Normal and surface-enhanced Raman spectroscopy of nitroazobenzene submonolayers and multilayers on carbon and silver surfaces

Raman and ultraviolet-visible (UV-Vis) absorption spectra were obtained for nitroazobenzene (NAB) chemisorbed on smooth and rough silver, and they were compared to published spectra for NAB on sp(2) hybridized pyrolyzed photoresist film (PPF) surfaces. High signal-to-noise ratio Raman spectra were obtained for 4.5 nm thick NAB films on PPF and smooth Ag due to significant enhancement of the NAB scattering relative to that observed in solution. The UV-Vis spectra of chemisorbed NAB exhibited a significant shift toward longer wavelength, thus bringing the NAB absorption closer to the 514.5 nm laser wavelength. The red shift was larger for PPF than for smooth Ag, consistent with the approximately 5x stronger Raman signal obtained on PPF. Deposition of Ag onto quartz without a chromium adhesion layer produced a rough Ag surface that enhanced the Raman spectrum of chemisorbed NAB by a factor of approximately 1000, as expected for roughened Ag due to electromagnetic field enhancement. The strong Raman signal permitted observation of NAB at low coverage and revealed changes in the NAB spectrum as the film progressed from submonolayer to multilayer thicknesses. Finally, deposition of Ag onto PPF/NAB samples through a metal grid produced Ag squares on top of the NAB, which enhanced the Raman scattering of the NAB layer by a factor of approximately 100. Deposition of a final conducting film on the Ag squares should permit in situ observation of a wide range of molecules in operating molecular electronic junctions.     

Determination of the structure and orientation of organic molecules tethered to flat graphitic carbon by ATR-FT-IR and Raman spectroscopy

Mono- and multilayers of nitroazobenzene (NAB), azobenzene (AB), nitrobiphenyl (NBP), biphenyl (BP), and fluorene (FL) were covalently bonded to flat pyrolyzed photoresist films (PPF) by electrochemical reduction of their diazonium derivatives. The structure and orientation of the molecular layers were probed with ATR-FT-IR and Raman spectroscopy. A hemispherical germanium ATR element used with p-polarized light at 65 degrees incidence angle yielded high signal/noise IR spectra for monolayer coverage of molecules on PPF. The IR spectra are dominated by in-plane vibrational modes in the 1000-2000-cm(-1) spectral range but also exhibit weaker out-of-plane deformations in the 650-1000-cm(-1) region. The average tilt angle with respect to the surface normal for the various molecules varied from 31.0 +/- 4.5 degrees for NAB to 44.2 +/- 5.4 degrees for FL with AB, NBP, and BP exhibiting intermediate adsorption geometries. Raman intensity ratios of NAB and AB for p- and s-polarized incident light support the conclusion that the chemisorbed molecules are in a predominantly upright orientation. The results unequivocally indicate that molecules electroreduced from their diazonium precursors are not chemisorbed flat on the PPF surface, but rather at an angle, similar to the behavior of Au/thiol self-assembled monolayers, Langmuir-Blodgett films, and porphyrin molecules chemisorbed thermally on silicon and PPF from alkyne and alkene precursors.     

Raman spectroscopic determination of the structure and orientation of organic monolayers chemisorbed on carbon electrode surfaces

Azobenzene (AB) and 4-nitroazobenzene (NAB) were covalently bonded to carbon surfaces by electrochemical reduction of their diazonium derivatives. The N(1s) features of XPS spectra of modified surfaces had intensities expected for monolayer coverage. However, the Raman spectra were significantly more intense than expected, implying an increase in scattering cross section upon chemisorption. A likely explanation is resonance enhancement of the carbon/adsorbate chromophore analogous to that reported earlier for dinitrophenylhydrazine (DNPH) chemisorption. Vibrational assignments indicate that the C-C vibration between azobenzene and the carbon surface is in the 1240-1280 cm(-1) region, and this conclusion is supported by spectra obtained from [(13)C]graphite. Observation of depolarization ratios for 4-nitroazobenzene and DNPH on graphite edge plane indicate that NAB is able to rotate about the NAB/carbon C-C bond, while chemisorbed DNPH is not. The partial multiple bond character of the DNPH linkage to graphite is consistent with the observation that the DNPH π system remains parallel to the graphitic planes.     

