Atomic Layer Deposition of Cobalt Phosphide for Efficient Water Splitting

Transition‐metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co‐P films were deposited by using PH₃ plasma as the phosphorus source and an extra H₂ plasma step to remove excess P in the growing films. The optimized ALD process proceeded by self‐limited layer‐by‐layer growth, and the deposited Co‐P films were highly pure and smooth. The Co‐P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction (HER) activities than similar Co‐P films prepared by the traditional post‐phosphorization method. Moreover, the deposition of ultrathin Co‐P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three‐dimensional (3D) architectures.     

Interactions between tri-methylaluminum molecules and their effect on the reaction of tri-methylaluminum with an OH-terminated Si (0 0 1) surface

We studied the interaction between tri-methylaluminum (Al(CH₃)₃, TMA) molecules and their effect on TMA reactions with a fully OH-terminated Si (0 0 1) surface for initial aluminum oxide thin-film growth using density functional theory. The reaction between an adsorbed TMA and the surface produced a di-methylaluminum (-Al(CH₃)₂, DMA) group, and further reaction to a uni-methylaluminum (-AlCH₃, UMA) group with energy barriers of 0.50 and 0.21 eV, respectively. A second TMA adsorbed near the already adsorbed TMA, DMA, or UMA group showed higher energy barriers (0.68-1.01 eV) for its reaction to produce a DMA group due to the interaction between them. Therefore, the fully OH-terminated Si (0 0 1) surface would be covered by the mixture of the adsorbed TMA and UMA groups at an intermediate surface temperature.     

Pt coated Cr2O3 thin films for resistive gas sensors

The resistive response of atomic layer deposited thin epitaxial α-Cr₂O₃(0 0 1) films, to H₂ and CO in air, was studied. The films were covered with Pt nanoislands formed by electron-beam evaporation of a sub-monolayer amount of the material. The gas measurements were performed at 250°C and 450°C. These temperatures led to different proportion of chemical states, Pt²⁺ and Pt⁴⁺, to which the Pt oxidized. The modification was ascertained by the X-ray photoelectron spectroscopy method. As a result of the modification, the response was fast at 250°C, but slowed at 450°C. A disadvantageous abundance of Pt⁴⁺ arising at 450°C in air could be diminished by high-vacuum annealing thus restoring the response properties of the system at 250°C.      

CO oxidation of bare and TiO2-coated NiO-Ni(OH)2 nanoparticles

CO oxidation reactivity of bare and TiO₂-coated nanoparticles consisting of both NiO and Ni(OH)₂ surfaces was studied. For the deposition of TiO₂, atomic layer deposition was used, and formation of three-dimensional domains of TiO₂ on NiO-Ni(OH)₂ could be identified. Based on the data of X-ray Photoelectron Spectroscopy, we suggest that upon TiO₂ deposition only Ni(OH)₂ was remained on the surface, whereas NiO surface disappeared. Both CO adsorption and CO oxidation took place on NiO-Ni(OH)₂ surfaces under our experimental conditions. CO adsorption was almost completely suppressed after TiO₂ deposition, whereas CO oxidation activity was maintained to large extent. It is proposed that bare NiO cannot be active for CO oxidation, and can only uptake CO under our experimental condition, whereas hydroxylated surface of NiO can be active for CO oxidation.     

On the relative stability of cobalt‐ and nickel‐based amidinate complexes against β‐migration

We present a first‐principles study on the relative stability of cobalt‐ and nickel‐based amidinate complexes against β‐migration using density functional theory. Factors that influence the reactivity of these compounds were carefully addressed and the calculated molecular structures are in excellent agreement with the available crystal structural data. Reaction energies as well as activation barriers of β‐migration were evaluated. The predicted relative stability of the selected compounds is consistent with experimental observations. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

以PVP纳米纤维为模板采用原子层沉积法制备MgxZn1-xO纳米纤维及其光学性质研究

采用静电纺丝方法制备聚乙烯吡咯烷酮(PVP)纳米纤维,并以其为模板采用原子层沉积(ALD)方法制备不同Mg掺杂浓度的MgxZn1-xO纳米纤维。研究了不同Mg掺杂浓度对复合纳米纤维结构和光学性质的影响。利用场发射扫描电子显微镜(FESEM)、光致发光(PL)和紫外-可见光(UV-Vis)吸收谱对样品测试并进行表征分析。结果表明,Mg元素的掺入并没有改变ZnO纳米纤维的形貌,所有样品的表面形貌极其相似,只是掺杂后纤维直径有所增大;随着Mg掺杂浓度的增加吸收边逐渐发生蓝移,表明所制备MgxZn1-xO纤维的带隙具有可调节性。与此同时,在PL谱中可以观察到样品的紫外(UV)发光峰从377nm移动至362nm,且与不掺杂的样品相比,MgxZn1-xO纳米纤维的UV发光强度明显增强。通过这种方法可以合成组分可控的MgxZn1-xO纳米纤维。在ZnO中掺入Mg元素可以有效地提高ZnO-PVP纳米纤维的禁带宽度以及UV发射强度。     

