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Potash–lime silicate (K2O–CaO–SiO2) glass dated to the Warring States Periods is one of the earliest glass types that have been found in China, but scientific research about this type of glass is scarce at home and abroad. In the present study, a total of 23 potash–lime silicate glass samples of the Warring States Period, excavated from different areas of China, were analyzed noninvasively using a portable X-ray fluorescence spectrometer (pXRF). The chemical composition of these K2O–CaO–SiO2 glasses was analyzed and compared with that of the potash silicate (K2O-SiO2) glasses of the Han Dynasties. The possible raw materials used to make the ancient K2O–CaO–SiO2 glasses were discussed. It appears that the ancient K2O–CaO–SiO2 glasses were produced in China and the potash glasses were of versatile origins. This research provides useful clues to trace the technical development of ancient Chinese glass.

In the present study, laser ablation inductively coupled plasma atomic emission spectroscopy (LA-ICP-AES) was successfully used to classify 26 ancient potash glass beads. These samples, mainly dated from the Han Dynasty to the Jin Dynasty, were from several provinces of both China and Vietnam. Quantitative analyses were done with both weathered and polished samples in order to consider the effects of surface weathering. Based on the characteristics of major, minor, and trace elements, we divided the samples into three subgroups (the percentage for each subgroup was 50%, 42%, and 8%, respectively) and also determined their main colorants. The results obtained provide new clues to trace the possible producing centers of ancient potash glasses in Asia. This study also reveals a complex network related to the trade of ancient potash glasses.

Laser ablation-inductively coupled plasma-atomic emission spectrometry (LA-ICP-AES) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) were applied to analyze ancient Chinese potash glass. The surfaces of glasses were polished over 100 μm, then pre-ablation was performed to avoid surface weathering effect, and laser ablation was performed in the designed route to eliminate influence of heterogeneity. The glasses were classified into three subgroups by their lime and alumina concentrations, and they may have different recipe and production center. There are various colorants in these glass including metallic copper, and ions of manganese, copper and cobalt. The characteristics of rare earth elements of Chinese potash glass were studied for the first time and it was successfully used to separate the potash glass of Fengmenling and Jiuzhiling. The features of two methods in the studies of ancient glass were discussed.

Thirty-seven glass beads excavated from the Han Dynasty tombs in Hepu county, Guangxi, China, were analyzed using a portable X-ray fluorescence (PXRF) spectrometer. Reference sample Corning glass D is used to check precision and accuracy of the equipment for major and minor components. The results of inductively coupled plasma atomic emission spectroscopy and PXRF are compared to evaluate the quality of equipment for trace elements. Combined with the contents of Al2O3 and CaO, a new criterion of subgroup division for potash glass based on the levels of trace elements (Rb and Sr) is proposed. The correlations of Rb and K, Rb and Al, and Sr and Ca are discussed. It is thought that saltpeter was the main flux used to produce potash glasses of different groups. The positive correlation between Rb and Al, and Rb and K indicates that potassium aluminosilicate minerals may be used as raw minerals for potash glasses of group II. The results indicate that the levels of Rb and Sr can be very helpful in subgroup definition and provide useful clues to the raw materials used for glassmaking and provenance study of the potash glass found in Guangxi, China. Copyright © 2013 John Wiley & Sons, Ltd.

This work aims to determine the formation mechanism as well as the major mineral and inclusions of black-green serpentine jade by Raman spectroscopy. Scanning electron microscopy with energy-dispersive spectrometry was used to analyze the chemical composition of the inclusions and major mineral. The major mineral of black-green serpentine jade was antigorite, and the inclusions were actinolite, chlorite, calcite, quartz, magnetite, and goethite. Jade quality was preliminarily evaluated based on the area ratio of antigorite to the inclusions by optical microscopy. Formation mechanism of black-green serpentine jade was inferred based on the analysis of the inclusions, which demonstrated a new application of Raman spectroscopy in mineralogy.

A total of 33 ancient glass beads unearthed from the Kizil reservoir cemetery and Wanquan cemetery in Xinjiang are studied using Raman spectroscopy, scanning electron microscopy with energy-dispersive spectrometry (SEM–EDS) and other methods. The detailed study of the glassy matrices, the crystalline inclusions and the microstructural heterogeneities for these glass beads has revealed some valuable information to help in the understanding of their possible manufacturing technology and provenance. At least two different types of glass were present in the two cemeteries. For the first time, antimony-based colourant/opacifier—for example, Pb2Sb2O7 or CaSb2O6—was systematically identified in some beads of plant-ash type soda–lime glass dated to about 1000–500 bc. The limited number of potash glass beads from the Kizil reservoir cemetery, which were dated to about 500–300 bc, used tin oxide as an opacifier. The diverse resources of the soda–lime and potash glasses indicate the existence of a complex trade network between China and the West much earlier than the Western Han Dynasty.

