富纳米硅氮化硅薄膜光致发光机制

对于富纳米硅氮化硅薄膜的光致发光,其电子-空穴对存在3类光激发-光发射过程.通过对富纳米硅氮化硅薄膜光致发光模型的数值模拟对比分析,提出富纳米硅氮化硅薄膜光致发光是量子限制模型和能隙态模型发光机制共同作用的结果.利用得到的结论,讨论一些已报道的富纳米硅氮化硅薄膜光致发光实验结果.     

利用FT-IR和XPS研究纳米和微米氮化硅粉体在不同气氛下的表面结构变化(英文)

采用红外光谱技术和光电子表面能谱技术比较纳米和微米氮化硅粉体表面结构在空气中和在氮气中的变化规律.研究结果显示,纳米氮化硅在空气中逐渐吸附氧气和有机物质,其表面形成了Si—OH、C—C、C—N等化学基团,而在惰性的氮气气氛中,纳米氮化硅的表面氧化被有效抑制.上述研究工作为纳米氮化硅的表面改性研究提供了一定的理论支持.     

不互溶体系的机械合金化非平衡结构的研究

应用ＴＥＭ，ＸＲＤ，ＤＳＣ等实验手段研究了不互溶Ｌａ－Ｆｅ元素混和粉（原子比Ｌａ∶Ｆｅ＝１∶５）机械合金化（ＭＡ）过程和微观结构．研究表明两元素之间无明显固态反应．在球磨作用下β－Ｌａ首先向α－Ｌａ转变，５５ｈ后形成非晶Ｌａ．同时Ｆｅ细化成纳米晶，形成纳米晶Ｆｅ和非晶Ｌａ的复合结构．非晶Ｌａ分布在纳米Ｆｅ晶粒之间，使Ｆｅ晶粒具有很好的热稳定性．应用原子尺寸模型能部分解释实验结果     

有序可控纳米银球阵列对a-SiN_x∶O薄膜光致发光增强的研究

采用聚苯乙烯(PS)纳米小球自组装技术结合激光退火方法制备了三种不同尺寸纳米银球阵列,研究不同尺寸纳米银球阵列对非晶掺氧氮化硅(a-SiN_x∶O)薄膜的光致发光的影响.首先,在p型硅衬底上铺有三种不同尺寸的聚苯乙烯(PS)纳米小球,再采用磁控溅射系统蒸镀银薄膜,然后用激光对该银薄膜进行处理.最后,采用等离子体增强化学气相沉积(PECVD)系统在样品表面生长非晶掺氧氮化硅薄膜.实验结果表明,相比于未引入纳米银球阵列的a-SiN_x∶O薄膜,引入170nm、220nm和300nm银球阵列的a-SiN_x∶O薄膜,其光致发光强度(PL)分别增强4.6、3.1和1.3倍.样品的原子力显微镜(AFM)图像显示,纳米银颗粒呈周期性排列且尺寸可控.荧光光谱分析表明,随着纳米银球阵列尺寸的增加,薄膜的发光峰位出现了红移.通过分光光度计UV-3600对a-SiN_x∶O薄膜的消光谱进行了测量计算.为了进一步研究不同尺寸纳米银球阵列对非晶掺氧氮化硅(a-SiN_x∶O)薄膜的光致发光的影响,对其消光谱和PL谱进行了对比分析.实验证实了a-SiN_x∶O薄膜光致发光的增强来自于金属银局域表面等离激元(LSP)与a-SiN_x∶O薄膜光发射之间的耦合.     

退火温度对Fe基纳米晶薄带结构特性影响研究

用隧道扫描显微镜和原子力显微镜对Fe基纳米非晶带和各种温度退火产生的晶带进行扫描,发现非晶带的自由面和贴辊面呈现不同的结构,自由面纳米颗粒比较小且呈现规则排列,贴辊面纳米颗粒比较大而优势团聚比较明显;非晶带在不同温度下进行退火,随着温度升高,内应力得到释放,晶带结构发生变化,在540℃退火温度下,非晶带晶化产生了α-Fe(Si)纳米晶相和非晶相共存的复合结构,出现了细小的α-Fe(Si)纳米晶粒,并均匀的散布在非晶基底中,此时自由面和贴辊面结构差异最小,软磁性能最好.     