Plasmon‐Driven Selective Reductions Revealed by Tip‐Enhanced Raman Spectroscopy

We successfully realized in‐situ monitoring plasmon‐driven selective reduction of 2,4‐dinitrobenzenethiol to 2,2′‐diamino‐dimercaptoazobenzene, revealed by high vacuum tip‐enhanced Raman spectroscopy (HV‐TERS). The HV‐TER spectra revealed that the 2‐nitro and the 4‐nitro of 2,4‐DNBT were selectively reduced to the 2‐amine and the –N = N– bond of 2,2′‐diamino‐dimercaptoazobenzene (2,2′DA‐DMAB). Raman‐active and IR‐active modes as well as Fermi resonance were simultaneously observed in HV‐TERS, which demonstrated the advantages of HV‐TERS over SERS, since only Raman‐active modes were observed in SERS. The intensities of molecular IR‐active modes can be manipulated by the distance between tip and substrate in the near field, due to different dependences of the plasmon gradient and plasmon intensity over the distance of nano gap. Our results in HV‐TERS are in‐situ “complete‐vibration modes” spectral analysis, which significantly extend the application of HV‐TERS in the field of ultrasensitive spectral analysis on the nano scale.     

电沉析条件对钛合金表面液相沉积类金刚石薄膜的影响

在钛合金表面沉积类金刚石膜能改进钛合金的生物相容性，拓展其在人体植入材料中的应用。探讨了用液相电解沉积法在钛合金表面制备类金刚石薄膜的新方法。讨论了不同沉积条件对膜的影响。在1650和1850V时可以得到坚固的棕色膜。沉积36h后，膜厚基本不变。沉积膜的Raman谱图表明，在1650和1850V沉积得到的是类金刚石薄膜，而在2000V时无法得到类金刚石薄膜。对膜的XPS分析表明，其主要成份是碳。XPS谱还表明在1650V时得到的膜可以将钛合金表面完全覆盖，而在1850V时则不能。以SEM分析表明在1650和1850V时得到的膜是由粒径约为400nm的小颗粒组成，而在2000V时得到只是疏松结构。并对类金刚石膜及钛合金的血液相容性进行了比较。     

A study of titanium thin films in transmission laser micro-joining of titanium-coated glass to polyimide

Electron beam evaporation (EB-PVD) and cathodic arc physical vapor deposition (CA-PVD) techniques were used for the preparation of titanium (Ti) thin films onto Pyrex borosilicate 7740 glass wafers and the deposited films were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques. The microstructure and surface morphology of the films were studied as a function of the film deposition techniques. Film properties such as, adherence, microstructure and roughness were interconnected to the laser joint strength between Ti coated glass wafers and polyimide films. Ti thin films on glass had a natural oxide layer on the surface as found from XPS. AFM study showed the formation of a uniform Ti coating consisted of packed crystallites with average size of 35 nm by EB-PVD. The root-mean-square surface roughness of the films was 1-2 nm. Whereas, films prepared by CA-PVD had crystallites with an average size of 120 nm and defects in the form of macro-particles which is a common attribute of this deposition system. The surface roughness of the film was 125 nm. The laser joint strength was found to be influenced by the Ti film quality on the glass substrate.     

Mono- and multilayer formation by diazonium reduction on carbon surfaces monitored with atomic force microscopy "scratching"

Contact mode atomic force microscopy (AFM) was used to intentionally scratch a monolayer deposited on a pyrolyzed photoresist film (PPF). The force was set to completely remove the monolayer but not to damage the underlying PPF surface. A line profile determined across the scratch with tapping mode AFM permitted determination of the monolayer thickness from the depth of the scratch. A statistical process was devised to avoid user bias in determining the monolayer thickness and was used to determine the thickness as a function of derivatization parameters. PPF surfaces modified by reduction of diazonium ions of stilbene, biphenyl, nitrobiphenyl, terphenyl, and nitroazobenzene (NAB) were scratched and their modification layer thicknesses determined. For single-scan derivatizations of 1 mM diazonium ions to -0.6 V versus Ag+/Ag, the biphenyl and stilbene monolayers exhibited thicknesses close to those expected for true monolayers. However, more extensive derivatization resulted in multilayers up to 6.3 nm thick for the case of NAB. Such multilayers imply that electrons are transmitted through the growing film during diazonium reduction, despite the fact that electron tunneling would not be expected to be operative over such long distances. The results are consistent with a conductance increase in the growing film, which yields a partially conductive layer that can support further diazonium ion reduction and additional layer growth.     

