Mass spectroscopy and ablation characteristics of nylon 6.6 in the ultraviolet

We report on the mass spectroscopic and the laser ablative characteristics of nylon 6.6 [-NH-(CH₂)₆-NH-CO-(-CH₂)₄-CO-] at 193 and 248 nm, using the ArF and KrF excimer lasers. The characteristic parameters of the laser ablative process, such as etch rate at different fluences, the threshold fluence, and the absorption coefficient for both wavelengths were determined. Even at low laser energy, there was a complete breaking of the polymeric chain bonds. The following photofragments were observed at 248 nm: H, H₂, C, CH, CH₂, N, NH, O, OH, H₂O, C₂H, C₂H₂, CN, C₂H₃, HCN, N₂, CO, C₂H₄, COH, C₂H₅, N₂H, NO, C₂H₆, H₂CO, N₂H₂, C₂, CH₂NH, O₂, C₃H₃, C₃H₄, C₃H₅, C₃H₆, CNO, HCNO, and H₂CNO. At 193 nm no photofragments were observed for m/e larger than 30 amu. The photofragments with two carbon atoms have a relatively higher probability to be dissociated from the parent monomer, than heavier photofragments with four carbon atoms. The mass spectroscopic studies and the absorption spectrum of nylon 6.6 in the ultraviolet, suggest photochemical bond-breaking at 248 and 193 nm. The monomer dissociates into fragments with the predominant mass at 28 amu for both laser wavelengths. Therefore the amide group is mainly involved in the photodissociation process of nylon 6.6 in the ultraviolet. The experimental results suggest that the photochemical dissociation of the polymeric chain is the dominant mechanism of the laser ablation of nylon 6.6 at 193 and 248 nm.     

Mass spectroscopic and degassing characteristics of polymeric materials for 157 nm photolithography

We report on the mass spectroscopic and the degassing characteristics of an epoxy novolac-based chemically amplified photoresist, with triphenylsulfonium hexafluoroantimonate as photoacid generator, using an F₂ pulsed discharge molecular laser at 157 nm. This photoresist has been used previously for optical (248 nm), e-beam, and X-ray microlithography both in wet and dry development processes. For laser energy of 1 mJ per pulse focused on the sample and 5 MW/cm² intensity, photofragments with m/e less than 40 amu have a higher probability of formation. These fragments are mainly attributed to the breaking of the substituents of the aromatic rings. The specific fragments observed are: H, H₂, C, CH, CH₂, CH₃, O, OH, H₂O, HF, C₂, C₂H, C₂H₂, C₂H₃, CO, C₂H₄, C₂H₅, C₂H₆, H₂CO, OCH₃, O₂, C₃H₃, C₃H₄, C₃H₅, C₃H₆, C₃H₇, C₂H₃O, C₃H₈, C₂H₅O, C₃O, C₃HO, C₃H₂O, C₃H₃O, C₃H₄O, C₃H₅O, C₂HO₂, C₂H₂O₂, C₂H₃O₂, C₂H₄O₂, C₂H₅O₂ and C₂H₆O₂. Comparison of these results with the ones obtained from samples with pure epoxy novolac polymer show that the direct fragmentation of the side polymer bonds is predominant over bond breaking arising from the presence of the triphenylsulfonium salt sensitizer.     

灯丝温度对原位吸收光谱和金刚石薄膜生长的影响

 报道了原位红外吸收光谱在气相合成金刚石薄膜生长过程中的应用，研究了灯丝温度对原位红外吸收光谱和金刚石薄膜生长的影响。较高的灯丝温度使甲烷分解更充分，从而产生更多诸如C₂H₂等可能对金刚石薄膜生长有利的基团，导致金刚石薄膜质量和生长速率的提高。     

Shadowgraphic and emission imaging spectroscopic studies of the laser ablation of graphite in an Ar gas atmosphere

Laser ablation of graphite in an Ar atmosphere at 560 Torr was done using a nanosecond-pulse Nd:YAG laser (1064 nm) at a fluence of 12 J/cm². Dynamics in the ejection of carbon species and in their confinement near the graphite surface (<1 mm) due to their numerous collisions with Ar atoms were investigated by shadowgraphy, emission imaging, and emission spectroscopy at delay times of 0.01-100 7s following the laser irradiation. A shock wave was generated, and temporally and spatially dependent emissions from Ar⁺ and Ar were observed in addition to those from carbon species (C, C⁺, and C₂) and the Bremsstrahlung radiation from a hot plasma. We suggest that the dissipation of the kinetic and thermal energies of the carbon species, their backward motion, and their collisions with each other lead to the formation of clusters and particles through the interaction with Ar atoms.     

