POSITRON ANNIHILATION STUDY OF YBa2(Cu1-xSnx)3Oy SUPERCONDUCTORS

The positron annihilation lifetime spectra and their temperature dependence for the YBa₂Cu₃O_y superconducting ceramics doped with Sn have been studied. The resutts of analyses indicate that the element Sn is substituted for Cu(1) sites, and this leads to the ordering of the oxygen atoms as well as the increase of local electronic density in the Cu(1)-O layer where Cu(1) is substituted by Sn.     

A theoretical analysis of the TiO2/Sn doped (1 1 0) surface properties

We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO₂/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO₂ is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sn, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices.     

Superconductivity in non-stoichiometric and tin-substituted La2CuO4: preparation, characterization, Mössbauer and microwave-absorption studies

Two samples of non-stoichiometric La₂CuO₄ were synthesized, one with La/Cu<2, and the other with 10% Sn substituting Cu. They were investigated by X-ray diffraction, Mössbauer spectroscopy, and microwave-absorption techniques. The microwave-absorption data indicated that they were both superconducting, with the transition temperatures T_c of 40.5 and 41.5 K, the one doped with Sn possessing the higher T_c. The Mössbauer spectra revealed that there exist two kinds of Sn(IV) atoms disordered with Cu. Their isomer shift, δ=−0.244(4) mm/s, is in agreement with Sn(IV) coordinated by oxygen. One site was characterized by a single Mössbauer line, being associated with a weakly distorted environment, wherein the Sn, coordinated more symmetrically, is surrounded by four Cu²⁺ ions. On the other hand, the other site, characterized by a Mössbauer doublet exhibited a quadrupole splitting Δ=1.07(2) mm/s, being associated with a highly distorted coordination, explained to be due to Sn occupying two adjacent cationic sites. To our knowledge, such a substitution for copper ions not resulting in a decrease of T_c has not been reported previously.     

Mössbauer-effect studies of multilayers and interfaces

The usefulness of Mössbauer spectroscopy for the investigation of magnetic multilayer systems is described. By applying ⁵⁷Fe Mössbauer spectroscopy, the behavior of ultrathin magnetic layers, such as FCC-like Fe films on Cu(0 0 1), is studied. Position-specified (depth-selective) information is available by preparing samples in which monatomic ⁵⁷Fe probe layers are placed at specific vertical positions, e.g. at interfaces or at the surface. As demonstrated for epitaxial chemically ordered Fe₅₀Pt₅₀ alloy films and polycrystalline nanostructured Tb/Fe multilayers, the Fe-spin structure can be determined directly, and a site-selective Fe-specific magnetic hysteresis loop can be traced in very-high-coercivity materials. For the studies of non-magnetic layers, on the other hand, hyperfine field observations by ¹⁹⁷Au and ¹¹⁹Sn probes are worthwhile. Spin polarizations in Au layers penetrating from neighboring ferromagnetic 3D layers are estimated ¹⁹⁷Au from Mössbauer spectra and are also studied by inserted ¹¹⁹Sn probes in Au/3D multilayers. In the Sn spectra for Cr/Sn multilayers, it was found that remarkably large spin polarization is penetrating into Sn layers from a contacting Cr layer, which suggests that Cr atoms in the surface layer have a ferromagnetic alignment.     

胺化葡萄糖及其铜配合物的光谱特性

研究了胺化D-葡萄糖的FTIR,1H-NMR特性及其与Cu(Ⅱ)形成配合物的UV光谱。在FTIR谱中,与D-葡萄糖相比,在1 629～1 608 cm-1出现δ_NH吸收峰,说明D-葡萄糖与乙二胺发生了反应;在1H-NMR谱中,在δ4.82～4.79的化学位移分别对应于葡萄糖C₁上的质子及与C₁直接相连的乙二胺的氨基上的质子,表明反应时乙二胺取代了葡萄糖C₁上的羟基,形成了胺化葡萄糖;在UV谱中,胺化葡萄糖在紫外光区并没有明显吸收,但与Cu(Ⅱ)形成配合物后,在236 nm附近出现最大吸收峰。在胺化葡萄糖-Cu(Ⅱ)配合物中,Cu2+与胺化葡萄糖的络合比接近于1∶1,该配合物稳定常数6.8×107 L·mol-1。     

