阴极荧光在表面等离激元研究领域的应用

表面等离激元以其独特的光学性质广泛应用于纳米尺度的局域电磁场增强、超高分辨成像及微弱光电探测.阴极荧光是电子与物质相互作用而产生的光学响应,利用电子束激发金属纳米结构能够实现局域等离激元共振,并在亚波长尺度实现对共振模式的调控,具有超高空间分辨的成像特点.阴极荧光探测通常结合扫描电子显微镜或透射电子显微镜而实现,目前己被应用于表面等离激元的探测及共振模式的分析.本文从阴极荧光物理机理出发,综述了单一金属纳米结构和金属耦合结构的等离激元共振模式阴极荧光研究进展,并总结了阴极荧光与角分辨、时间分辨以及电子能量损失谱等关键技术相结合的应用,进一步分析了其面临的关键问题,最后展望了阴极荧光等离激元研究方向.     

New possibilities and some artifacts of the cathodoluminescent mode in scanning electron microscopy

Lightning inside the chamber of a scanning electron microscope (SEM), caused by electrons being scattering from a sample (and parts of the chamber), is observed and analyzed. These electrons generate the luminescence in a Thornly–Everhart collector. This parasitic effect (artifact) must be considered and eliminated in all experiments with the cathodoluminescent (CL) mode of SEM. A new technique for measuring surface potential on dielectric samples is proposed. It is based on variations in the CL signal during electron irradiation of a sample in SEM.     

Defect detection in semiconductor layers with built-in electric field with the use of cathodoluminescence

Cathodoluminescence (CL) in scanning electron microscopy (SEM) is commonly accepted as revealing local properties of a specimen region illuminated by an electron beam. CL is widely used to visualize defects in semiconductor structures. However, the presence of a strong electric field in, for example, heterojunctions or p–n junctions causes a separation of generated electron–hole (e–h) pairs and suppresses recombination in the specimen region excited by the beam. As a result CL – a radiative recombination – becomes quenched. At the same time, electron beam-induced current (EBIC) flows throughout the structure, which may produce secondary electroluminescence that is registered by the CL detector. Consequently, the CL measurement is distorted and if there are defects in the structure, they remain unrevealed. The current study shows that registration of the CL signal for different values of electron beam current (including high ones) enables true defect detection in semiconductor layers with built-in electric field. Results for a special test structure prepared with focused ion beam on AlGaAs/GaAs laser heterostructures with an 8 nm InGaAs quantum well are presented.     

Structural and cathodoluminescence assessment of transition metal oxide nanostructures grown by thermal deposition methods

Nanostructures of two transition metal oxides, WO₃ and α-Fe₂O₃, have been grown by a thermal deposition method without a catalyst and characterized by x-ray diffraction, scanning electron microscopy (SEM), high-resolution transmission electron microscopy and cathodoluminescence (CL) in the SEM. WO₃ micro and nanorods exhibit CL emission two orders of magnitude higher than CL intensity from the untreated oxide. α-Fe₂O₃ nanostructures with different morphologies (wires, belts, rods, urchins) were grown at different temperatures on Fe substrates. CL spectra of these nanostructures show emission bands related to charge transfer and ligand field transitions.     

Tuning the cathodoluminescence of porous silicon films

We have obtained intense cathodoluminescence (CL) emission from electron beam modified porous silicon films by excitation with electrons with kinetic energies below 2 keV. Two types of CL emissions were observed, a stable one and a non-stable one. The first type is obtained in well-oxidized samples and is characterized by a spectral peak that is red shifted with respect to the photoluminescence (PL) peak. The physically interesting and technologically promising CL is however the CL that correlates closely with the PL. Tuning of this CL emission was achieved by controlling the average size of the nanostructure thus showing that the origin of this CL emission is associated with the quantum confinement and the surface chemistry effects that are known to exist in the porous silicon system. We also found that the electron bombardment causes microscale morphological modifications of the films, but the nanoscale features appear to be unchanged. The structural changes are manifested by the increase in the density of the nanoparticles which explains the significant enhancement of the PL that follows the electron irradiation.     

