硅甲烷CARS光谱的研究

测量和分析了硅甲烷(SiH_4)v_1带和v_3带的CARS光谱,并采用偏振CARS技术,解除了v_1带的影响,获得了完全的v_3带的CARS谱.偏振测量和理论模拟计算给出了v_1带和v_3带Q支峰值间的频率位移及两者喇曼跃迁截面平方的比值.     

激光诱导荧光方法对SiH4／N2混合气体放电等离子体的研究

用激光诱导荧光方法对SiH_4/N_2混合气体射频放电等离子体进行了研究,实验上首次检测到SiH_4分子射频放电离解过程的中间产物Si_2.     

过渡区p型氢化硅氧薄膜结构和光电特性的研究

采用射频等离子体增强化学气相沉积技术,利用二氧化碳(CO_2)、氢气(H_2)、硅烷(SiH_4)和乙硼烷(B_2H_6)作为气源,制备出一系列p型氢化硅氧薄膜.利用拉曼光谱、傅里叶变换红外光谱和暗电导测试,研究了不同二氧化碳流量对薄膜材料结构和光电特性的影响,获得了从纳米晶相向非晶相转变的过渡区P层.研究表明:随着二氧化碳流量从0增加到1.2 cm~3·min~(-1),拉曼光谱的峰值位置从520 cm~(-1)逐渐移至480 cm~(-1).材料红外光谱表明,随着二氧化碳流量的增加,薄膜中的氧含量逐渐增加,氢键配置逐渐由硅单氢键转换为硅双氢键.P层SiO:H薄膜电导率从3S/cm降为8.3×10~(-6)S/cm.所有p型SiO:H薄膜的光学带隙(Eopt)都在1.82—2.13 eV之间变化.在不加背反射电极的条件下,利用从纳米晶相向非晶相转变的过渡区P层作为电池的窗口层,且在P层和I层之间插入一定厚度的缓冲层,制备出效率为8.27%的非晶硅薄膜电池.     

分时窄带CARS光谱技术在测量烯烃浓度方面的应用

基于相干反斯托克斯拉曼散射(CARS)光谱技术机理,针对甲醇制烯烃(MTO)产物中多种组分烃类的探测需求,搭建了一套扫描式窄带CARS光谱实验装置。采用该装置对甲烷,乙烷,乙烯,丙烯分别进行CARS光谱扫描,获得了各分子的特征拉曼谱;并在相同实验条件下进行比对试验,得到不同分子特征峰处的CARS信号强度与目标气体浓度及其他背景气体之间的关系。通过建立简化模型对不同分子的CARS信号特征峰强度信息进行解析,提出了一种分时窄带CARS光谱探测多种拉曼活性气体浓度的方法,用于快速在线分析催化化工等领域中各类流体的组分。利用这种方法探测了甲烷,乙烯,丙烯的浓度,将实验误差控制在9%以内。     

SiH_4-GeH_4混合体系的红外光分解

研究了在944.19cm~(-4)的红外激光场中SiH_4—GeH_4混合体系的光分解。生成产物是H_2,Si_2H_6,SiH_3GeH_8 少量Si_3H_8和固体粉末聚合物。没有检测到Ge_2H_6。测量了反应物的分解速率和产物的每脉冲产额。阐述了混合体系的反应机理。     

在CWCO_2激光作用下SiH_4的分解

研究了低浓度SiH_4在CW CO_2激光作用下的分解,对分解机理进行了分析.理论结果与实验较好地符合.     

红外光谱法研究射频功率对微晶硅薄膜微结构的影响

采用射频等离子体增强化学气相沉积(RF-PECVD)技术,在硅衬底上以不同的射频功率生长微晶硅(μc-Si:H)薄膜,利用傅里叶变换红外透射光谱技术对薄膜进行测试.通过对红外透射光谱的高斯拟合分析,结果表明薄膜中的氢含量和硅氢键合模式跟射频功率密切相关;当射频率从30W增加到110W时,薄膜中的氢含量先减少后慢慢增加,而结构因子逐渐增加后再减小,并且硅氢键合模式由以SiH为主转变为以SiH2为主.并讨论了这些参量随射频功率变化的机理.     

光谱分析、光谱测量

O433.1 2004010074 射频辉光放电硅烷等离子体的光发射谱研究=Optical emission spectroscopy invesugation on the RF-generated SiH_4plasma[刊,中]/杨恢东(南开大学光电所,天津(300071)),吴春亚…∥光电子·激光.—2003,14(4)—375-379 通过对RF-PECVD技术沉积氢化非晶/微晶硅(a-Si:H/μc-Si:H)薄膜沉积过程中硅烷(SiH_4)等离子体的光发射谱(OES)原位测量,系统地研究了不同的等离子体工艺     

显微激光拉曼光谱原位观测甲烷水合物生成与分解的微观过程

采用显微激光拉曼光谱技术对高压透明毛细管中甲烷水合物的生成与分解的微观过程进行了原位观测,初步探讨了甲烷水合物笼型结构的变化规律.结果表明,甲烷水合物在生成过程中,甲烷分子的拉曼峰(2 917 cm-1)逐渐分裂为两个峰(2 905和2 915 cm-1),表明溶解态甲烷分子从单一的化学环境进入了两个有差异的化学环境中...     

