The profile of the 2140 cm(-1) solid CO band on different substrates

We have studied the profile of the 2140 cm(-1) fundamental band of solid carbon monoxide (CO) at low temperature (10-15 K) by infrared transmission spectroscopy and by reflection absorption infrared (RAIR) spectroscopy. In particular, transmission spectra have been taken after CO had been adsorbed on a bare crystalline silicon substrate and on pre-adsorbed solid N(2) layers of different thickness. RAIR spectra have been taken after CO had been adsorbed on a bare gold substrate and on pre-adsorbed solid N(2) layers of different thickness. Laboratory spectra show that the profile of the fundamental CO band at about 2140 cm(-1) is different in the different instances considered. In particular, we have found that the relative intensity of the LO and TO modes of the CO band depends on the thickness of the N(2) layer. Here we present the experimental results and show that these can be predicted by the elementary electromagnetic theory.     

Theoretical calculations of refractive indices and optical effects in spectra of nitric acid and nitric acid monohydrate crystals

The theoretical infrared refractive indices of two systems related to atmospheric research, nitric acid (NA) and nitric acid monohydrate (NAM) crystals, have been computed using a methodology based on first-principles. The effects of lack of coherence in the infrared beam in RAIR and transmission spectra have also been treated using a model based on classical optics. The optical constants of NA crystals are presented for the first time; the results on NAM are compared to empirical values previously published with good general agreement. With the optical constants of NA, polarized reflection-absorption infrared spectra are predicted and compared to experimental spectra recorded also for the first time, for a set of varying film thickness. The global agreement is satisfactory. The effects of a number of experimental factors in transmission spectra of NAM are assessed, in an attempt to explain observed differences among experimental spectra. It is concluded that the spectral disparities are probably due to differences in the nature of the samples.     

Optical properties of synthetic carbon nanoparticles as model of cosmic dust

Carbon nanoparticles synthesised by laser pyrolysis of small hydrocarbons are deposited at low energy on a silicon substrate. Infrared spectroscopy of the as-formed films are studied as a function of the synthesis parameters and post-treatments, such as annealing and heavy ion irradiation. Correlation between infrared spectroscopy and multiscale organisation of the samples is made through transmission electron microscopy, including image analysis. Changes in infrared spectra are analysed in terms of the carbon network building. The relevance of the results to model the structure and spectroscopy of carbon dust in the carbon-rich circumstellar media is discussed.     

Characterization of Langmuir-Blodgett films of a ferroelectric liquid crystal

Molecular orientation, structure, and phase transition behaviors in Langmuir-Blodgett (LB) and cast films of a ferroelectric liquid crystal of sec-butyl 6-(4-(nonyloxy)benzoyloxy)-2-naphthoate (FLC-1) are determined by ultraviolet (UV) spectroscopy, X-ray diffraction, and infrared (IR) spectroscopy. It is found that the orientation angle of chromophores theta in LB films is 41 degrees from the surface normal. The tilt angle of the chromophore changes at 56, 70, and 88 degrees C, respectively, which denotes the presence of phase transitions. Two kinds of layered or isomeric crystal structures of the LB films with layer spacings of 3 and 3.5 nm at room temperature have been found while the latter disappears above 45 degrees C, as confirmed by measurement of temperature-dependent IR spectra.     

Polarized Raman spectroscopy of oligothiophene crystals to determine unit cell orientation

Raman spectra were recorded experimentally and calculated theoretically for bithiophene, terthiophene, and quaterthiophene samples as a function of excitation polarization. Distinct spectral signatures were assigned and correlated to the molecular/unit cell orientation as determined by X-ray diffraction. The ability to predict molecular/unit cell orientation within organic crystals using polarized Raman spectroscopy was evaluated by predicting the unit cell orientation in a simulated terthiophene crystal given a random set of simulated polarized Raman spectra. Polarized Raman spectroscopy offers a promising tool to quickly and economically determine the unit cell orientation in known organic crystals and crystalline thin films. Implications of our methodologies for studying individual molecule conformations are discussed.     