Structural stabilities and electrical properties of Ba_8Ga_(16-x)Cu_xSn_(30) single crystals under high temperatures

Single crystalline samples of type-I and type-VIII Ba_8Ga_(16-x)Cu_xSn_(30)(x = 0,1) clathrates are prepared by the Snflux method.Effects of Cu-doping on stability and electrical properties of Ba8Ga16Sn30 single crystal are explored by first-principle and experiment.All samples are heated to different high temperatures and maintained at these temperatures for 120 min and then cooled to room temperature to explore their structural stabilities.Results from DTA and powder xray diffraction analysis indicate that type-I Ba_8Ga_(16)Sn_(30) structure is transformed into type-VIII phase after the sample has been heated to 185℃.Type-VIII BGS is stable during heating and cooling,but type-VIII Ba_8Ga_(15)CuSn_(30) decomposes into Sn and Ba(Ga/Sn)_4 during cooling.Meanwhile,the electrical properties of type-I samples are measured,their electrical conductivities are enhanced,and the Seebeck efficient is reduced with Cu substitution.The type-I samples after phase transformations show the electrical characteristics of type-VIII samples.     

Study of the effects of an adatom Sn on the Cu surface electromigration using a first principles method

It is well known that the doped Sn can effectively suppress the electromigration of Cu thin-film interconnects in integrated circuits. In this paper, the first-principles method was introduced to investigate the suppression mechanism. All the calculations were performed on Sn or Cu adatom/Cu (0 0 1), (1 1 0) and (1 1 1) surface systems within local density approximation. As a Sn adatom was attached to the Cu surface, stable CuSn bonds were formed. The energy calculations show that the Sn/Cu system was more stable than Cu/Cu system with the same structure. Analysis of density of states shows that the nearest neighbor Cu atoms were stabilized by CuSn bond relative to the Cu atoms which are far away from the adatom. The diffusion barrier energies were calculated and found to be consistent with the experimental results. Also, bond population analysis shows that stronger covalent bonds were formed between Sn and Cu relative to that between Cu and Cu. All the results indicate that the CuSn bond plays an important role in the suppression of Cu electromigration.     

热迁移对Cu/Sn/Cu焊点液-固界面Cu6Sn5生长动力学的影响

电子封装技术中, 微互连焊点在一定温度梯度下将发生金属原子的热迁移现象, 显著影响界面金属间化合物的生长和基体金属的溶解行为. 采用Cu/Sn/Cu焊点在250℃和280℃下进行等温时效和热台回流, 对比研究了热迁移对液-固界面Cu₆Sn₅生长动力学的影响. 等温时效条件下, 界面Cu₆Sn₅生长服从抛物线规律, 由体扩散控制. 温度梯度作用下, 焊点冷、热端界面Cu₆Sn₅表现出非对称性生长, 冷端界面Cu₆Sn₅生长受到促进并服从直线规律, 由反应控制, 而热端界面Cu₆Sn₅生长受到抑制并服从抛物线规律, 由晶界扩散控制. 热端Cu 基体溶解到液态Sn中的Cu原子在温度梯度作用下不断向冷端热迁移, 为冷端界面Cu₆Sn₅的快速生长提供Cu 原子通量. 计算获得250℃和280℃下Cu原子在液态Sn中的摩尔传递热Q^*分别为14.11和14.44 kJ/mol, 热迁移驱动力F_L分别为1.62×10^-19和1.70×10^-19 N.     

