Thermal vaporization-vacuum ultraviolet laser ionization time-of-flight mass spectrometry of single aerosol particles

Single aerosol particles of ethylene glycol and oleic acid are vaporized on a heater at temperatures between 500 and 700 K, and the resulting vapor plume is ionized by a 10.5-eV vacuum ultraviolet (VUV) laser. The mass spectra are compared to those obtained by CO2 laser vaporization followed by VUV laser ionization. The relative intensities of the parent and fragment ion peaks are remarkably similar for the two modes of vaporization. A Maxwell-Boltzmann distribution of speeds accurately describes the dependence of the signal as a function of the VUV laser pulse timing. The signal levels obtained with this design are sufficient to obtain good-quality mass spectra.     

Quantitative detection of aromatic compounds in single aerosol particle mass spectrometry

Most laser-based aerosol mass spectrometers rely on a single ultraviolet laser to both ablate and ionize the aerosol particle. This technique produces complex and fragmented mass spectra, especially for organic compounds. The approach presented here achieves a more robust and quantitative analysis using a CO2 laser to evaporate the aerosol particle and a vacuum ultraviolet laser to ionize the vapor plume. Vacuum ultraviolet laser ionization produces little fragmentation in the mass spectra, making the identification of an aerosol particle's constituents more straightforward. An analysis of simple, three-component mixtures of aniline, benzyl alcohol, and m-nitrotoluene shows that the technique also provides a quantitative analysis for all the components of the mixture. Furthermore, the detection of predominantly parent ion signal from anthracene particles demonstrates the utility of the technique in the analysis of lower vapor pressure, solid-phase aerosols. Finally, we discuss the potential and limitations of this technique in analyzing organic atmospheric aerosols.     

Enhancing the detection of sulfate particles for laser ablation aerosol mass spectrometry

A major limitation to the application of laser ablation aerosol mass spectrometry for the detection of particles less than 200 nm in diameter is a low ablation efficiency for sulfate particles. (Ablation efficiency is the probability that an ablated particle produces a detectable ion signal.) A method is described here to enhance the ablation efficiency of sulfate particles by coating them with a UV-absorbing compound. The method can be applied in-line with the aerosol mass spectrometer in a manner that does not significantly alter the aerosol size distribution. It is shown that a 12-nm coating of 1-naphthyl acetate increases the ablation efficiency of 136-nm ammonium sulfate particles by at least a factor of 20, while similar coatings on oleic acid and ammonium nitrate particles do not significantly alter the ablation efficiency. The results suggest that "undetected" particles, presumably sulfate, in ambient aerosol can be assessed.     

Analysis of Xanthate Derivatives by Vacuum Ultraviolet Laser-Time-of-Flight Mass Spectrometry

A series of liquid O,S-dialkyl dithiocarbonates (xanthate esters) have been synthesized, and time-of-flight (TOF) mass spectra were recorded for their vapors using both ultraviolet (UV) and vacuum ultraviolet (VUV) laser excitation. These compounds are chemical derivatives of low vapor pressure xanthate salts which have found important commercial application as collectors in mineral sulfide flotation circuits. Our experiments demonstrate that esters ionized by short-wavelength VUV light can be detected by parent mass with high efficiency and minimal fragmentation. In contrast, the mass spectra of the same compounds obtained by UV light excitation exhibit a large number of low molecular mass peaks. A preliminary quantitative analysis of the composition of a gas-phase mixture of xanthate esters has also been achieved, which indicates possible subfemtomole detection limits.     

Single photon ionization (SPI) via incoherent VUV-excimer light: robust and compact time-of-flight mass spectrometer for on-line,real-time process gas analysis

