratios. The π-system of the excited triplet state is deduced to deviate from D_4h symmetry in the end zinc porphyrin groups. The obtained results show that interaction of the porphyrin end group with the main chain of the polymer significantly influences the excited singlet state properties of the porphyrin, while its triplet state properties were affected to a lesser extent.     

Photoluminescence of nanostructured cubic-lattice silicon carbide films grown on a silicon wafer

The light-emitting properties of cubic-lattice silicon carbide SiC films grown on Si(100) and Si(111) substrates with VPE at low temperatures (T _gr ∼ 700°C) are discussed. Investigations of the grown films reveal a homogeneous nanocrystalline structure involving only the 3C-SiC phase. When the electron subsystem of the structure is excited by a He-Cd laser emitting at λ_exit = 325 nm, the photoluminescence (PL) spectra contain a rather strong emission band shifted by about 3 eV toward a short-wave spectral region. At low temperatures, the PL integral curve is split into a set of Lorentz components. The relation between these components and the peculiarities of the energy spectrum of electrons in the nanocrystalline grains of the silicon carbide layers is discussed.     

Structural and Interaction Properties of Porphyrin Layers — A Quantum Chemical Study

This paper is proposed to understand the interaction of porphyrin layers with diatomic molecules interacting at their interior regions by applying ab initio and density functional theory(DFT) methods. We have used NO, CO, and O2 diatomic molecules to interact with the porphyrin layers. The most common Fe-centered metalloporphyrin structure with tetra-pyrrlic rings having N4 core is chosen for the study. The optimization of Porphyrin-Porphyrin(P I-P II)and Porphyrin-Diatomic molecule-Porphyrin(P I-AB-P II)(AB = NO, CO, and O2) complexes are performed using HF method. In order to understand the planarity and appropriate stacking size of porphyrins and also to infer the separation of diatomic molecules between porphyrin layers the behavior of P I-AB-P II complexes(where AB = NO, CO, and O2)are analyzed using structural properties and molecular electrostatic potentials(MEP). The MEPs are calculated using hybrid exchange correlation functional B3PW91 of DFT along with 6-31+G* basis set for the P I-P II and P I-AB-P II complexes obtained from HF method.     

Influence of nonplanar distortions of the tetrapyrrole macroring on the electronic states of porphyrin dications

Quantum-chemical calculations of the excited electronic states of a porphyrin dication have been performed by the CNDO/S method for different angles determining the saddle-like and ruffled distortions of the porphyrin macroring. It is shown that saddle-like distortions arising as a result of a tilt of the pyrrole rings have a significant influence on the energies of the molecular orbitals and energies of the excited electronic states of porphyrin molecules, especially on the oscillator strength of the G→Q transition. The results of the calculations performed are in good agreement with the experimental spectra of porphyrin dications. To whom correspondence should be addressed. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 559–562, July–August, 1999.     

基于电子顺磁共振的ZnTPP激发态及其TEMPO各向异性的研究

为了研究卟啉类敏化剂的光致激发态能量转移和电子转移问题,本文基于紫外可见光谱仪和电子顺磁共振波谱仪,构建了以锌卟啉为研究对象的"锌卟啉-稳态自由基-二甲苯"实验体系.锌卟啉的紫外可见光谱显示,在可见光谱的B带和Q带出现明显的特征峰,是锌卟啉分子中电子由基态能级跃迁至激发态能级产生的.低温条件下受紫外可见光辐照的实验体系的电子顺磁共振波谱,检测到了稳态自由基四甲基哌啶氧化物的增强吸收电子顺磁共振波谱.根据分子激发态相关理论、光化学物理反应理论和化学诱导电子自旋极化理论对实验结果进行了分析,结果表明,四甲基哌啶氧化物稳态自由基电子顺磁共振波谱的增强吸收对应于锌卟啉光致激发态的能量转移和电子转移;四甲基哌啶氧化物在低温(143 K)下的电子顺磁共振波谱表现出的各向异性特征现象来源于氮氧自由基电子与氮核的各向异性超精细相互作用.     

Influence of the Substrate Orientation on the Silicon Capture into A- and B- Sublattices of Gallium Arsenide in Molecular Beam Epitaxy

The influence of crystallographic orientation of the growth surface near (100) and (111)A GaAs singular faces on the silicon capture into A- and B-sublattices of gallium arsenide in molecular beam epitaxy is investigated by the electrophysical and photoluminescence methods. It is demonstrated that the silicon dopand is incorporated into GaAs layers not only as simple Si_Ga donors but also as elemental Si_Ga acceptors and more complex defects, namely, Si_As–V_As complexes. The concentration of defects of different types in layers depends on the orientation of the growth surface, and the amphoteric properties of silicon on the (111)A face are manifested stronger than those on the (100) face.