Optical emission spectroscopy of Ar-N2 mixture plasma

Optical emission spectroscopy measurements are presented to characterize the different excitation and ionization processes of both atomic and molecular species in Ar-N₂ mixture plasma under different discharge conditions. Particularly, the emission intensities of nitrogen (0-0) band of second positive system at 337.1 nm and (0-0) band of first negative systems at 391.4 nm are used to determine the dependence of their radiative states on argon fraction in the mixture. It is observed that the addition of argon gas influences the radiative states differently due to their different populating mechanisms. The results demonstrate that the addition of argon to nitrogen plasma remarkably enhance the population of N₂(C³Π_u) radiative state through Penning excitation involving argon metastable states. The electron temperature is determined from Ar-I spectral line intensities, using Boltzmann's plot method and is found to depend on argon fraction in the mixture.     

Near infrared emission spectrum of HCN

To record the infrared emission of hot molecular gases an optimized emission apparatus for the Bruker IFS 120 HR high-resolution FT-IR spectrometer has been constructed. Using this apparatus the hot gas emission spectrum of HCN at 1420 K has been recorded in the wavenumber region of 6000-6800 cm⁻¹ with a resolution of 0.044 cm⁻¹. This work reports the analysis of 33 bands with 58 subbands (9200 line positions). Thirty-seven rovibronic states of HCN including at 12 603 cm⁻¹ have been characterized for the first time and for 25 other states it was possible to improve the existing spectroscopic constants substantially. The very dense emission spectrum with many overlapping features was analyzed with new spectrum analysis software implemented using the Mathematica^TM computer algebra system. Spectroscopic constants have now been determined for 220 HCN rovibronic states. For 102 states the rovibrational spectroscopic constants have been determined for the first time or improved substantially using emission spectra measured in Giessen.     

Corona discharge as a temperature probe of atmospheric air microwave plasma jet

We developed and tested a new method for temperature measurements of near-LTE air plasmas at atmospheric pressure. This method is specifically suitable for plasmas at relatively low gas temperature (800–1700 K) with no appropriate radiation for direct spectroscopic temperature measurements. Corona discharge producing cold non-equilibrium plasma is employed as a source of excitation and is placed into the microwave plasma jet. The gas temperature of the microwave plasma jet is determined as the rotational temperature of N₂? produced in the corona discharge. The corona probe temperature measurement was tested by the use of a thermocouple. We found a fairly good agreement between the two methods after correcting the thermocouple measured temperatures for radiative losses. The corona probe method can be generally applied to determine the temperature of the near-LTE plasmas and contrary to the thermocouple it can be used for higher plasma temperatures and is not affected by radiative losses and problems of interaction with the microwave plasma and electromagnetic fields.     

Dynamics of NF3 in a condensed film on Au(1 1 1) as studied by electron-stimulated desorption

We report a low-temperature dynamics study of condensed layers of NF₃ on Au(1 1 1) by time-of-flight electron-stimulated desorption ion angular distribution (TOF-ESDIAD), temperature-programmed desorption (TPD) and low-temperature scanning tunneling microscopy (LT-STM). Upon adsorption at 30 K, molecular NF₃ adsorption occurs first at the step edges and at minor terrace defect sites with the formation of 2D islands. Within the islands, NF₃ is adsorbed in an upright conformation via the nitrogen lone pair electrons projecting fluorine atoms away from the surface as judged by the presence of only a sharp F⁺ central beam in the ESDIAD pattern. At higher coverages, 3D islands start to populate the surface. Electron bombardment of a thick NF₃ (∼6 ML) layer adsorbed on the Au(1 1 1) surface leads to emission of F⁺, N⁺, NF⁺, and ions as observed in the TOF-ESD distribution. Upon heating to ∼37 K, a sudden decrease of the and ion yield, which is not related to thermal desorption, is observed which reflects the surface migration of NF₃ molecules, leading to local thinning of the film. The thinning process occurs at the temperature of onset of molecular rotations and self-diffusion in the bulk NF₃ crystal. In this process, some NF₃ molecules move closer to the surface which results in higher efficiency for ion neutralization by the underlying metal surface. In the TPD spectra, the monolayer desorption is observed to begin at ∼65 K, exhibiting zero-order kinetics with an activation energy of 21 kJ/mol.     

