Sign and amplitude of charge density waves in 1T-TaS2 and TaSe2

The effect of charge density waves has been observed in X-ray photoelectron spectra of 1T-TaS₂ and TaSe₂ as a perturbation of the core-electron binding energies. In the commensurate CDW range the Ta 4f levels show a marked splitting; in the quasi-commensurate and incommensurate states they show broadening of magnitude comparable to this splitting.     

Search for a sliding charge density wave in layered compounds

Non-linear voltage-current behavior is observed in the quasi one dimensional compound NbSe₃, due to the contribution of a sliding Charge Density Wave (CDW) to the conductivity. We have looked for a non-linear voltage-current characteristics in the incommensurate CDW state of the layered compounds 2H-TaSe₂ and 1T-TaS₂ and find no evidence for such up to $\text{1.0V}\text{cm}$ and $\text{10V}\text{cm}$, respectively. These values are several orders of magnitude higher than the minimum depinning field observed in NbSe₃.     

Anomalous magnetoresistance in 1T-TaS2

Transverse magnetoresistance of 1T-TaS₂ was measured in magnetic fields up to 100 kOe in the semiconductive region corresponding to the commensurate charge density wave (CDW) state.     

Cathodoluminescence degradation of PLD thin films

The cathodoluminescence (CL) intensities of Y₂SiO₅:Ce³⁺, Gd₂O₂S:Tb³⁺ and SrAl₂O₄:Eu²⁺,Dy³⁺ phosphor thin films that were grown by pulsed laser deposition (PLD) were investigated for possible application in low voltage field emission displays (FEDs) and other infrastructure applications. Several process parameters (background gas, laser fluence, base pressure, substrate temperature, etc.) were changed during the deposition of the thin films. Atomic force microscopy (AFM) was used to determine the surface roughness and particle size of the different films. The layers consist of agglomerated nanoparticle structures. Samples with good light emission were selected for the electron degradation studies. Auger electron spectroscopy (AES) and CL spectroscopy were used to monitor changes in the surface chemical composition and luminous efficiency of the thin films. AES and CL spectroscopy were done with 2 keV energy electrons. Measurements were done at 1×10⁻⁶ Torr oxygen pressure. The formation of different oxide layers during electron bombardment was confirmed with X-ray photoelectron spectroscopy (XPS). New non-luminescent layers that formed during electron bombardment were responsible for the degradation in light intensity. The adventitious C was removed from the surface in all three cases as volatile gas species, which is consistent with the electron stimulated surface chemical reaction (ESSCR) model. For Y₂SiO₅:Ce³⁺ a luminescent SiO₂ layer formed during the electron bombardment. Gd₂O₃ and SrO thin films formed on the surfaces of Gd₂O₂S:Tb³⁺ and SrAl₂O₄:Eu²⁺,Dy³⁺, respectively, due to ESSCRs.     

Comment on ‘structure of α-Fe2O3 single crystal surfaces following Ar+ ion bombardment and annealing in O2’ by R.J. Lad and V.E. Henrich

A recent paper by Lad and Henrich [Surface Sci. 193 (1988) 81], on the phase changes induced by Ar⁺ bombardment and annealing in O₂ at Fe₂O₃ single crystal surfaces, is commented upon. It is pointed out that quantitative XPS analysis would have provided more direct information on phase changes induced by surface treatments. It is suggested that chemical effects contribute to the O 1s spectrum asymmetry observed in Ar⁺ bombarded Fe₂O₃ surfaces.     

High-pressure X-ray diffraction study of 1T-TaS2

We present a room temperature high-pressure X-ray diffraction study of the layered compound 1T-TaS₂ up to 20 GPa. This material is known to exhibit a variety of structural phase transitions that are ascribed to the stabilization of charge density wave states. It has been recently shown that at pressures larger than 3 GPa and up to 25 GPa, 1T-TaS₂ becomes superconductor below about 5 K. It was suggested that this superconductivity coexists with different CDW states, an hypothesis that can be tested by X-ray diffraction. Our first results at room temperature show that at around 1.9 GPa, the nearly-commensurate (NCCDW) phase transforms into a phase similar to the high temperature incommensurate phase (ICCDW). Above 9 GPa, we show the existence of another IC phase, still discernable up to 20 GPa despite the pressure-induced crystal damage above 13 GPa. These results are consistent with resistivity measurements, but call for a complete exploration of the P–T phase diagram of 1T-TaS₂.     