Al2O3绝缘栅AlGaN/GaN MOS-HEMT器件温度特性研究

采用原子层淀积(ALD)实现了10nm Al₂O₃为栅介质的高性能AlGaN/GaN金属氧化物半导体高电子迁移率晶体管(MOS-HEMT). 通过对MOS-HEMT器件和传统MES-HEMT器件室温特性的对比,验证了新型MOS-HEMT器件饱和电流和泄漏电流的优势. 通过分析MOS-HEMT器件在30—180℃之间特性的变化规律,与国内报道的传统MES-HEMT器件随温度退化程度对比,得出了器件饱和电流和跨导的退化主要是由于输运特性退化造成的,证明栅介质减小了引 关键词： 原子层淀积 AlGaN/GaN MOS-HEMT器件 温度特性     

Enhanced interface properties of diamond MOSFETs with Al_2O_3 gate dielectric deposited via ALD at a high temperature

The interface state of hydrogen-terminated(C–H) diamond metal–oxide–semiconductor field-effect transistor(MOSFET) is critical for device performance. In this paper, we investigate the fixed charges and interface trap states in C–H diamond MOSFETs by using different gate dielectric processes. The devices use Al_2O_3 as gate dielectrics that are deposited via atomic layer deposition(ALD) at 80℃ and 300℃, respectively, and their C–V and I–V characteristics are comparatively investigated. Mott–Schottky plots(1/C~2–VG) suggest that positive and negative fixed charges with low density of about 1011 cm~(-2) are located in the 80-℃-and 300-℃ deposition Al_2O_3 films, respectively. The analyses of direct current(DC)/pulsed I–V and frequency-dependent conductance show that the shallow interface traps(0.46 e V–0.52 e V and0.53 e V–0.56 e V above the valence band of diamond for the 80-℃ and 300-℃ deposition conditions, respectively) with distinct density(7.8 × 10~(13) e V~(-1)·cm~(-2)–8.5 × 10~(13) e V-1·cm~(-2) and 2.2 × 1013 e V~(-1)·cm~(-2)–5.1 × 10~(13) e V~(-1)·cm~(-2) for the80-℃-and 300-℃-deposition conditions, respectively) are present at the Al_2O_3/C–H diamond interface. Dynamic pulsed I–V and capacitance dispersion results indicate that the ALD Al_2O_3 technique with 300-℃ deposition temperature has higher stability for C–H diamond MOSFETs.     

Dual‐Shelled RbLi(Li3SiO4)2:Eu2+@Al2O3@ODTMS Phosphor as a Stable Green Emitter for High‐Power LED Backlights

The stability of luminescent materials is a key factor for the practical application in white light‐emitting diodes (LEDs). Poor chemical stability of narrow‐band green‐emitting RbLi(Li₃SiO₄)₂:Eu²⁺ (RLSO:Eu²⁺) phosphor hinders their further commercialization even if they have excellent stability against thermal quenching. Herein, we propose an efficient protection scheme by combining the surface coating of amorphous Al₂O₃ and hydrophobic modification by octadecyltrimethoxysilane (ODTMS) to construct the moisture‐resistant dual‐shelled RLSO:Eu²⁺@Al₂O₃@ODTMS composite. The growth mechanisms of both the Al₂O₃ inorganic layer and the silane organic layer on the phosphor surface are investigated. The results remarkably improve the water‐stability of this narrow‐band green emitter. The evaluation of the white LED by employing this composite as the green component demonstrates that RLSO:Eu²⁺@Al₂O₃@ODTMS is a promising candidate for the high‐performance display backlights, and this dual‐shelled strategy provides an alternative method to improve the moisture‐resistant property of humidity‐sensitive phosphors.     

金属氧化物与现代微电子学——过渡金属前体化合物及转化为材料的化学过程

金属氧化物薄膜如HfO₂（被称为高k电介质）是现代微电子器件的关键组件,广泛用于计算机（平板电脑,笔记本电脑和台式机）、智能电话、智能电视、汽车和医疗设备中。具有大介电常数（k）的金属氧化物已经取代了介电常数小的SiO₂（k=3.9）,从而使得微电子元件进一步小型化。过渡金属化合物在化学气相沉积（CVD）和原子层沉积（ALD）中被广泛用作前体,通过与O₂、H₂O或O₃的反应生成金属氧化物薄膜。微电子金属氧化物膜是纳米材料最广泛应用的一个领域。本文概观该领域的最新进展,包括我们对d⁰过渡金属配合物与O₂反应的研究。