纳米氮化硅粉末的表面处理研究

采用溶液聚合法合成了丙烯酸丁酯-甲基丙烯酸-丙烯腈(BA-MAA-AN)三元共聚物,使用该三元共聚物作为大分子表面改性剂对纳米氮化硅进行表面处理,运用TEM、FTIR、XPS等仪器对处理后的纳米氮化硅粉末的结构及表面特性进行系统地研究.结果表明:纳米氮化硅处理后,在有机溶剂中分散性良好,大分子改性剂包覆在其表面,并与其发生了化学作用.     

基于氮化硅薄膜纳米孔制备及DNA分子检测

通过对影响聚焦离子束溅射氮化硅纳米孔的溅射时间和离子束束流2个主要参数的研究,优化了聚焦离子束溅射纳米孔加工工艺.提出了利用聚焦离子束对氮化硅薄膜进行减薄后再溅射纳米孔的加工工艺.采用该加工工艺不仅可以减小纳米孔的直径和厚度,还可以减小纳米孔的锥度.最后利用氮化硅纳米孔研究了不同孔径的纳米孔对48 kbλ-DNA过孔姿态的影响,结果表明,孔径较大时,DNA分子过孔存在多种过孔姿态,孔径越小,DNA分子越容易被拉直过孔.同时针对DNA过孔时引起的阻塞电流,提出了简易的计算模型.     

我国非晶、纳米晶材料技术获重大突破

本刊讯 3月24日，北京市重大科技项目“非晶、纳米晶制品研究及产业化”通过市科委组织的验收。该项目是北京市科委2002年立项投入1200万元支持的由安泰科技股份有限公司、北京科技大学和中科院物理所共同承担的重大项目。包括4个课题：“纳米晶合金超薄带产业化”、“非晶、纳米晶丝材及其应用研究”、“大块非晶材料技术研究”、“非晶、纳米晶共性技术平台及信息化”。通过该项目的实施，开发了一系列非晶、纳米晶新材料，突破了非晶、纳米晶生产关键技术，     

铁磁性非晶合金中受磁化调制的局域流变

本文研究了铁磁性非晶合金的磁化和不均匀结构的动态弛豫过程的相互作用.研究发现,铁磁性非晶合金的磁化态可以通过表面磨损来被改变.伴随磁化态的改变,非晶合金在纳米压痕实验下的局域动态力学行为发生变化.结合三参量黏弹性模型和态转变理论分析发现,通过磁化,非晶合金的微观结构可以被明显改变,其类液区的有效体积、黏度和弛豫时间可以增加3倍以上.与上述现象相反,通过在弹性极限下的纳米压痕循环加载试验,非晶合金的类液区在纳米尺度上的局域流变可以擦除其磁化效应.非晶合金的磁化和局域流变过程的相互作用与其中的自旋-轨道耦合有关;其磁化态和类液区的变化并不影响其与理想玻璃态相关的瞬时剪切模量.该研究有助于理解非晶态磁性材料的动态磁-力学性能,对其应用有着重要的意义.     

SiN薄膜纳米孔芯片制造工艺实验研究

针对第3代基因测序的需求,提出一种大规模的氮化硅薄膜纳米孔芯片制造技术.通过测量不同膜厚氮化硅薄膜的应力,选择适用于纳米孔制造的最佳厚度为100 nm.采用低压化学气相沉积、反应离子刻蚀和释放工艺制备出高成品率的氮化硅纳米薄膜芯片.在此基础上,使用聚焦离子束和高能电子束实现氮化硅薄膜纳米孔的制造.研究聚焦离子束刻蚀时间、电流与纳米孔直径的关系.实验结果表明,采用聚焦离子束将氮化硅薄膜的厚度减薄至40 nm以下时,制作纳米孔的效果更好.采用聚焦离子束制造的氮化硅薄膜纳米孔最小直径为26 nm,而采用电子束制备的最小直径可达3.5 nm.该方法为基于固体纳米孔的DNA测序检测提供了有力的支撑.     

