Chalcogen based treatment of InAs with [(NH4)2S/(NH4)2SO4]

A sulphur based chemical, ([(NH₄)₂S/(NH₄)₂SO₄]) to which S has been added not previously reported for the treatment of (111)A InAs surfaces is introduced and benchmarked against the commonly used passivants Na₂S·9H₂O and ((NH₄)₂S + S), using Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It has been found that the native oxide layer present on the InAs surface is more effectively removed when treated with ([(NH₄)₂S/(NH₄)₂SO₄] + S) than with ((NH₄)₂S + S) or Na₂S·9H₂O. AES depth profiles of the sulphurized layers revealed the formation of a thin (less than 8.5 nm) In–S surface layer for both ((NH₄)₂SO₄ + S) and ([(NH₄)₂S/(NH₄)₂SO₄] + S) treatments. No evidence for the formation of As―S bonds was found. Treatment with ([(NH₄)₂S/(NH₄)₂SO₄] + S) also affected a significant improvement compared to the more established sulphur treatments in the surface morphology of the otherwise poor as-received n-InAs (111)A surface.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Optimisation of the ammonium sulphide (NH4)2S passivation process on In0.53Ga0.47As

The passivation of III-V semiconductor materials with sulphur is widely reported to reduce interface state defects and improve semiconductor device performance. The most common approach utilises ammonium sulphide ((NH₄)₂S), however there are wide variations in the reported processing parameters involved in this procedure. This study provides a comprehensive review of the various parameters used as well as determining the optimal processing conditions in terms of sample pre-treatments, temperature of the (NH₄)₂S solution, length of time the sample is in the solution and (NH₄)₂S concentration, by measuring the level of residual native oxides and surface roughness by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively.     

中性(NH4)2S溶液钝化GaAs(100)表面的研究

采用同步辐射光电子能谱(SRPES)结合扫描电子显微镜(SEM)和称量法，研究了中性(NH₄)₂S溶液钝化GaAs(100)表面，并与常规(NH₄)₂S碱性溶液钝化方法进行了比较- SRPES结果表明该处理方法可以产生较厚的Ga硫化物层和较强的Ga—S键，Ga的硫化物有好的稳定性-称量法表明该方法有更低的腐蚀速率-SEM结果表明该方法钝化处理的GaAs表面所产生的腐蚀坑数目少，直径小- 关键词：     

H nuclear magnetic resonance study of the ferroelastic and superionic phase transitions of (NH4)4LiH3(SO4)4 single crystals

We investigated the temperature dependences of the line shape, spin-lattice relaxation time, T₁, and spin-spin relaxation time, T₂, of the ¹H nuclei in (NH₄)₄LiH₃(SO₄)₄ single crystals. On the basis of the data obtained, we were able to distinguish the “ammonium” and “hydrogen-bond” protons in the crystals. For both the ammonium and hydrogen-bond protons in (NH₄)₄LiH₃(SO₄)₄, the curves of T₁ and T₂ versus temperature changed significantly near the ferroelastic and superionic phase transitions at T_C (=232 K) and T_S (=405 K), respectively. In particular, near T_S, the ¹H signal due to the hydrogen-bond protons abruptly narrowed and the T₂ value for these protons abruptly increased, indicating that these protons play an important role in this superionic phase transition. The marked increase in the T₂ of the hydrogen-bond protons above T_S indicates that the breaking of O-H?O bonds and the formation of new H-bonds with HSO₄^- contribute significantly to the high-temperature conductivity of (NH₄)₄LiH₃(SO₄)₄ crystals.     

AC electrical properties of the mixed crystal (NH4)3H(SO4)1.42(SeO4)0.58

The frequency dependence of the AC conductivity of (NH₄)₃H(SO₄)_1.42(SeO₄)_0.58 (NHSSe) has been presented in the temperature range (299-393 K). The conductivity data has been analysed in terms of two theoretical models: hopping over a potential barrier model and quantum-tunnelling model. Values of the exponent s, decrease from 1.08 to 0.91 with increasing temperature and the experimental data revel that the hopping model is the rate determining mechanism.     

