磁控溅射(Ti,N)/Al纳米复合薄膜的微结构和力学性能

采用Al和TiN靶通过磁控共溅射方法, 制备了一系列Ti:N≈1的不同(Ti, N) 含量的铝基纳米复合薄膜, 利用X射线能量分散谱仪、X射线衍射仪、透射电子显微镜和纳米力学探针表征了薄膜的成分、 微结构和力学性能, 研究了(Ti, N)含量对复合薄膜微结构和力学性能的影响. 结果表明: Ti, N原子的共同加入使复合薄膜形成了同时具有置换固溶和间隙固溶特征的"双超过饱和固溶体", 薄膜的晶粒随着溶质含量的增加逐步纳米化, 并进一步形成非晶结构, 晶界区域形成溶质原子的富集区. 相应地, 复合薄膜的硬度在含1.8 at.%(Ti, N) 时就可迅速提高到3.9 GPa; 随着TiN含量的增加, 薄膜的硬度进一步提高到含17.1 at.%(Ti, N)时的8.8 GPa. 以上结果显示出Ti和N"双超过饱和固溶"对Al薄膜极其显著的强化效果.     

基于第一性原理的含空位a-Fe和H原子相互作用研究

氢致裂纹是制约超高强度钢应用的关键问题,掌握扩散氢的分布行为有助于弄清氢致裂纹的形成机理.本文采用第一性原理方法计算了H原子占据α-Fe晶格间隙和空位时的情况,得到了晶体的稳定构型及能量,并据此分析了H原子在晶格间隙和空位中的溶解倾向;从Mulliken布居、电子密度分布、态密度分布等角度分析了H原子与α-Fe晶体间隙和空位之间的相互作用.结果表明:间隙H原子倾向占据α-Fe四面体间隙位,其1s轨道电子与Fe的4s轨道电子呈微弱共轭杂化;空位是强氢陷阱, H原子倾向占据空位内壁附近的等电荷面.在真空0 K条件下单空位最多稳定溶解3个H原子,且H原子之间未表现出自发形成H2的倾向;间隙和空位中的H原子溶入改变了Fe晶格内电子分布导致原子结合力弱化,并在局部区域形成反键.基于第一性原理能量计算结果开展热力学分析,分析结果表明大多数情况下间隙H原子都是H主要的固溶形式, H平衡溶解度计算结果与实际符合良好.     

Co、Ni和Ga合金化对DO_(19)-Ti_3Al弹性性能影响的第一性原理研究

采用第一性原理的方法研究了Co、Ni和Ga元素对DO_(19)-Ti_3Al晶体的弹性性能的影响,结果表明:Co和Ni原子倾向于置换Ti原子而Ga原子则更倾向于置换Al原子;Co和Ni元素固溶可以减弱晶体内部电子杂化效应从而增大Ti_3Al晶体的本征塑性,其中Co元素的对晶体的本征塑性的增大效果显著;Ga元素固溶后Ti_3Al晶体的强度和硬度将得到提高.     

Si1-xGex合金半导体中CiCs和CiOi缺陷随Ge含量的变化

采用从头计算(ab initio)的方法对Si和Si1-xGex合金半导体材料中CiCs 缺陷的性质进行探讨,同时也对比调查了CiOi 缺陷在Si和Si1-xGex合金中的性质. 在不同Ge含量的Si1-xGex合金中CiCs和CiOi缺陷的结构都具有较好的稳定性;从能量学角度,Ge原子不能与C或O原子直接成键. CiCs缺陷的A型和B型结构在Si1-xGex合金中表现出的行为基本类似,但是A型结构随着Ge含量的增加形成能逐渐减小,结构越来越稳定,而B型结构的形成能先有所下降后逐渐增加;A型和B型结构的能量差值随着Ge含量的增加先在小范围内变化后迅速下降. CiOi缺陷形成能的变化特征较为复杂. 纯Si体系在1000K及以上温度的等温退火过程中,CiCs缺陷的A型结构会向B型结构转变;Si1-xGex合金在进行等温退火时CiCs缺陷的A型结构的变化特征与退火温度、Ge含量和Ge取代的位置等因素有关.     

X射线驻波方法研究半导体超薄异质外延层

利用双晶单色器和精密二圆衍射仪,在北京同步辐射装置建立了同步辐射X射线驻波实验技术,并用这一实验技术结合X射线衍射方法,研究了Si晶体中外延生长的超薄Ge原子层的微结构.实验结果表明,由于Ge原子的偏析,在Si晶体样品中形成了共格生长的Ge_xSi_1－x合金层,浓度平均值为x≈0.13;650℃退火会使Ge原子向表面扩散,Si晶体中的合金层消失,在晶体表面形成接近纯Ge的单原子层.     