A study of OH radicals in an atmospheric AC discharge plasma using near infrared diode laser cavity ringdown spectroscopy combined with optical emission spectroscopy

Simultaneous measurements of absolute concentrations of H₂O and OH radicals in an atmospheric AC discharge using continuous wave cavity ringdown spectroscopy (cw-CRDS) are reported. Formation of OH radicals and plasma temperatures are characterized by optical emission spectroscopy. The concentration of OH radical at the edge of the discharge plume at 380 K is measured by the cw-CRDS technique to be 1.1 ×10¹⁵ molecule cm^-3. Ringdown measurements of the H₂O (120-000) band and the OH first overtone around 1515 nm enable us to determine an OH generation yield, , to be 4.8 ×10^-3, where N_OH and are the number densities of OH and H₂O, respectively. The minimum detectable absorption coefficient of the cw-CRDS system is 8.9 ×10^-9  cm^-1, which corresponds to a 1σ detection limit of OH number density of 1.2 ×10¹³ molecule cm^-3 in the discharge. This experimental approach is demonstrated for the first time ever in an AC discharge, and can be applied in general to a variety of atmospheric plasmas to help study OH formation mechanisms and OH-related plasma applications.     

Temperature dependence of current-voltage characteristics of Sn/p-Si Schottky contacts

The current-voltage (I-V) characteristics of Sn/p-Si Schottky barrier diode have been measured over a wide range of temperature (80-300 K) and interpreted on the basis of thermionic emission mechanism by merging the concept of barrier inhomogeneities through a Gaussian distribution function. The analysis has revealed an anomalous decrease of apparent barrier height Φ_b0, increase of ideality factor n, and nonlinearity of the activation energy plot at lower temperatures. A Φ_b0 versus 1/T plot has been drawn to obtain evidence of a Gaussian distribution of barrier heights, and values of 0.97 eV and 0.084 V for the mean barrier height and standard deviation σ₀ have been obtained, respectively, from this plot. A modified ln(I₀/T²)−(q²σ₀²/2k²T²) versus 1/T plot gives and Richardson constant A** as 0.95 eV and 15.6 A cm⁻² K⁻², respectively. It can be concluded that the temperature dependent I-V characteristics of the Sn/p-Si Schottky barrier diode can be successfully explained on the basis of a thermionic emission mechanism with Gaussian distribution of the barrier heights. We have also discussed whether or not the junction current has been connected with thermionic field-emission mechanism.     

Rotational levels of the (0 0 0) and (0 1 0) states of D2O from hot emission spectra in the 320-860 cm region

The far-infrared emission spectra of deuterated water vapour were measured at different temperatures (1370, 1520, and 1950 K) in the range 320-860 cm⁻¹ at a resolution of 0.0055 cm⁻¹. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 1150 new measured lines for the D₂¹⁶O molecule corresponding to transitions between highly excited rotational levels of the (0 0 0) and (0 1 0) vibrational states are reported. These new lines correspond to rotational states with higher values of the rotational quantum numbers compared to previously published determinations: J_max=26 and for the (0 0 0) ← (0 0 0) band, J_max=25 and for the (0 1 0) ← (0 1 0) band, and J_max=26 and for the (0 1 0) ← (0 0 0) band. The estimated accuracy of the measured line positions is 0.0005 cm⁻¹. To our knowledge no experimentally measured rotational transitions for D₂¹⁶O within an excited vibrational state have been available in the literature so far. An extended set of experimental rotational energy levels for (0 0 0) and (0 1 0) vibration states including all previously available data has been determined. For the data reduction we used the generating function model. The root mean square (RMS) deviation between observed and calculated values is 0.0012 cm⁻¹ for 692 rotational levels of the (0 0 0) state and 0.0010 cm⁻¹ for 639 rotational levels of the (0 1 0) vibrational state. A comparison of the observed energy levels with the best available values from the literature and with the global predictions from molecular electronic potential energy surface [J. Chem. Phys. 106 (1997) 4618] for the (0 0 0) and (0 1 0) states is discussed.     