A total of ten ancient colored glass beads were analyzed by confocal Raman microspectroscopy for the non-destructive identification of microcrystals within them. These beads were excavated from different regions of China, including Xinjiang, Henan, Hubei and Guangxi Provinces, and were dated mainly from the 10th century BC to the 9th century AD. For the first time, either tin or antimony-based opacifiers/colorants including calcium antimonate (CaSb2O6, Ca2Sb2O7), bindheimite (Pb2Sb2O7), lead tin yellow type II (PbSn1-xSixO3) and cassiterite (SnO2) were identified in nine samples. In addition, other crystalline phases such as cuprite (Cu2O), α-wollastonite (CaSiO3), diopside (CaMgSi2O6), feldspar (KAlSi3O8), calcite (CaCO3) and quartz (SiO2) were also detected. Another interesting phenomenon first observed in this study was the coexistence of Sn- and Sb-based opacifiers/colorants in one mosaic bead from Guangxi. The possibility to use Sb- and Sn-based opacifiers/colorants for dating and provenance study of ancient glass found in China is discussed briefly. Copyright © 2013 John Wiley & Sons, Ltd.

Lantian jade is a kind of ancient Chinese jades. The modified external-beam proton-induced X-ray emission (PIXE), X-ray diffraction (XRD), laser Raman spectroscopy (LRS) and the scanning electron microscopy (SEM) were employed to analyze the chemical and mineral composition of the modern Lantian jade from Shaanxi Province. The jade samples can be categorized into two classes. The first class consists of mainly of antigorite and the level of serpentinization is high. One sample exhibited Raman characteristic bands of lizardite, a serpentine mineral which was described for the first time in Lantian jade. Therefore, Lantian jade can be further subdivided into Lantian antigorite jade and Lantian lizardite jade, which can be distinguished from each other by the XRD and Raman spectra. The second class consists mainly of calcite, serpentine and augite, with traces of talc, dolomite and tremolite. Also Mn, Zn and Zr contents are higher compared to the other trace elements. Lantian jade formed when dolomitic marble was converted to serpentine minerals by magmatic hydrothermal metasomatism at low temperature. These characteristics can provide useful data for archeological research on Lantian jade.

A simple method to optically synthesize Ag nanoparticles in Ge 2 Sb 2 Te 5 phase change matrix is described. The fine structures of the locally formed phase change chalcogenide nanocomposite are characterized by high-resolution transmission electron microscopy. The formation mechanism of the nanocomposite is discussed with temperature evolution and distribution simulations. This easy-prepared metal nano-particle-embedded phase change microstructure will have great potential in nanophotonics applications, such as for plasmonic functional structures. This also provides a generalized approach to the preparation of well-dispersed nanoparticle-embedded composite thin films in principle.

Glow discharge mass spectrometry (GD-MS) was applied to study the nephrite minerals formed by different metallogenic mechanisms and geological environments from deposits in China, Canada, New Zealand and Russia. The GD-MS analysis and multivariate statistic analysis results indicated that two types of nephrite minerals of different metallogenic mechanisms could be classified by some typical elements. It was shown that serpentine-related nephrite minerals had higher concentrations of Cr, Co and Ni than dolomitic-marble-related nephrite minerals. Meanwhile, nephrite samples from Wenchuan had higher concentrations of Mn, V than other deposits and nephrite samples from Xiaomeiling had higher concentrations of Sr, K and Na than other deposits, which were consistent with their geological environments. These analytical results of nephrite samples by GD-MS showed that both metallogenic mechanisms and geological environments could affect the elemental concentrations in nephrite minerals.

Element characteristics of nephrite minerals were determined by glow discharge mass spectrometry (GD-MS) through surface adherence method. To solve the conductivity problem of non-conductive nephrite samples, high purity indium pin (>99.9999%) was used as discharge host. During the preparation procedure, a small piece of nephrite sample was ground into powder (about 200 meshes), and then the sample powder was coated on the surface of indium pin to form a rod sample. Typical elements of nephrite minerals were analyzed by GD-MS, and the relative standard deviations showed that the stability and reproducibility of this method were good. Meanwhile, four nephrite samples from two different deposits were further studied by this method. The GD-MS results of major elements and trace elements revealed that typical elements of the nephrite minerals from same deposit were similar, and those from different deposits exhibited significant difference. In addition, results of external-beam proton induced X-ray emission (PIXE) were consistent with the result of GD-MS determination. The present approach had been proven to be simple, efficient to perform the rapid screening and multi-element semi-quantitative analysis of nephrite samples.