金属Fe与间隙H原子相互作用的密度泛函研究

采用基于密度泛函理论的第一性原理方法, 研究了不同摩尔比下H在α-Fe和γ-Fe晶格中的间隙占位情况, 计算了稳态晶体的总能量、结合能、溶解热、电子态密度、电荷差分密度和电荷布居, 分析了间隙H原子和Fe晶格之间的相互作用, 讨论了H溶解对α-Fe和γ -Fe晶体电子结构的影响. 结果表明: H溶解引起α-Fe和γ-Fe晶体点阵晶格畸变, 体积膨胀率随着溶氢量的增加而增加. 从能量角度分析发现, H优先占据α-Fe的四面体间隙位, 而在γ -Fe中优先 占据八面体间隙位. 态密度、电荷差分密度以及电荷布居分析发现, 间隙H原子与Fe晶格的相互作用仅由H的1s轨道电子和Fe的4s轨道电子所贡献, 二者作用力相对较弱, 这是造成H在Fe晶格中固溶度较低的主要原因之一. 关键词： 金属Fe 间隙H原子 第一性原理 溶解热     

H,O,N,He原子掺杂Al原子的第一性原理研究

采用密度泛函理论框架下的第一性原理平面波赝势方法,对Al中分别加入H,O,N和He原子后的晶体状态进行了研究.通过晶体结构和形成能分析比较了杂质原子占据不同位置的难易程度及对晶体稳定性的影响,并从态密度、电荷密度和电荷布居的角度,分析了其电子结构.结果表明:H、O和N原子占据金属Al的四面体间隙最稳定,而He原子主要占据金属Al的八面体间隙. O和N原子与Al原子具有强烈的共价作用,H原子与Al原子存在共价作用但相对较弱,而He原子与Al原子的相互作用以范德华力为主.进一步揭示了四种原子在金属Al中不同行为的电子机制.     

Ge(SiO2)n团簇结构和电子性质的密度泛函理论研究

采用密度泛函理论中的广义梯度近似(GGA)对Ge(SiO2)n (n = 1—7)团簇的几何构型进行优化,并对能量、频率和电子性质进行了计算。 结果表明,Ge(SiO2)n的最低能量结构是在(SiO2)n端位O原子以及近邻端位O原子的Si原子上吸附一个Ge原子优化得到;随着锗原子数的增加,增加的锗原子易与原来的锗原子形成锗团簇。掺杂锗原子后团簇的能隙比(SiO2)n团簇的能隙小,当多个Ge原子掺杂到(SiO2)3团簇时,其能隙随着Ge原子个数的增加出现了振荡,Gem(SiO2)3的能隙从可见光区到近红外光区变化。二阶能量差分、分裂能表明Ge(SiO2)2和Ge(SiO2)5团簇是稳定的。     

Ge( SiO2)n团簇结构和电子性质的密度泛函理论研究

采用密度泛函理论中的广义梯度近似(GGA)对Ge(SiO2)n(n=1～7)团簇的几何构型进行优化,并对能量、频率和电子性质进行了计算.结果表明,Ge(SiO2)n的最低能量结构是在(SiO2)n端位O原子以及近邻端位O原子的Si原子上吸附一个Ge原子优化得到;随着锗原子数的增加,增加的锗原子易与原来的锗原子形成锗团簇.掺杂锗原子后团簇的能隙比(SiO2)n团簇的能隙小,当多个Ge原子掺杂到(SiO2)3团簇时,其能隙随着Ge原子个数的增加出现了振荡,Gem(SiO2)3的能隙从可见光区到近红外光区变化.二阶能量差分、分裂能表明Ge(SiO2)2和Ge(SiO2)5团簇是稳定的.     

Ti, C, N在α-Fe基中的合金化效应及对键合性质的影响

基于第一性原理赝势平面波方法研究了合金元素Ti, C, N对α-Fe基电子结构及键合性质的影响, 计算了含Ti, C, N的Fe基固溶体的总能量、结合能, 分析了态密度、电荷布居数、交叠布居数和电荷密度, 从理论上解释了在Fe基中固溶Ti, C, N后其性能改善的原因. 结果表明, 随着Fe基固溶体中Ti(0-12.5 at%), C(0-11.11 at%), N(0-11.11 at%)含量增加, 结合能略有增加; Ti, C, N的固溶使各Fe基固溶体在费米能级处强烈成键, 结合能力增强, 并且在费米能级附近出现赝能隙, 表明固溶体中金属键与共价键共存; 随着Ti, C, N含量的增加, C, N分别与Ti, Fe之间的共价键结合强度加强, 部分C, N原子会与Ti原子结合形成TiC, TiN颗粒, 起到沉积相颗粒强韧化作用.     