TiO2光催化剂的掺N过程研究

以饱和尿素溶液水解沉淀钛酸四丁酯制备水合TiO2，再于温度400-700℃的空气气氛下煅烧2h，制得淡黄色的掺氮TiO2光催化剂。对样品的物相、粒径、比表面积及吸光性能进行了测试和表征，表明样品的粒径10-30nm，比表面积30-70m^2／g，有明显的可见光吸收效应；通过TG-DTA、FT-IR及XPS等测试结果，分析了氮的掺杂过程，表明掺杂氮源主要以形成配合物分子形式均匀存在于煅烧前驱体中，并在TiO2从无定形转为锐态矿型的过程中以Ti-N化学键的形式进入TiO2晶格。     

Chemical bond analysis of amorphous carbon films

Hydrogen-free carbon films with the various sp³ bond fractions between 83% and 40% were prepared by mass-separated ion beam deposition (MSIBD). These sp³ bond fractions were obtained by electron energy loss spectroscopy (EELS). Chemical bond analysis of these carbon films was performed by x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and Raman spectroscopy, and the comparison of these methods was examined. XPS C1s spectra of carbon films show two contributions at the energies of 284.5 and 285.5 eV, which are originated from sp²-bonds and sp³ bonds, respectively. The sp³ bond fractions obtained by XPS are in good agreement with the values given by EELS. The fine structure of AES spectra at the kinetic energy region between 245 and 265 eV reflects the sp³ bond fraction. AES spectra are changed from the diamond-like feature to the graphite-like one with decreasing the sp³ bond fraction. Raman spectra show two broad peaks of G band and D band, the ratio of two peak intensities is independent on the sp³ bond fraction of films. The shift of G peak position has a correlation with the sp³ bond fraction in the sp³ bond rich region.     

Characteristics and mechanical properties of titanium-containing diamond like carbon films deposited by cathodic arc evaporation

Depositions of titanium-containing diamond-like carbon (Ti-DLC) films were conducted by mixing C+ and Ti+ plasma streams originated from cathodic arc plasma sources in argon (Ar). The deposition was processed at Ti target current ranging from 20 Amp to 70 Amp. Film characteristics were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS). Film microstructures were evaluated using field emission scanning electron microscopy (FEGSEM), an atomic force microscope (AFM), X-ray diffractometry (XRD) and high-resolution transmission electron microscopy (HRTEM). Mechanical properties were investigated by using a nanoindentation tester and ball on disc wear test. Results shows that surface roughness (Ra) of the films ranged between 2.4 and 7.2 nm and roughness increased relative to the increase in Ti target current. The FESEM studies showed that the surface micrographs of Ti-DLC films revealed a cauliflower-like microstructure and the cross-sectional micrograph revealed a snake-skin like structure. HRTEM studies showed that the Ti-DLC films consisted of nano scale TiC particles which were comparable with low angle XRD and XPS results. XPS analysis established that the Ti2p spectrum is present when the Ti target current reaches 30 Amp or higher. Ti concentration increased as the Ti target current was increased. An extremely thin TiO2 layer exists on the top of the Ti-DLC films which was comparable with the AES results. The film thickness which could be deposited for Ti-DLC is much higher than that of conventional DLC films. Nanoindentation tests show that the nanohardness of the films ranging 15-22 GPa, with Er values ranging from 145 to 175 GPa. The wear test demonstrates the friction coefficient of the 420SS substrate, DLC and Ti-DLC films were about 0.8, 0.3 and 0.2, respectively. Obviously, the friction coefficients of the Ti-DLC films were lower than that of the DLC films.     

Orientation of ethyl mercaptan on Cu(111) surface

X-Ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) studies have been performed on ethyl mercaptan adsorbed on a clean Cu(111) surface at 85 K. At submonolayer coverage (0.36 ML), two different states of sulfur (thiolate) are identified with the aid of XPS investigations. Polarization dependence of S K-edge NEXAFS of the submonolayer phase indicates that the S---C bond for the two thiolate phases are tilted 33±7° and 30±7° from the surface.     

