Infrared absorption of silane,ammonia, acetylene and diborane in the range of the CO2 laser emission lines: Measurements and modelling

Absorption spectra of the gases SiH₄, NH₃, C₂H₂ and of SiH₄/Ar and SiH₄/B₂H₆ mixtures have been measured in the spectral range of the CO₂ laser from 9.2 to 10.8 µm. In agreement with literature, silane shows the highest absorption (absorption coefficient = 3.3 × 10^–2 Pa^–1 m^–1). The deviation of the measured absorption behaviour of silane from literature, as far as the pressure dependence is concerned, can be explained by the enhanced spectral energy density in our experiment. This is confirmed by a rate-equation model involving the basic mechanisms of V-V and V-T energy transfer between vibrationally excited silane molecules. In contrast to silane, the absorption coefficient of NH₃ at the 10P(20) laser line is 4.5 × 10^–4 Pa^–1 m^–1 atp = 20 kPa and has its maximum of 4.5 × 10^–3 Pa^–1 m^–1 at the 10R(6) laser line. For C₂H₂ and B₂H₆, is even less ( 2.1 Ò 10^–5 Pa^–1 m^–1 for C₂H₂).     

Study of processes of translational,rotational, and vibrational relaxation based on CARS spectra line shapes

This paper reviews the various physico-chemical processes responsible for actual linewidths encountered in high-resolution coherent anti-Stokes Raman spectroscopy (CARS). Most of the experimental data are based on linewidth measurements using a pulseamplified CARS spectrometer with an emission bandwidth (FWHM) of 2×10^–3 cm^–1. Detailed rotational and vibrational relaxation constants have been obtained from the analysis of theQ-branch profiles of C₂H₂, N₂, CH₄, and SiH₄.     

Supertransferred hyperfine interaction in magnetic insulators (II)

The important mechanisms of supertransferred hyperfine (STHF) interactions in N–O–M chains are briefly discussed: (i) spin polarization ofns states in the N-ion due to the s-d exchange interaction,H _STHF ^sd ; (ii) contributions of spin-polarized states of the intervening O-ion,H _STHF ^II ; (iii) transfer of d-electrons of the M-ion to emptyns states in the N-ion,H _STHF ^III . The dependence ofH _STHF upon the N–O–M bond configuration, electronic structure, and orbital state of the M-ion is presented in a convenient form. The STHF interactions in the chains Sn⁴⁺–O^2––Fe³⁺, Cr³⁺ in compounds with slightly distorted Perovskite structure are considered. The STHF field in the chain Sn⁴⁺–O^2––Cr³⁺ is shown to change the sign within the range of angles near 170°. This conclusion is in line with published data on the isoelectronic chain Sn⁴⁺–O²–Mn⁴⁺ in the compounds Ca_1–x Sr _x MnO₃. The results obtained for the N–O–Fe³⁺ chain are rationalized by the predicted angular dependence ofH _STHF=+ cos + cos². Features of the STHF interactions in N–O–M chains with an M-ion in an orbital degenerate state are examplified by a preliminary analysis of N–O^2––V³⁺ chains in orthovanadites.     

The hall effect in PdSi-based amorphous alloys containing Co.

The Hall effect in amorphous Pd₈₀Si₂₀ and Pd_80–x Si₂₀Co _x , wherex=2, 4, 6 (at.% are implied throughout) alloys was investigated. Measurements were carried out at r.t. in fields up to 17·5 kG. Also the electrical conductivity was measured. The Hall effect was found negative in all alloys of the above composition. Observedx-dependence of the Hall constantR _H tends to change the sign of the effect and is interpreted on the assumption that an extraordinary Hall effect manifests itself besides the ordinary one in Co-containing alloys. The value ofR _H for the basal alloy should be looked upon as an evidence of electron transfer from glass-former (Si) to transition metal (Pd) empty d-states. The values ofR _H obtained for the alloys withx=0, 2, 4, 6 are respectively, –7·8; –8·7; –8·3; –5·2 (×10^–5 cm³/A. sec throughout).     

Sulphidation-induced changes in the metallic phase of Fe-Cr alloys

The influence of sulphidation on the metallic phase in a series of Fe_100–x Cr _x alloys (x<15) was investigated by means of⁵⁷Fe Mössbauer spectroscopy. The results obtained gave evidence that the sulphidation at 1073 K is selective in the atmosphere of H₂/H₂S, with the partial pressure of sulphur ranging from 10^–7 to 10^–9 atm. Atx _cr=5.0(1) at.%, a change of the sulphidation preference occurs. Forx<5.0 at.%, the sulphidation results in an enrichment of the metallic phase in chromium, while forx> 5.0 at.%, in iron.     

