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.     

Improved GaSb surfaces using a (NH4)2S/(NH4)2S04 solution

Bulk (1 0 0) n-GaSb surfaces have been treated with a sulphur based solution ((NH₄)₂S/(NH₄)₂SO₄) to which sulphur has been added, not previously reported for the passivation of GaSb surfaces. Au/n-GaSb Schottky barrier diodes (SBDs) fabricated on the treated material show significant improvement compared to that of the similar SBDs on the as-received material as evidenced by the lower ideality factor (n), higher barrier height (?_b) and lower contact resistance obtained. Additionally, the reverse leakage current, although not saturating, has been reduced by almost an order of magnitude at −0.2 V. The sample surfaces were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The native oxide, Sb–O, present on the as-received material is effectively removed on treating with ([(NH₄)₂S/(NH₄)₂SO₄]+S) and (NH₄)₂S. Analysis of the as-received surface by XPS, prior to and after argon sputtering, suggests that the native oxide layer is ≤8.5 nm.     

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：     

Hydrothermal preparation and characterization of Cd0.9Mn0.1S nanorods

Cd_0.9Mn_0.1S semiconductor nanorods were successfully prepared by the hydrothermal reaction of CdCl₂·2.5H₂O and MnCl₂·5H₂O with (NH₄)₂S in aqueous solution. Atomic absorption spectrometry (AAS) and energy dispersive spectroscopy (EDS) were used to determine the Mn contents of these complex nanorods. The samples were characterized by scanning electron microscopy (SEM-EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis absorption spectra, photoluminescence (PL) and compared with the undoped CdS nanorods. The results showed that nanostructured multiplex compounds with high aspect ratio were obtained via hydrothermal method. The products showed almost totally rod-like morphology with approximately identical diameter about 20 nm and the maximal length up to 200 nm.     

Chlorine K X-ray absorption-edge structures of CIS-[Pt(NH3)2Cl2], trans-[Pt(NH3)2Cl2], trans-[Pd(NH3)2Cl2] and (NH4)2PdCl4

The K absorption-edge spectra of the ligand chlorine ion in square-planar complex compounds cis- and trans-[Pt(NH₃)₂Cl₂], trans-[Pd(NH₃)₂Cl₂], and (NH₄)₂PdCl₄ are reported and discussed in connection with the chlorine K absorption spectra of K₂PtCl₄ and K₂PdCl₄, reported previously. The observed chemical shift of a white line at the absorption threshold is interpreted in terms of the difference of the ligand-field splitting of electronic states for metal ions. The white line is attributed to the electronic transition from the Cl^? ls level to the lowest unoccupied antibonding molecular orbital (MO), which is specified by a $\text{MO}\text{b}{}_{\mathrm{1g}}\text{(σ}{}^1\text{)}$ in the square-planar complex with D_4h symmetry. The other absorption structures are regarded as continuum “shape resonances” of the outgoing electron trapped by the cage of the surrounding atoms. The effect of geometrical isomerism is found in the chlorine K absorption spectra of cis- and trans-[Pt(NH₃)₂Cl₂].     

Extremely large binding energy of biexcitons in an organic-inorganic quantum-well material (C4H9NH3)2PbBr4

We have confirmed biexciton formation in an organic-inorganic hybrid quantum-well material (C₄H₉NH₃)₂PbBr₄ by photoluminescence and two-photon absorption measurements. The biexciton has extremely large binding energy, 60 meV, which to our knowledge is the largest value ever reported for a semiconductor. By analyzing the spectrum of biexciton luminescence, the biexciton gas temperature was found to be much higher than the bath temperature due to a higher local temperature arising from the large biexciton binding energy.     