多色宽带相干反斯托克斯拉曼散射过程的理论与实验研究

宽带相干反斯托克斯拉曼散射(coherent anti-Stokes Raman scattering,CARS)光谱技术能够同时获取完整的分子CARS光谱信息,以准确识别和定量分析混合物中的不同成分或未知成分.在宽带CARS光谱技术中,由于超连续谱激光有效光谱范围内各光谱成分的作用不同,分别会产生双色和三色CARS过程.这里我们在理论上分析了宽带激发条件下两种CARS过程的产生条件,以及不同CARS光谱信号强度与各激发光功率之间的关系.在此基础上,搭建了基于SC激光的宽带CARS光谱系统,分别实现了双色和三色CARS过程.通过对获得的苯甲腈样品的CARS光谱信号进行函数拟合分析,实验验证了上述两个过程中CARS信号的强度与各激发光强度之间的函数关系.理论和实验研究结果为进一步优化宽带时间分辨CARS光谱探测和显微系统,实现同时获取物质分子完整的CARS光谱信号提供了指导.     

基于CARS技术的超燃冲压发动机点火过程温度测量

相干anti-Stokes Raman散射（coherent anti-Stokes Raman scattering,CARS）技术作为一种非接触测量手段,已广泛应用于多种发动机模型燃烧室温度测量及地面试验.然而,目前的工作主要集中在稳态燃烧场温度的测量,缺乏用高分辨率的单脉冲来测量瞬变的燃烧火焰温度及组分浓度的研究.基于CARS理论,结合多参数拟合算法,开发了基于MATLAB的CARS光谱计算和拟合程序CARSCF;利用McKenna平面火焰炉在不同工况下进行了温度测量,并与DLR测量结果进行对比,结果显示开发的CARSCF具有较高的测量重复性和准确性;最后将CARS技术应用于测量超燃冲压发动机点火过程中的温度测量,获取了点火过程中的温度.结果显示,在来流Mach数为3的条件下,H₂/air点火过程中温度呈现急剧上升然后缓慢下降,而CARS信号则呈现急剧上升然后急剧下降随后又缓慢上升的趋势,并且在点火过程中最高温度为1 511 K.      

Herman-Wallis factor to improve thermometric accuracy of vibrational coherent anti-Stokes Raman spectra of H2

The Herman-Wallis factor is a molecular parameter that measures the influence of centrifugal force on the intensity of spectral lines. Understandably, the effect is significant for very light molecules that necessarily have large couplings between vibrational and rotational degrees of freedom. Although known, the conceptual basis of the Herman-Wallis factor are nevertheless not clearly established in the literature. Over the years, different approaches have been proposed to explain the corrections to spectral line-strengths and, recently, an experimental study has demonstrated that Q-branch Raman transitions of H₂ are highly sensitive to the theoretical model employed to determine the Herman-Wallis factor. In this paper, this fact is used to analyze the consequences on thermometry based on coherent anti-Stokes Raman scattering (CARS) designed to probe H₂ molecules in combustion studies. It is found that the different Herman-Wallis factors lead to relative thermometric disagreements from several tens up to hundreds of degrees. This analysis could explain why H₂ CARS thermometry has been considered less reliable than thermometric predictions based on CARS of more common molecules such as N₂, O₂ and others. In particular, it is remarked that unreliable expressions of Herman-Wallis factors have been used so far to interpret Q-branch H₂ CARS experiments.     

Narrow-band BoxCARS applied to CO2 laser discharges

Summary CARS (Coherent Anti-Stokes Raman Scattering) has developed into a powerful tool for studying molecular systems. One of its possibilities is to derive vibrational and rotational temperatures as well as concentrations of molecules from measurements of the energy level population differences. A very good spatial resolution of CARS technique is one of its important advantages. This feature has been utilized for making spatially resolved measurements of the vibrational and rotational temperatures of N₂ in a d.c.-excited transverse-flow CO₂ laser discharge. Apart from that also spectra of CO₂, CO and O₂ in the discharge have been taken, which allowed us to evaluate the spatial distributions of those components in the discharge. Additionally first investigations of a microwave-excited CO₂ laser module have been performed for comparison. Paper presented at the ?XI European CARS Workshop?, Florence, Italy, 23–25 March, 1992.     

High‐resolution narrowband CARS spectroscopy in the spectral fingerprint region

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy is an important technique for spectroscopy and chemically selective microscopy, but wider implementation requires dedicated versatile tunable sources. We describe an optical parametric oscillator (OPO) based on a magnesium oxide‐doped periodically poled lithium niobate crystal, with a novel variable output coupler, used as a tunable coherent light source. The OPO's signal wavelength ranges from 880 to 1040 nm and its idler wavelength from 1090 to 1350 nm. We use this OPO to demonstrate high‐resolution narrowband CARS spectroscopy on bulk polystyrene from 900 to 3600 cm⁻¹, covering a large part of the molecular fingerprint region. Recording vibrational spectra using narrowband CARS spectroscopy has several advantages over spontaneous Raman spectroscopy, which we discuss. We isolate the resonant part of the CARS spectrum and compare it to the spontaneous Raman spectrum of polystyrene using the maximum entropy method of phase retrieval; we find them to be in extremely good agreement. Copyright © 2009 John Wiley & Sons, Ltd.     