IVB族过渡金属氮化物弹性与光学性质研究

基于密度泛函理论平面波方法研究了IVB族过渡金属氮化物TiN, ZrN, HfN的电子结构、 弹性性质和光学性质. 研究表明, IVB族过渡金属氮化物晶格的电子结构分别体现了共价性、 离子性和金属性, 且基态下体系呈金属性. 各晶格在坐标基矢方向上的杨氏模量的数值与体对角线方向上的差距明显, 体现出典型的弹性性质各向异性, 这导致了实验研究在制备其薄膜时不可避免地产生晶格畸变与微裂纹. 伴随着态密度中赝隙的红移, TiN, ZrN, HfN的金属性依次增强, 使得材料在力学性能方面脆性减弱, 单晶的各向异性程度提升, 以及光学性质方面电子跃迁机理由带内跃迁到带间跃迁转变所需入射光子能量的蓝移和光谱选择性能的下降. 因此, 通过降低IVB族过渡金属氮化物中自由电子的组分以加强材料的共价性, 有利于提高材料弹性性质的各向同性, 改善材料的光谱选择性能. 关键词： 第一性原理 弹性性质 光学性质     

Acoustical and elastic properties of transition metal nitrides

Elastic moduli of transition metal nitrides, TiN, ZrN and HfN, have been evaluated using electrostatic and Born repulsive potentials. Acoustical dissipation due to phonon-phonon (p-p) interaction, thermoelastic mechanism and dislocation damping due to screw and edge dislocations has been evaluated in the temperature range 50-500 K along the three crystallographic directions of propagation, viz. [1 0 0], [1 1 0] and [1 1 1] for longitudinal and shear modes. Grüneisen numbers, acoustic coupling constants and their ratios have been evaluated for the longitudinal and shear waves. Results are in good agreement with available data.     

界面对ZrN/TaN纳米多层膜固氦性能的影响

采用射频磁控溅射方法, 在混合气氛下制备了ZrN/TaN多层膜. 利用X射线衍射、慢正电子束分析、增强质子背散射、扫描电子显微镜, 分别对ZrN/TaN多层膜中相结构、氦相关缺陷、氦含量、截面形貌等进行了分析. 结果表明, 调制周期为30 nm的ZrN/TaN多层膜在600℃退火后, 氦的保持率仍能达到45.6%. 在适当的调制周期下, ZrN/TaN多层膜能够耐氦损伤并且其界面具有一定的固氦性能. 关键词： ZrN/TaN 纳米多层膜 界面 固氦     

界面和择优取向对TiN/ZrN纳米多层膜硬度变化的影响

利用射频反应磁控溅射方法，制备了调制比约为4，调制周期不同的一系列TiN/ZrN纳米多层膜. 利用X射线衍射仪(XRD)、高分辨电子显微镜(HRTEM)和纳米压痕仪(Nanoindentation)对多层膜的调制结构、界面状态和力学性能进行了表征. 研究结果表明TiN/ZrN多层膜具有很好的调制结构，但是在TiN层和ZrN层之间存在一定厚度的界面混合层. 力学性能分析表明：当调制周期小于15 nm时，TiN/ZrN多层膜的硬度介于单一TiN和ZrN薄膜的硬度之间；当调制周期为15.24 nm时，硬度达到最大，但随着调制周期增加，多层膜的硬度基本上保持为常数. 分析了TiN/ZrN多层膜硬度变化的机制，认为界面厚度和择优取向是导致硬度变化的主要原因. 关键词： TiN/ZrN多层膜 界面宽度 择优取向 硬度变化     

Synthesis and characterization of titanium nitride, niobium nitride, and tantalum nitride nanocrystals via the RAPET (reaction under autogenic pressure at elevated temperature) technique

TiN, NbN, and TaN nanocrystals have been selectively prepared through a simple, solvent-free, and convenient reaction under autogenic pressure at moderate temperature (RAPET) process at 350 °C for 12 h, reacting transition metal chlorides and sodium azide. The nanostructures obtained are characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). A reaction mechanism is suggested based on the experimental results. These rapid reactions produce nanocrystals of TiN, NbN, and TaN with average sizes of approximately 30, 28, and 27 nm, respectively (as calculated from X-ray line broadening). An octahedral inorganic fullerene was detected among the various structures of the TiN.     