Preparation and properties of a new polytype of tantalum disulfide (4Hb-TaS2)

A new polymorph of the layered compound tantalum disulfide, 4Hb-TaS₂, has been prepared in single crystal form. Measurements of magnetic susceptibility, electrical resistivity, and differential heat capacity show two first order transitions at 20 and 315°K. The 315°K transition involves only a small volume and enthalpy change, as in the previously observed transitions of another polymorph, 1T-TaS₂. The resistivity measurements show metallic like conductivity, as in 2H-TaS₂, when the current is parallel to the layers, but semiconducting like conductivity, as in 1T-TaS₂, when perpendicular to the layers. The properties of 4Hb-TaS₂ are moderately well described as a ‘mix’ of those of 1T-TaS₂ and 2H-TaS₂.     

Electron beam induced green luminescence and degradation study of CaS:Ce nanocrystalline phosphors for FED applications

Green luminescence and degradation of Ce³⁺ doped CaS nanocrystalline phosphors were studied with a 2 keV, 10 μA electron beam in an O₂ environment. The nanophosphors were synthesized by the co-precipitation method. The samples were characterized using X-ray diffraction, Transmission electron microscopy, Scanning electron microscopy/electron dispersive X-ray spectroscopy and Photoluminescence (PL) spectroscopy. Cubic CaS with an average particle size of 42 ± 2 nm was obtained. PL emission was observed at 507 nm and a shoulder at 560 nm with an excitation wavelength of 460 nm. Auger electron spectroscopy and Cathodoluminescence (CL) were used to monitor the changes in the surface composition of the CaS:Ce³⁺ nanocrystalline phosphors during electron bombardment in an O₂ environment. The effect of different oxygen pressures ranging from 1 × 10⁻⁸ to 1 × 10⁻⁶ Torr on the CL intensity was also investigated. A CaSO₄ layer was observed on the surface after the electron beam degradation. The CL intensity was found to decrease up to 30% of its original intensity at 1 × 10⁻⁶ Torr oxygen pressure after an electron dose of 50 C/cm². The formation of oxygen defects during electron bombardment may also be responsible for the decrease in CL intensity.     

Ion survival probabilities for 3 keV Ar+ scattering from La,Yb, and chemisorbed H2, O2, and H2O on La surfaces

TOF spectra of scattered primary and surface recoiled neutrals and ions for 3 keV Ar⁺ bombardment of clean La and Yb and H₂, O₂, and H₂O saturated La surfaces are presented. The spectra are analyzed in terms of single (SS) and multiple (MS) scattering of the primary ions and surface recoiling (SR) of adsorbate atoms. Measurement of spectra of neutrals + ions and neutrals alone allows determination of scattered ion fractions Y. The Y values for the SS event are high for clean La (37%) and lower for adsorbate covered La (32% for H₂, 13% for O₂, and 8% for H₂O); Yb exhibits a similar behavior, i.e. 16% for clean Yb and 5% for O₂ + H₂O covered Yb. Photon emission accompanying the scattering collision has been observed from clean La and Yb and adsorbate covered La. A preferential inelastic energy loss of 15 ± 3 eV for the SS event has been observed for scattered neutrals as opposed to ions for La and H₂ saturated La at 135°. These results are interpreted within the models for Auger and resonant electronic charge exchange transitions during approach or departure of an ion with a surface and the electron promotions occuring during close atomic encounters where the electron shells are interpenetrating.     

An XPS study on the surface reduction of V2O5(0 0 1) induced by Ar ion bombardment

The effect of the irradiation with Al Kα X-rays during an XPS measurement upon the surface vanadium oxidation state of a fresh in vacuum cleaved V₂O₅(0 0 1) crystal was examined. Afterwards, the surface reduction of the V₂O₅(0 0 1) surface under Ar⁺ bombardment was studied. The degree of reduction of the vanadium oxide was determined by means of a combined analysis of the O1s and V2p photoelectron lines. Asymmetric line shapes were needed to fit the V³⁺2p photolines, due to the metallic character of V₂O₃ at ambient temperature. Under Ar⁺ bombardment, the V₂O₅(0 0 1) crystal surface reduces rather fast towards the V₂O₃ stoichiometry, after which a much slower reduction of the vanadium oxide occurs.     

Water adsorption on the (001) plane of Fe2O3: An XPS,UPS, Auger,and TPD study

Thermal programmed desorption, ultraviolet photoelectron spectroscopy, and X-ray photoelectron spectroscopy have been used to study the reaction of H₂O with stoichiometric and partially reduced single crystals of α-Fe₂O₃. On the stoichiometric surface only ice condensation below 200 K was observed. Oxygen deficient surfaces were prepared by Ar bombardment giving rise to a decrease in the work function of the crystal of up to 1 eV. On these surfaces OH species were formed as detected by UPS that were stable up to 320 K. Annealing the defective surfaces between 475 and 700 K increased the work function by values between 0.5 and 0.7 eV respectively. These surfaces contained reduced Fe²⁺ species in subsurface layers as shown by UPS and XPS, but were inactive towards H₂O chemisorption. The Fe²⁺ species were stable for long periods of time at temperatures of up to 775 K. Potassium deposited on the surface forms a strongly bound monolayer compound. With H₂O it produced a complex that resulted in H₂ evolution upon annealing.     