宽带相干反斯托克斯喇曼散射法诊断固体燃剂燃烧场

 报道了采用单次脉冲非稳腔空间增强探测 相干反斯托克斯喇曼散射（USED CARS）技术诊断常压下固体燃剂瞬态燃烧场温度和氮气浓度。采用宽带USED CARS技术，在固体燃剂瞬态燃烧场获得了较高信噪比的单次激光脉冲氮气Q支CARS实验谱，用CARS理论计算软件拟合CARS实验谱，给出了固体燃剂瞬态燃烧场温度和氮气浓度在不同高度的分布，固体燃剂燃烧场温度约2 250K、氮气相对浓度16%～20%。     

Polarization coherent anti‐stokes Raman scattering using noisy light

Several polarization studies on the noisy light version of coherent anti‐Stokes Raman scattering (CARS) exist in the literature. However, the full advantages of polarization CARS (P‐CARS), which are so useful in conventional and short‐pulse CARS methods, have not yet been exploited in the noisy light version. This work presents experimental realization of fully functional P‐CARS using noisy light. Several examples demonstrate the advantages brought by P‐CARS. This includes the ‘classic’ example of benzene in carbon tetrachloride. Also presented are the carbon–carbon double bond stretches in acrylonitrile and 1‐hexene. An interesting, and not fully understood, detection polarization angle dependence is discussed. Applications to an m‐xylene/benzene mixture and an alkaline solution of the amino acid phenylalanine are presented. Copyright © 2006 John Wiley & Sons, Ltd.     

甲烷-空气预混V形火焰的CARS实验研究

本文将相干反斯托克斯(CARS)理论光谱计算和实验光谱分析的方法应用于预混V形火焰燃烧的温度测量实验,利用N2的Q支CARS谱线,使用单脉冲宽带方法获得了预混V形火焰的CARS信号光谱强度特性,测量了V形火焰水平方向和竖直方向上的温度分布特征,从中得出了火焰锋面的厚度,分析了火焰锋面的皱褶与摆动对CARS信号的影响。同时测量了不同燃料系数下V形火焰燃烧产物的温度,得出了温度随燃料系数的变化趋势,为进一步研究预混 V形火焰的结构提供了依据。     

Adsorption of silane and methylsilane on gold surfaces

The adsorption of silane and methylsilane on the (1 1 0) and polycrystalline surfaces of gold is examined using vibrational electron energy loss spectroscopy (VEELS), angle-resolved ultraviolet photoelectron spectroscopy (ARUPS) and X-ray photoelectron spectroscopy (XPS). Adsorption of silane onto the Au(1 1 0) surface at low temperatures is dissociative and yields an SiH₂ and possibly also SiH₃ surface species. Further dissociation occurs at room temperature to yield adsorbed SiH, which is tilted on the surface, with complete dissociation to Si occurring by 110 °C. The similarity in the UP spectra for silane adsorbed on the polycrystalline sample suggests that the same surface species are present over that temperature range. Above 200 °C, spectral changes suggest rearrangement of the Si atoms, which, by 350 °C, have diffused into the bulk. Adsorption of methylsilane onto the (1 1 0) surface at low temperatures initially produces adsorbed CH₃SiH or CH₃SiH₂, with undissociated methylsilane physisorbing at higher exposures. By room temperature, desorption and decomposition leaves (or direct adsorption yields) only adsorbed CH₃Si. After further heating, the hydrogen-carbon bonds of the CH₃ group break to leave an adsorbed SiC species. On the polycrystalline surface, methylsilane adsorption is the same at low temperatures as on (1 1 0). In contrast to the latter, though, the UP spectra indicate that direct exposures at room temperature yield adsorbed Si or SiC initially, with CH₃Si again adsorbing at higher exposures. Upon further heating to 330 °C, little if any methyl-groups remain on the surface and the Si has started to diffuse into the bulk.     

CARS temperature measurement in a LOX/CH4 spray flame

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy has been used to investigate cryogenic liquid oxygen/gaseous methane (LOX/CH₄) flames on a medium‐size test facility at a pressure of 0.24 MPa and mass flow of 0.025 kg/s. Single‐shot, broadband CARS spectra with simultaneous detection of the Q‐branches of hydrogen and water molecules were recorded with good signal‐to‐noise ratio. Temperature was deduced from the H₂ and H₂O CARS profiles. The spatial temperature distribution in a comparatively harsh environment has been measured successfully. The measurements took place in the windowed combustion chamber of the DLR M3 test facility, aiming to provide data for validation of rocket combustor modeling. Copyright © 2010 John Wiley & Sons, Ltd.