On the superconductivity of the tin-hydrogen system

Conductivity and superconductivity studies of amorphous [Sn_1–y Cu _y–]_1–x H _x samples in connection with¹¹⁹Sn Mössbauer effect experiments on¹¹⁹Sn_1–x H _x give strong evidence that the observed increase of the superconducting transition temperatureT _c in the Sn–H-system is caused by the stabilization of an amorphous structure. Thus the Sn–H-system is very similar to the Sn–Cu-system and no H-specific effect is needed to explain the increase ofT _c.     

Magnetic behavior of amorphous Sm-Co alloy films

Amorphous films of Sm_100–x Co _x with 70x90 were made by vapor deposition on flat glass substrates kept at 300 K. The films crystallize above 700 K. The film plane is the easy plane with the planar anisotropy of the order of 10⁷ erg cm^–3, indicating a local anisotropy of the order 10⁸ erg cm^–3. With regard to local anisotropy and magnetization, the films appear to correspond to the random anisotropy concept of amorphous magnets. Films evaporated in a magnetic field parallel to the film plane have an induced uniaxial anisotropy of the order of 10⁶ erg cm^–3. Hysteresis loops in fields parallel to the easy axis are perfectly rectangular with coercive fieldsH _c in the range 30 Oe<H _c<3000 Oe, depending on composition, temperature and heat treatment. The magnetization reverses by a thermally activated domain nucleation and growth process having a narrow distribution of time constants. Aging at temperatures below the crystallization temperature reduces the anisotropies andH _c.     

Far infrared emission spectra from stratospheric hydrogen peroxide

Synthetic emission spectra from two stratospheric altitude observations have been analyzed for the presence of H₂O₂ in the far infrared region. The calculations are made with a high spectral resolution (10^–3 cm^–1 or 10^–4 cm^–1) greater than those in experimental measurements which are in the region of 3.10^–3 cm^–1. Spectra cover a spectral interval between 40 and 120 cm^–1 showing the best features of H₂O₂ susceptible to observation in a stratospheric spectrum. The optimum conditions for identification have been considered. Using the variations in H₂O₂ abundance in the measurement data and photochemical models, the H₂O₂ features detection limits have been studied.     

Reaction of the muonium substituted cyclohexadienyl radical with 2,3-dimethyl-1,3,-butadiene

The rate constant for the title reaction is represented by log (k _M/M^–1s^–1)=6.9(4)–700(350)K/T between 279 and 343K, whereas the H analogous radical, C₆H₇, reacts at room temperature withk _H 12 M^–1s^–1 with dimethylbutadiene. The title reaction is proposed to be transfer of the light hydrogen isotope, Mu, and the large kinetic isotope effect is discussed.Support by the Swiss National Foundation for Scientific Research and by the Swiss Institute for Nuclear Research (SIN) are gratefully acknowledged.     

Photoelectric properties of Pb1−x−y Sn x Ge y Te:In epitaxial films

Pb_1–x–y Sn _x Ge _y Te:In epitaxial films are examined in a wide temperature interval and at various background fluxes. These films have high sensitivity to infrared radiation in the spectral range <20m. The lifetime depends exponentially on temperature and varies from several seconds at T=10 K to 10^–2 s at T=20 K. The two-electron model of Jahn-Teller centers is proposed to explain the results. Multielement photoresistors based on these films are fabricated and D*=1.7×10¹³ cm Hz^1/2 W^–1 at T=25 K is achieved. Noise of the photoresistors is independent of background flux when it varies from 10¹² cm^–2 s^–1 to 10¹⁸ cm^–2 s^–1. As compared with Si:Ga and Ge:Hg photoresistors, the responsitivity is several orders larger at the operating temperature 25–30 K.     

Study of the interaction of Na9[SbW9O33]·19.5H2O with bovine serum albumin: Spectroscopic and voltammetric methods

The interaction of Na₉[SbW₉O₃₃]·19.5H₂O (SbW) with bovine serum albumin (BSA) is studied by spectroscopic and voltammetric methods. Absorption spectroscopy of BSA and the linear sweep voltammetry of SbW proved the formation of ground-state SbW–BSA complex. Fluorescence quenching of serum albumin by SbW is also found to be a static quenching process. The binding constant K_a is 4.13×10⁴ L mol⁻¹ for SbW–BSA at pH 7.40 Tris–HCl buffer at 295 K. The number of binding sites and the apparent binding constants at different temperatures are obtained from the analysis of the fluorescence quenching data. The thermodynamic parameters determined by the Van’t Hoff analysis of the binding constants (ΔH=−80.01 kJ mol⁻¹ and ΔS=−182.85 J mol⁻¹ K⁻¹) clearly show that the binding is absolutely entropy driven. Hydrogen bonding and van der Waals interaction force play major role in stabilizing the complex. The effect of SbW on the conformation of BSA is analyzed using synchronous fluorescence spectroscopy.     