Phase transitions and molecular motions in [Zn(NH3)4](BF4)2 studied by nuclear magnetic resonance, infrared and Raman spectroscopy

Middle infrared absorption, Raman scattering and proton magnetic resonance relaxation measurements were performed for [Zn(NH₃)₄](BF₄) in order to establish relationship between the observed phase transitions and reorientational motions of the NH₃ ligands and BF₄⁻ anions. The temperature dependence of spin-lattice relaxation time (T₁(¹H)) and of the full width at half maximum (FWHM) of the bands connected with ρ_r(NH₃), ν₂(BF₄) and ν₄(BF₄) modes in the infrared and in the Raman spectra have shown that in the high temperature phase of [Zn(NH₃)₄](BF₄)₂ all molecular groups perform the following stochastic reorientational motions: fast (τ_R≈10⁻¹² s) 120° flips of NH₃ ligands about three-fold axis, fast isotropic reorientation of BF₄⁻ anions and slow (τ_R≈10⁻⁴ s) isotropic reorientation (“tumbling”) of the whole [Zn(NH₃)₄]²⁺ cation. Mean values of the activation energies for uniaxial reorientation of NH₃ and isotropic reorientation of BF₄⁻ at phases I and II are ca. 3 kJ mol⁻¹ and ca. 5 kJ mol⁻¹, respectively. At phases III and IV the activation energies values for uniaxial reorientation of both NH₃ and of BF₄⁻ equal to ca. 7 kJ mol⁻¹. Nearly the same values of the activation energies, as well as of the reorientational correlation times, at phases III and IV well explain existence of the coupling between reorientational motions of NH₃ and BF₄⁻. Splitting some of the infrared bands at T_C2=117 K suggests reducing of crystal symmetry at this phase transition. Sudden narrowing of the bands connected with ν₂(BF₄), ν₄(BF₄) and ρ_r(NH₃) modes at T_C3=101 K implies slowing down (τ_R?10⁻¹⁰ s) of the fast uniaxial reorientational motions of the BF₄⁻ anions and NH₃ ligands at this phase transition.     

Brillouin scattering study of phase transitions in LiK0.80(NH4)0.20SO4 mixed crystals

Brillouin spectroscopy was used to study the phase transitions of LiK_0.80(NH₄)_0.20SO₄ mixed crystals in the temperature range 10-300 K. The relevant elastic stiffness coefficients were evaluated at room temperature. The quasi-longitudinal γ₁₆ and the quasi-transverse γ₁₇ mode frequencies were measured in the above temperature range. From their frequency vs. temperature curve, three different phase transitions were determined. Two of the four phases presented by the crystal were found to be ferroelastic. The observed phases are tentatively assigned through a comparison with the phase transitions undergone by LiKSO₄ and LiK_0.96(NH₄)_0.04SO₄ crystals. An anomalous behavior of the Brillouin linewidth near the 260 K phase transition was observed.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

Optical studies of (NH4)2SO4 single crystal in the paraelectric phase

Transmittance and absorbance spectra of (NH₄)₂SO₄ single crystals along [010] direction were measured at different temperatures (296, 308, 318, 328 and 348 K) in the paraelectric phase. The absorption coefficient was computed and the analysis of the data revealed the existence of two optical transitions in (NH₄)₂SO₄ single crystals. The direct and indirect band gaps were shifted towards the longer wavelength with increasing temperature. The data on the allowed indirect transition was analyzed and interpreted in terms of two valence bands originated by spin orbit interaction and crystal field splitting. The momenta E_p were calculated as the difference between E_g1, the first valence to conduction band, and E_g2 for the second valence band at different temperatures. The results of extinction coefficient (k), the refractive index (n), and dielectric constants (ε) were also discussed and calculated as a function of wave length (λ). The heat treatment of the crystals proved that the variations of these optical parameters can be consequence of the internal microstructure changes caused by annealing.     

Studies of thermal decomposition of (NH4)2Fe(SO4)2·6H2O

Thermal decomposition products of the Mohr salt (NH₄)₂Fe(SO₄)₂·6H₂O have been studied and identified using the Mössbauer effect, X-ray diffraction, infrared spectroscopy, and the gravimetric and thermal differential methods. It has been found that the Mohr salt heated for 96 hr. in air at 520K changes to a single substance identified as NH₄Fe(SO₄)₂ with a single Mössbauer line (width 0.30 mm/sec; isomeric shift 0.30 mm/sec). When the Mohr salt is heated for 1 hr. in air at 770 K it changes to Fe₂(SO₄)₃ with a single Mössbauer line (width 0.33 mm/sec; isomeric shift 0.31 mm/sec) strikingly similar to line of NH₄Fe(SO₄)₂.     