Ti/Al_2O_3界面的光电子能谱研究

用X射线光电子谱（XPS）和俄歇电子能谱（AES）研究了Ti／Al_2O_3界面形成的过程。研究表明，活性金属Ti在室温下能与衬底Al2O3（1102）形成约20nm强结合的界面区。从Al，O，Ti的光电子谱形状变化以及它们随着Ti覆盖度的增加而出现结合能位移表明，在界面处形成的反应层中，最初几个单层的Ti很容易被Al2O3表面的活性氧所氧化，从而使Ti／Al2O3界面逐步由具有更强相互作用的TiOx／Al2O3界面所代替，并形成由多相混合体［Ti-O相，（Ti，Al）2O3相以及金属Al相］所组成的界面区。就是说，Ti通过Al—O键的O2-离子转移其电子给Al3 并使它还原成金属Al，从而形成Ti－O键所致。本文用AES强度剖面分析观察到了这种被还原的Al。     

Surface-enhanced Raman spectroscopy of soft-landed polyatomic ions and molecules

Surface-enhanced Raman spectroscopy (SERS) was used to detect and characterize polyatomic cations and molecules that were electrosprayed into the gas phase and soft-landed in vacuum on plasma-treated silver substrates. Organic dyes such as crystal violet and Rhodamine B, the nucleobase cytosine, and nucleosides cytidine and 2'-deoxycytidine were immobilized by soft landing on plasma-treated metal surfaces at kinetic energies ranging from near thermal to 200 eV. While enhancing Raman scattering 10(5)-10(6)-fold, the metal surface effectively quenches the fluorescence that does not interfere with the Raman spectra. SERS spectra from submonolayer amounts of soft-landed compounds were sufficiently intense and reproducible to allow identification of Raman active vibrational modes for structure assignment. Soft-landed species appear to be microsolvated on the surface and bound via ion pairing or pi-complexation to the Ag atoms and ions in the surface oxide layer. Comparison of spectra from soft-landed and solution samples indicates that the molecules survive soft landing without significant chemical damage even when they strike the surface at hyperthermal collision energies.     

添加元素对TiMeXN多元膜XPS谱的影响

采用XPS方法研究了TiMeXN多元膜内各元素的化学状态,结果表明,添加元素改变了TiN中Ti元素特征峰的位置和形状.首先,使Ti、N峰强度增大,O峰强度减弱;其次,使Ti2p1/2峰、Ti2p3/2峰和N 1 s的双峰现象基本消失,氮化物薄膜中Ti的化学状态基本趋于一致;再次,随着微量元素总含量的增高,Ti2p峰的多重分裂值减小,直至使Ti2p1/2峰和Ti2p3/2峰部分重迭.在多元膜中,微量添加元素本身以"正离子"或"负离子"的形式存在,形成微量第二相.     

Hardness and nitrogen bonding structure of AlxTi1-xN/CrN multilayer hard coating

AlxTi1-xN/CrN multilayer coatings were fabricated by magnetron sputtering and those hardness variations were studied by observing the crack propagation and measuring the chemical bonding state of nitrides by Ti addition. While AlN/CrN multilayer shown stair-like crack propagation, AlxTi1-xN/CrN multilayer illustrated straight crack propagation. Most interestingly, Ti addition induced more broken nitrogen bonds in the nitride multilayers, leading to the reduction of hardness. However, the hardness of Al0.25Ti0.75N/CrN multilayer, having high Ti contents, increased by the formation of many Ti-N bond again instead of Al-N bond. From these results, we found that linear crack propagation behavior was dominated by broken nitrogen bonds in the AlxTi1-xN/CrN multilayer coatings.     

磁过滤真空弧源沉积C/C多层复合膜的结构和力学性能研究

采用磁过滤直流阴极真空弧源沉积技术在不锈钢基体表面制备了C/C多层复合膜,通过X射线光电子能谱、Raman光谱对薄膜的结构进行表征;C/C多层膜大气下的摩擦损性能在销盘式摩擦磨损试验机上进行;用洛氏压痕法研究了薄膜与基体的结合强度.结果表明：C/C多层复合膜为类金刚石结构.它与SiC球大气下的摩擦系数为0.10左右,其摩损性能由于多层膜的引入而显著提高.Ti过渡层的引入显著提高了膜基结合力.     