Fast on-line detection of organic compounds from complex mixtures, such as industrial process gas streams, require selective and sensitive analytical methods. One feasible approach for this purpose is the use of mass spectrometry (MS) with a selective and soft (fragment-free) ionization technique, such as chemical ionization (CI) or photo ionization (PI). Single photon ionization (SPI) with vacuum ultraviolet (VUV) light is a particularly sof tionization technique, well-suited for detection of both aromatic and aliphatic species. Problematic, however, is the generation of the VUV light. In general, the vacuum ultraviolet (VUV) light sources for SPI-MS are based either on lasers (e.g., 118-nm radiation generated by frequency-tripling of the third harmonic of a Nd:YAG laser) or on conventional VUV lamps, such as deuterium lamps. Althoughthe laser-based techniques are very sophisticated and expensive, the conventional lamps have serious drawbacks regarding their optical parameters, such as low-output power, low spectral power density, and broad emission bands. In this work, a novel excimer VUV light source, in which an electron beam is used to form rare gas excimer species, is used. The excimer VUV light sourceproduces brilliant and intense VUV light. The novel VUV light source was coupled to a compact and mobile time-of-flight mass spectrometer (TOFMS). A special interface design, including optical (VUV optics) as well as electronic measures (e.g., pulsed ion extraction) was realized. The use of the excimer VUV lamp for SPI will allow the realization of very compact, rugged, and sensitive SPI-TOFMS devices, which preferably will be adapted for process analytical application or monitoring issues (e.g., chemical warfare detection). The excimer VUV-lamp technology delivers VUV light with a good beam quality and high-output power at low costs. Furthermore, it allows changing the emitted wavelength as well as the bandwidth of the excimer VUV lamp in t he 100-200-nm region by changing the gas filling. Consequently, SPI-TOFMS with an excimer light source is a fast detection technique that can be used for online monitoring, for example, in environmental studies or industrial manufacturing processes. In this paper, technology and characteristics of the new excimer light source, as well as the combination with the TOFMS, are presented. Furthermore, a first characterization of the SPI-TOFMS instrument, regarding analytical parameters such as detection limits and selectivity, is given. This includes a discussion of potential improvements that probably will be achievable within a future prototype genertation. Finally, first applications of the system for on-line measurement of organic trace species in a complex gas mixture (here, motorcycle exhaust gas) are presented.     

金属涂层SPR的单端面LPFG折射率传感器

提出了一种新型的单端面反射的镀有金属膜的长周期光纤光栅传感器.这种基于表面等离子体谐振的具有三层结构的传感器分为两个部分,光栅部分用连续CO2激光脉冲制作,金属膜是由真空镀膜制成.在光栅上镀上各种不同厚度的薄金属膜来激发表面等离子体波,用这种光纤光栅传感器来测量液体的折射率,并研究它的反射谐振谱的特性.在标准气压下,镀有80 nm银膜的光栅从水(ns=1.33)到酒精(ns=1.36)中光栅谐振波长改变了1.14nm,其敏感度达到折射率变化～5×10-4谐振波长改变20 pm.研究发现不同厚度的不同金属膜显示了不同的敏感度.通过比较光栅在空气,水,酒精,甘油,以及在它们的混合物溶液中的谐振波长,得到这种反射式的长周期光纤光栅传感器的敏感特性.为制作一种高性能的用来测量折射率的光纤光栅传感器提供了一个有益的参考.     

Surface mass spectrometry of biotinylated self-assembled monolayers

Biotin and biotinylated self-assembled monolayers (SAMs) on gold have been investigated using time-of-flight secondary ion mass spectrometry, direct laser desorption, laser desorption with 193 nm photoionization of ion- and laser-desorbed species, and laser desorption with vacuum ultraviolet (VUV, 118 nm) photoionization. Our results indicate that direct laser desorption and laser desorption combined with 193 nm multiphoton ionization can detect a chromophoric molecule like biotin that is covalently bound to a SAM. However, secondary ion mass spectra were dominated by fragmentation, and ion desorption/193 nm photoionization detected no species related to biotin. The dominant features of the laser desorption/VUV mass spectra were neat and Au-complexed dimers of intact and fragmented biotinylated SAM molecules. Multiphoton and single-photon ionization of laser-desorbed neutrals from biotinylated SAMs both led to the production of ions useful for chemical analysis of the monolayer. Multiphoton ionization with ultraviolet radiation was experimentally less challenging but required a chromophore for ionization and resulted in significant fragmentation of the adsorbate. Single-photon ionization with VUV radiation was experimentally more challenging but did not require a chromophore and led to less fragmentation. X-ray photoelectron spectra indicated that the biotinylated SAM formed a disordered, 40-60 ? thick monolayer on Au. Additionally, projection photolithography with a Schwarzschild microscope was used to pattern the biotinylated SAM surface and laser desorption/photoionization was used to detect biotinylated adsorbates from the ～10 μm sized pattern.     

Development of optical coatings for 157-nm lithography. I. Coating materials

In a basic study to identify low-loss optics for applications in F2 lithography, five potential coating materials (AlF3, Na3AlF6, MgF2, LaF8, and GdF3) and three deposition methods (thermal evaporation by a resistance heater and by electron beam and ion-beam sputtering) were investigated in the vacuum ultraviolet (VUV) region. Samples were supplied as single-layer coatings on CaF2 substrates by four Japanese coating suppliers. Refractive indices (n) and extinction coefficients (k) of these coatings at 157 nm were evaluated; the transmittance and the reflectance were measured by a VUV spectrometer and were compared. As a result, resistance heating thermal evaporation is seen to be the optimal method for achieving low-loss antireflection coatings. The relation among optical constants, microstructures, and stoichiometry is discussed.     