Influence of surface morphology of cpTi on the adsorption and attachment of collagen/chitosan

The surface microtopography of implant influences distinctly the rate of bone-formation and the ratio of bone-implant contact. However, it is indicated that the surface of titanium implant existed contamination after different surface treatments. Chitosan is one of the most abundant natural polymers for its adsorption property for metal ions. In this study, we report on the pretreatment of the metal surface and aim to compare the efficacy of three treatments for the binding ability of collagen/chitosan (CL/CS). The compound of collagen and chitosan was immobilized on the titanium oxide and the morphology and chemical composition were used to characterize the titanium surfaces by scanning electron microscope (SEM), X-ray photoelectron spectrometry (XPS). The result showed that the surface displayed irregularities after roughness treatments and the rough surface was beneficial to the adsorption and attachment of CL/CS. The combination of CL/CS was related with the titanium surface character.     

形貌依赖的ZnO阴极射线发光性质研究

采用溶剂热法,通过调节水和乙醇混合液的比例制备了多种形貌的ZnO微米结构。利用扫描电子显微镜（SEM）对ZnO微米结构的形貌及尺寸进行了观察。采用可以实现纳米级微观区域光谱采集的阴极射线发光（CL）技术,对不同形貌的单个粒子的光谱进行精细表征,获得了位置依赖的ZnO阴极射线发光数据。实验结果表明：ZnO材料的发光性质与形貌有关,由于形貌差异导致其局部结晶质量、界面缺陷、表面电荷分布、表面晶面等方面的差异,几种因素共同作用决定其最终的发光性质。     

Ar离子溅射生成碳纳米管

用扫描电子显微镜(SEM)和透射电子显微镜(TE),研究了离子溅射石墨表面的形貌特征和结构,证实了碳纳米管可通过溅射原子在表面形貌突起部位沉积生长.     

Electron beam induced structural changes in Bi2Sr2CaCu2O8+x studied by cathodoluminescence microscopy and secondary electron emission

2 Sr₂CaCu₂O_8+x superconducting ceramics have been irradiated in the scanning electron microscope (SEM), and the irradiation-induced effects investigated by cathodoluminescence (CL), secondary electron emission (SEE) and X-ray microanalysis. Electron beam irradiation causes a slight Bi depletion and an inhomogeneous Ca distribution. A higher CL intensity emission is found in the irradiated areas, where besides an enhancement of the oxygen content related 2. 4 eV band, another CL bands probably related to new non-superconducting phases induced by irradiation can be observed. SEE yield measurements allow to detect an oxygen depleted region surrounding the irradiated areas. X-ray microanalysis shows that this intermediate region retains the cationic composition of the unaffected material. CL spectra from bright zones inside the same area also show a dominant 2. 4 eV emission band, which supports its relation with oxygen deficiency or rearrangement in high- superconductors. Received: 30 July 1996/Accepted: 8 October 1996     

Improvement of surface wettability and interfacial adhesion of poly-(p-phenylene terephthalamide) by incorporation of the polyamide benzimidazole segment

In order to investigate the effect of the polyamide benzimidazole group on the surface wettability and interfacial adhesion of fiber/matrix composites, surface features of two kinds of aramid fibers, poly (p-phenylene terephthalamide) fiber (Kevlar-49) and poly-(polyamide benzimidazole-co-p-phenylene terephthalamide) (DAFIII), have been analyzed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and contact angle analysis (CAA) system, respectively.The results show that with the incorporation of the polyamide benzimidazole segment, more polar functional groups exist on DAFIII surface. The contact angles of water and diiodomethane on DAFIII surface get smaller. The surface free energy of DAFIII increases to 36.5 mJ/m², which is 2.3% higher than that of Kevlar-49. In addition, DAFIII has a larger rough surface compared with that of Kevlar-49 due to different spinning processes. The interfacial shear strength (IFSS) of DAFIII/matrix composite is 25.7% higher than that of Kevlar-49/matrix composite, in agreement with the observed results from surface feature tests. SEM micrographs of failed micro-droplet specimens reveal a strong correlation between the fracture features and the observed test data.     

The effect of different gas atmospheres on luminescent properties of pulsed laser ablated SrAl2O4:Eu,Dy thinfilms

SrAl₂O₄:Eu²⁺,Dy³⁺ thin films were grown on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique to investigate the effect of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological, photoluminescence (PL) and cathodoluminescence (CL) properties of the films. The films were ablated using a 248 nm KrF excimer laser. Atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and fluorescence spectrophotometry were used to characterize the thin films. Auger electron spectroscopy (AES) combined with CL spectroscopy were employed for the surface characterization and electron-beam induced degradation of the films. Better PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres with respect to those prepared in vacuum. A stable green emission peak at 515 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions were obtained with less intense peaks at 619 nm, which were attributed to transitions in Eu³⁺. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The CL intensity increased under prolonged electron bombardment during the removal of C due to electron stimulated surface chemical reactions (ESSCRs) on the surface of the SrAl₂O₄:Eu²⁺, Dy³⁺ thin films. The CL stabilized and stayed constant thereafter.     