PRELIMINARY TEST FOR AGEING EFFECT OF DRIFT CHAMBERS

The degradation of some performances of the drift chambers irradiated with 5 MeV electron beam has been tested. The gas mixtures filled were Ar/CO₂, Ar/CH₄ and C₄H₁₀ in proportion.
The dark current, the pulse height, the energy resolution and the counting rate plateau have been measured during the irradiation.     

Electron Scattering by C4H10 and C6H6 in the Energy Range 100--1000eV

We investigate the applicability of the independent atom model （IAM） to elastic electron scattering from complex polyatomic molecules, namely C4H10 and C6H6, in the energy range 100-1000eV. The cross sections of the elastic electron scattering are calculated by employing the IAM together with the relativistic partial waves. The incorporation of both the modified absorption potential and the extended structural factor in the IAM makes the elastic differential cross sections and momentum transfer cross sections have a good agreement with the available experimental data. The present simple model seems to be insensitive to the complexity of the target molecules so that the proposed procedure can be quite useful for calculation of electron scattering from bio-molecules.     

Additivity Rule for Electron-Molecule Total Cross Section Calculations at 50-5000 eV： A Geometrical Approach

To quantify the changes of the geometric shielding effect in a molecule as the incident electron energy varies, we present an empirical fraction, which represents the total cross section （TCS） contributions of shielded atoms in a molecule at different energies. Using this empirical fraction, a new formulation of the additivity rule is proposed. Using this new additivity rule, the TCSs for electron scattering by CO2, C2H2, C6H12 （cyclo-hexane） and CsH16 （cyclo-octane） are calculated in the range 50-5000 e V. Here the atomic cross sections are derived from the experimental TCS results of simple molecules （H2, O2, CO）. The quantitative TCSs are compared with those obtained by experiments and other theories, and good agreement is attained over a wide energy range.     

Optical characterisation of the photolytic decomposition of ferrocene into nanoparticles

Optical emission from the photolytic dissociation of ferrocene Fe(C₅H₅)₂, often abbreviated as FeCp₂, in argon atmosphere was studied. The dissociation was performed by using an ArF excimer laser, operating at a wavelength of 193 nm. Two pressure regions were examined. At low (0.1 mbar) pressure, several emission lines of Fe could be identified, however no C, C₂, or CH emission lines/bands were found. At a higher (20 mbar) pressure of the FeCp₂/Ar gas mixture, a broadband emission identified as blackbody radiation was observed. This blackbody radiation originates from nanoparticles with a mean size of 30 nm, which consist of both metallic iron and amorphous carbon. The initial colour temperature of the particles was 2600 K.     

Flame structure of laminar premixed anisole flames investigated by photoionization mass spectrometry and photoelectron spectroscopy

Two laminar, premixed, fuel-rich flames fueled by anisole-oxygen-argon mixtures with the same cold gas velocity and pressure were investigated by molecular-beam mass spectrometry at two synchrotron sources where tunable vacuum-ultraviolet radiation enables isomer-resolved photoionization. Decomposition of the very weak O–CH₃ bond in anisole (C₆H₅OCH₃) by unimolecular decomposition yields the resonantly-stabilized phenoxy radical (C₆H₅O). This key intermediate species opens reaction routes to five-membered ring species, such as cyclopentadiene (C₅H₆) and cyclopentadienyl radicals (C₅H₅). Anisole is often discussed as model compound for lignin to study the phenolic-carbon structure in this natural polymer. Measured temperature profiles and mole fractions of many combustion intermediates give detailed information on the flame structure. A very comprehensive reaction mechanism from the literature which includes a sub-scheme for anisole combustion is used for species modeling. Species with the highest measured mole fractions (on the order of 10^?3–10^?2) are CH₃, CH₄, C₂H₂, C₂H₄, C₂H₆, CH₂O, C₅H₅ (cyclopentadienyl radical), C₅H₆ (cyclopentadiene), C₆H₆ (benzene), C₆H₅OH (phenol), and C₆H₅CHO (benzaldehyde). Some are formed in the first destruction steps of anisole, e.g., phenol and benzaldehyde, and their formation will be discussed and with regard to the modeling results. There are three major routes for the fuel destruction: (1) formation of benzaldehyde (C₆H₅CHO), (2) formation of phenol (C₆H₅OH), and (3) unimolecular decomposition of anisole to phenoxy (C₆H₅O) and CH₃ radicals. In the experiment, the phenoxy radical could be measured directly. The phenoxy radical decomposes via a bicyclic structure into the soot precursor C₅H₅ and CO. Formation of larger oxygenated species was observed in both flames. One of them is guaiacol (2-methoxyphenol), which decomposes into fulvenone. The presented speciation data, which contain more than 60 species mole fraction profiles of each flame, give insights into the combustion kinetics of anisole.     