EFFECT OF THE SUBSTITUTION OF Ga AND Sn FOR Cu ON THE ELECTRONIC STRUCTURE AND SUPERCONDUCTIVITY OF La1.85Sr0.15CuO4

The electronic structure of La_1.85Sr_0.15CuO₄, as well as the two cases of substitution of Ga and Sn for Cu, has been studied by the recursion method. The change of hole concentration and the effective local magnetic moment have also been calculated. Our calculations show that Ga and Sn destroy the two-dimensional character of the CuO₂ plane and lead to the disorder of the electronic structure, accompanied by the migration of electrons which canines the decrease of the hole concentration in the CuO₂ planes. From our point of view, these changes may be responsible for the destruction of superconductivity of the Ga and Sn-doped systems.     

电镀法在氧化铟锡上制备铜锌锡硫薄膜的光谱特征

低成本、环境友好的铜锌锡硫替代含贵金属和有毒金属的铜铟镓硒,是薄膜太阳能电池的最佳选择。电镀法是一种无需真空设备和靶材的低成本方法。一种更简单的制膜方法是在水溶液中共电镀沉积Cu-Zn-Sn（CZT)合金于FTO衬底上。采用氩气保护气氛下在550 ℃硫化电镀法制得的CZT合金前驱体,成功制备了CZTS薄膜。采用三电极体系将CZT合金前驱体电镀在FTO上,其中FTO作为工作电极,铂（Pt）网和Ag/AgCl分别作为对电极和参比电极。电解质由CuSO₄,ZnSO₄,SnSO₄,络合剂-三乙醇胺（TEA）和柠檬酸钠组成。前驱体在氩气保护气氛下550℃硫化得到CZTS薄膜。采用X射线衍射（XRD）、拉曼光谱、扫描电子显微镜（SEM）、紫外可见光光谱仪和光电化学测量（PEC）等方法,表征了CZTS薄膜的结构、形貌、成分和光谱学性质。XRD和拉曼光谱证明了550 ℃硫化后的CZTS薄膜具有锌黄锡矿结构。一个Raman主峰位于342 cm-1,两个Raman次强峰分别位于289和370 cm-1,这些峰位与锌黄锡矿CZTS的峰位相吻合。SEM结果证明优化后CZTS薄膜成分接近CZTS的理想化学计量比,CZTS薄膜中Cu/(Zn+Sn）和 S/(Zn+Sn+Cu)分别为0.52和1.01,这表明CZTS薄膜中S的含量非常合适。PEC结果证实,采用前照射或后照射FTO/CZTS均产生光电流,并且两种照射下产生的光电流方向一致。通过紫外可见光光谱测量并由此计算出的CZTS能隙为1.45 eV。通过上述分析证明制备的CZTS薄膜具有高品质,可用于制备CZTS薄膜太阳能电池。     

PLD制备的Cu掺杂SnS薄膜的结构和光学特性

利用脉冲激光沉积(PLD)在玻璃衬底上制备了Cu掺杂SnS薄膜.靶材是由SnS和Cu₂S粉末混合压制而成(Cu和Sn的量比分别为0%、2.5%、5%、7.5%和10%).利用X射线衍射(XRD)、拉曼光谱仪(Raman)、原子力显微镜(AFM)、紫外-可见-近红外分光光度计(UV-Vis-NIR)、Keithley 4200-SCS半导体参数分析仪研究了Cu掺杂量对SnS薄膜的晶体结构、表面形貌、光学性质和电学性能的影响.结果表明:所制备的SnS薄膜样品沿(111)晶面择优取向生长, SnS :5%Cu薄膜的结晶质量最好且具有SnS特征拉曼峰.随着Cu掺杂量的增大, 平均颗粒尺寸逐渐增大.不同Cu掺杂量的薄膜在可见光范围内的吸收系数均为10⁵ cm^-1数 量级.SnS :5%Cu薄膜的禁带宽度E_g为2.23 eV, 光暗电导率比值为2.59.同时, 在玻璃衬底上制备了p-SnS :Cu/n-ZnS 异质结器件, 器件在暗态及光照的条件下均有良好的整流特性, 并具有较弱的光伏特性.     