Remote plasma processing of sapphire substrates for deposition of TiN and TiO2

The paper uses remote plasma assisted deposition, oxidation and nitridation processes for depositing thin films of metallic TiN on crystalline sapphire (0001) substrates. These films on sapphire substrates are being studied as window materials for high power radio frequency (RF) power tubes. A sequence of four process steps has been performed in a reactor chamber that isolates the deposition and surface-processing chamber from the plasma generation region. The chamber is part of an ultra-high-vacuum (UHV) compatible multi-chamber cluster in which the sequence of four process steps can be interrupted after each step, and surface chemistry changes can be identified by in-line Auger electron spectroscopy (AES). The four process steps, performed after an ex-situ chemical clean and blow-dry in nitrogen gas, are (i) a remote plasma-assisted oxidation (RPAO) in which surface contaminants including adventitious carbon are removed; (ii) a remote plasma-assisted nitridation (RPAN) process which forms a superficial layer of generic AION used to increase surface adhesion of the TiN films; (iii) a remote plasma-enhanced chemical-vapor deposition (RPECVD) process for deposition of 2 to 5 nm thick TiN films, and finally (iv) a second RPAN step that increases the ratio of Ti-N bonding in the TiN films with respect to adventitious O-atom incorporation from the Ti precursor, Ti tetra-butoxide.     

常压化学气相沉积方法制备非晶硅薄膜及其光致发光性能研究

使用改进的常压化学气相沉积(APCVD)系统制备了非晶硅薄膜,测量了样品的光致发光特性,使用Raman光谱和X射线光电子能谱(XPS)谱测量了薄膜的微结构特征.样品在523 nm出现发光峰,Raman光谱和XPS谱表明制备的薄膜结构中存在富氧相和富硅相的分相现象,分析认为相界面的存在是产生发光的原因.Raman光谱分峰结果表明薄膜中存在纳米晶粒.     

Investigation of Ti layer thickness dependent structural, magnetic, and photoemission study of nanometer range Ti/Ni multilayer structures

Structural, magnetic, and electronic properties of Ti/Ni multilayer (ML) samples as a function of Ti layer thickness are studied and reported in this paper. For this purpose [Ti (t nm)/Ni (5 nm)] x 10 ML samples, where t = 3, 5, and 7 nm have been deposited by using electron beam evaporation technique under UHV conditions at room temperature. Structure of ML samples were determined by using XRD (X-ray diffraction) technique and observed that Titanium is deposited mainly in amorphous nature with FCC structure at lower Ti layer thickness of 3 nm, which transform to crystalline HCP structures above than this Ti layer thickness. Corresponding fitted GIXRR (grazing incidence X-ray reflectivity) patterns shows asymmetric nature of Ti-Ni and Ni-Ti interfaces because of heavy intermixing and interdiffusion of Ni and Ti atoms at Ti-Ni interfaces at lower Ti layer thickness. The depth profiling core level and valence band measurements carried out by using XPS (X-ray photoelectron spectroscopy) technique confirms the interdiffusion and intermixing leading to Ti-Ni alloy phase formation at interfaces during deposition, particularly at lower Ti layer thickness of 3 nm. The corresponding magnetization behavior of ML samples has been investigated using Magneto-Optical Kerr Effect (MOKE) technique and observed that, coercitivity decreases while saturation magnetization increases with Ti layer thickness variations. These results are interpreted and discussed in terms of observed micro-structural changes due to Ti layer thickness vitiations in Ti/Ni multilayer samples.     

Luminescence properties of spark-processed SiC

The photoluminescence (PL) properties of spark-processed SiC (sp-SiC) have been studied at various temperatures. Furthermore, scanning electron micrographs (SEM), X-ray diffraction (XRD) measurements, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy have been applied. The luminescence properties of sp-SiC are quite different from unspark-treated reference 6 H SiC. Specifically, the PL intensities of sp-SiC are at least two orders of magnitude larger than the reference SiC. Furthermore, the room temperature PL spectrum of sp-SiC exhibits two luminescence bands peaking at 3.18 eV, which are considerably blue shifted from SiC band gap of 2.9 and 2.43 eV. However, these two luminescence bands show an unusual red-shift of PL peak energies with decreasing temperature. Raman spectroscopy studies of sp-SiC display the emergence of a crystalline Si vibrational mode, whereas vibrational modes associated with 6H SiC are completely annihilated. XRD analysis exhibits the formation of polycrystalline Si after spark processing. Vibrational modes obtained from FTIR for sp-SiC are mainly composed of Si–O modes with some OH vibration. The results of low temperature PL studies, FTIR, XRD, XPS and Raman spectroscopy demonstrate that the luminescence properties of sp-SiC are similar to spark-processed Si.