Scanning electron microscopy with energy dispersive spectrometer (SEM-EDS) and laser Raman spectroscopy (LRS) were used to analyse the chromite inclusions found in four samples of the mineral nephrite that were obtained from Taiwan (one), Manasi in China (two) and New Zealand (one). The chromite inclusions found in sample HL-1 (Taiwan) contain low contents of Mg and Al, as well as a characteristically high Zn content. The most significant finding, however, was that HL-1 could also be distinguished from the other samples by the lower wavenumbers of the positions of the peaks that belong to the A1g, F2g(1) and Eg modes. Compared to the difference in compositions, the difference in the positions of the peaks in the Raman spectra of the chromite inclusions, as revealed by LRS, can more easily be used to distinguish between samples of nephrite that have been obtained from different deposits, and in particular to identify the provenance of the raw material used in ancient nephrite artefacts, in view of the fact that LRS is non-destructive and easy to apply. Copyright © 2011 John Wiley & Sons, Ltd.

Smooth thin films of three metal(II) complexes were prepared by spin-coating process from 2,2,3,3- tetrafluoro-1-propanol solution and characterized atomic force microscopy (AFM). In order to examine their possible use as blu-ray recording media, the spin-coated films of the metal(II) complexes on K9 glass substrate with a silver reflective layer were evaluated by static optical recording testing system with a 406.7 nm laser. The morphologies of the thin films are smooth and have a root mean square surface roughness (RMS) of 0.34-0.41 nm with in 5 μ × 5 μ area. The results of the static optical recording test demonstrate that high reflectivity contrast (> 54 %) can be obtained at an optimum laser writing power and pulse width with high-to-low polarity, and the recording marks are durable even after 15000 times readout. In addition, the recording marks on the cobalt (II) complex thin film are very clear and circular, and their size can reach 200 nm or less.

In laser direct writing technology, the pattern is usually written in a photoresist. In this work, we use the chalcogenide phase change thin films as the laser direct writing materials, and patterned structures with different shapes and sizes were directly written with different laser wavelengths. Compared with traditional photoresist materials, the patterned structures can be directly formed in the chalcogenide phase change thin films without developing and etching procedures, and also can be directly written with different laser wavelengths. By tuning the laser parameters precisely, patterned structures with different sizes and shapes could be obtained as well. The analysis indicates that the formation mechanism of the patterned structure is mainly due to the volume expansion caused by material vaporization and the interior of the patterned structure is hollow with some solid leavings, and the chalcogenide phase change thin films are very good candidate materials for patterned structure formation.

External-beam PIXE was used to determine the major, minor and trace elements of 45 nephrite minerals from 14 different deposits, including China and other countries. Depending on the R ∗ value (mole percent of Mg 2+ /(Mg 2+ + Fe 2+(3+) )) and content of Cr, Co and Ni, two types of nephrite minerals from dolomite and serpentinized ultramafic deposits can be more accurately distinguished. Besides, the nephrite minerals from Xiaomeiling and Wenchuan deposit can be distinguished with others from dolomite deposits, through the content of Sr and Mn/Fe value, respectively. Moreover, depending on the Sr content, clear evidence was given to prove that the raw materials of ancient nephrite artifacts from Liangzhu culture ruins are not from Xiaomeiling nephrite deposit. Furthermore, PIXE as a non-destructive method will be more used to study ancient nephrite artifacts, so these results can provide scientific basis for seeking the provenance of nephrite raw materials.

Tetrafluoropropanol soluble, metal(II) hydrazone complexes derived from alkyl substituted isoxazole and barbituric acid were synthesized and evaluated as suitable optical recording materials for the recordable blu-ray disc system. The behaviour and relationships of the absorption, reflectivity and optical constants (complex refractive indices N = n + ik ) for different metal(II) complexes in spin-coated films were discussed. In addition, the important thermal decomposition data of these metal(II) complexes from simultaneous TG–DSC analyses were presented as well. As an example of the utility of dye-based blu-ray recording media, we used the nickel(II) hydrazone complex thin film as recording layer for static optical recording performance test. Results showed that high reflectivity contrast over 45% and durable information marks (after repeatedly reading 20,000 times) could be achieved under optimum laser writing power and pulse width conditions, indicative of producing a very promising optical recording medium for blu-ray disc-recordable system.

Three novel metal(II) complexes, CoL2, NiL2 and CuL2 (L = (Z)-4-(2-(1,3-dimethyl-5-oxo-1H-pyrazol-4(5H)-ylidene)hydrazinyl)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one were synthesized. Their structures were postulated based on elemental analyses, 1H NMR, ESI-MS, FT-IR spectra and UV-vis spectra. The effect of different central metal(II) ions on absorption bands of the metal(II) complexes in CHCl3 solutions was researched. The result indicates that the bathochromic shift is CuL2 > NiL2 > CoL2. The absorption properties of thin films and thermal stability of these complexes are also discussed. In addition, the optical constants (complex refractive index N=n+ik) and thickness of the complex thin films on polished single-crystal silicon substrates were measured by spectroscopic ellipsometry. Results indicate that the metal(II) complexes would be a promising recording medium candidate for blu-ray recordable optical storage system due to good absorption at 405 nm, high thermal stability and sharp thermal decomposition, and a high n values of 1.35–1.45 and a low k values of 0.33–0.39.

