A double-layer current conduction model for high-κ gate dielectric materials with interfacial oxide or silicate layer

The current-voltage (I-V) characteristics of metal-oxide-semiconductor (MOS) structures with hafnium oxide as the gate dielectric film were studied. Sharp shifts from a low-voltage ohmic regime to a tunneling conduction were observed in the high-voltage range. The paper demonstrates that this behavior can be described very well with a double-layer dielectric model. Excellent fittings of the experimental curves were obtained and the related key structural and physical parameters were obtained. The model fitting further suggests the optimal annealing conditions for preparing the hafnium oxide films.     

化学气相沉积生长氧化铪薄膜研究进展

氧化铪薄膜具有高介电常数、大击穿场强、高热稳定性、高力学强度等优势,是新一代高集成芯片中的理想介质材料。本文总结了氧化铪薄膜的主要特性、制备技术及在芯片介质层中的应用。针对芯片介质层的电、热、力学性能与生产要求,以氧化铪薄膜制备技术的发展历程为主线,重点介绍各类化学气相沉积方法的特点与典型研究成果,讨论了氧化铪薄膜制备技术存在的问题,并对该领域未来的发展趋势进行了展望。     

Kinetics of Reaction between Iron Ore Fines and Coal or Char Fines

Iron ore fines and coal fines can be made to react to produce direct reduced iron (DRI) fines. There are three ways to achieve the reactions, namely, (a) using homogeneous mixtures, (b) arranging the ore and coal fines in separate but adjacent layers and (c) by fluidizing a mixture of iron ore fines and coal fines by air. This paper mainly discusses the work done by the author and his coworkers on the kinetic aspects of reactions in such systems.     

Kinetics of high temperature oxidation of chromium rich HfC reinforced cobalt based alloys

Mostly known to improve the high temperature oxidation resistance of superalloys, hafnium may also form carbides. Several per cents of Hf allow developing a dense carbide network to mechanically strengthen alloys. Here, the high temperature oxidation behaviour of three HfC containing cobalt alloys was characterised at all steps of a thermogravimetry test: heating, isothermal stage and cooling, compared with two Co–Cr–C model alloys. The five alloys were heated in synthetic air, maintained at 1200°C during 50 h and then cooled. The mass gains were plotted versus time or according to (m×dm/dt?=?Kp–m×Kv) to specify the isothermal kinetic constants, or versus temperature to determine how oxidation acts during heating and oxide spallation occurs during cooling. Compared to the ternary alloys, the oxidation of the HfC reinforced alloys starts earlier but leads to lower mass gains during heating, the isothermal oxidation is faster and oxide spallation occurs later.     

Synthesis of ultra-fine hafnium carbide powders combining the methods of liquid precursor conversion and plasma activated sintering

Ultra-fine hafnium carbide (HfC) powders were synthesized using a novel method combining liquid precursor conversion and plasma activated sintering (PAS). Solution-based processing was used to achieve a fine-scale mixing of the reactants, and further treatment by PAS allowed fast formation of HfC. We investigated the effect of the type of acid used during the liquid precursor conversion on the synthesized powders, where mixtures were prepared using salicylic acid, citric acid, or a combination of these. The results show that pure HfC powders (with an average particle sizes of 350 nm) were obtained at a relatively low temperature (1550 °C) using a HfOCl₂·8H₂O precursor with the mixed acids. The oxygen content of the synthesized powders was only 0.97 wt%. The type of acid had a significant effect on the synthesis product. When using only citric acid, the temperature required to produce pure hafnium carbide increased to 1700 °C. In the case of a salicylic acid precursor, pure HfC was not obtained, even at a synthesis temperature of 1700 °C.     

Significant improvement of high-temperature oxidation resistance of HfC/SiC ceramic nanocomposites with the incorporation of a small amount of boron

Oxidation behavior of boron-containing HfC/SiC nanocomposites (SHBC) at temperatures up to 1500 °C and with exposure time up to 100 h was investigated. Two strategies to improve the oxidation resistance of the HfC/SiC ceramics are proposed. First concept involves the incorporation of a small amount of boron (ca. 0.6 wt.%) into the nanocomposite via a single-source-precursor approach, which contributes significantly to the enhancement of its oxidation resistance. Parabolic oxidation rate constants of 10⁻³ to 10^-4 mg²/(cm⁴ h) at 1300−1500 °C were measured for SHBC and were several orders of magnitude lower than those recorded for boron-free HfC/SiC. The second improvement concept is realized via passivation of the samples upon short-term oxidation at 1400 °C, providing an excellent oxidation resistance over a wide temperature range. This is a crucial step especially when considering the poor oxidation behavior of HfC and the sluggish formation of protective silica scale at moderate temperatures.     