Vacuum ultraviolet postionization of aromatic groups covalently bound to peptides

Experiments demonstrate that peptides with ionization potentials (IPs) above 7.87 eV can be single-photon-ionized in the gas phase with a molecular fluorine laser following prior chemical derivatization with one of several aromatic tags acting as chromophores. 4-(Dimethylamino)benzoic acid, 1-naphthylacetic acid, and 9-anthracenecarboxylic acid (denoted Benz, Naph and Anth, respectively) behave as chromophores, allowing single-photon ionization for vacuum ultraviolet (VUV) laser light by lowering the IP of the tagged peptide. Anth-tagged peptides that are laser-desorbed from a substrate and subsequently postionized produce mass spectra dominated by the intact radical cation, although protonated ions and fragmented species are also observed. Electronic structure calculations on Anth-tagged peptides indicate that in addition to lowering the ionization potential, the presence of the aromatic tag increases charge localization on and delocalization across the ring structure, which presumably stabilizes the radical cation. Measurements on several tagged peptides confirm this calculation and show that the stabilizing effect of the tag increases with the size of the conjugated system in the order Benz < Naph < Anth. The tagged hexapeptide Anth-GAPKSC exhibits the parent ion, whereas the Benz- and Naph-tagged peptides do not. These results are supported by the experimental comparison of Anth-tagged vs untagged tryptophan, further suggesting that VUV postionization of tagged high-IP species is a promising method for expanding the capabilities of mass spectrometric analyses of molecular species.     

Using volatile solvents for ion formation in liquid molecular beam expansion mass spectrometry

Cocrystallization between analyte and matrix is required by matrix-assisted laser desorption/ionization and can represent a significant limitation of the technique. A molecular beam expansion, mass spectrometric method has been developed to explore the possibility of using pure solvents as matrix to avoid cocrystallization. Two kinds of solvent, liquid CS2 and liquid or supercritical CO2, have been studied with 266-nm UV laser irradiation. We successfully ionized a number of compounds, including caffeine, guanine, cholesterol, and mixed fullerenes. Under some conditions, the mass spectra reflect parent radical cations formed by photoionization. Under other conditions, protonated, sodiated (and with CS2 even sulfated) ions are seen reflecting a nonunimolecular ionization process. When UV-transparent CO2 is used as a solvent, only analyte molecules with a UV chromophore are detected. However, with UV-absorbing CS2, we demonstrate ionization of molecules lacking a UV chromophore. This work provides strong evidence that one can form solvent clusters containing analyte, that laser photoionization of the solvent precedes ionization of the analyte, and that solvent evaporation along with the indirect ionization leads to reduced parent ion fragmentation. The exploration of this now demonstrated concept with other solvents would appear fruitful for future work.     

Optical emission and absorption spectra of Zn–ZnO core-shell nanostructures

The core-shell Zn–ZnO nanostructures were fabricated from Zn-powder embedded in graphite (i.e. carbon matrix) in a thin-films form by an inexpensive vacuum arc technique followed by laser ablation. The grazing incidence X-ray diffraction pattern shows that intensity of Zn-peak decreases, and subtle ZnO-peak increasing with the increase in laser power. The high resolution transmission electron microscopic study clearly exhibits the formation of a core-shell nanostructure as fabricated by laser ablation. The emission characteristics of laser ablated (with different powers) samples show a strong exciton peak at 388 nm, and a few more weak peaks (due to weak defect states in the visible range). The optical absorption spectra were obtained from the excitonic peaks (from 344 nm to 317 nm) on decreasing laser power. These peaks occur due to the coupling of exciton absorption (from ZnO shell layer) and core metal interband absorption. The Zn–ZnO core-shell nanostructure is useful for nanophotonic applications.     

The Degradation of Optical Properties in a Sulfuric Acid Anodized Aluminum Coating System Exposed to Vacuum or Vacuum-Ultraviolet Radiation

A model for the optical property changes of a sulfuric acid anodized aluminum coating system was formulated to include the effects of water loss and cracking of the coating when the coating is exposed to either vacuum or vacuum-ultraviolet (VUV) radiation. The coating system was modeled as a single layer on an aluminum substrate and a discontinuous layer on an aluminum substrate in the case of cracks being present. Multiple scattering interactions were neglected because of thick film approximations. The effects of the water loss-induced densification and cracking of the coating were modeled independently to produce relationships which can be used to model the reflectance spectra. Densification of the coating with water loss theoretically reduces coating transmittance and total reflectance; cracks tend to reduce the effective reflecting area, resulting in a decrease in total reflectance. The overall models correlate well with experimental reflectance data which show significant changes at the short wavelength region.     