Structural and compositional changes in ion-bombarded Ta2O5

A detailed study of the effect of heavy-ion bombardment on Ta₂O₅ has been undertaken using a combination of radioactive tracer techniques, electron microscopy, and Rutherford backscattering. Crystalline Ta₂O₅ is amorphized at ~6 × 10¹³ ions cm^?2, while at a dose of ~5 × 10¹⁶ ions cm^?2 the electron microscopy reveals the development of random grains of a new crystalline phase. By ~1 × 10¹⁷ ions cm^?2 the grains are not yet overlapping but still yield a diffraction pattern consistent with either δ-Ta-O (not to be confused with TaO) or Ta_1?xO₂, thus indicating that Ta₂O₅, like most other transition-metal oxides, is subject to preferential sputtering. Preferential sputtering was confirmed by backscattering analysis of specimens bombarded to high doses, where the average surface composition was found to be Ta_1.8±0.2O₂ or, equivalently, Ta₂O_2.2±0.2. The surface alteration had an average composition independent of the mass and energy of the incident ions.     

Isotope effects in Raman spectra of crystalline alkali-metal chlorates and bromates

Halogen and oxygen atom isotope effects have been observed in Raman spectra of single crystal NaClO₃, KClO₃, NaBrO₃, and KBrO₃. Orientational splitting of ³⁵Cl¹⁶O₂¹⁸O^? and ³⁷Cl¹⁶O₂¹⁸O^? ion vibrational modes was observed in KClO₃. Splitting of the v₁ mode of ⁷⁹Br and ⁸¹Br isotopes of singly substituted ¹⁷O and ¹⁸O bromate ions in NaBrO₃ and KBrO₃ is on the order of 1.5 cm^?1 in agreement with a calculation of isotopic frequencies. However, the predicted splitting between v₁ of the major isotopes, ⁷⁹Br¹⁶O₃^? and ⁸¹Br¹⁶O₃^?, was not observed, and the results of a band contour analysis suggest that a single k = 0 phonon is derived from the totally symmetric stretching mode of both species.     

X-ray photoelectron spectroscopy analysis for undegraded and degraded Gd2O2S:Tb phosphor thin films

This paper presents the X-ray Photoelectron Spectroscopy (XPS) analysis for the undegraded and degraded Gd₂O₂S:Tb³⁺ thin film phosphor. The thin films were grown with the pulsed laser deposition (PLD) technique. XPS measurements were done on Gd₂O₂S:Tb³⁺ phosphor thin films before and after electron degradation. The XPS technique has proven the presence of Gd₂O₃ on the degraded and undegraded thin film spots. The presence of the SO₂ bonding was also detected after degradation. This clearly indicates that surface reactions did occur during prolonged electron bombardment in an oxygen atmosphere.     

Relation between magnetic hyperfine field distribution and cation order in natural hedenbergite

Mössbauer and magnetic measurements have been performed at various temperatures between 1.5K and 300K on a natural hedenbergite Ca_0.96 Mg_0.19 Fe_0.82Mn_0.02Si₂O₆. The magnetic measurements are consistent with a ferromagnetic alignment of the Fe²⁺ moments inside each zig-zag M1 chain and antiferromagnetic alignment of the moments of neighbouring chains. Above T_N (Mössbauer)=29±2K, a single quadrupole doublet attributed to Fe²⁺ in the M1 sites is observed. At 4.2K, the Mössbauer spectra can be accounted for by a discrete distribution of six hyperfine field components which can be related to all the possible Fe²⁺?Mg²⁺ configurations up to second cation neighbours surrounding a central⁵⁷Fe²⁺ probe.     

High pressure luminescence study of Sm3+: K–Ba–Al fluorophosphate glass

The luminescence spectra and decay curves for the ⁴G_5/2 level of Sm³⁺ ions in 55.95P₂O₅+14K₂O+6KF+14.95BaO+9Al₂O₃+0.1Sm₂O₃ glass, referred to as PKFBASm01, have been studied as a function of pressure up to 40.5 GPa at room temperature. With the increase in pressure, a continuous red shift of the ⁴G_5/2→⁶H_{9/2, 7/2, 5/2} transitions and a progressive increase in the magnitude of the crystal-field splittings for these transitions are observed. The decay curves for the ⁴G_5/2 level of the Sm³⁺ ions in PKFBASm01 glass are found to exhibit single exponential behavior at ambient pressure and become non-exponential at higher pressures, accompanied by shortening of lifetimes. A generalized Yokoto–Tanimoto model has been used to explain the pressure-induced non-exponential nature of the decay curves.     