Observation of rare-earth segregation in silicon nitride ceramics at subnanometre dimensions

Silicon nitride (Si3N4) ceramics are used in numerous applications because of their superior mechanical properties. Their intrinsically brittle nature is a critical issue, but can be overcome by introducing whisker-like microstructural features. However, the formation of such anisotropic grains is very sensitive to the type of cations used as the sintering additives. Understanding the origin of dopant effects, central to the design of high-performance Si3N4 ceramics, has been sought for many years. Here we show direct images of dopant atoms (La) within the nanometre-scale intergranular amorphous films typically found at grain boundaries, using aberration corrected Z-contrast scanning transmission electron microscopy. It is clearly shown that the La atoms preferentially segregate to the amorphous/crystal interfaces. First-principles calculations confirm the strong preference of La for the crystalline surfaces, which is essential for forming elongated grains and a toughened microstructure. Whereas principles of micrometre-scale structural design are currently used to improve the mechanical properties of ceramics, this work represents a step towards the atomic-level structural engineering required for the next generation of ceramics.     

Si3N4的结构状态对放电等离子烧结制备Sialon陶瓷的影响

以纳米非晶-Si3N4、微米α-Si3N4、微米AlN、纳米Al2O3和纳米Y2O3为初始原料,采用放电等离子烧结工艺制备了Sialon陶瓷。通过调整配方中Si3N4对应原料的种类,研究了不同结构的Si3N4对合成Sialon陶瓷的影响。通过XRD和SEM对试样的物相和显微结构进行了表征,同时测试了试样的体积密度、抗弯强度、断裂韧性和维氏硬度。实验结果表明,配方中的Si3N4全部采用α-Si3N4,经SPS烧结后可获得α/β-Sialon陶瓷,当用纳米非晶-Si3N4逐步替换α-Si3N4时,所合成的Sialon陶瓷中的α-Sialon晶相的相对含量减少;当全部采用纳米非晶-Si3N4时,则试样中仅含有β-Sialon相。     

TiN/Si3N4界面结构对Ti-Si-N纳米晶复合膜力学性能的影响

采用多层膜模拟的方法研究了Ti-Si-N纳米晶复合膜中Si3N4界面相的存在方式,以探讨纳米晶复合膜的超硬机制。研究结果表明：Si3N4层厚对TiN／Si3N4多层膜的微结构和力学性能有重要影响。当Si3N4层厚小于0．7nm时,因TiN晶体的“模板效应”,原为非晶态的Si3N4晶化,并反过来促进TiN的晶体生长,从而使多层膜呈现TiN层和Si3N4层择优取向的共格外延生长。相应地,多层膜产生硬度和弹性模量升高的超硬效应,最高硬度和弹性模量分别为34．0GPa和352GPa．当层厚大于1．3nm后,Si3N4呈现非晶态,多层膜中TiN晶体的生长受到Si3N4非晶层的阻碍而形成纳米晶,薄膜的硬度和弹性模量亦随之下降。由此可得,Ti-Si-N纳米晶复合膜的强化与多层膜中2层不同模量调制层共格外延生长产生的超硬效应相同。     

Fabrication of silicon nitride／boron nitride nanocomposite powder

Si3N4/BN nanocomposite powders with the microstructure of the micro-sized α-Si3N4 particles coated with nano-sized BN particles were synthesized via the chemical reaction boric acid,urea,and α- Si3N4 powder in a hydrogen gas.The results of XRD,TEM,and selected area electron diffraction showed that amorphous BN and a little amount of turbostratic BN(t-BN) were coated on Si3N4 particles as the second phase after reaction at 1100℃.After re-heating the composite powders at 1450℃ in a nitrogen gas,the amorphous and turbostratic BN is transformed into h-BN.These nanocomposite powders can be used to prepare Si3N4/BN ceramic composites by hot-pressing at 1800℃,which have perfect machinability and can be drilled with normal metal tools.     

Reaction behavior of trace oxygen during combustion of falling FeSi75 powder in a nitrogen flow

To explore the reaction behavior of trace oxygen during the flash combustion process of falling FeSi75 powder in a nitrogen flow, a flash-combustion-synthesized Fe-Si₃N₄ sample was heat-treated to remove SiO₂. The samples before and after the treatment were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, and the formation mechanism of SiO₂ was investigated. The results show that SiO₂ in the Fe-Si₃N₄ is mainly located on the surface or around the Si₃N₄ particles in dense areas, existing in both crystalline and amorphous states; when the FeSi75 particles, which are less than 0.074 mm in size, fell in up-flowing hot N₂ stream, trace oxygen in the N₂ stream did not significantly hinder the nitridation of FeSi75 particles as it was consumed by the surface oxidation of the generated Si₃N₄ particles to form SiO₂. At the reaction zone, the oxidation of Si₃N₄ particles decreased the oxygen partial pressure in the N₂ stream and greatly reduced the opportunity for FeSi75 particles to be oxidized into SiO₂; by virtue of the SiO₂ film developed on the surface, the Si₃N₄ particles adhered to each other and formed dense areas in the material.     