Pulsed laser deposition of tantalum pentoxide film

We report thin tantalum pentoxide (Ta₂O₅) films grown on quartz and silicon substrates by the pulsed laser deposition (PLD) technique employing a Nd:YAG laser (wavelength 5=532 nm) in various O₂ gas environments. The effect of oxygen pressure, substrate temperature, and annealing under UV irradiation using a 172-nm excimer lamp on the properties of the grown films has been studied. The optical properties determined by UV spectrophotometry were also found to be a sensitive function of oxygen pressure in the chamber. At an O₂ pressure of 0.2 mbar and deposition temperatures between 400 and 500 °C, the refractive index of the films was around 2.18 which is very close to the bulk Ta₂O₅ value of 2.2, and an optical transmittance around 90% in the visible region of the spectrum was obtained. X-ray diffraction measurements showed that the as-deposited films were amorphous at temperatures below 500 °C and possessed an orthorhombic (#-Ta₂O₅) crystal structure at temperatures above 600 °C. The most significant result of the present study was that oxygen pressure could be used to control the composition and modulate optical band gap of the films. It was also found that UV annealing can significantly improve the optical and electrical properties of the films deposited at low oxygen pressures (<0.1 mbar).     

高温高压下C3N6H6分解产物的研究

 采用高温高压方法分解缩聚三聚氰胺（C₃N₆H₆），得到一种棕黑色粉末。经过X射线粉末衍射分析，产物主要由未完全分解的原料、碳和分解过程中的过渡相组成。透射电镜观察结果显示，过渡相在某一方向具有长周期结构；在扫描电镜下观察形貌，产物为片状组织，且其中有少量气孔；X射线能散结果表明，C∶N≈3.27∶1（原子比）；此外，进行了红外吸收谱和X射线光电子能谱测试，产物主要键合状态是C(sp²)＝N和C(sp²)—N。     

Adsorption Mechanism of Hydrogen on Boron-Doped Fullerenes

The C35BH-H2 complex and two other possible isomers, C34BCaH-H2 and C34BCbH-H2, are investigated using the local-spin-density approximation （LSDA） method. The results indicate that a single hydrogen molecule could be strongly adsorbed on two isomers, C34BCaH and C34BCbH, with binding energies of 0.42 and 0.47eV, respectively, and that these calculated binding energies are suitable for reversible hydrogen adsorption/desorption near room temperature. However, it is difficult for the H2 molecule to be firmly adsorbed on C35BH. We analyze the interaction between C34BCxH （x= a, b） and the H2 molecule using dipole moments and molecular orbitals. The charge analysis showed there was a partial charge （about 0.32e） transfer from 1-12 to the doped fullerenes. These calculation results should broaden our understanding of the mechanisms of hydrogen storage using borondoped fullerenes.     

An experimental study of the premixed benzene/oxygen/argon flame with tunable synchrotron photoionization

A comprehensive experimental study of the premixed benzene/oxygen/argon flame at 4.0 kPa with a fuel equivalence ratio (?) of 1.78 has been performed with the tunable synchrotron photoionization and molecular-beam sampling mass spectrometry. Isomers of most observed species in the flame have been unambiguously identified by measurements of the photoionization efficiency spectra. Mole fraction profiles of species up to C₁₆H₁₀ have been measured at the selective photon energies near ionization thresholds, and the flame temperature profile is obtained using Pt/Pt-13%Rh thermocouple. Compared with previous studies on benzene flames by Bittner and Howard, and by Defoeux et al., a number of new species are observed in the present work. These new combustion intermediates should be included in the kinetic models of the growth of polycyclic aromatic hydrocarbons (PAHs) and benzene oxidation. Free radicals detected in the flame include CH₃, C₂H, C₂H₃, C₂H₅, C₃H, C₃H₃, C₃H₅, C₄H, C₄H₃, C₄H₅, C₄H₇, C₅H₃, C₅H₅, C₅H₇, C₆H₅, C₆H₅O, C₇H₇, and C₉H₇. More significantly, isomers of some PAHs have been identified, which should be of importance in understanding the mechanism of soot formation.     