Magnetic hyperfine fields of Zr in nickel and iron measured by the DPAD method

The magnetic hyperfine fields of Zr in nickel and iron were measured by the DPAD method. Using the 8⁺ isomeric states in⁹⁰Zr and⁸⁸Zr these fields were found to beH _hf(ZrNi)=–4.65(10) T andH _hf(ZrFe)=–27.4(4) T, respectively.     

Ab initio study of the chemical states of water on Cr2O3(0 0 0 1): From the isolated molecule to saturation coverage

The reactivity of the (0 0 0 1)-Cr–Cr₂O₃ surface towards water was studied by means of periodic DFT + U. Several water coverages were studied, from 1.2H₂O/nm² to 14.1H₂O/nm², corresponding to ¼, 1, 2 and 3 water/Cr at the (0 0 0 1)-Cr₂O₃ surface, respectively. With increasing coverage, water gradually completes the coordination sphere of the surface Cr atoms from 3 (dry surface) to 4 (1.2 and 4.7H₂O/nm²), 5 (9.4H₂O/nm²) and 6 (14.1H₂O/nm²). For all studied coverages, water replaces an O atom from the missing above plane. At coverages 1.2 and 4.7H₂O/nm², the Cr–O_s (surface oxygen) acid–base character and bond directionality govern the water adsorption. The adsorption is molecular at the lowest coverage. At 4.7H₂O/nm², molecular and dissociative states are isoenergetic. The activation energy barrier between the two states being as low as 12 kJ/mol, allowing protons exchanges between the OH groups, as evidenced by ab inito molecular dynamics at room temperature. At coverages of 9.4 and 14.1H₂O/nm², 1D- (respectively, 2D-) water networks are formed. The resulting surface terminations are –Cr(OH)₂ and –Cr(OH)₃– like, respectively. The increased stability of those terminations as compared to the previous ones are due to the stabilization of the adsorbed phase through a H-bond network and to the increase in the Cr coordination number, stabilizing the Cr (t_2g) orbitals in the valence band. An atomistic thermodynamic approach allows us to specify the temperature and water pressure domains of prevalence for each surface termination. It is found that the –Cr(OH)₃-like, –Cr(OH)₂ and anhydrous surfaces may be stabilized depending on (T, P) conditions. Calculated energies of adsorption and OH frequencies are in good agreement with published experimental data and support the full hydroxylation model, where the Cr achieves a 6-fold coordination, at saturation.     

Sensitive intracavity photoacoustic measurements with a CO2 waveguide laser

A photoacoustic intracavity configuration is presented; a resonant photoacoustic cell excited in its first longitudinal mode is placed inside the cavity of a CO₂ waveguide laser. Due to the high laser power and the sharp intracavity focus, saturation effects occur in the excitation and relaxation process of absorbing C₂H₄ molecules. A more optimal configuration is applied to measure the C₂H₄ emission of several Rumex species. A detection sensitivity of 6 ppt (parts per trillion) C₂H₄ is reached, equivalent to a minimal detectable absorption of 1.8×10^–10 cm^–1.     

ArF laser CVD of hydrogenated amorphous silicon: The role of buffer gases

ArF laser-induced CVD has been employed to generate hydrogenated amorphous silicon (a-Si:H) from Si₂H₆ gas dilute with He, Ar, or H₂. The formation of amorphous films or powder is found to depend critically on the kind of buffer gas, the stationary total and partial gas pressures, and the substrate temperature. These dependences have been investigated in the 1–5 Torr pressure and 100–400 °C temperature ranges. They are semiquantitatively discussed in terms of ArF laser photolysis of disilane, gas heating by heat flow from the substrate and laser irradiation, diffusion, and gas phase polymerization. Furthermore, photo ionization has been observed but found irrelevant for the a-Si:H layer properties. The photo and dark conductivities ( _ph, _d) of the semiconductor layers are determined by the substrate temperature. The _ph values range between 10^–7 and 10^{–4 –1} cm^–1 and the _d values between 10^–11 and 10^{–8 –1} cm^–1. The maximum ratio _ph/ _d amounts to 4×10⁴. The layers are further characterized by their optical band gap and activation energy. The layer properties are compared to literature values of amorphous films prepared by various photo, HOMO, and plasma CVD methods.     

