Improved quantum efficiency of Sr(Al,Si)5(O,N)7:Ce3+ by selection of Ce raw material

The luminescence properties of yellow-emitting Ce³⁺-doped Sr-containing sialon phosphor Sr(Al,Si)₅(O,N)₇:Ce³⁺ were notably improved by the Ce raw material selection. By changing the Ce raw material from oxides to nitrides or chlorides, the emission wavelength shifted to above 560 nm, which is beneficial for higher color rendering index white light-emitting diodes. This result from an increase in the covalency of the host crystal being associated with a decrease in the oxygen content. When Ce chloride was used, both the absorption and internal quantum efficiency increased, resulting in an increase in the external quantum efficiency up to 65%–72%. Inductively coupled plasma mass spectrometry, X-ray diffraction, and electron spin resonance measurements showed that the reason for the absorption increase is an increase in Ce³⁺ content and suppression of the generation of the second phase, and the reason for the increase in the internal quantum efficiency is a decrease in the host crystal absorption via suppression of anion vacancy generation. It was found that Ce chloride not only suppresses oxygen impurities but also acts as a flux that results in improved crystallinity.     

Effects of post annealing on removal of defect states in silicon oxynitride films grown by oxidation of silicon substrates nitrided in inductively coupled nitrogen plasma

Ultra thin (5 nm) silicon oxynitride (SiON) films were fabricated at a low temperature using nitrogen plasma generated by an inductively coupled plasma system. Effects of post-metalization annealing (PMA) of Al/SiON/Si MOS structure on the electrical properties of the SiON films were studied and correlations between the charge trapping states and the leakage current were established. Positive charge trapping by interface states generated by plasma damage was characterized by the hysteresis in high-frequency capacitance-voltage (C-V) characteristics. Hysteresis was observed to be completely removed by PMA while interface state density at the Si mid band gap reduced from 2.2×10¹³ to 3.7×10¹¹/eV/cm² and the oxide fixed charge density changed from 3.3×10¹² to −4×10¹¹/cm². The leakage current also decreased significantly, by more than two orders of magnitude, with PMA. The analysis of the leakage current using trap assisted tunneling (TAT) mechanism indicated that with PMA, the trap energy level in the SiON film becomes shallower from 1.3 to 0.7 eV. The positive trapped charges were observed to be annihilated by PMA and the trapping sites became neutral trap centers in the SiON film. This could lead to the reduction in the leakage current component given rise to by TAT.     

Oxidation of porous nanocrystalline titanium nitride. II. Scale structure and composition

We have used x-ray phase analysis to study the composition of the products of reaction between oxygen and nanocrystalline powders with particle sizes 15, 40, 55, and 80 nm, and also specimens pressed (and sintered) from them. The powders were oxidized in air at 100°C (400 h) to 500°C (5 min), while the sintered specimens were oxidized at 600–900°C for 15, 120, and 240 min. In all cases, in the initial oxidation step the oxynitride Ti(O_xN_y) is formed, which over time is oxidized to TiO, Ti₂O₃, Ti₃O₅, TiO₂ (anatase) and TiO₂ (rutile). In the range 600–800°C, formation of a continuous oxide layer and conversion of anatase to rutile slows down diffusion of oxygen in the scale. We have established that at 900°C, the growth rate of the scale thickness increases and so the reflections from the oxynitride are barely noticeable on the diffraction patterns taken from the surface of the oxidized specimen. In these diffraction patterns, along with strong reflections from the rutile, we also observed weak reflections from lower oxides and anatase, which may be due to reaction between oxygen and the titanium ions diffused to the scale surface. We have concluded that at T > 850°C, the mechanism for oxidation of TiN changes. This is due to superposition of counterdiffusion of titanium ions on the diffusion of oxygen. __________ Translated from Poroshkovaya Metallurgiya, Nos. 3–4(448), pp. 72–78, March–April, 2006.     

Mössbauer Study of the Influence of Fe-Si-N Liquid in the Synthesis of β-Si3N4 from Silica

Mössbauer spectra of the products obtained by carbothermal reduction and distribution of silica in the presence of iron in the temperatures range 1200^o to 1540^o were studied. The preponderance of β- Si₃N₄ over the α form at a higher reaction temperature were assumed to be related to the formation of an Fe-Si-N liquid. The liquid did not alter its composition with the variation of reduction-temprature, Iron had no effect on the reaction mechanism below 1300^oC.     

Synthesis of silicon oxynitride by infiltration-mediated combustion

Silicon oxynitride Si₂N₂ O was synthesized from a mixture of Si, SiO₂, and Si₃N₄ by infiltrationmediated combustion in nitrogen gas. The chemical/phase composition of product and process parameters (temperature and burning velocity) were studied upon variation in charge composition and initial pressure of gas reagent. Parameters of the reaction yielding single-phase Si₂N₂O have been optimized.      