Study of TiN and ZrN thin films grown by cathodic arc technique

Thin films of TiN and ZrN were grown on stainless steel 316 substrate using the pulsed cathodic arc technique with different number of discharges (one to five discharges). The coatings were characterized in terms of crystalline structure, microstructure, elementary chemical composition and stoichiometric by X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy for chemical analyses (XPS), respectively. The XRD results show that for TiN as for ZrN, the preferential direction occurs in the plane (2 0 0), and this result stays when increasing the number of discharges. The grain size is increased with the increase of the number of discharges for both nitrides, the roughness for the TiN film is greater than for the ZrN film; these results were determined by AFM. XPS analysis determined that there is a higher nitrogen presence in the ZrN film than in the TiN film.     

Atomic structures and electronic properties of interfaces between aluminum and carbides/nitrides: A first-principles study

We perform a first-principles investigation of the atomic structures and electronic properties of interfaces between aluminum and four kinds of ceramics, TiC, TiN, VC and VN, under three orientations (001), (110) and (111). We find that the stable interfaces are those with bonding between Al atom and metalloid C (or N) atom, which is attributed to the overlap of p states of Al and d states of metalloid atoms at Femi level forming covalent components. Among the interfaces with the three orientations, the (111) interfaces are found to possess the largest adhesion energy in that the stacking of atoms follows intrinsic atomic distribution and this interfacial bonding is relatively strong. It is also found that the interfaces between Al and metal carbides (TiC and VC) are more stable than those between Al and metal nitrides (TiN and VN).     

Effect of temperature and surface coverage on the samarium interaction with Si(111)

The interaction of Sm atoms with Si(111) has been studied. The study was carried out by low-energy electron diffraction, Auger-electron spectroscopy, and contact-potential difference method over a broad range of temperatures (from room temperature to 1140 K) at which samarium was deposited on the silicon sample surface. The surface coverage varied from zero to 55 monolayers. It was shown that the shape of the low-energy Auger spectrum of samarium depends on coverage, and that its variation correlates with that of the Sm atom valence state. It was established that no ordered structures form when samarium is deposited on silicon at room temperature, and that partial mixing of the metal and semiconductor atoms takes place in the initial stages of this process. If samarium is deposited on heated silicon (900 and 1140 K), an adsorbed film (transition layer), whose structure is determined by the coverage and temperature, is the first to form. After that, three-dimensional silicide crystallites begin to grow on this transition layer. Their shape depends on the substrate temperature. This dependence accounts for the relation between temperature and the coverage at which the crystallites coalesce. Fiz. Tverd. Tela (St. Petersburg) 40, 1937–1944 (October 1998)     

Structural stability,electronic structure and mechanical properties of 4d transition metal nitrides TMN (TM=Ru,Rh, Pd)

Ab initio calculations are performed to investigate the structural stability, electronic, structural and mechanical properties of 4d transition metal nitrides TMN (TM=Ru, Rh, Pd) for five different crystal structures, namely NaCl, CsCl, zinc blende, NiAs and wurtzite. Among the considered structures, zinc blende structure is found to be the most stable one among all three nitrides at normal pressure. A structural phase transition from ZB to NiAs phase is predicted at a pressure of 104 GPa, 50.5 GPa and 56 GPa for RuN, RhN and PdN respectively. The electronic structure reveals that these nitrides are metallic. The calculated elastic constants indicate that these nitrides are mechanically stable at ambient condition.     

Structure and functional characteristics of HTSC composites based on Bi-2223 with nitride nanoadditives

The interaction of a number of nanosized (20–50 nm) and larger (3–4 μm) additives of refractory nitrides (AlN, HfN, TiN, ZrN, NbN, Si₃N₄, etc.) with the ceramic superconducting compound (Bi,Pb)₂Sr₂Ca₂Cu₃O_{10 + δ} has been considered. The phase composition of the compounds, the cation composition of the existing phases, the morphology of the matrix grains and precipitates, and a number of functional characteristics (T _C, J _C, magnetization, density, and hardness) have been investigated. The possibility of increasing the critical current density and magnetization at 4.2 and 77 K by a factor of more than 3, as well as the physicomechanical properties (density and hardness), has been established.