New experiments on origin of anisotropy in Permalloy films

A series of new experiments has been performed to determine the origin of the uniaxial anisotropy in Permalloy films. By means of a double magnetic shield enclosing the vacuum system, it was possible to deposit films in extremely small ambient fields (10^–6 to 10^–3 oersted). It was found that for deposition field strengths higher than about 10^–1 oersted, the anisotropy constant and the squareness of the hysteresis loop are essentially invariant with respect to the value of the deposition field. However, forH _d <10^–1 oersted, both the anisotropy and squareness of the loop decreases dramatically. From these experimental results, it appears that both the anisotropic Fe-pair orientation and anisotropic imperfection-alignment are deposition-field induced.     

Enhancement of upconversion luminescence in Tm/Er/Yb-codoped glass ceramic containing LiYF4 nanocrystals

A transparent Er³⁺–Tm³⁺–Yb³⁺ tri-doped oxyfluoride glass ceramics containing LiYF₄ nanocrystals were prepared. Under 980 nm laser diode (LD) pumping, intensive red, green and blue upconversion (UC) was obtained. The blue, green, and red UC radiations correspond to the transitions ¹G₄→³H₆ of Tm³⁺, ²H_11/2/⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2 of Er³⁺ ions, respectively. This is similar to that in Tm³⁺–Yb³⁺ and/or Er³⁺–Yb³⁺ co-doped glass ceramics. However, the blue UC radiations of the Er³⁺–Yb³⁺ co-doped glass ceramics is two-photon process due to cooperative energy transfer. The UC mechanisms were proposed based on spectral, kinetic, and pump power dependence analyses.     

Rashba polarization in HgCdTe inversion layers at large depletion charges

The Rashba effect in metal–insulator–semiconductor (MIS) structures based on zero-gap HgCdTe is investigated experimentally and theoretically over a wide doping range N_A–N_D=3×10¹⁵–3×10¹⁸ cm⁻³. Increase of doping enlarges the magnitude of the effect at the same 2D concentration and strengthens a gate-voltage dependence of the Rashba splitting. The results demonstrate values of Rashba polarization as high as P_R0.5 and a capability to control the Rashba effect strength at constant electron concentration.     

Observation of muonic HF molecule formation with TF μ− SR

Negative muon polarization has been measured in pure gaseous Ne (24 atm) and in Ne+H₂ mixtures (24 atm Ne+1.8 atm H₂, 8 atm H₂ and 16 atm H₂). The experiment was performed at JINR (Dubna) on aSR-spectrometer [1] with 200 G transverse magnetic field at room temperature. In pure Ne no polarization was observed (a ₀=0.09±0.1%) while in Ne+H₂ mixtures clear precession signals were detected at the free-muon frequency with asymmetries a_1.8=0.33±0.13%,a ₈=0.33±0.14% anda ₁₆=0.59±0.09%. The fact that polarization appears in the muonic HF molecule shows that at the moment of the molecule formation (t10^–10 s) the muon is not completely depolarized. The estimate of the reaction constantk=(2.3±1.6)×10^–11cm³ s^–1 agrees with the experimental values obtained by other methods. The result achieved demonstrates that ^– SR-method can be applied for studying fast kinetics processes in the gas phase and in particular for measuring chemical reaction rates of halogen atoms and ions.     

Consolidation of hydrogenation–disproportionation–desorption–recombination processed Nd–Fe–B magnets by spark plasma sintering

We have successfully consolidated hydrogenation–disproportionation–desorption–recombination (HDDR) processed Nd–Fe–Co–Zr–B–Ga powder by spark plasma sintering (SPS). The field compacted samples were sintered at different temperatures (T_S) from 550 to 600 °C with compressive pressure of 80 MPa for 20 min. Microstructural investigations by transmission electron microscopy indicated that the sintered specimen exhibits Nd₂Fe₁₄B grains of ~300 nm with Nd-rich grain boundary phase. The optimum magnetic properties of B_r: 1.22 T, H_c: 928 kA/m, _BH_c: 600 kA/m, (BH)_max: 210 kJ/m³ were obtained in the sample sintered at 550 °C. The strategy for further improving the coercivity and remanence is discussed based on the microstructure-property relationships.