Electrical and thermal studies in the commensurate incommensurate phase region of (NH4)2ZnCl4 single crystal

DC electrical conductivity for a virgin and poled annealed (NH₄)₂ZnCl₄b-axis single crystal shows a defect controlled property. A Schottky mechanism is a probable mechanism of conduction in regions of strong structural transitions. The rise of conductivity in the incommensurate and paraelectric phases is linked to an increase in discommensurations density. The activation energies (ΔE) in the three phases region were calculated. DTA measurements shows that the crystal is stable up to 200 °C and the phase transition temperatures were observed at 42, 94.8 and 137 °C. The effective activation energy (E_e) was obtained using Kissinger and Mahadevan equations. It was found to be equal to 0.49 eV. This correlates with the value obtained through DC conductivity.     

Low temperature electrical conductivity,dielectric constant,and phase transitions in (NH4)2SO4 and (ND4)2SO4

Careful axiswise measurements of d.c. conductivity and dielectric constants of (NH₄)₂SO₄ from 50 to - 196°C establish two distinct phase transitions, instead of one, at temperatures -49.5 and -58°C which remain unchanged in (ND₄)₂SO₄. Explanation based on successive distortions of non-equivalent (NH₄)⁺ is offered. Low temperature transport process in the crystal also is discussed.     

Effect of chemical surface treatments on interfacial and electrical characteristics of atomic-layer-deposited Al2O3 films on Ge substrates

The Ge surfaces were cleaned and passivated by two kinds of chemical pretreatments: conventional combination of HF + (NH₄)₂S, and new one of HBr + (NH₄)₂S. The chemical states and stability at passivated Ge surfaces were carefully characterized. The influence of chemical surface treatments on the interface and electrical properties of Al₂O₃ gate dielectric films on Ge grown by atomic layer deposition (ALD) has been investigated deeply. It is found that the combination of HBr and (NH₄)₂S can remove more Ge-O bonds on the Ge surface compared to that of conventional HF and (NH₄)₂S with excellent stability. X-ray photoelectron spectroscopy (XPS) reveals that HBr and (NH₄)₂S treated Ge surface has a mixture states of GeO_x (9.25%) and GeS (7.40%) while HF and (NH₄)₂S treated Ge surface has a mixture states of GeO_x (16.45%) and GeS (3.37%). And the Ge-S peak from the surface of Ge substrates decreases a little after the HBr and (NH₄)₂S treated Ge surface was exposed in the ambient for 300 min, which suggests the Ge surface is stable to oxidants. The Al₂O₃ films on HBr and (NH₄)₂S treated Ge substrates exhibits better electrical properties such as large capacitance, decreased leakage current density by ∼two orders of magnitude, and less C-V hysteresis. This indicates that a reduction in charge traps possibly at the interface and more interface traps are terminated by sulfur. The surface treatment of HBr and (NH₄)₂S seems to be very promising in improving the quality of high-k gate stack on Ge substrates.     

Proton conduction in (NH4)3 H(SO4)2 single crystals

D.C. electrical conductivity, DTA and coulometric studies on (NH₄)₃ H(SO₄)₂ single crystals are made. Conductivity is markedly anisotropic with maximum along c¹ direction. A sudden jump in the conductivity plot along c¹ direction at 413 K is supported by a large endothermic peak in DTA, confirming the presence of transition at this temperature. The values of activation energy calculated from conductivity measurements indicated that the charge carriers are protons. This was further confirmed by coulometric experiment where the gas evolved was hydrogen, as established by a gas chromatograph and the volume of H₂ released agreed with that expected from electrolysis. The mechanism of protonic conduction in this crystal is discussed.     