A novel ligand, (Z)-1,5-dimethyl-4-(2-(3-methyl-5-oxo-1-phenyl-1H-pyrazol-4(5H)-ylidene)hydrazinyl)-2-phenyl-1,2-dihydropyrazol-3-one] and its metal(II)–azo complexes were synthesized and characterized using elemental analyses, proton NMR, electrospray ionization mass spectrometry, FT-IR and UV–visible absorption. Smooth thin films of the metal(II)–azo complexes were prepared using spin-coating, and the absorption spectra of the films were measured. The thermal properties of the metal(ІІ)–azo complexes were investigated using TGA and DSC. The optical constants (complex refractive index N = n + ik ) of the films on single-crystal silicon were determined using variable-angle scanning ellipsometry from which the complex dielectric function ( ɛ ) and absorption coefficient ( α ) were calculated. The photostabilities of the metal(II)–azo complex films were also investigated.

In this work, we used the multilayered ZnS–SiO2/AgOx/ZnS–SiO2 films as the laser direct writing materials, and pattern structures with different shapes and sizes were directly written with green laser (λ=488 nm). Compared with traditional photoresist materials, the pattern structures can be directly formed in this film structures without developing and etching procedures and also can be directly written by very low laser power. By tuning the laser parameters precisely, pattern structures with different sizes and shapes could be obtained as well. The analysis indicates that the formation mechanism of the pattern structure is mainly due to the volume expansion caused by AgOx decomposition into silver particles and oxygen. The oxygen applies pressure to the ZnS–SiO2 layer and makes a hollow shell under the film. The aspect ratios of the patterns rapidly increase from the minimum of 0.012 in laser power of 3.0 mW to the maximum of 0.201 in laser power of 5.0 mW. The thermal stability of the patterns was also qualitatively studied.

Using pivaloylacetonitrile as starting material and coupling component, a novel hydrazone ligand and four, highly organosoluble metal(II) complexes were synthesized via the procedure of oximation, cyclization, diazotization, coupling and metal chelation. In addition to elemental analysis, the structures of the novel compounds were postulated based on a series of spectroscopic methods. Smooth thin films of these metal(II) complexes on K9 glass substrates were prepared by spin-coating from 2,2,3,3-tetrafluoro-1-propanol solutions. The behaviour and relationships of the absorption bands both in solution and in spin-coated films are discussed; the thermal properties, photostability and the solubility of the metal(II) complexes were investigated. The synthesized Ni(II) complex exhibited a remarkable combination of excellent solubility and photostability, suitable absorption band and desirable thermal properties and, therefore, offers the potential of becoming a recording material for the recordable blu-ray disc system.

Based on study of non-isothermal crystallization kinetics and orthogonal test of pulsed-laser crystallization parameters of Ge1Sb4Te7, minimum nanosecond laser pulse duration (threshold) for crystallization recording was used for optical–electrical hybrid operation. The crystallized bits arrays were optically recorded with minimum pulse duration of 40 ns and electrically read out with maximum current signal contrast of ∼20 times.

Thermal decomposition kinetics of ML2 (M = Ni(II) and Co(II); L = 5-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione) complexes were investigated by thermogravimetric analysis (TGA). The first decomposition process of the NiL2 and CoL2 complexes occurs in the temperature range of 320–350 °C. Kinetics parameters corresponding to this step, such as activation energy, Eα, and apparent pre-exponential factor, ln Aaap, were calculated from the thermogravimetric data at the heating rates of 5, 10, 15 and 20 K min−1 by differential (Friedman's equation) and integral (Flynn–Wall–Ozawa's equation) methods. The results show that the activation energy evidently depends on the extent of conversion. As far as their activation energy is concerned, NiL2 complex shows a higher thermal stability than the CoL2 complex.

Four novel metal(II) complexes, Ni(L)2, Co(L)2, Cu(L)2, and Zn(L)2 (L = 5-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono)-1,3-diethyl-2-thioxo-dihydropyrimidine-4,6(1H,5H)-dione), were synthesized using the procedure of diazotization, coupling and metallization. Their structures were identified by elemental analyses, 1H NMR, ESI-MS and FT-IR spectra. The effect of different central metal(II) ions on absorption bands of the metal(II) complexes was researched. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Furthermore, the thermodynamic parameters, such as activation energy (E*), enthalpy (∆H*), entropy (∆S*) and free energy of the decomposition (∆G*) are calculated from the TG curves applying Coats–Redfern method. The results show that the metal(II) complexes have suitable electronic absorption spectra with blue-violet light absorption at about 350–450 nm, high thermal stability with sharp thermal decomposition thresholds.