Temperature and pressure effects on the spin state of ferric ions in the [Fe(sal2-trien)][Ni(dmit)2] spin crossover complex

Thermal and pressure effects have been investigated on the [Fe(sal₂-trien)][Ni(dmit)₂] spin crossover complex by means of Mössbauer spectroscopic, calorimetric, X-ray diffraction and magnetic susceptibility measurements. The complex displays a complete thermal spin transition between the and spin states of Fe^III near 245 K with a hysteresis loop of ca. 30 K. This transition is characterised by a change of the enthalpy, ΔH_HL=7 kJ/mol, entropy, ΔS_HL=29 J/Kmol, and the unit cell volume, ΔV_HL=15.4 Å³. Under hydrostatic pressures up to 5.7 kbar the thermal transition shifts to higher temperatures by ca. 16 K/kbar. Interestingly, at a low applied pressure of 500 bar the hysteresis loop becomes wider (ca. 61 K) and the transition is blocked at ∼50% upon cooling, indicating a possible (irreversible) structural phase transition under pressure.     

Direct recognition of non-radiative recombination centers in semi-insulating LEC InP:Fe using double excitation photoluminescence

In order to observe the effect of intra-band gap excitation on the photoluminescence (PL) properties of undoped InP and iron doped InP (InP:Fe), PL measurements were performed in InP crystals with thickness of 360 μm and area of about 4×3 mm², grown by the liquid encapsulated Czochralski (LEC) technique upon excitation with both Ar-ion laser and 980 nm light. The PL intensities for InP:Fe under 980 nm wavelength light illumination relative to no illumination increased by about 52%, 33%, and 12% for the 1.337, 1.380, and 1.416 eV peaks, respectively, at 10 K, whereas there was no illumination effect for undoped InP. This is a strong indication that Fe centers play a role as non-radiative recombination centers to decrease the PL intensity. PL experiments were performed in the spectral range of 1320-1440 meV for InP in the sample temperature range of 10-160 K. The electron and hole photoionization cross-sections at 980 nm wavelength light illumination were calculated as and , respectively.     

Electrical and chemical characteristics of nano-meter gold encapsulated in mesoporous and microporous channels and cages of FSM-16 and Y zeolites

The dc and ac conductivities as well as the dielectric constant () were measured for different zeolites encapsulated gold (AuCl₃) samples at different temperatures (300-500 K) and various frequencies (5 kHz-1 MHz). The conductivity was found to change in the order Au/FSM-27>Au/NaY>Au/FSM-47. Sorbed water contained inside zeolites assists greatly the proton mobility (zeolite protons) and the ion mobility (Na⁺ and Au⁺) and hence enhance the electric conduction in the temperature range 300-373 K. Raising the temperature over 373 K induces dehydration effect that assists the metallic gold formation and thus a dramatic loss in conductivity was revealed. The conduction mechanism was expected to be partially ionic and partially electronic. The IR study showed that the exposure of Au zeolites to CO gas produced a characteristic band of Au⁺-CO at 2180 cm⁻¹ that tends to decrease with temperatures and even vanishes at 376 K in favor of Au⁰-CO at 2128 cm⁻¹. Similarly, a phase transition at 338 K, that occurs in the range 300-376 K, was confirmed by DTA to further emphasize the temperature regions of either Au⁺ cations (338 K) or Au⁰ (376 K) formation.     