Mg-Sn-Si合金中Mg2(Si,Sn)复合相的结构与性能研究

研究了铸态Mg-Sn-Si合金中Mg₂(Si,Sn)复合相的结构、 特性以及该相对Mg-Sn-Si合金变质作用的影响. 结果表明: Sn原子能取代Mg₂Si中的部分Si生成Mg₂(Si,Sn)复合相, 该三元相与Mg₂Si, Mg₂Sn相的结构相同, 属于面心立方结构, Mg₂(Si,Sn)相的元素含量并不固定, 在Si富集区形成的Mg₂(Si,Sn)相中, Si元素含量高, 在Si贫乏区形成的Mg₂(Si,Sn)相中, Si元素含量低. Si含量较多的Mg₂(Si,Sn)相性能与Mg₂Si相接近, Sn含量较多的Mg₂(Si,Sn)相性能与Mg₂Sn相接近, 实验中发现Mg₂(Si,Sn)复合相的纳米硬度、 弹性模量与维氏硬度等物理性能介于Mg₂Si与Mg₂Sn之间, Mg₂(Si,Sn)相对汉字状Mg₂Si相的变质处理起到桥梁作用. 关键词： Mg-Sn-Si合金 2Si')" href="#">Mg₂Si 2Sn')" href="#">Mg₂Sn 2(Si,Sn)复合相')" href="#">Mg₂(Si,Sn)复合相     

Mg-Sn-Si系合金的热力学基础及合金相演变过程分析

研究了Mg-Sn-Si系合金的热力学基础及合金相的演变过程. 结果表明: 对于Mg-Sn-Si系合金, 合金相的比热容随着温度增加而增加, 在低温下变化迅速, 而在高温下变化平缓, 其热膨胀系数在低温范围内随温度升高呈指数形式增加, 而在高温范围内呈线性增大. 在Mg₂ (Si_x, Sn_1-x)、Mg₂ (Sn_x, Si_1-x)相结构中, Sn(Si)原子的取代位置不固定, 可以是面心, 也可以是顶点. 常规凝固过程中, 由于处于非平衡状态, x的取值范围有所波动, 对于Mg₂ (Si_x, Sn_1-x)和Mg₂ (Sn_x, Si_1-x) 两种结构, x的取值范围在0.25或0.75附近. Mg₂ (Si, Sn)的生成温度较高, 可从液相中直接析出, 也可由Mg₂Si转化而来, 而Mg₂ (Sn, Si)的生成温度较低, 只能从基体中析出, 随着Sn含量的增加, 开始析出Mg₂ (Sn, Si)相的温度升高.     

Improvement of Cu2ZnSnS4 thin film morphology using Cu–Zn–Sn–O precursor fabricated by sputtering

The new precursor of Cu–Zn–Sn–O (CZTO) was proposed for Cu₂ZnSnS₄ (CZTS) thin film fabrication to improve film morphology. The CZTS thin film grown from Cu–Zn–Sn (CZT) precursors has many bumps. We deposited CZTO precursors on Mo/soda-lime glass (SLG) substrates by RF sputtering using a CZT (Cu:Zn:Sn = 2:1:1) target in Ar and O₂ atmosphere at various O₂ partial pressures (0%, 5%, 17% and 20%). Subsequently, the CZTO precursors were sulfurized in Ar and S atmosphere to fabricate CZTS thin films. The CZTO precursors were amorphous. The morphology of the CZTS thin films was improved by the CZTO precursors. All of the CZTS films fabricated in this study had the same crystal structure. Composition analysis revealed that 50% of O were detected in the CZTO precursor, but O was not detected after sulfurizing process, indicating that O was substituted by S. The CZTS thin film from the CZTO precursor fabricated at O₂ partial pressure of 20% had similar composition for solar cell absorber.     