Protection of iron against corrosion by coverage with Au nanoparticles and n-hexylthiol mixed films

Through a one-step thermal reaction, Au nanoparticles were synthesized and self-assembled mixed films of Au nanoparticles and n-hexylthiol were prepared on iron surface. The size distribution and shape of Au nanoparticles were examined using transmission electron microscopy (TEM). Results of two electrochemical methods - electrochemical impedance spectroscopy (EIS) and polarization curves indicate that self-assembled mixed films can form on the iron surface and prevent it from corrosion effectively. Energy-dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM) measurements were applied to identify the formation of the mixed films on iron surface.     

Synthesis and characterization of silicon-doped gallium oxide nanowires for optoelectronic UV applications

Silicon-doped gallium oxide nanowires have been synthesized by thermal methods using either a mixture of gallium oxide and silicon powders or metallic gallium with silicon powder as precursor materials. The growth mechanism has been found to be a vapour–liquid–solid (VLS) or vapour–solid (VS) process, respectively, depending on the precursor used. In the former case, silicon oxide droplets at the end of the nanowires have been observed. Their possible role during the growth of the nanostructures is discussed. Structural and morphological characterization of the doped nanowires has been performed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The results show a high crystalline quality and a uniform distribution of silicon along the nanowires. Room temperature cathodoluminescence (CL) in the SEM shows that slight variations in the composed UV–blue emission band appear due to the influence of Si impurities in the oxygen vacancy defect structure.     

Auger electron/X-ray photoelectron and cathodoluminescent spectroscopic studies of pulsed laser ablated SrAl2O4:Eu,Dy thin films

Auger electron/X-ray photoelectron and cathodoluminescent (CL) spectroscopic studies were conducted on pulsed laser deposited SrAl₂O₄:Eu²⁺,Dy³⁺ thin films and the correlation between the surface chemical reactions and the decrease in the CL intensity was determined. The Auger electron and the CL data were collected simultaneously in a vacuum chamber either maintained at base pressure or backfilled with oxygen gas. The data were collected when the films were irradiated for 14 h with 2 keV electrons. The CL emission peak attributed to the 4f⁶5d¹ → 4f⁷ transitions was observed at ∼521 nm and the CL intensity of the peaks degraded at different rates in different vacuum conditions. X-ray photoelectron spectroscopy (XPS) data collected from degraded films suggest that strontium oxide (SrO) and aliminium oxide (Al₂O₃) were formed on the surface of the film as a result of electron stimulated surface chemical reaction (ESSCR).     

Determination of norfloxacin using gold nanoparticles catalyzed cerium(IV)-sodium sulfite chemiluminescence

A rapid flow-injection chemiluminescence (CL) method is proposed for the determination of norfloxacin (NFLX). The method is based on the fact that the weak CL from the redox reaction of Ce(IV)-Na₂SO₃ can be greatly strengthened by gold nanoparticles (NPs). UV-visible spectra, fluorescence spectra and transmission electron microscopy (TEM) studies are carried out before and after the CL reactions to investigate the CL reinforcing mechanism. The mechanism is supposed to originate from the reinforcer of gold NPs, which facilitates the radical generations and electron-transfer processes taking place on the surface of the gold NPs. Under the selected experimental conditions, a linear relationship was obtained between the CL intensity and the concentrations of NFLX in the range 7.9×10⁻⁷ to 1.9×10⁻⁵ M and the detection limit was 8.2×10⁻⁸ M. This method is successfully applied to the determination of NFLX in human urine.     

Degradation of Y2SiO5:Ce phosphor powders

The degradation of the cathodoluminescence (CL) intensity of cerium-doped yttrium silicate (Y₂SiO₅:Ce) phosphor powders was investigated for possible application in low voltage field emission displays (FEDs). Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and CL spectroscopy were used to monitor changes in the surface chemical composition and luminous efficiency of commercially available Y₂SiO₅:Ce phosphor powders. The degradation of the CL intensity for the powders is consistent with a well-known electron-stimulated surface chemical reaction (ESSCR) model. It was shown with XPS and CL that the electron stimulated reaction led to the formation of a luminescent silicon dioxide (SiO₂) layer on the surface of the Y₂SiO₅:Ce phosphor powder. XPS also indicated that the Ce concentration in the surface layer increased during the degradation process and the formation of CeO₂ and CeH₃ were also part of the degradation process. The CL intensity first decreased until about 300 C cm⁻² and then increased due to an extra peak arising at a wavelength of 650 nm.     