PECVD方法用于梯度薄膜材料的研究

本文研究了ＰＥＣＶＤ方法制备Ｓｉ－Ｏ－Ｍ系梯度薄膜材料，并运用计算机控制技术成功地制备了涂层折射率随膜深成正弦波形式连续变化的Ｒｕｇａｔｅ单通带滤波器样品。结果表明，采用ＰＥＣＶＤ方法可以制备性能上乘、结构复杂的梯度薄膜材料，ＰＥＣＶＤ方法在研究、开发高级光学涂层领域有着宽广的应用前景。     

常压CVD法制备氮氧化硅薄膜沉积特性的研究

采用常压化学气相沉积方法(atmospheric pressure chemical vapor deposition,APCVD)制备了氮氧化硅(Si—O—N)薄膜,研究了影响其沉积速率和生长模式的因素。在φ(NH_3):φ(SiH_4)=20:1,基板温度为650℃的条件下,当混合气体流量小于720ml/min时,薄膜的形成主要受气体扩散过程控制;当混合气体流量大于720 ml/min时,则主要受表面气相反应过程控制;混合气体流量为720 ml/min的条件下,氮氧化硅薄膜的沉积过程主要受基板表面的气相反应过程控制,薄膜沉积厚度与沉积时间成线性关系,反应速率为常数1640 nm/min,表面活化能为283 kJ/mol。通过SEM分析发现:氮氧化硅薄膜的形成方式符合三维成核模型,即反应初期Si,N,O等原子在基板表面相遇结合在一起形成原子团,一定数量的原子团构成临界核;反应中期临界核长大为岛状结构,岛不断长大,岛与岛之间相互接合形成通道网络结构;反应后期,原子不断填补网络空洞,最后成为连续薄膜。     

Effect of Ti–Si–Fe alloys on microstructure and properties of nitride/oxynitride bonded SiC ceramics sintered under CO/N2 atmosphere

Ti–Si–Fe alloys extracted from high-titanium blast furnace slag were utilized to replace part of the silicon powders, and then nitride/oxynitride bonded SiC ceramics were prepared by reactive sintering in graphite bed. Ti–Si–Fe alloys could react with CO/N₂ at a low temperature (1200 °C), and the addition of Ti–Si–Fe alloys could reduce the nitriding temperature of Si. Density functional theory calculations suggested that Ti–Si–Fe alloys enhanced reaction activity via weakening the strength of CO and NN bonds. The regional equilibrium phase diagrams of Si–C–N–O and Ti–Si–C–N–O under CO/N₂ atmosphere were calculated by thermodynamics. The change of whiskers morphology was observed by scanning electron microscope. Furthermore, the bulk density, the cold modulus of rupture, and the cold compressive strength improved with Ti–Si–Fe alloys content. The results showed that the addition of Ti–Si–Fe alloys not only significantly promoted nitriding of Si and formation of Si₃N₄ whiskers, but also improved the mechanical properties of the samples.     

Potentiometric CO2 gas sensor with lithium phosphorous oxynitride electrolyte

Potentiometric cell, Au/LiCoO₂ 5 m/o Co₃O₄/Li_2.88PO_3.73N_0.14/Li₂CO₃/Au, has been fabricated and investigated for monitoring CO₂ gas. A LiCoO₂–Co₃O₄ mixture was used as the solid-state reference electrode instead of a reference gas. The idea is to keep the lithium activity constant on the reference side using thermodynamic equilibrium at a given temperature. The thermodynamic stability of the reference electrode was studied from the phase stability diagram of Li–Co–C–O system. The Gibb’s free energy of formation of LiCoO₂ was estimated at 500°C from the measured value of the cell emf. The sensors showed good reversibility and fast response toward changing CO₂ concentrations from 200 to 3000 ppm. The emf values were found to follow a logarithmic Nernstian behavior in the 400–500°C temperature range. CH₄ gas did not show any interference effect. Humidity and CO gas decreased the emf values of the sensor slightly. NO and NO₂ gases affect this sensor significantly at low temperatures. However, increased operating temperature seems to reduce the interference.     

Raman spectra and structural analysis in ZrOxNy thin films

Raman spectroscopy has been used as a local probe to characterize the structural evolution of magnetron-sputtered decorative zirconium oxynitride ZrO_xN_y films which result from an increase of reactive gas flow in the deposition. The lines shapes, the frequency position and widths of the Raman bands show a systematic change as a function of the reactive gas flow (a mixture of both oxygen and nitrogen). The as-deposited zirconium nitride film presents a Raman spectrum with the typical broadened bands, due to the disorder induced by N vacancies. The recorded Raman spectrum of the zirconium oxide film is typical of the monoclinic phase of ZrO₂, which is revealed also by X-ray diffraction. Raman spectra of zirconium oxynitride thin films present changes, which are found to be closely related with the oxygen content in films and the subsequent structural changes.