On the power-law behavior of the AC conductivity of the mixed crystal (NH4)3H(SO4)1.42(SeO4)0.58

A power law used to describe the AC conductivity from 299 to 393 K of the mixed crystal (NH₄)₃H(SO₄)_1.42(SeO₄)_0.58 led to fractional exponent values ranging from 1.08 to 0.91, depending on structural changes induced on temperature variation [B. Louati, M. Gargouri, K. Guidara and T. Mhiri, J. Phys. Chem. Solids 66 (2005) 762]. In the present note, we suggest that the fractional law exhibits features of lattice relaxation. Despite the structural changes, the parameters of the power law are mutually interconnected to yield a temperature independent phenomenon. Such behavior is probably of general validity and characterizes the universal fractional dispersion of the AC conductivity, as it was also observed in glasses of different composition.     

Magnetic susceptibility studies of (CH2)3(NH3)2FeCl2Br2 and (CH2)6(NH3)2FeCl2Br2

The magnetic susceptibility of the layered compounds (CH₂)₃(NH₃)₂FeCl₂Br₂ and (CH₂)₆(NH₃)₂FeCl₂Br₂ has been measured in the range 80 < T < 300 K. The results follow a Curie-Weiss behavior in the range 120 < T < 300 K but are field dependent for T < 120 K. The results are interpreted in terms of a two-dimensional antiferromagnetic interaction which is canted. A comparison with the corresponding pure chloride compounds is given.     

Synthesis and luminescence properties of red-emitting phosphors NaY0.87Eu0.13(WO4)1.2(MoO4)0.8

A series of NaY_1−yEu_y(WO₄)_2−x(MoO₄)_x (x=0−2 and y=0.06−0.15) phosphors have been prepared by a combustion route. X-ray powder diffraction, photoluminescence excitation and emission spectra were used to characterize the resulting samples. The excitation spectra of these phosphors show the strongest absorption at about 396 nm, which matches well with the commercially available n-UV-emitting GaN-based LED chip. Their emission spectra show an intense red emission at 616 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. As the Mo content increases, the intensity of the ⁵D₀→⁷F₂ emission of Eu³⁺ activated at wavelength of 396 nm increases and reaches a maximum when the relative ratio of Mo/W is 2:3. The intense red-emission of the tungstomolybdate phosphors at near-UV excitation suggests that the material is a potential candidate for white light emitting diode (WLEDs).     

New quasi-one-dimensional tetracyanidoplatinate,Cs4[Pt(CN)4](CF3SO3)2: Synthesis,structure, and physical characterization

The synthesis and some physical properties of a new quasi-one-dimensional tetracyanidoplatinate, Cs₄[Pt(CN)₄](CF₃SO₃)₂ (CsCP(OTf)) are reported and described in comparison to the well-known K₂[Pt(CN)₄]Br_0.30·3.2H₂O (KCP). Single-crystal X-ray diffraction reveals Pt–Pt spacings to be greater than those of KCP by 5% longitudinal and 38% transverse, but much shorter than comparable spacings in other non-partially oxidized platinates. Anomalies are observed between temperatures 100 K and 200 K: (1) Longitudinal DC conductivity is two orders of magnitude higher and is non-monotonic with temperature, showing a minimum at around 170 K. (2) Nuclear magnetic resonance (NMR) longitudinal relaxation time T₁ is at least three orders of magnitude higher than that of KCP, and is also non-monotonic with temperature, showing a sharp peak at around 120 K. Since X-ray diffraction reveals no structural transition at 120 K, these suggest a possible lattice freezing or stiffening at around 120 K.     

Aimantation a basse temperature de deux sels ferromagnetiques uniaxes. Cu(NH4)2Br4, 2H2O ET CuRb2Br4, 2H2O

The low temperature spontaneous magnetization of the spin 1/2 b.c.c. ferromagnet has been computed using the self-consistently renormalized spin-wave theory of Bloch, taking into account weakly anisotropic exchange. A good agreement with our experimental data in Cu(NH₄)₂Br₄, 2H₂O and CuRb₂Br₄, 2H₂O is observed for 0 < T/T_{c < 0.5}, using the following anisotropy fields at 0°K: (293 ± 25) oe in Cu(NH₄)₂Br₄, 2H₂O and (300 ± 25)oe in CuRb₂Br₄, 2H₂O.