Smooth thin films of nickel(II), cobalt(II) and zinc(II) complexes with azo barbituric acid were prepared by the spin-coating method. Absorption spectra of the thin films on K9 glass substrates in 300–700 nm wavelength region were measured. Optical constants (complex refractive index N = n + i k ) of the thin films prepared on single-crystal silicon substrates in 275–695 nm wavelength region were investigated on rotating analyzer–polarizer type of scanning ellipsometer, and dielectric constant ɛ ( ɛ = ɛ 1 + i ɛ 2 ) as well as absorption coefficient α of thin films were calculated at 405 nm. In addition, static optical recording properties of the cobalt(II) complex thin film with an Ag reflective layer was carried out using a 406.7 nm blue-violet laser and a high numerical aperture (NA) of 0.90. Clear recording marks with high reflectivity contrast (>60%) at proper laser power and pulse width were obtained, and the size of recording mark was as small as 250 nm. The results indicate that these metal(II) complexes are promising organic recording medium for the blu-ray optical storage system.

We report on three-dimensional precipitation of Au nanoparticles in gold ions-doped silicate glasses by a femtosecond laser irradiation and further annealing. Experimental results show that PbO addition plays the double roles of inhibiting hole-trapped centers generation and promoting formation and growth of gold nanoparticles. Additionally, glass containing PbO shows an increased non-linear absorption after femtosecond laser irradiation and annealing. The observed phenomena are significant for applications such as fabrications of three-dimensional multi-colored images inside transparent materials and three-dimensional optical memory, and integrated micro-optical switches. (c) 2007 Elsevier B.V. All rights reserved.

Two new hydrazone chelating ligands, 2-(2-(5-methylisoxazol-3-yl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione (HL 1 ) and 2-(2-(5- tert -butylisoxazol-3-yl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione (HL 2 ), and their nickel(II) and copper(II) complexes were synthesized using the procedure of diazotization, coupling and metallization. Their structures were postulated based on elemental analysis, 1 H NMR, ESI-MS, FT-IR spectra and UV–vis electronic absorption spectra. Smooth films of these complexes on K9 glass substrates were prepared using spin-coating and their absorption properties were evaluated. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential thermogravimetry (DTG). Different thermodynamic and kinetic parameters namely activation energy ( E ∗ ), enthalpy of activation (Δ H ∗ ), entropy of activation (Δ S ∗ ) and the free energy change of activation (Δ G ∗ ) were calculated using the Coats–Redfern (CR) equation.

Thiazolyl heterocyclic azo dye and its metal (Ni2+, Co2+)-azo complexes were synthesized. Their structures were confirmed by elemental analysis, UV-VIS absorption spectra, FT-IR, H-1 NMR and MALDI-MS. The thermal properties of metal complexes were studied by DSC-TGA. The optical constants (complex refractive index N=n + ik) and thickness of the complex thin films on polished single-crystal silicon substrates were investigated on a scanning ellipsometer. Results indicate that thiazolyl metal-azo complexes possess good optical and thermal properties. They would be a promising recording medium candidate for NVD with the Super-resolution near field structure (Super-RENS) technology. (c) 2007 Elsevier B.V. All rights reserved.

This paper reports the fabrication and measurement of organic light-emitting devices comprised of indium-tin-oxide (ITO)/4,4',4''-tris(N-carbazolyl)-triphenylamine (TCTA, 8 nm)/2-pyrenyl-9-phenyl-9-pyrenylfluorene(2P9PPF, 30 nm)/ bathocuproine (BCP, with different thickness)/Alq3 : DCJTB (DCJTB = 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7- tetramethyljulolidyl-9-enyl)-4H-pyran, Alq3 = tris(8-hydroxyquinolino) aluminium(III), 2% in mass ratio, 30 nm)/Mg : Ag(250 nm). The dependence of electroluminescence (EL) spectra on the BCP layer thickness and operating voltage has been investigated quantitatively. It is shown that the emission colour of the devices changes from red to blue at 8 V when the BCP layer thickness changes from 1 to 10 nm. The emission colour of the devices also varies with the applying voltage even in a given device. The ratio of blue emission originating from 2P9PPF to the red emission originating from DCJTB increases with the applying voltage. Based on the hole blocking effect of the BCP layer, we deduced the dependence of this ratio on the BCP layer thickness and simulated the experimental result well. It is also proposed that the variation of the EL spectrum with the voltage can be attributed to the varying hole blocking effect under the varying electric field, which resulted in a recombination zone shift, and the exciton dissociation effect in the electric field.