Laser power dependence of mass spectral signatures from individual bacterial spores in bioaerosol mass spectrometry

Bioaerosol mass spectrometry is being developed to analyze and identify biological aerosols in real time. Characteristic mass spectra from individual bacterial endospores of Bacillus subtilis var. niger were obtained in a bipolar aerosol time-of-flight mass spectrometer using a pulsed 266-nm laser for molecular desorption and ionization. Spectra from single spores collected at an average fluence of approximately 0.1 J/cm2 frequently contain prominent peaks attributed to arginine, dipicolinic acid, and glutamic acid, but the shot-to-shot (spore-to-spore) variability in the data may make it difficult to consistently distinguish closely related Bacillus species with an automated routine. Fortunately, a study of the laser power dependence of the mass spectra reveals clear trends and a finite number of "spectral types" that span most of the variability. This, we will show, indicates that a significant fraction of the variability must be attributed to fluence variations in the profile of the laser beam.     

Detection of negative ions from individual ultrafine particles

Aerosol mass spectrometers can be used to classify individual airborne particles on the basis of chemical composition. While positive ion mass spectra are normally used to characterize ultrafine particles (defined here as particles smaller than 200 nm in diameter), negative ion mass spectra can provide complementary information. To effectively utilize the negative ion mass spectra of ultrafine particles, it is important to understand biases in the formation and detection of negative ions. It is found that the intensity of negative ions is generally less than that of positive ions, due to the creation of electrons in the ablation process that must react to form negative ions. The ablation efficiency, defined as the probability that an ablated particle produces a detectable ion signal, exhibits both size and composition dependencies. The ablation efficiency for detection of negative ions follows the same trends as the ablation efficiency for the detection of positive ions: sodium chloride and ammonium nitrate have higher ablation efficiencies than oleic acid, and the ablation efficiency decreases with the particle diameter. The ablation efficiency of negative ions is less than or equal to the ablation efficiency of positive ions, and the relative difference increases as the particle diameter decreases. Pure ammonium sulfate particles exhibit an ablation efficiency too low to be measured in the present experiments. However, trace amounts of sulfate in mixed-composition particles can be readily detected in the negative ion mass spectra.     

An all solid-state narrow bandwidth optical parametric oscillator and its applications to the high resolution spectroscopy of free radicals

The paper describes the design, performance and illustrative spectroscopic applications of a high power, pulsed, injection seeded, narrow bandwidth and continuously tuneable optical parametric oscillator (OPO) based on two β-barium borate (BBO) nonlinear crystals. A ring cavity OPO was injection seeded with an external cavity diode laser in the spectral range 755–855 nm. The OPO generated high power transform limited nanosecond light pulses in this range and, simultaneously, at 606–667 nm. Spectral parameters of the OPO were investigated as a function of pump power for two different cavity lengths. A bandwidth of ～120 MHz (0.004 cm^-1) in the visible has been achieved with a 40-cm-long cavity. The potential of the OPO system is demonstrated by recording high resolution sub-Doppler spectra in the UV of PF and C₃ radicals in a pulsed supersonic jet expansion.     

Compact, broadly tunable, mid-IR source for the spectroscopic investigation of molecular reference lines in the 27- to 33-THz range

We report on the improvement of a tunable, high resolution, diode laser-based, difference-frequency spectrometer using an AgGaS(2) nonlinear crystal. We use a type-II cut crystal as a part of the improvement compared with a type-I cut, which was used in our preliminary setup. The two tunable laser-diodes are operating near lambda(3)=778 nm (pump) and lambda(2)=842 nm (signal) with a sub-100-kHz linewidth. The high resolution spectrometer is being developed as an alternative to CO(2) laser spectrometers in the 9- to Il-mum range. Using a dual-arm cavity to enhance the two radiation powers, and with 35 mW in front of the 778-nm arm and 100 mW in front of the 842 nm arm, about 70 nW of the tunable 10-mum radiation are generated. This power level is enough to investigate the linear absorption spectroscopy of SF(6). Doppler-limited spectra over 2 GHz, are recorded, showing the wide continuous tunability of the spectrometer.     