Y2O3:Tm,Yb nanophosphors for correlative upconversion luminescence and cathodoluminescence imaging

We present a phosphor nanoparticle that shows both upconversion luminescence (UCL) and cathodoluminescence (CL). With this particle, low-autofluorescence, deep-tissue and wide-field fluorescence imaging can be achieved with nanometer-order high-spatial-resolution imaging. We synthesized Y₂O₃:Tm,Yb nanophosphors that emit visible and near-infrared UCL under 980 nm irradiation and blue CL via electron beam excitation. The phosphors were applied to fluorescent imaging of HeLa cells. The photostability of the phosphors was superior to that of a conventional organic dye. We show that after uptake by HeLa cells, the particles can be imaged with SEM and CL contrast in a cellular section. This indicates that correlative UCL and CL imaging of biological samples could be realized.     

Characteristic properties of Y2SiO5:Ce thin films grown with PLD

Three different gases (nitrogen (N₂), oxygen (O₂) and argon (Ar)) were used as background gases during the growth of pulsed laser deposition (PLD) Y₂SiO₅:Ce thin films. A Krypton fluoride laser (KrF), 248 nm was used for the PLD of the films on silicon (Si) (1 0 0) substrates. The effect of the background gases on the surface morphology, crystal growth and luminescent properties were investigated. All the experimental parameters, the gas pressure (455 mT), the substrate temperature (600 °C), the pulse frequency (8 Hz), the number of pulses (4000) and the laser fluence (1.6±0.2) J/cm² were kept constant. The only parameter that was changed during the deposition was the ambient gas species. The surface morphology and average particle sizes were monitored with scanning electron microscopy (SEM) and atomic force microscopy (AFM). X-ray diffraction (XRD) and Auger electron spectroscopy (AES) were used to determine the crystal structure and composition, respectively. Cathodo- (CL) and photoluminescence (PL) were used to measure the luminescent intensities for the different phosphor thin films. The nature of the particles, ablated on the substrate, is related to the collisions between the ejected particles and the ambient gas particles. The CL and PL intensities also depend on the particle sizes. A 144 h (coulomb dose of 1.4×10⁴ C cm⁻²) electron degradation study on the thin films ablated in the Ar gas environment resulted in a decrease in the main CL intensity peak at 440 nm and to the development of a new very broad luminescent peak spectra ranging from 400 to 850 nm due to the growth of a SiO₂ layer on the surface.     

有机化合物对Luminol-KIO4-H2O2体系化学发光的抑制和增强

研究了36种有机化合物对鲁米诺-高碘酸钾-过氧化氢(luminol-KIO₄-H₂O₂)体系化学发光的影响,发现其大部分能抑制或增强体系化学发光强度,并且抑制或增强化学发光强度的能力与化学发光体系的pH值以及有机化合物分子结构中芳香环上功能基(—OH和—NH₂)的数目、位置,取代基的电子效应、空间效应等有关。讨论了化学发光强度抑制或增强的机理。基于24种有机化合物对体系化学发光的抑制或增强考察了其分析应用的可能性,发现数个化合物的检测限可达ng·mL^-1水平。     

Radiation-induced cathodoluminescent signatures in calcite

At ambient temperatures, a permanent change due to neutron irradiation has been identified in the luminescent properties of the common mineral calcite. Calcite is one of many ubiquitous minerals that are known to exhibit luminescence under electron bombardment, a process known as cathodoluminescence (CL). The UV–Visible spectra of individual calcite grains were measured with CL spectroscopy before and after neutron irradiation. Exposure to neutrons causes additional crystal lattice defects (beyond those naturally-occurring) that leave a permanent, readily-measurable CL signature in the 515 nm region of the spectrum. Dose response results following irradiation have been measured and a spectroscopic signature is described that increases proportionately to neutron dose. The CL measurements are complicated by a dependence on the orientation relative to direction of excitation. When taken into account, the total dose to the crystal can be estimated, and possibly even the direction of the neutron source can be determined. This signature could potentially be developed into a nuclear forensics tool to help identify locations where special nuclear materials have been stored.