Bay capping via acetylene addition to polycyclic aromatic hydrocarbons: Mechanism and kinetics

The bay-capping mechanism on PAH armchair edges and the kinetics of acetylene addition to 6–6–5 and 5–6–5 bays have been explored by ab initio/RRKM-ME calculations. The bays on the edges were modeled by C₂₁H₁₁ and C₂₀H₉ radicals produced by H abstractions from 7H-benzo[c]cyclopenta[e]pyrene and dicyclopenta[cf]pyrene. The C₂₀H₉ + C₂H₂ reaction is shown to have a low entrance barrier and to rapidly form the capped product, indaceno[2,1,8,7-cdefg]pyrene, along with ethynyl substituted dicyclopenta[cf]pyrene at temperatures above 1400 K. The reactivity of C₂₁H₁₁ is shown to be governed by the location of the unpaired electron; the π radical R1 formed by H abstraction from the CH₂ group in 7H-benzo[c]cyclopenta[e]pyrene reacts with C₂H₂ very slowly owing to a high entrance barrier, with the bay-capping rate constant approaching 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ only at temperatures above 2000 K. This result reaffirms that the growth of π aryl radicals via acetylene addition is inefficient and reflects the generally low reactivity of such radicals where the spin density is highly delocalized over the entire polyaromatic system. Alternatively, the σ C₂₁H₁₁ radical R2 produced by H abstraction from the five-membered ring at the bay rapidly reacts with C₂H₂ forming the bay-capped product, with the rate constant on the order of 10⁻¹² cm³ molecule⁻¹ s⁻¹ at T ≥ 1500 K. Rate constants for the capping reactions at the 6–6–5 and 5–6–5 bays are compared with those at the 6–0–6, 6–6–6, and 6–5–6 bays. The site-specific bay-capping rate constants have been utilized in kMC simulations of the PAH growth and the results showed measurable differences when the 6–6–5 and 5–6–5 bay-capping reactions are taken into account, including an increase of the growth rate and the formation of closed-shell PAH and a rise of the number of embedded five-membered rings accompanied with a slight decrease of their overall amount.     

Leed and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 AND C) chemisorbed on the rhodium (111) and (100) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₄, C₂H₂ and C has been studied on the clean Rh(111) and (100) surfaces. LEED, AES and thermal desorption were used to determine the surface structures, disordering and desorption temperatures, displacement and decomposition characteristics for each species. All of the molecules studied readily chemisorbed on both surfaces. A large variety of ordered structures was observed, especially on the (111) surface. The disordering temperatures of most ordered surface structures on the (111) surface were below 100°C. It was necessary to adsorb the gases at 25° C or below in order to obtain well-ordered surface structures. Chemisorbed oxygen was readily removed from the surface by H₂ or CO gas at crystal temperatures above 50°C. CO₂ appears to dissociate to CO upon adsorption on both rhodium surfaces as indicated by the identical ordering and desorption characteristics of these two molecules. C₂H₄ and C₂H₂ also had very similar ordering and desorption characteristics and it is likely that the adsorbed species formed by both molecules is the same. Decomposition of ethylene produced a sequence of ordered carbon surface structures on the (111) face as a result of a bulk-surface carbon equilibrium. The chemisorption properties of rhodium appear to be generally similar to those of iridium, nickel and palladium.     

一维爆轰波不稳定性的数值模拟

 对当量比为1的乙烷与空气的混合气体的一维爆轰不稳定问题进行数值模拟，得到了不同大小的网格对爆轰不稳定问题数值模拟结果的影响。网格大小Δx由从ZND模型分析得到的导引长度L_in确定，网格大小从0.2L_in变到0.002 5L_in。随着网格变细，没有得到振幅趋于一致的解，每一种网格尺寸得到的解的振幅都互不相同。当网格大小为Δx=0.01L_in、0.005L_in时，得到有规则的爆轰激波阵面压力的振荡，振荡的模式是峰值一大一小的振荡。网格更细时，爆轰波的振荡在计算范围内由一些有规则的振荡和一些较不规则的振荡组成。但爆轰激波阵面压力振荡的波长最后趋于一致，为91~93 mm，与实验得到的胞格长度88 mm很接近。     