Smooth thin films of three kinds of nickel(II)–azo complexes were prepared by the spin-coating method. Absorption spectra of the thin films on K9 glass substrate in the 300–600 nm wavelength region were measured. Optical constants (complex refractive index N = n + i k ) and thickness of the thin films prepared on single-crystal silicon substrate in the 300–600 nm wavelength region were investigated on rotating analyzer–polarizer type of scanning ellipsometer, and dielectric constants e ( e = e 1 + i e 2 ) , absorption coefficients α as well as reflectance R of thin films were then calculated at 405 nm. In addition, in order to examine the possible use of nickel(II)–azo complex thin film as an optical recording medium, one of the nickel(II)–azo complex thin film prepared on K9 glass substrate with an Ag reflective layer was also studied by atomic force microscopy and static optical recording. The results show that the nickel(II)–azo complex thin film is smooth and has a root mean square surface roughness of 2.25 nm, and the recording marks on the nickel(II)–azo complex thin film are very clear and circular, and their size can reach 200 nm or less.

A series of benzothiazole-containing fluorene molecules have been designed and their one- and two-photon absorption properties have been investigated theoretically by using the ZINDO method. The effects of electron-excessive/deficient heterocyclic bridges as auxiliary donors (auxD)/ acceptors (auxA) on TPA cross-sections were studied. The results show that the molecules with D–π–auxA-A, D-auxD–π–A, or D-auxD–π–auxA-A structure types have large TPA cross-section, which can be a valuable strategy in the design of two-photon absorption materials. Also, a linear relationship between the first hyperpolarizability and the TPA cross-section is observed.

The NiOx thin films were deposited by reactive dc-magnetron sputtering from a nickel metal target in Ar + O-2 with the relative O-2 content 5%. The as-deposited NiOx, thin films could represent a two-component system comprising crystalline NiO particles dispersed in an amorphous Ni2O3. Decomposition temperature of the as-deposited NiO, thin films was at about 263 degrees C. After annealed at 400 degrees C for 30 min in air, the surface morphology of the films became very rough due to the decomposition of the Ni2O3, leading to the changes of the optical properties of the NiO, thin films. The reflectivity of the films annealed at 400 degrees C was lower than that of the as-deposited one and the optical contrast was 52% at 405 nm. (c) 2006 Elsevier B.V. All rights reserved.

One- and two-photon absorption properties of a series of fluorene derivatives with symmetrical charge transfer D–π–D and A–π–A structural motifs have been theoretically investigated with ZINDO/S method. The optimized structures and the characterization of frontier molecular orbitals were obtained by using AM1 calculations. Two-photon absorption properties of molecules have been studied using three-state model. The calculation results have shown that fluorene–thiophene derivatives exhibit larger two-photon absorption cross-section as compared with other studied molecules. To illustrate the results, the crucial effects of thiophene ring on fluorene-thiophene derivatives and the net charge changes on the π-conjugated bridges are analyzed theoretically.

The non-resonant third-order non-linear optical properties of some amorphous chalcogenide films were studied experimentally by the method of the femtosecond optical heterodyne detection of the optical Kerr effect. The real and imaginary parts of the complex third-order optical non-linearity could be effectively separated and their values and signs could be also determined. Amorphous chalcogenide films showed a very fast response in the range of 200 fs under ultrafast excitation. The ultrafast response and large third-order non-linearity are attributed to the ultrafast distortion of the electron orbitals surrounding the average positions of the nucleus of chalcogen atoms. The high third-order susceptibility and a fast response time of amorphous chalcogenide films make them promising materials for application in advanced techniques especially in optical switching.

The non-resonant third-order non-linear optical properties of amorphous Ge20As25Se55 films were studied experimentally by the method of the femtosecond optical heterodyne detection of optical Kerr effect. The real and imaginary parts of complex third-order optical non-linearity could be effectively separated and their values and signs could be also determined, which were 6.6 x 10(-12) and -2.4 x 10(-12) esu, respectively. Amorphous Ge20As25Se55 films showed a very fast response in the range of 200 fs under ultrafast excitation. The ultrafast response and large third-order non-linearity are attributed to the ultrafast distortion of the electron orbitals surrounding the average positions of the nucleus of Ge, As and Se atoms. The high third-order susceptibility and a fast response time of amorphous Ge20As25Se55 films makes it a promising material for application in advanced techniques especially in optical switching. (c) 2005 Elsevier B.V. All rights reserved.

Three kinds of new nickel(II) complexes of α-isoxazolylazo-β-diketones with blue-violet light absorption were synthesized. Their structures were postulated based on elemental analysis, MS and FT-IR spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. The absorption properties and thermal stability of these complexes were discussed. The static optical recording test for high density digital versatile disc-recordable (HD-DVD-R) system was also studied.

Two new azo dyes of alpha-isoxazolylazo-beta-diketones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni2+ and Cu2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability.