Dissolution behavior and dissolution mechanism of palygorskite in HCl solution

The 1 mol/L, 3 mol/L and 5 mol/L HCl solutions were employed to leach two palygorskites with different trioctahedral contents in their crystal structure for different period of time. The results of the dissolution experiments show that the dissolution process could be divided into three steps, and that this dissolution behavior can be attributed to its higher Mg2+ content, and is restricted by the extraction behavior of Si4+. The preferential extraction for Mg2+ promotes the extraction behavior of Si4+ from Si-O framework. Because the Si4+ in the form of amorphous SiO2 is adsorbed onto the surface of palygorskite fibre, the reaction between palygorskite and acid is obstructed. With the elapsing of time, or the increasing of the acid concentration, the amorphous SiO2 flocculates, and then the channels of chemical reaction are reopened. The ratio value of Mg2+/(Fe3++Al3+) in leaching solution tends to a fixed value, showing that the acid attacks not only the surface but also the structural channels. There are no obvious three steps observed during the acid attack on the palygorskite with a lower trioctahedral content. The differential behavior for two palygorskites is discussed.     

Si含量和基片温度对Ti-Si-N纳米复合薄膜的影响

通过多靶磁控反应溅射方法沉积了Ti-Si-N系纳米复合薄膜。采用电子能谱仪（EDS）、X－射线衍射（SRD）、透射电子显微镜（TEM）、X－射线光电子能谱（XPS）和显微硬度仪分析Ti-Si-N系薄膜的微观结构和力学性能，以及基片温度对薄膜微结构和硬度的影响。结果表明，薄膜中的Si以非晶Si3N4形式抑制TiN晶粒的生长，使之形成纳米晶甚至非晶；薄膜硬度在a(Si)=4.14%时达到最大值（36GPa），继续增加Si的含量，薄膜硬度逐渐降低。基片温度的提高减弱了Si3N4对TiN晶粒长大的抑制作用，因而高的沉积温度使薄膜呈现出硬度峰值略低和硬度降幅减缓的特征。     

Morphology of α-Si3N4 in Fe–Si3N4 prepared via flash combustion

The state and formation mechanism ofα-Si3N4 in Fe–Si3N4 prepared by flash combustion were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results indicate thatα-Si3N4 crystals exist only in the Fe–Si3N4 dense areas. When FeSi75 particles react with N2, which generates substantial heat, a large number of Si solid particles evaporate. The prod-uct between Si gas and N2 is a mixture ofα-Si3N4 andβ-Si3N4. At the later stage of the flash combustion process,α-Si3N4 crystals dissolve and reprecipitate asβ-Si3N4 and theβ-Si3N4 crystals grow outward from the dense areas in the product pool. As the temperature decreases, the α-Si3N4 crystals cool before transforming into β-Si3N4 crystals in the dense areas of Fe–Si3N4. The phase composition of flash-combustion-synthesized Fe–Si3N4 is controllable through manipulation of the gas-phase reaction in the early stage and theα→βtrans-formation in the later stage.     

真空炉冷非晶态合金钎料的微观组织

研究了真空熔化炉冷晶态及非晶态Ｎｉ（８０－ｘ）Ｃｒ１０Ｂ２．５Ｓｉ４．５Ｆｅ３Ｃｕｘ合金钎料真空熔化炉冷组织形态,分析了铜的添加对合金钎料组织的影响．研究结果表明：非晶态钎料真空熔化炉冷后与相应的晶态比较组织上无大的差异,仅仅是固溶体含量的增加及共晶相更弥散分布．     

由氨解法制备的Si_3N_4粉末的表面元素状态

用XPS表面分析,研究了由氨解法在不同温度下热解所得的Si_3N_4粉末,并与由硅粉氮化所得的商用Si_3N_4粉末作了比较。由氨解法制备的Si_3N_4粉末其表面存在两种状态的氧:结合状态的氧和吸附态的氧,其表面组成为Si_(2.2-2.7)N_(2.9-3.7)O。由硅粉氮化所制得Si_3N_4其表面也存在两种状态的氧,其表面组成则为Si_(0.8)N_(0.8)O。