Spectroscopic studies of trimetoxypropylsilane and bis(trimethoxysilyl)ethane sol-gel coatings on aluminum and copper

Trimethoxypropylsilane (TMPS) and bis(trimethoxysilyl)ethane (BTMSE) were used as surface modifiers of metal vie the sol-gel process and dip coating. In addition to the single coating of Al, Cu and Sn, double treatments of Al were also conducted by combining coatings with these sol-gels in different sequences. Reflection and absorption infrared spectroscopy (RAIR) was employed to characterize and to trace the proceeding of the sol-gel process of the films. It was found that the silanol condensation occurs in the coating films on Al and the covalent linkage exists between the TMPS film and copper surface. From the assigned vibration modes, two conformers were identified in pure TMPS, TMPS sol-gel and coated film. A series of dip coating experiments with different concentrations of TMPS sol-gel was conducted, and the results from the collected RAIR spectra of the coated samples suggested that the coated Cu consistently has a better RAIR spectrum than that of the coated Al. The TMPS sol-gel appeared to have a better affinity to Cu than to Al. The temperature effect and the aging effect in the coating films were studied. X-ray photoelectronic spectroscopy (XPS) was employed to characterize the coated film, and the XPS data confirm the formation of the siloxane film from the silane coupling agents (SCA). Electrochemical impedance spectra (EIS) have been collected for bare Al and Cu, BTMSE sol-gel coated Al, and TMPS sol-gel coated Cu in 0.15M NaCl solution. The corresponding electronic circuit parameters have been determined to match the experimental EIS data.     

Infrared spectroscopic study of molecular interaction of tacticity-controlled poly(N-isopropylacrylamide) in a cast film deposited on a solid substrate

Analytical results of a series of poly(N-isopropylacrylamide) (PNiPA) with different tacticities using infrared spectroscopy are presented for studying the influence of the solvation and molecular interactions between the polymeric chains. Infrared spectra of solid matter samples of the compounds exhibit a systematic band intensity change for three band components at 1,680, 1,659, and 1,628 cm⁻¹ involved in the amide I band. The three components correspond to the free, half, and full hydrogen bondings of the secondary amide group, which reflect the molecular configuration depending on the tacticity. When cast films of the compounds prepared on a solid surface are analyzed by infrared transmission spectrometry, another factor of the solvent used for the film preparation is found to be another factor which plays an important role in determining the molecular architecture in the films. This molecular imprint mechanism after the solvation is confirmed by measuring infrared multiple-angle incidence resolution spectra of annealed films. The molecular interactions in the polymeric samples have been revealed by the use of infrared spectroscopy and the tacticity-controlled samples.     

Rubbing-induced anisotropy of long alkyl side chains at polyimide surfaces

Molecular organization at polyimide surfaces used as alignment layers in liquid crystal displays was investigated using vibrational sum frequency generation (SFG) spectroscopy. We focus on the orientation of the long alkyl side groups at the polymer surface using polarization-selected SFG spectra of the CH(3)- and CH(2)-stretch modes of the side chain. Mechanical rubbing and baking, an accepted industrial procedure used to produce pretilt of the liquid crystal, was found to induce pronounced azimuthal anisotropy in the orientational distribution of the alkyl side chains. Orientational analysis of the SFG vibrational spectra in terms of the azimuthal and tilt angles (in and out of plane, respectively) of the alkyl side chains shows their preferential tilt along the rubbing direction, with the azimuthal distribution narrower for stronger rubbed polymer samples.     

衬底温度对ZnO薄膜晶体结构和电学性质的影响研究

ZnO films were deposited on glass substrates by gas discharge reaction evaporation. The influences of substrate temperature on the surface morphology, crystal structure and electric properties of ZnO films were studied by scanning electron microscopy, atomic force microscopy, X-ray diffraction spectroscopy and complex impedance spectroscopy. The results show that the films with dense and amorphous structure and lower grain boundary resistance were deposited at room temperature. When the substrate temperature is higher than 50 ℃, the films with certain c-axis orientation can be deposited. With the increase of the substrate temperature, the preferential orientation of ZnO films along c-axis is augmented, the tensile stress along c-axis orientation decreases and the grain boundary resistance increases in a marked degree. When the substrate temperature is higher than 100 ℃, the increasing trend of the preferential orientation of ZnO films along c-axis slows down. ZnO films possess high preferential c-axis orientation and best crystalline quality at 180-200 ℃. These possess a smooth surface, symmetrical grain dimension (i.e. 30-40 nm), inerratic crystal shape, less tensile stress and 0.965 epitaxial degree along the c-axis direction. Here the grain boundary effect increases and the grain boundary resistance is evidently more than that of the films deposited at room temperature. The mechanism by which substrate temperature affects crystal structure and grain boundary properties were also discussed.     

