Thermal behaviour of hexanuclear titanium(IV) oxo isopropoxide carboxylates,and their usability as a single-source TiO2 CVD precursors

Hexanuclear oxo titanium(IV) isopropoxide carboxylates, of the general formula [Ti₆O₆(OPrⁱ)₆(O₂CR)₆] (R = Bu^t (1), CH₂Bu^t (2)) and [Ti₆O₆(OPrⁱ)₆(O₂CC(CH₃)₂Et)₆] · 0.5(C₇H₈) (3), have been synthesized as polycrystalline powders in order to study their thermal properties and usability as TiO₂ CVD precursors. Analysis of thermogravimetric and variable temperature (VT-IR) data shows that the thermal stability of the synthesized complexes decreases as follows 3 > 2 > 1. The composition of the vapors formed during the thermolysis of 1–3 were qualitatively analysed with VT-IR methods and mass spectrometry (MS-EI). According to obtained results, the decomposition of 1 and 2 proceeds with a partial decomposition and the formation of a volatile and stable titanium species, sufficient for their transport in vapors. The formation of volatile titanium-containing derivatives is an important factor that decides the application of 1 and 2 as precursors in CVD experiments. The high stability of 3 causes the thermal decomposition of this complex to be observed just above 573 K, and volatile titanium-containing derivatives were not detected in vapors. These results indicate that 3 could not be used as a precursor in CVD processes.     

Thermal and MS studies of silver(I) 2,2-dimethylbutyrate complexes with tertiary phosphines and their application for CVD of silver films

[Ag₂(CH₃CH₂C(CH₃)₂COO)₂] (1), [Ag₂(CH₃CH₂C(CH₃)₂COO)₂(PMe₃)₂] (2) and [Ag₂(CH₃CH₂C(CH₃)₂COO)₂(PEt₃)₂] (3) were prepared and characterized by MS-EI; ¹H, ¹³C, ³¹P NMR, variable temperature IR (VT-IR) spectroscopy and thermal analysis. MS and VT-IR data analysis suggests bidentate bridging carboxylates and monodentately bonded phosphines in the solid phase. The same methods used for gas phase analysis of 1–2 proved [(CH₃CH₂C(CH₃)₂COO)Ag₂]⁺ as the main ion, which could be transported in the gas phase during the CVD process. In the case of 3, similar intensity to the latter ion revealed [Ag{P(C₂H₅)}]⁺ and it is responsible for the CVD performance of 3. Thermal analysis results revealed that decomposition of 1–3 proceed in one endothermic process, with metallic silver formation between 197 and 220 °C. In the case of 1, VT-IR studies of the gaseous decomposition products demonstrate the presence of ester molecules and CO₂, whereas for 2 the main gaseous product appeared to be acid anhydride. Therefore, 2 was not used as a silver CVD precursor. Metallic layers were produced from 3 in hot-wall CVD experiments, (between 200 and 280 °C), under a total reactor pressure of 2.0 mbar, using argon as a carrier gas. Thin films deposited on Si(1 1 1) substrate were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Silver films obtained at moderate temperature (220–250 °C) revealed a thickness below 50 nm, and were whitish colored and slightly matt.     

Comparison of GexSi1—x Grown by UHV／CVD from Si2H6／GeH4 and SiH4／GeH4

Using double crystal X-rays diffraction (DCXRD) and atomic force microscopy (AFM), the results of Ge x Si 1- x grown by UHV/CVD from Si 2H 6 and SiH 4 are analyzed and compared. Adsorbates can migrate to the energy-favoring position due to the slow growth rate from SiH 4. In this case, a Si buffer that isolates the effect of substrate on epilayer could not be grown, which results in a pit penetrating into epilayer and buffer. The FWHM is 0.055° in DCXRD from SiH 4. The presence of diffraction fringes is an indication of an excellent crystalline quality. The roughness of the surface is improved if grown by Si 2H 6; however, the crystal quality of the Ge x Si 1- x material became worse than that from SiH 4 due to much larger growth rate from Si 2H 6. The content of Ge is obtained from DCXRD, which indicates the growth rate from Si 2H 6 is largest, then GeH 4, and that from SiH 4 is least.     