Characterization of new-layered Cr(III)-doped chlorocadmiumphosphate, Cd(HPO4)Cl·[H3N(CH2)6NH3]0.5 crystal by EPR and optical studies

Cr(III)-doped Cd(HPO₄)Cl·[H₃N(CH₂)₆NH₃]_0.5, a new-layered cadmium phosphate, is synthesized in acidic condition at room temperature. EPR and optical studies are carried out at room temperature. Polycrystalline EPR spectrum reveals the presence of two sites of Cr(III) ions in this layered phosphate lattice with zero-field splitting values of 24.24 and 7.65 mT, indicating that Cr(III) ions are in distorted octahedral sites. The optical absorption spectrum of the sample indicates near octahedral symmetry for the dopant ions. Crystal field, inter-electronic and bonding parameters are evaluated by collaborating EPR and optical data. The evaluated parameters suggest the mode of entry of Cr(III) ion into the layered phosphate as interstitial site, and bonding between the metal and ligand is partially covalent.     

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.     

X-ray diffraction, vibrational and photoluminescence studies of the self-organized quantum well crystal H3N(CH2)6NH3PbBr4

We have prepared new semiconductor H₃N(CH₂)₆NH₃PbBr₄ crystals which are self-assembled organic-inorganic hybrid materials. The grown crystals have been studied by X-ray diffraction, infrared absorption and Raman spectroscopy scattering. We found that the title compound, abbreviated 2C₆PbBr₄, crystallizes in a two-dimensional (2D) structure with a P2₁/a space group. In the inorganic semiconductor sub-lattice, the corner sharing PbBr₆ octahedra form infinite 2D chains. The organic C₆H₁₈N₂⁺ ions form the insulator barriers between the inorganic semiconductor layers. Such a packing leads to a self-assembled multiple quantum well structure. Raman and infrared spectra of the title compound were recorded in the 50-500 and 400-4000 cm⁻¹ frequency regions, respectively. The assignment of the observed Raman lines was performed by comparison with the homologous compounds. Transmission measurements on thin films of 2C₆PbBr₄, obtained by the spin coating method, revealed a strong absorption peak at 380 nm. Luminescence measurements showed an emission line at 402 nm associated with radiative recombinations of excitons confined within the PbBr₆ layers. The electron-hole binding energy is estimated at 180 meV.     

Li2SO4—Li2B2O4,Li2SO4—(NH4)2SO4赝二元系相图及离子导电性研究

本文用差热分析和X射线衍射方法对Li₂SO₄-Li₂B₂O₄和Li₂SO₄-[NH₄]₂SO₄两个赝二元系相图进行了研究。Li₂SO₄-Li₂B₂O₄是共晶体系,共晶温度为720℃ 关键词：     

PASSIVATION OF THE InP(100) SURFACE USING (NH4)2Sx

InP(100) surface treated with (NH₄)₂S_x has been investigated by using photolumines-cence(PL), Auger electron spectroscopy and X-ray photoelectron spectroscopy, It is found that PL intensity increased by a factor of 3.3 after (NH₄)₂S_x passivation and the sulfur remained on the surface only bonded to indium, not to phosphorus. This suggests that the sulfur atoms replace the phosphorus atoms on the surface and occupy the phosphorus vacancies.     

Magnetic resonances in (CH3NH3)2MnCl4

We have studied the magnetic excitations of (CH₃NH₃)₂MnCl₄ in the antiferromagnetic and in the spin-flop regimes by means of magnetic resonance in the millimeter range (60–100 GHz). Rather odd line shapes of the resonance absorption line for narrow lines are explained as interference effects between the resonant and the non-resonant circular wave in the sample. For the antiferromagnetic resonance (AFMR) and for the paramagnetic resonance (EPR, above the Néel temperature), we have also studied the line width as a function of temperature.     

The crystal structures of the ion conductors (NH+4)Zr2(PO4)3and (H3O+)Zr2(PO4)3

The crystal structures of (NH⁺₄)Zr₂(PO₄)₃ and (H₃O⁺)Zr₂(PO₄)₃ have been determined from neutron time-of-flight powder diffraction data obtained at 15 K. Both compounds are rhombohedral, $\text{R}\text{3}\text{c}$, with cell parameters a=8.7088(1) and c=24.2197(4) Å for the ammonium compound and a=8.7528(2), c=23.6833(11) Å for the hydronium compound. In both cases the ions are completely localized in the type I cavities and hydrogen bonded to lattice oxygens. The measured unit cell parameters are relatively large for this class of compounds but the entrance ways into the cavities are still too small to allow for unrestricted movement of the ions. Thus the low conductivity of the hydronium ion is related to this and other structural features.     