高聚物P(EO)n-CuBr2薄膜在流体静高压下离子电导率和介电常数的提高（Ⅱ）——添加增塑剂方法的应用

 选用分子量为500万的聚氧化乙烯和无水溴化铜,通过混溶蒸发法制备出一系列高聚物P(EO)_n-CuBr₂（n=4,8,12,16,24）薄膜,并在0.1～2443 MPa范围不同的静水压下详细测量了它们的相对介电常数。分别探讨了增塑剂（C₄H₆O₃）含量对室温常压下离子电导率和介电常数的影响,及其对高压下离子电导率和介电常数的影响。实验结果表明：P(EO)₁₆-CuBr₂薄膜在添加介电常数较高和本体粘度较低的增塑剂C₄H₆O₃后,当其相对浓度n_PC/n_total=20%时,不仅使该薄膜的室温常压离子电导率明显提高6.8倍,而且使其在高压力下的离子电导率提高1（0.1～100 MPa）至2（350～800 MPa）个数量级,非常有利于在高压环境中应用。     

A combustion chemistry study of tetramethylethylene in a laminar premixed low-pressure hydrogen flame

The combustion chemistry of tetramethylethylene (TME) was studied in a premixed laminar low-pressure hydrogen flame by combined photoionization molecular-beam mass spectrometry (PI-MBMS) and photoelectron photoion coincidence (PEPICO) spectroscopy at the Swiss Light Source (SLS) of the Paul Scherrer Institute in Villigen, Switzerland. This hexene isomer with the chemical formula C₆H₁₂ has a special structure with only allylic CH bonds. Several combustion intermediate species were identified by their photoionization and threshold photoelectron spectra, respectively. The experimental mole fraction profiles were compared to modeling results from a recently published kinetic reaction mechanism that includes a TME sub-mechanism to describe the TME/H₂ flame structure. The first stable intermediate species formed early in the flame front during the combustion of TME are 2-methyl-2-butene (C₅H₁₀) at a mass-to-charge ratio (m/z) of 70, 2,3-dimethylbutane (C₆H₁₄) at m/z 86, and 3-methyl-1,2-butadiene (C₅H₈) at m/z 68. Isobutene (C₄H₈) is also a dominant intermediate in the combustion of TME and results from consumption of 2-methyl-2-butene. In addition to these hydrocarbons, some oxygenated species are formed due to low-temperature combustion chemistry in the consumption pathway of TME under the investigated flame conditions.     

Temperature distribution above a heated surface in a CVD reactor with hydrocarbon-containing gaseous mixtures

Pyrolysis of C₂H₂ and CH₄ gases near a heated surface was investigated using coherent anti-Stokes Raman spectroscopy (CARS). Gas temperature and hydrocarbon density spatial profiles above the surface of deposition were measured. Although the measured hydrocarbon density distribution above the surface showed a gradual decrease upon approaching the surface, the observed temperature distribution revealed the presence of a temperature maximum at distances of 300-600 7m from the surface. The appearance of this maximum is explained by the release of condensation energy in the region where intensive homogeneous nucleation of carbon clusters takes place.     

A study of the relative brönsted acidities of surface complexes on Ag(110)

The relative acidities of a number of Brönsted acids have been established on the Ag(110) surface under UHV conditions. For acids which react completely with adsorbed oxygen atoms on this surface to form H₂O, relative acidities were determined by means of acid-base titration reactions. Adsorbed species such as carboxylates, alkoxides, etc., were formed by reaction of the parent acids with O(a) and then displaced from the surface by titration with stronger acids. Relative acidities of the acids which did not react to completion with O(a) were established on the basis of their relative extents of reaction. The relative acidity scale on Ag(110), according to the reaction BH(g) + B'(a) B'H(g) + B(a) was found to be HCOOH ≈ CH₃COOH>C₂H₅OH> C₂H₂>CH₃OH>C₃H₆, H₂O>C₂H₄, C₂H₆, H₂. This order is in excellent agreement with the acidity scale for these species in the gas phase according to BH(g)B^?(g) + H⁺ (g); it cannot be explained by aqueous dissociation constants or homolytic bond dissociation energies. This result is in accord with the appreciable anionic character of the adsorbed species, since the electron affinity of the base, B, is a strong thermodynamic factor in the acidity in the gas phase. Both XPS and UPS results for adsorbed species on the Ag(110) surface are consistent with this interpretation.