In situ ATR-FTIR studies on MgCl2-diisobutyl phthalate interactions in thin film Ziegler-Natta catalysts

To study the surface structure of MgCl(2) support and its interaction with other active components in Ziegler-Natta catalyst, such as electron donors, we prepared a thin film analogue for Ziegler-Natta ethylene polymerization catalyst support by spin-coating a solution of MgCl(2) in ethanol, optionally containing a diester internal donor (diisobutyl-ortho-phthalate, DIBP) on a flat Si crystal surface. The donor content of these films was quantified by applying attenuated total internal reflection-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Changes in the interaction of DIBP with MgCl(2) at various temperatures were monitored by in situ ATR-FTIR. Upon increasing the temperature, a shift in the (C═O) band toward lower wavenumbers was observed together with the depletion of (O-H) stretching band due to the desorption of residual ethanol. We assign this shift to gradual redistribution of adsorbed DIBP from adsorption sites on the MgCl(2) (104) surface toward the more acidic MgCl(2) (110) surface. The morphologies of MgCl(2) and MgCl(2)/DIBP films were studied by transmission electron microscopy (TEM) revealing a preferential orientation of ClMgCl layers (001) parallel to the lateral film dimensions. This orientation becomes more pronounced upon annealing. In the absence of donor, the MgCl(2) grow in to large crystals aligned in large domains upon annealing. Both crystal growth and alignment is impeded by the presence of donor.     

Molecular recognition of cytosine- and guanine-functionalized nucleolipids in the mixed monolayers at the air-water interface and Langmuir-Blodgett films

Molecular recognition of mixed nucleolipids of 1-(2-octadecyloxycarbonylethyl)cytosine and 7-(2-octadecyloxycarbonylethyl)guanine in the monolayers at the air-water interface and Langmuir-Blodgett (LB) films has been investigated in detail using surface pressure/potential-area isotherms, infrared reflection-absorption spectroscopy (IRRAS), and Fourier transform infrared (FTIR) transmission spectroscopy, respectively. Prior to molecular recognition, the cytosine moieties in the monolayer were hydrogen bonded with an almost flat-on orientation, the alkyl chains were uniaxially oriented with respect to the film normal, the guanine moieties in the monolayer were stacked probably through pi-pi interaction with an end-on orientation, and the C-C-C planes of the alkyl chains were preferentially oriented parallel to the water surface. In the monolayer of equimolar mixture, molecular recognition between the cytosine and guanine moieties occurred together with the ring planes of base pairing and the C-C-C planes of the alkyl chains favorably oriented parallel to the water surface. The guanine moieties underwent an orientation change from an end-on mode before molecular recognition to a flat-on one after molecular recognition. The base pairing between the cytosine and guanine moieties in the monolayers was achieved since the N7-substituted guanine derivatives suppressed the formation of guanine tetramers. Both the IRRAS spectra of the monolayers and the FTIR spectra of the LB films presented the exact sites in the cytosine and guanine moieties for the formation of triple hydrogen bonds. The base pairing resulted in a change in molecular orientation and interaction, and the corresponding LB film exhibited a different phase transition behavior from a typical crystal transition for the cytosine-functionalized nucleolipids and an analogous glass transition for the guanine-functionalized nucleolipids. The thermal stability of the mixed LB film was improved in comparison to the LB films of pure components.     

Spin-coated polyethylene films probed by single molecules

We have studied ultrathin spin-coated high-density polyethylene films by means of single-molecule spectroscopy and microscopy at 1.8 K. The films have been doped with 2.3,8.9-dibenzanthanthrene (DBATT) molecules, which function as local reporters of their immediate environment. The orientation distributions of single DBATT probe molecules in 100-200 nm thin films of high-density polyethylene differ markedly from those in low-density films. We have found a preferential orientation of dopant molecules along two well-defined, mutually perpendicular directions. These directions are preserved over at least a 2 mm distance. The strong orientation preference of the probe molecules requires the presence of abundant lateral crystal faces and is therefore not consistent with a spherulitic morphology. Instead, a "shish-kebab" crystal structure is invoked to explain our results.     