Highly conducting graphitic carbon films and nano patterns from poly(p-phenylenevinylene) prepared on the surface of silicon wafers by the CVD method

We could prepare highly electrically conducting graphitic carbon films and nano patterns by carbonizing the poly(p-phenylenevinylene) (PPV) films and nano patterns prepared on the silicon surface by the chemical vapor deposition polymerization method of α,α'-dichloro-p-xylene. When the PPV films on silicon wafers were thermally treated at 850°C highly oriented graphitic carbon films were obtained which exhibit an electrical conductivity higher than 0.7 x 10³ Scm⁻¹. This conductivity value is more than 10 times the value for the carbon films obtained from bulk PPV films or glassy carbons heat treated at the same temperature. Moreover, nano patterns of graphitic carbons were easily obtained on silicon wafers through carbonization of nano patterned PPV obtained by the CVD polymerization method.     

线形同轴耦合式微波等离子体CVD法硬质合金微型钻头金刚石涂层沉积

本文介绍了利用线形同轴耦合式微波等离子体CVD法在硬质合金微型钻头(微钻)上沉积金刚石涂层的初步实验结果.微型钻头的直径为0.5mm,其中WC晶粒的尺寸约为0.5μm.在沉积前,先用Murakami溶液(10gKOH+10gK3[Fe(CN)6]+100ml H2O)对微钻刻蚀10min,使其表面粗化,然后用硫酸-双氧水溶液(10ml98wt;H2SO4+100ml 38;m/vH2O2)对其浸蚀60s,以去除其表面的Co.在金刚石涂层过程中发现,由于微钻尖端在微波电磁场中产生较集中的辉光放电现象,因而在微钻尖端很难获得金刚石涂层.针对这种金刚石涂层过程中的"尖端效应",尝试使用了金属丝屏蔽的方法以改变微钻周围的微波电磁场分布,克服了上述金刚石涂层过程中的"尖端效应",首次成功地采用微波等离子体CVD法在微钻上沉积了厚度为1.5μm的金刚石涂层.     

Effect of titanium powder assisted surface pretreatment process on the nucleation enhancement and surface roughness of ultrananocrystalline diamond thin films

A superior, easy and single-step titanium (Ti) powder assisted surface pretreatment process is demonstrated to enhance the diamond nucleation density of ultrananocrystalline diamond (UNCD) films. It is suggested that the Ti fragments attach to silicon (Si) surface form bond with carbon at a faster rate and therefore facilitates the diamond nucleation. The formation of smaller diamond clusters with higher nucleation density on Ti mixed nanodiamond powder pretreated Si substrate is found to be the main reason for smooth UNCD film surface in comparison to the conventional surface pretreatment by only nanodiamond powder ultrasonic process. The X-ray photoelectron spectroscopic study ascertains the absence of SiC on the Si surface, which suggests that the pits, defects and Ti fragments on the Si surface are the nucleation centers to diamond crystal formation. The glancing-incidence X-ray diffraction measurements from 100 nm thick UNCD films evidently show reflections from diamond crystal planes, suggesting it to be an alternative powerful technique to identify diamond phase of UNCD thin films in the absence of ultra-violet Raman spectroscopy, near-edge X-ray absorption fine structure and transmission electron microscopy techniques.     

单壁碳纳米管的轴向能带工程

单壁碳纳米管具有优异的电子学特性,是制备新一代高性能集成电路的重要材料.碳纳米管芯片之路存在诸多挑战,包括直径和手性的控制生长方法、金属性和半导体性单壁碳纳米管的分离方法、器件加工与集成方法等.这些课题从本质上讲大多属于化学问题,因此碳纳米管芯片研究为化学家们提供了新的机遇与挑战.过去10年来,我们围绕单壁碳纳米管的轴向能带工程这一研究思路,开展了一系列碳纳米管芯片的基础探索工作,发展了若干有效的单壁碳纳米管局域能带的调控方法,包括温度阶跃生长法、脉冲供料生长法、基底调控法以及形变调控法等.本文系统地阐述了这些局域能带调控方法,为使读者对该领域的研究进展有一个较为全面的了解,文中对其他课题组开展的代表性工作也给予了综述性介绍.