Frozen methanol bombarded by energetic particles: Relevance to solid state astrochemistry

Methanol is an important precursor of many complex prebiotic species and is found abundantly, in solid phase, in several astrophysical environments, such as comets and protostars. These environments are, in general, subjected to some form of ionizing particles as cosmic rays, solar wind particles and/or photons. To simulate physico chemical effects of cosmic rays on methanol and to investigate in particular its fragmentation and cluster emission from the solid phase, condensed methanol at 55 K was bombarded with ∼65 MeV heavy ions constituted by ²⁵²Cf fission fragments. Mass spectra of positive desorbed ions were obtained using a time-of-flight Plasma Desorption Mass Spectrometry (PDMS-TOF), giving information on the fragmentation pattern and abundance of the ionic species released from the frozen sample surface. Since and CH₃O⁺ are the most abundant species detected, the hydrogenation and de-hydrogenation of methanol result to be the predominant ionic processes in the methanol surface. Furthermore, the hydrogenation yields emission of the (CH₃OH)_nCH₃ cluster series, while the CH₃O⁺ species does not attach to methanol molecules. The production of other cluster ion series, some of them with mass/charge up to 300 u/e was also analyzed by PDMS.     

Temperature dependent analysis of three classes of fluorescence spectra from p-6P nanofiber films

Discontinuous nanofiber films of para-hexaphenylene molecules can be routinely fabricated via vacuum deposition on muscovite mica. The fibers emit upon UV illumination blue fluorescence with excitonic spectral peaks. Their intense fluorescence makes them very attractive for the use in photonic devices, given that the spectra are reproducible for varying surface temperatures. A detailed investigation as a function of surface temperature variation from 300 to 30 K reveals three classes of spectra: (a) spectra with well resolved excitonic peaks, which shift 35 meV to the blue with decreasing temperature, (b) similar spectra with an additional intermediate broadening around 150 K, and (c) excitonic spectra similar to (b), but with a green defect emission band. Quantitative fitting of type (a) spectra results in an exciton-phonon coupling factor of and an average phonon temperature of . The Huang-Rhys factor decreases linearly from 1.2 at 300 K to 1.0 at 30 K. Fitting of type (b) spectra reveals that the apparent intermediate temperature broadening is due to additional fluorescence peaks, the relative importance of which increasing with decreasing temperature.     

Aromatic interactions in the close packing of phenyl-imides at Cu(1 1 0) surfaces

The oxidation of aniline at Cu(1 1 0) surfaces at 290 K has been studied by XPS and STM. A single chemisorbed product, assigned to a phenyl imide (C₆H₅N(a)), is formed together with water which desorbs. Reaction with preadsorbed oxygen results in a maximum surface concentration of phenyl imide of 2.8 × 10¹⁴ mol cm⁻² and a surface dominated by domains of three structures described by , and unit meshes. However, concentrations of phenyl imide of up to 3.3 × 10¹⁴ mol cm⁻² were obtained from the coadsorption of aniline and dioxygen (300:1 mixture) resulting in a highly ordered biphasic structure with and domains. Comparison of the STM and XPS data shows that only half the phenyl imides at the surface are imaged. Pi-stacking of the phenyl rings is proposed to account for this observation.     

Fourier transform emission spectroscopy of CoCl in the 500 nm region

Fourier transform emission spectra of CoCl were obtained with a tube furnace-DC discharge source in the 450-500 nm spectral region. In addition to observing two different band systems, which were assigned as [20.7] and [21.3] by Adam et al. [J. Mol. Spectrosc. 212 (2002) 111], we obtained data for additional sub-bands and vibrational levels. In contrast to the previous work, intense Q branches are seen in the [21.3]- bands which indicate that these bands are likely ΔΛ≠0 transitions. The equilibrium rotational constant B_e for the ground state is 0.1801104(28) cm⁻¹, the equilibrium bond length is 2.065122(16) Å and ΔG_1/2 is 430.418(5) cm⁻¹.