Effect of residual excess carbon on the densification of ultra-fine HfC powder

The residual carbon content of ultra-fine hafnium carbide (HfC) powder was controlled by the optimization of the synthesis process, and the effect of residual carbon on the densification of HfC powder was analyzed. The amount of residual carbon in the HfC powder could be reduced by the de-agglomeration of HfO₂ powder before the carbo-thermal reduction (CTR) process. The average particle size of HfO₂ powder decreased from 230 to 130 nm after the de-agglomeration treatment. Ultra-fine (d₅₀: 110 nm) and highly pure (metal basis purity: >99.9 % except for Zr) HfC powder was obtained after the CTR at 1600 °C for 1 h using the C/Hf mixing ratio of 3.3. In contrast, the C/Hf ratio increased to 3.6 without the de-agglomeration treatment, indicating that a large amount of excess carbon was required for the complete reduction of the agglomerated HfO₂ particles. HfC ceramics with high relative density (>98 %) were obtained after spark plasma sintering at 2000 °C under 80 MPa pressure when using the HfC powder with low excess carbon content. In contrast, the densification did not complete at a higher temperature (2300 °C) and pressure (100 MPa) when the HfC powder contained a large amount of residual carbon. The results clearly indicated that residual carbon suppressed the densification of HfC powder in case the carbide powder had low oxygen content, and the residual carbon content could be controlled by the optimization of the synthesis process. The average grain size and Vickers hardness of the sintered specimen were 6.7(±0.7) μm and 19.6 GPa, respectively.     

Synthesis of HfB2 powders by mechanically activated borothermal reduction of HfCl4

HfB₂ powders were synthesized via a borothermal reduction route from mechanically activated HfCl₄ and B powder blends. Mechanical activation of the powder blends was carried out for 1 h in a high-energy ball mill using hardened steel vial and balls. Mechanically activated powders were subsequently annealed at 1100 °C for 1 h under Ar atmosphere. Then, purification processes such as washing with distilled water and leaching in HCl solution were applied for the elimination of the undesired boron oxide (B₂O₃) phase and the probable Fe impurity. The effect of boron amount on the microstructure of the resultant powders was investigated. The boron amount in the starting blends plays an important role in the formation of the HfO₂ phase. HfB₂ powders without any detectable HfO₂ were prepared by adding 20 wt% excess amount of boron. Microstructural analyses of the mechanically activated, annealed and purified powders were performed using X-ray diffractometer (XRD), particle size analyzer (PSA), stereomicroscope (SM), scanning electron microscope/energy dispersive spectrometer (SEM/EDS) and transmission electron microscope (TEM).     

Liquid‐Liquid Extraction of Tetravalent Hafnium from Acidic Chloride Solutions using Bis(2,4,4‐trimethylpentyl) Dithiophosphinic Acid (Cyanex 301)

Abstract

Liquid‐liquid extraction studies of tetravalent hafnium from acidic chloride solutions have been carried out with bis(2,4,4‐trimethylpentyl) dithiophosphinic acid (Cyanex 301) as an extractant diluted in kerosene. Increase of acid concentration decreases the percentage extraction of metal. Plot of log D vs. log [HCl] gave a straight line with a negative slope of 2±0.1 indicating the exchange of two moles of hydrogen ions for every mole of Hf(IV) extractacted into the organic phase. Extraction of Hf(IV) increases with increase of extractant concentration. The plot of log D vs. log [HA] is linear with slope 2±0.1, indicating the association of two moles of extractant with the extracted metal species. The addition of sodium salts enhanced the percentage extraction of metal, and followed the order NaSCN>Na₂SO₄> NaNO₃>NaCl. Stripping of metal from the loaded organic (LO) with HCl and H₂SO₄ indicated sulphuric acid as the best stripping agent. Increase of temperature increases the percentage extraction of metal indicating the process is endothermic. Regeneration and recycling capacity of Cyanex 301, extraction behavior of associated elements such as Zr(IV), Ti(IV), Al(III), Fe(III), and IR spectra of the Hf(IV)‐Cyanex 301 complex was studied.     

Fabrication of high-performance Y2O3 stabilized hafnium dioxide refractories

Y₂O₃ stabilized HfO₂ ceramics with 5 mol% and 8 mol% Y₂O₃, respectively, were successfully fabricated by pressureless sintering at 1600 °C for 1 h. The phase distribution and transformation, microstructure, and relative density were investigated for Y₂O₃ stabilized HfO₂ ceramics. Cubic phase was observed in the Y₂O₃ stabilized hafnium dioxide while pure HfO₂ showed monoclinical phase only. The SEM images of fractured surface indicated two kinds of structures existed in modified HfO₂, the solid solution region and uniform polygon grains, and some holes caused by Kirkendall effect. Refractoriness test showed that high temperature volumetric stability of the material can be effectively enhanced by adding Y₂O₃ into HfO₂.