Driving forces for layer-by-layer self-assembly of films of SiO2 nanoparticles and heme proteins

Heme protein hemoglobin (Hb) or myoglobin (Mb) and silica nanoparticles in a variety of charge states were assembled layer-by-layer into films on solid surfaces to investigate the driving forces for film assembly. Cyclic voltammetry (CV), quartz crystal microbalance (QCM), X-ray photoelectron spectroscopy (XPS), and UV-vis and reflectance absorption infrared (RAIR) spectroscopy were used to characterize the different [SiO2/protein]n films. Even when the proteins and silica were both negatively charged, stable layer-by-layer [SiO2/protein]n films were successfully fabricated, although amounts of protein were smaller than when nanoparticles and proteins had opposite charges. Results suggest the importance of localized Coulombic attractions between the negative nanoparticle surface and positively charged amino acid residues on the Mb or Hb surfaces in the assembly and for the stability of [SiO2/protein]n films.     

Structure Studies on Ion Coordination in 2,4-Dihydroxy-N-Octadecybenzylideneamine LB Films by UV-Vis Absorption and FTIR Spectroscopy

The coordination reaction of Cu(2+) ions with the Schiff base amphiphile 2,4-dihydroxy-N-octadecylbenzylideneamine in ultrathin organic LB films was probed by Fourier transform infrared (FTIR) transmission spectroscopy and UV-Vis electronic absorption spectroscopy. FTIR spectral changes owing to LB films of 2,4-dihydroxy-N-octadecylbenzylideneamine contacting aqueous Cu(OAC)(2) solution suggest the formation of ion-coordination films, which is corroborated by UV-Vis absorption spectra. The coordination reaction of the annealing film at different temperatures suggests that the microstructure of LB films had an important effect on the reaction rate. Detailed analysis shows that ion-coordination films take an isotropic unaxial orientation and exhibit phase transition behavior, which is determined by the different complex structures of headgroups and of subphase and surface film. Copyright 2000 Academic Press.     

Infrared method for measuring orientation in polyethylene films

An infrared method is described for measuring crystalline phase orientation in polyethylene films. The method uses the absorbances of the 730 and 719 cm^?1 bands in the polarized spectra of an oriented film and in the spectra of an unoriented film made from the same polymer to estimate the orientation parameters of the orthorhombic crystal cell axes. © 1992 John Wiley & Sons, Inc.     

Effect of thermal annealing on the microstructure of P3HT thin film investigated by RAIR spectroscopy

The influence of thermal annealing on the structural ordering and orientation rearrangement of as cast P3HT thin film (<100 nm) has been studied by reflection absorption infrared spectroscopy (RAIR). In order to erase the effect of temperature on the spectral intensity, two thermal procedures have been used to investigate the annealing-induced structural change of P3HT thin film. One is the continuous heating mode, in which the RIAR spectra were in situ collected during the heating process. The other is the stepwise heating mode, that is the isothermal annealing, and the spectra were ex situ collected at room temperature after the thermal treatment. It is found that thermal annealing can enhance the π–π interaction in P3HT crystal domain, whereas the improvement on the degree of crystallinity is not so obviously. Meanwhile, our results suggest that annealing-induced structural rearrangement on π–π stacking is irreversible, whereas the change on hexyl side chain packing is reversible.     