Chemical reactions induced by 40 keV He+ ions in Fe3O4 and α-Fe2O3

The chemical reactions induced by 40 keV He⁺ ions in α-Fe₂O₃ and Fe₃O₄ were investigated by the conversion electron Mössbauer spectroscopy(CEMS). Magnetite(Fe₃O₄) was formed upon the bombardment of α-Fe₂O₃, whereas no change was observed in Fe₃O₄. The initial G value for Fe₃O₄ formation is estimated to be 3.5×10^?4 for 100 nm depth from the surface. The application of CEMS and sputtering technique to ion bombardment chemistry is discussed.     

The energy transfer processes in LaMgB5O10:Pr, Mn

Pr³⁺, Mn²⁺ singly doped and co-doped LaMgB₅O₁₀ samples were prepared by solid-state reaction and their spectroscopic properties were investigated by synchrotron radiation VUV light. Significant spectra overlap between the Mn²⁺⁶A_1g→(⁴E_g, ⁴A_1g) excitation (centered at 412 nm) and the Pr³⁺¹S₀→(¹I₆, ³P_J) emission (410 nm) provided the possibility of energy transfer from Pr³⁺ to Mn²⁺. In the LaMgB₅O₁₀:Pr³⁺, Mn²⁺ samples investigated, the expected energy transfer process was observed as comparing the emission spectra of LaMgB₅O₁₀:Pr³⁺, Mn²⁺ samples with that of the LaMgB₅O₁₀:Mn²⁺. The shorter decay time of the ¹S₀→(¹I₆, ³P_J) transition in the co-doped samples was also an evidence of energy transfer from Pr³⁺ to Mn²⁺. By analyzing the energy transfer process, it was found that the energy transfer process in LaMgB₅O₁₀:Pr³⁺, Mn²⁺ was likely of resonant energy transfer and the re-absorption process can be excluded. The critical distances of energy transfer based on the electric dipole-dipole interaction and electric dipole-quadrupole interaction were calculated to be 4.78 and 9.46 Å in LaMgB₅O₁₀:Pr³⁺, Mn²⁺, respectively, which are smaller than the mean distance of Pr³⁺ and Mn²⁺ (17 Å) in the highest concentration-doped sample. The near neighboring PrMn clusters formed in the LaMgB₅O₁₀ host is responsible for the energy transfer process.     

Photoluminescence and phosphorescence properties of MAl2O4:Eu, Dy (M=Ca, Ba, Sr) phosphors prepared at an initiating combustion temperature of 500 °C

Eu²⁺ and Dy³⁺ co-doped calcium aluminate, barium aluminate and strontium aluminate phosphors were synthesized at an initiating combustion temperature of 500 °C using urea as an organic fuel. The crystallinity of the phosphors was investigated by using X-ray diffraction (XRD) and the morphology was determined by a scanning electron microscope (SEM). The low temperature monoclinic structure for both CaAl₂O₄ and SrAl₂O₄ and the hexagonal structure of BaAl₂O₄ were observed. The effect of the host materials on the photoluminescence (PL) and phosphorescence properties were investigated by using a He-Cd Laser and a Cary Eclipse fluorescence spectrophotometer, respectively. The broad band emission spectra observed at 449 nm for CaAl₂O₄:Eu²⁺, Dy³⁺, 450 nm (with a shoulder-peak at 500 nm) for BaAl₂O₄:Eu²⁺, Dy³⁺ and 528 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ are attributed to the 4f⁶5d¹ to 4f⁷ transition in the Eu²⁺ ion in the different hosts.     

The effect of different gas atmospheres on luminescent properties of pulsed laser ablated SrAl2O4:Eu,Dy thinfilms

SrAl₂O₄:Eu²⁺,Dy³⁺ thin films were grown on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique to investigate the effect of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological, photoluminescence (PL) and cathodoluminescence (CL) properties of the films. The films were ablated using a 248 nm KrF excimer laser. Atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and fluorescence spectrophotometry were used to characterize the thin films. Auger electron spectroscopy (AES) combined with CL spectroscopy were employed for the surface characterization and electron-beam induced degradation of the films. Better PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres with respect to those prepared in vacuum. A stable green emission peak at 515 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions were obtained with less intense peaks at 619 nm, which were attributed to transitions in Eu³⁺. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The CL intensity increased under prolonged electron bombardment during the removal of C due to electron stimulated surface chemical reactions (ESSCRs) on the surface of the SrAl₂O₄:Eu²⁺, Dy³⁺ thin films. The CL stabilized and stayed constant thereafter.