Zero-field current-voltage characteristics in high-temperature superconductors

We have observed the anomalous magnetization of Bi₂Sr₂CaCu_2−xNi_xO₈ (x = 0 and 0.02) single crystals. Anisotropy decreases with iodine intercalation although it expands the space between CuO₂ layers. Iodine intercalation seems to suppress the magnetization anomaly for Ni = 1% crystals, but not for Ni = 1% substituted crystals. We have discussed these results in terms of the increase of anisotropy by Ni substitution and the dimensional crossover of flux lines. Effects of both oxygen concentration and substitution of a magnetic element for the Cu site on the anisotropy of Bi₂Sr₂CaCu₂O₈ crystals show the same tendency as the case of the YBa₂Cu₃O₇ superconductor.     

Effect of Sn doping on the magnetic and transport properties of LaMnO3+δ

We report the influence of the Sn doping on the magnetotransport properties of the LaMnO_3+δ perovskite. Two series of samples with nominal LaSn_xMn_1−xO_3+δ (I series) and La_{(1−x)/(1+x)}Sn_xMn_1−xO_3+δ (II series) compositions (x=0, 0.025, 0.05 and 0.10) were prepared at T_s=750°C. The M(T) data under 0.01 and 0.5 T for the I series reveal a depressed magnetization as the Sn content increases suggesting the presence of magnetic clusters with a superparamagnetic behavior. Resistivity measurements indicate an insulator material for all Sn content independently of the applied magnetic field. On the contrary, for the II series the M(T) and M(H) data reveal FM behavior and an improvement of the magnetization as Sn increases. These samples show magnetoresistance. The magnetotransport properties are discussed in terms of the presence of A-site cation vacancies.     

热-电应力下Cu/Ni/SnAg_(1.8)/Cu倒装铜柱凸点界面行为及失效机理

微互连铜柱凸点因其密度高、导电性好、噪声小被广泛应用于存储芯片、高性能计算芯片等封装领域,研究铜柱凸点界面行为对明确其失效机理和组织演变规律、提升倒装封装可靠性具有重要意义.采用热电应力实验、在线电学监测、红外热像测试和微观组织分析等方法,研究Cu/Ni/SnAg_1.8/Cu微互连倒装铜凸点在温度100—150℃、电流密度2×10~4—3×10~4 A/cm~2热电应力下的互连界面行为、寿命分布、失效机理及其影响因素.铜柱凸点在热电应力下的界面行为可分为Cu_6Sn_5生长和Sn焊料消耗、Cu_6Sn_5转化成Cu_3Sn、空洞形成及裂纹扩展3个阶段,Cu_6Sn_5转化为Cu_3Sn的速率与电流密度正相关.热电应力下,铜凸点互连存在Cu焊盘消耗、焊料完全合金化成Cu_3Sn、阴极镍镀层侵蚀和层状空洞4种失效模式.基板侧Cu焊盘和铜柱侧Ni镀层的溶解消耗具有极性效应,当Cu焊盘位于阴极时,电迁移方向与热迁移方向相同,加速Cu焊盘的溶解以及Cu_3Sn生长,当Ni层为阴极时,电迁移促进Ni层的消耗,在150℃,2.5×10~4 A/cm~2下经历2.5h后,Ni阻挡层出现溃口,导致Ni层一侧的铜柱基材迅速转化成(Cu_x,Ni_y)_6Sn_5和Cu_3Sn合金.铜柱凸点互连寿命较好地服从2参数威布尔分布,形状参数为7.78,为典型的累积耗损失效特征.研究结果表明:相比单一高温应力,热电综合应力显著加速并改变了铜柱互连界面金属间化合物的生长行为和失效机制.     