Adsorption of 1- and 2-butylimidazoles at the copper/air and steel/air interfaces studied by sum frequency generation vibrational spectroscopy

The structure of thin films of 1- and 2-butylimidazoles adsorbed on copper and steel surfaces under air was examined using sum frequency generation (SFG) vibrational spectroscopy in the ppp and ssp polarizations. Additionally, the SFG spectra of both isomers were recorded at 55 °C at the liquid imidazole/air interface for reference. Complementary bulk infrared, reflection-absorption infrared spectroscopy (RAIRS), and Raman spectra of both imidazoles were recorded for assignment purposes. The SFG spectra in the C-H stretching region at the liquid/air interface are dominated by resonances from the methyl end group of the butyl side chain of the imidazoles, indicating that they are aligned parallel or closely parallel to the surface normal. These are also the most prominent features in the SFG spectra on copper and steel. In addition, both the ppp and ssp spectra on copper show resonances from the C-H stretching modes of the imidazole ring for both isomers. The ring C-H resonances are completely absent from the spectra on steel and at the liquid/air interface. The relative intensities of the SFG spectra can be interpreted as showing that, on copper, under air, both butylimidazoles are adsorbed with their butyl side chains perpendicular to the interface and with the ring significantly inclined away from the surface plane and toward the surface normal. The SFG spectra of both imidazoles on steel indicate an orientation where the imidazole rings are parallel or nearly parallel to the surface. The weak C-H resonances from the ring at the liquid/air interface suggest that the tilt angle of the ring from the surface normal at this interface is significantly greater than it is on copper.     

Determination of the molecular orientation of very thin films on solid substrates: surface liquid crystal layers and rubbed polyimide films

The molecular orientation of very thin films on solid substrates can be determined quantitatively by measuring the polarized infrared (IR) absorption spectra of samples as a function of angle of incidence. The quantitative molecular orientation is derived by fitting the incident angle dependence and the dichroic ratio with theoretical calculations. We applied this method to a technologically important system: liquid crystal (LC)/rubbed polyimide film. To understand the alignment mechanism of LC molecules in contact with rubbed polyimide films, we have quantitatively determined the molecular orientation of rubbed polyimide films and a surface LC layer in contact with a rubbed polyimide film. In this paper two relations are discussed: (1) correlation between the inclination angle of polyimide backbone structures in rubbed films and the pretilt angle of bulk LC in contact with them, and (2) relation among the molecular orientation of a rubbed polyimide film and those of surface and bulk LC layers in contact with it.     

A polarised ATR study of structural orientation in dry and humid thin HPMC films

The structure of thin films of the polymer hypromellose (HPMC) have been investigated under dry and ambient humidity conditions using polarised attenuated total reflectance (ATR) infrared spectroscopy. In particular spectra were recorded in the C–H and O–H stretching regions for spin coated films deposited on silicon, germanium and zinc selenide internal reflection elements (IREs). A recent development in the field of polarised ATR has demonstrated a simple quantitative relationship between complementary s- and p-polarised spectra of orientationally ordered monolayer films, which yields the spectrum uniquely in the direction perpendicular to the surface, the “z-polarised” spectrum. As well as recording s- and p-polarised spectra this work examines the z-spectra derived from the experimental s- and p-polarisation spectra. For the C–H band all three polarisation spectra reveal no change in the preferred orientation of the transition dipole between humid and dry films on germanium or silicon but with a marginally increased orientation parallel to the surface on zinc selenide. On the other hand the O–H band spectra show an increased orientation of the transition dipole parallel to the surface for both humid and dried films for all three IREs when compared to the corresponding C–H band spectra. This effect was greater in the dried film, i.e. with free water removed, than in the humid film.     

Chemical structure and orientation of ethylene on Si(114)-(2 x 1)/c(2 x 2)

The basic chemical structure and orientation of ethylene chemisorbed on Si(114)-(2 x 1) at submonolayer coverage is characterized in ultrahigh vacuum using transmission Fourier transform infrared (FTIR) spectroscopy. The spectra are consistent with di-sigma bonding of ethylene to the surface with a preferential molecular orientation over macroscopic lengths. These results are supported by density functional theory (DFT) calculations of vibrational frequencies for optimized ethylene-Si(114) structures occupying the dimer and rebonded atom surface sites. A detailed analysis of the strong angular and polarization dependence of the C-H stretching mode intensities is also consistent with the adsorption structures identified by DFT, indicating that ethylene chemisorbs with the C-C bond axis parallel to the structural rows oriented along the [10] direction on the Si(114)-(2 x 1) surface. The results indicate that the unique structure of this surface makes it an excellent template for elucidating relationships between surface structure and organic reaction mechanisms on silicon.