The real and imaginary parts of third-order susceptibility of amorphous GeSe2 film were measured by the method of the femtosecond optical heterodyne detection of optical Kerr effect at 805 nm with the 80 fs ultra fast pulses. The results indicated that the values of real and imaginary parts were 8.8 x 10(-12) esu and -3.0 x 10(-12) esu, respectively. An amorphous GeSe2 film also showed a very fast response within 200 fs. The ultra fast response and large third-order non-linearity are attributed to the ultra fast distortion of the electron orbits surrounding the average positions of the nucleus of Ge and Se atoms. (c) 2005 Elsevier B.V. All rights reserved.

Three-photon absorption (3PA) of two fluorene-based molecules with D-pi-D structural motifs (abbreviated as BPAF and BCZF) has been determined by using a Q-switched Nd: YAG laser pumped with 38 ps pulses at 1064 nm in DMF. The measured 3PA cross-sections are 222 and 140 x 10(-78) cm(6) s(2) for BPAF and BCZF, respectively. AM1 calculations show that attaching different donors changes the charge density distribution of the fluorene skeleton, and it is observed that the 3PA cross-section can be enhanced with increasing intramolecular charge transfer character, measured by the parameter Delta p(1)/Delta p(2)/Delta p(1)'. (c) 2005 Elsevier B.V. All fights reserved.

In this paper, GdFeCo/DyFeCo exchange-coupled double-layer films used for center aperture type magnetically induced super resolution were investigated through experiments and theoretical calculation. The samples were prepared by magnetron sputtering method. The polar Kerr effect was measured to prove the spin reorientation of the readout layer. Theoretical study of magnetization profiles was performed on the basis of the mean-field theory and the continuum model. The theoretical results showed that the magnetization orientation of the readout layer changed gradually from in-plane to out-of-plane with the rise of the temperature. Theoretical analysis explained the experimental results successfully.

A new humidity-resistant highly sensitive acrylamide-based photopolymeric holographic recording material has been developed. The photopolymer is resistant to the humidity of environment. Diffraction efficiencies near 50% are obtained with exposure energy of 60 mJ/cm(2) in materials of 150 mu m. thickness. Diphenyl iodonium chloride is added to the material and can increase the exposure sensitivity by a factor of more than 4 (to about 28 mJ/cm(2)). An image has been successfully stored in the material with a small distortion. (C) 2005 Elsevier B.V. All rights reserved.

The three-photon absorption effect (3PA) of two novel symmetrical charge transfer fluorene-based molecules (abbreviated as BASF and BMOSF) has been determined by using a Q-switched Nd:YAG laser pumped with 38 ps pulses at 1064 nm in DMF. The measured 3PA cross-sections are 84 x 10(-78) and 114 x 10(-78) cm(6) s(2), respectively. The geometries and electronic excitations of these two molecules are systematically studied by PM3 and ZINDO/S methods. The relationships between 3PA cross-sections and intramolecular charge transfer are discussed micromechanically. The experimental and theoretical results have shown that the larger intramolecular charge transfer, which was characterized by the charge density difference between the ground state (SO) and the first excited state (S-I), the greater enhancement of the 3PA cross-sections. (c) 2005 Elsevier B.V. All rights reserved.

Smooth thin films of three kinds of azo dyes of 2-(5′- tert -butyl-3′-azoxylisoxazole)-1, 3-diketones and their copper (II)-azo complexes were prepared by the spin-coating method. Absorption spectra of the thin films on a glass substrate in the 300–600 nm wavelength region were measured. Optical constants (complex refractive index N = n + ik ) and thickness of the thin films prepared on single-crystal silicon substrate in the 300–600 nm wavelength region were investigated on rotating analyzer–polarizer type of scanning ellipsometer, and dielectric constants e ( e = e 1 + ie 2 ), absorption coefficients α as well as reflectance R of thin films were then calculated. In addition, one of the copper (II)-azo complex thin film prepared on glass substrate with an Ag reflective layer was also studied by atomic force microscopy (AFM) and static optical recording. AFM study shows that the copper (II)-azo complex thin film is very smooth and has a root mean square surface roughness of 1.89 nm. Static optical recording shows that the recording marks on the copper (II)-azo complex thin film are very clear and circular, and the size of the minimal recording marks can reach 200 nm.

We report the space selective precipitation of Pd nanoparticles in Pd2+ -doped silicate glass by ultrashort laser pulses irradiation and further annealing. Absorption spectra, transmission electron microscopy, refractive index measurement and Z-scan technique demonstrated that metallic Pd nanoparticles were precipitated in the glass sample after irradiation by an 800-nm femtosecond laser and subsequent annealing at 600 degrees C. We discuss a refractive index change and nonlinear absorption that combines the precipitation of Pd nanoparticles. Crown Copyright (c) 2005 Published by Elsevier B.V. All rights reserved.