A LEED, TPD and HREELS investigation of NO adsorption on Sn/Pt(111) surface alloys

The adsorption of NO on Pt(111), and the (2 × 2)Sn/Pt(111) and (√3 × √3)R30°Sn/Pt(111) surface alloys has been studied using LEED, TPD and HREELS. NO adsorption produces a (2 × 2) LEED pattern on Pt(111) and a (2√3 × 2√3)R30° LEED pattern on the (2 × 2)Sn/Pt(111) surface. The initial sticking coefficient of NO on the (2 × 2)Sn/Pt(111) surface alloy at 100 K is the same as that on Pt(111), S₀ = 0.9, while the initial sticking coefficient of NO on the (√3 × √3)R30°Sn/Pt(111) surface decreases to 0.6. The presence of Sn in the surface layer of Pt(111) strongly reduces the binding energy of NO in contrast to the minor effect it has on CO. The binding energy of β-state NO is reduced by 8–10 kcal/mol on the Sn/Pt(111) surface alloys compared to Pt(111). HREELS data for saturation NO coverage on both surface alloys show two vibrational frequencies at 285 and 478 cm⁻¹ in the low frequency range and only one N-O stretching frequency at 1698 cm⁻¹. We assign this NO species as atop, bent-bonded NO. At small NO coverage, a species with a loss at 1455 cm⁻¹ was also observed on the (2 × 2)Sn/ Pt(111) surface alloy, similar to that observed on the Pt(111) surface. However, the atop, bent-bonded NO is the only species observed on the (√3 × √3)R30°Sn/Pt(111) surface alloy at any NO coverage studied.     

Pd-Sn双金属催化剂催化1, 3-丁二烯加氢反应的仲氢诱导极化研究

本文首先利用等体积共浸渍法合成了一系列Pd/Sn比（原子比）不同的Pd₁-Sn_x/Al₂O₃双金属催化剂,然后通过多相催化仲氢诱导极化（PHIP）技术研究了Pd-Sn/Al₂O₃双金属催化剂上1, 3-丁二烯选择性加氢反应.结果发现催化剂的Pd/Sn比会影响1, 3-丁二烯反应活性和丁烯选择性：随着Pd/Sn比的下降,反应中1, 3-丁二烯转化率降低,丁烯选择性提高.利用PASADENA（parahydrogen and synthesis allow for dramatically enhanced nuclear alignment）技术,发现Pd/Sn比的变化影响了1-丁烯与2-丁烯之间的异构化过程：随着Pd/Sn比的下降,1-丁烯异构化率降低,这是由于Sn组分含量的提高减少了表面暴露的Pd组分,使得催化剂反应活性降低;Sn组分含量的提高同时导致了Pd电子密度的上升,使得选择性还原产物丁烯更易脱附,阻止其进一步加氢生成丁烷,并抑制了1-丁烯异构化反应过程.     

非等电子Sb替换Cu和Te后黄铜矿结构半导体Cu_3Ga_5Te_9的热电性能

热电材料是一类能够实现热与电相互转换的功能材料,在制冷和发电领域极具应用潜力.本文采用金属Sb元素非等电子替换Cu3Ga5Te9化学式中的Cu和Te,观察到材料Seebeck系数和电导率提升的现象.这些电学性能的改善与载流子浓度和有效质量的增大及迁移率基本维持不变有关.载流子浓度的提高是由于Sb原子占位在Te晶格位置后费米能级进入到价带所产生的空穴掺杂效应所致,同时也与Cu含量减少后铜空位(V-1Cu)浓度增大相关联.另外,非等电子替换后,阴离子(Te2-)移位导致了晶格结构缺陷参数u和η的改变,其改变量fiu和fiη与材料晶格热导率(κL)的变化密切相关.在766 K时,适量的Sb替换量使材料的最大热电优值(ZT)达到0.6,比Cu3Ga5Te9提高了近25%.因此,通过选择替换元素、被替换元素及替换量有效地调控了材料的电学及热学性能,在黄铜矿结构半导体中实现了非等电子元素替换改善热电性能的思想.