Synthesis and characterization of a new monophosphate [2,5-(CH3)2C6H3NH3]H2PO4

Chemical preparation, calorimetric studies, crystal structure and spectroscopic investigations are given for a new noncentrosymmetric organic cation monophosphate [2,5-(CH₃)₂C₆H₃NH₃]H₂PO₄. This compound is orthorhombic P2₁2₁2₁ with the following unit-cell parameters: a=5.872(4), b=20.984(3), c=8.465(1) Å, Z=4, V=1043.0(5) Å³ and D_x=1.396 g cm⁻³. Crystal structure has been solved and refined to R=0.048 using 2526 independent reflections. Structure can be described as an inorganic layer parallel to (a,b) planes between which organic groups [2,5-(CH₃)₂C₆H₃NH₃]⁺ are located. Multiple hydrogen bonds connecting the different entities of compound thrust upon three-dimensional network a noncentrosymmetric configuration.     

Luminescent properties of PEG-added nanocrystalline YVO4:Eu phosphor prepared by a hydrothermal method

In an effort to obtain enhanced luminescence under photoexcitation as well as to clarify the underlying correlation between non-radiative sites and a surface modifier in a nanoscale phosphor, YVO₄:Eu³⁺ was synthesized via a polyethylene glycol (PEG)-assisted hydrothermal process. The temperature variable photoluminescence reveals that the overall emission behaviors of PEG-added YVO₄:Eu³⁺ phosphor was similar to those of a post-annealed sample without PEG addition. This polymeric agent induces a rough thin layer onto the YVO₄:Eu³⁺ nanoparticle during synthetic procedure, resulting in the prevention of surface-adsorbed species known as non-radiative sites such as NH₄⁺ as well as hydroxyl groups.     

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.     

Nonexponential proton relaxation in (NH4)2 HPO4

Nonexponential relaxation of protons in (NH₄)₂HPO₄ was found from 420 K to 110 K and was interpreted by the three-bath model below 167 K; inter-NH₄ group dipolar coupling above 167 K, and was attributed to non-equivalent NH₄ groups in a molecule.     

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.     

Improvement of Atomic-Layer-Deposited Al2O3/GaAs Interface Property by Sulfuration and NH3 Thermal Nitridation

Fermi level pinning at the interface between high-h gate dielectric and GaAs induced by unstable native oxides is a major obstacle for high performance GaAs-based metal-oxide-semiconductor （MOS） devices. We demonstrate the improved Al2O3/GaAs interracial characteristics by （NH4）2S immersion and NH3 thermal pretreatment prior to A1203 deposition. X-ray photoelectron spectroscopy （XPS） analysis confirms that sulfuration of GaAs surface by （NH4 ）2S solution can effectively reduce As-O bonds while Ga-O bonds and elemental As still exist at Al2O3 /GaAs interface. However, it is found that N incorporation during the further thermal nitridation on sulfurated GaAs can effectively suppress the native oxides and elemental As in the sequent deposition of Al2O3. Atomic force microscopy （AFM） shows that the further thermal nitridation on sulfurated GaAs surface can also improve the surface roughness.     

Calorimetric and x-ray diffraction studies of the (NH4)3WO3F3 and (NH4)3TiOF5 perovskite-like oxyfluorides

The heat capacity and unit cell parameters of the (NH₄)₃WO₃F₃ and (NH₄)₃TiOF₅ perovskite-like oxyfluorides were measured in the temperature interval from 80 to 300 K; the existence of two and one phase transitions in these compounds, respectively, was demonstrated, and their thermodynamic parameters were determined. The effect of a hydrostatic pressure of up to 0.5 GPa on the phase transition temperatures was studied. Triple points and high-pressure phases were found in the T vs. p diagrams. An analysis of entropy changes suggests that all the structural transformations revealed are associated with the ordering of structural blocks. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 5, 2004, pp. 888–894. Original Russian Text Copyright ? 2004 by Flerov, Gorev, Fokina, Bovina, Laptash.