Synchrotron radiation based aerosol time-of-flight mass spectrometry for organic constituents

A synchrotron radiation based aerosol time-of-flight mass spectrometer using tunable vacuum-ultraviolet (VUV) light is described for real-time analysis of organic compounds in ultrafine and large aerosol particles. Particles are sampled from atmospheric pressure and are focused through an aerodynamic lens assembly into the mass spectrometer. As the particles enter the source region, they impinge on a cartridge heater and are vaporized. The particle vapor expands back into the source region and is softly ionized with tunable, quasicontinuous VUV light generated with synchrotron radiation. The radiation can be tuned to an energy close to the ionization energy of the sample molecules, thus minimizing the complications resulting from ion fragmentation. Photoionization efficiency scans (photon scans) can be readily collected, which permit measurement of the molecule's ionization energy and fragmentation onsets. Four high molecular weight, low vapor pressure organic compounds of importance in atmospheric aerosols are analyzed and their ionization energies measured with uncertainties of +/-60 meV. These are oleic acid (8.68 eV), linoleic acid (8.52 eV), linolenic acid (8.49 eV), and cholesterol (8.69 eV).     

A mobile mass spectrometer for comprehensive on-line analysis of trace and bulk components of complex gas mixtures: parallel application of the laser-based ionization methods VUV single-photon ionization, resonant multiphoton ionization, and laser-induced electron impact ionization

A newly developed compact and mobile time-of-flight mass spectrometer (TOFMS) for on-line analysis and monitoring of complex gas mixtures is presented. The instrument is designed for a (quasi-)simultaneous application of three ionization techniques that exhibit different ionization selectivities. The highly selective resonance-enhanced multiphoton ionization (REMPI) technique, using 266-nm UV laser pulses, is applied for selective and fragmentationless ionization of aromatic compounds at trace levels (parts-per-billion volume range). Mass spectra obtained using this technique show the chemical signature solely of monocyclic (benzene, phenols, etc.) and polycyclic (naphthalene, phenathrene, indol, etc.) aromatic species. Furthermore, the less selective but still fragmentationless single photon ionization (SPI) technique with 118-nm VUV laser pulses allows the ionization of compounds with an ionization potential below 10.5 eV. Mass spectra obtained using this technique show the profile of most organic compounds (aliphatic and aromatic species, like nonane, acetaldehyde, or pyrrol) and some inorganic compounds (e.g., ammonia, nitrogen monoxide). Finally, the nonselective ionization technique laser-induced electron-impact ionization (LEI) is applied. However, the sensitivity of the LEI technique is adjusted to be fairly low. Thus, the LEI signal in the mass spectra gives information on the inorganic bulk constituents of the sample (i.e., compounds such as water, oxygen, nitrogen, and carbon dioxide). Because the three ionization methods (REMPI, SPI, LEI) exhibit largely different ionization selectivities, the isolated application of each method alone solely provides specific mass spectrometric information about the sample composition. Special techniques have been developed and applied which allow the quasi-parallel use of all three ionization techniques for on-line monitoring purposes. Thus, a comprehensive characterization of complex samples is feasible jointly using the characteristic advantages of the three ionization techniques. Laboratory applications show results on rapid overview characterization of mineral oil-based fuels and coffee headspace. The first reported field applications include timely resolved on-line monitoring results on automobile exhausts and of waste incineration flue gas.     

激光辐照制备搪瓷涂层

激光辐照制备的搪瓷涂层表面粗糙,与金属基材结合牢固。一般由 Si,Al,Na,K,B,F,O等元素组成。在激光辐照过程中 K,Na 明显地挥发,从而在涂层中的含量明显减少;Co,Ni,主要分布在界面附近;Fe 元素也由基材进入涂层,呈梯度状分布,在界面过渡区含量很高,在涂层内含量很低。搪瓷涂层的形成与激光辐照参数,特别与激光功率间存在极为密切的关系;只有选用合理的参数,才能制得搪瓷涂层。     

Passively Q-switched 1.57-microm intracavity optical parametric oscillator

We demonstrate an eye-safe KTP-based optical parametric oscillator (OPO) driven intracavity by a diode-pumped 1064-nm Nd:YAG laser, passively Q-switched by a Cr4+:YAG crystal. The characteristics of this system, which operates at 1570 nm with a repetition rate as high as 50 Hz, are studied as a function of Cr4+:YAG optical density. Under optimum conditions the OPO generates 1.5-mJ, 3.4 +/- 0.1-ns pulses in a single transverse mode. For a Cr4+:YAG Q-switch element with an optical density of 0.5 the conversion efficiency of the intracavity energy is approximately 45% with the ratio of OPO to Nd:YAG peak-pulse intensity exceeding unity. These and other OPO characteristics compare favorably with a simple rate equation model of the OPO dynamics.