A novel azo dye containing isoxazole ring and β-diketone derivative (TIAD) and its two nickel (II) complexes (Ni (II)–ETIAD and Ni (II)–HTIAD) were synthesized in order to obtain a blue-violet light absorption and better thermal stability as a promising organic storage material for next generation of high density digital versatile disc-recordable (HD-DVD-R) systems that uses a high numerical aperture of 0.85 at 405 nm wavelength. Their structures were confirmed on the basis of elemental analysis, MS, FT-IR, UV–Vis and magnetic data. Their solubility in 2,2,3,3-tetrafluoro-1-propanol (TFP) and absorption properties of thin film were measured. The difference of absorption maximum from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated.

Static recording characteristic of super-resolution near-field structure with antimony (Sb) is investigated in this paper. The recording marks are observed by a scanning electron microscopy (SEM), a high-resolution optical microscopy with a CCD camera and an atomic force microscopy (AFM). The super-resolution mechanism is also analyzed based on these static recording marks. Results show that the light reaching on recording layer is composed of two parts, one is the linear transmissive light (propagating field) and the other is the nonlinear evanescent light in the optical near field. The evanescent light may be greatly enhanced in the center of the spot because Sb will transit from a semiconductor to a metal when it is melted under the high laser power irradiation. This local melted area in the spot center may be like a metal tip in the optical near field that can collect and enhance the information that is far beyond the diffraction limit, which leads to the super-resolution recording and readout.

Two novel symmetrical charge transfer fluorene derivatives (abbreviated as BCZF and BVCZF) with carbazole end-group as the donor moieties have been synthesized. Three-photon absorption cross-sections of these two compounds have been determined by using a Q-switched Nd:YAG laser pumped with 38 ps pulses at 1064 nm in DMF. The measured 3PA cross-sections are 140 x 10(-78) and 400 x 10(-78) cm(6) s(2) for BCZF and BVCZF, respectively. The geometries, electronic structures and electronic spectra of these two compounds are systematically studied by AM1 and ZINDO/S methods. On the basis of correct UV-vis spectra, the influence of different molecular structure on three-photon absorption cross-sections is discussed micromechanically. (C) 2005 Elsevier B.V. All rights reserved.

The emission cross section for the 2F5/2–2F7/2 transition of Yb3+ has been determined from absorption and emission measurements of niobosilicate glasses at room temperature. Using systematic variations in the spectroscopic properties, relative to composition, a glass host with emission cross sections of >2.00 pm2 and fluorescence lifetimes of >0.8 ms is obtained. This glass has advantages over some laser glasses that have been reported in other published papers.

Super-resolution near-field structure (super-RENS) with bismuth (Bi) mask layer (Bi-super-RENS) is reported for the first time in this paper. Bi thin films with various thicknesses were studied by atomic force microscopy and grazing incident X-ray diffraction. Static optical recording tests with and without super-RENS were carried out using 650 nm semiconductor laser at recording power of 14 mW and 7 mW with pulse duration of 100 ns. The recording marks were observed by scanning electron microscopy and high-resolution optical microscopy with a CCD camera. Results showed that the Bi mask layer can also concentrate energy into the center of a laser beam at low laser power similar to the traditional Sb mask layer. Moreover, a (ZnS)80(SiO2)20 protection layer performed better than the SiN protection layer in the Bi-super-RENS. The direct observation of laser-recording marks may help better understand the working mechanism of the super-RENS, super-resolution ablation, and other nonlinear switch phenomena.

By using the classical nucleation and growth dynamics to describe the melting process of superheated solid materials induced by ultrafast laser pulse irradiation, we found that the melting process of highly superheated solid materials is governed by explosively homogeneous nucleation. For the superheating degree of 1.6–1.9, the melting time for aluminum is several tens of picoseconds. In this case the lattice is heated within a few picoseconds, thus the total melting time of the solid materials is governed by the explosively homogeneous nucleation. However, for the very short laser pulse irradiation, such as femtosecond laser pulses with high fluences, the nonthermal mechanism plays a critical role in the melting process, and the classical homogeneous nucleation theory and growth dynamics is not useful. That is to say, the classical homogeneous nucleation theory and growth dynamics is useful for describing the rapid thermal melting process, however, is not suitable for explaining the nonthermal melting process.

A new azo nickel chelate (Ni(azo) 2 ) thin film has been developed for digital versatile disc recordable (DVD-R) by means of a spin-coating method. The absorption and reflectivity of the film matches very well with the wavelength of the GaAlInP semiconductor diode laser (650 nm). Optical parameters of the thin film were measured by a spectroscopic ellipsometer system. Thermal property of azo nickel chelate indicated that the rapid decomposition of the dye happens in the narrow temperature zone. The performance of DVD-R disc of the Ni(azo) 2 thin film exhibited that low jitter and high modulated amplitude could be achieved under optimistic write power.