玉米农田土壤呼吸作用动态与模拟研究

利用动态密闭气室法(Licor-6400-09)，对锦州玉米生长季(5～9月)农田土壤呼吸作用动态及其影响因子进行连续两年的野外动态观测，分析表明，在植株尺度上，玉米地土壤呼吸作用存在明显的空间异质性，较高的土壤呼吸速率通常出现在靠近玉米植株的地方。玉米地土壤呼吸作用的日变化为不对称的单峰型曲线，最小值和最大值分别出现在6:00～7:00和13:00左右。2005年玉米生长季土壤呼吸速率均值为3.16 µmol CO2 •m-2•s-1，最大值为4.77 µmol CO2 •m-2•s-1，出现在7月28日，最小值为1.31 µmol CO2 •m-2•s-1，出现在5月4日。 植物根系生物量的分布格局是影响土壤呼吸作用空间异质性的关键因素。土壤呼吸作用与根系生物量呈显著的线性关系，而土壤湿度、土壤有机质、全氮和碳氮比对土壤呼吸作用空间异质性的影响并不显著。在土壤呼吸作用日变化中，土壤呼吸速率(SR, µmol CO2 •m-2•s-1)与10 cm土壤温度(T, ℃)均呈显著的指数函数关系 。在季节尺度上，参数α和β是波动的，玉米净第一性生产力(NPP, g •m-2 •d-1)和生物量(B, g •m-2)分别为影响参数α和β季节性波动的主导因素。鉴于此，建立了方程 用以模拟土壤呼吸作用的季节变化。土壤温度、NPP和生物量共同影响着玉米生长季土壤呼吸作用的季节性变化，它们共同解释了土壤呼吸作用季节变化的93%。 小时尺度上，土环中的根系生物量是影响土壤呼吸速率空间变异的关键因子，土壤呼吸速率与根系生物量呈线性关系 ;日时间尺度上，土壤呼吸速率与根系生物量线性方程中的参数α和β是波动，土壤温度是影响α和β波动的主导因素，于是得到方程 。季节时间尺度上，土壤呼吸作用可表达为 ，土壤温度、土壤湿度和玉米NPP共同驱动着玉米生长季土壤呼吸作用的时间变化和空间变异，它们可以解释玉米生长季土壤呼吸作用时空变化的74%。 通过建立土壤呼吸作用与玉米根系生物量的回归方程，对根系呼吸作用占土壤呼吸作用的比例进行了间接估算。玉米生长季根系呼吸作用占土壤呼吸作用的比例在43.1～63.6%之间波动，均值为54.5%。假定玉米果实和秸杆中的碳在收获期间没有从农田中转移走，2005年整个生长季玉米生态系统的碳收支为–1127.0 gC•m-2，碳交换速率在 0.52～-18.05 g C•m-2 •d-1 之间波动。玉米生长初期，玉米生态系统表现为C的弱碳源;玉米播种后35天一直到收获，玉米生态系统表现为碳汇。

Hafnia nanoparticles - a model system for graphene growth on a dielectric

We study graphene growth on hafnia (HfO2) nanoparticles by chemical vapour deposition using optical microscopy, high resolution transmission electron microscopy and Raman spectroscopy. We find that monoclinic HfO2 nanoparticles neither reduce to a metal nor form a carbide while nucleating nanometer domain-sized few layer graphene. Hence we regard this as an interesting non-metallic catalyst model system with the potential to explore graphene growth directly on a (high-k) dielectric. HfO2 nanoparticles coated with few layer graphene by atmospheric pressure CVD with methane and hydrogen at 950 °C. (© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) Graphene growth on hafnia (HfO2) nanoparticles by chemical vapour deposition (CVD) is studied. It is found that monoclinic HfO2 nanoparticles neither reduce to a metal nor form a carbide while nucleating nanometer domain-sized few layer graphene. Hence the authors of this Letter regard this as an interesting non-metallic catalyst model system with the potential to explore graphene growth directly on a (high-k) dielectric. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Complementary metal-oxide-semiconductor-compatible and self-aligned catalyst formation for carbon nanotube synthesis and interconnect fabrication

We have for the first time developed a self-aligned metal catalyst formation process using fully CMOS (complementary metal-oxide-semiconductor) compatible materials and techniques, for the synthesis of aligned carbon nanotubes (CNTs). By employing an electrically conductive cobalt disilicide (CoSi 2) layer as the starting material, a reactive ion etch (RIE) treatment and a hydrogen reduction step are used to transform the CoSi 2 surface into cobalt (Co) nanoparticles that are active to catalyze aligned CNT growth. Ohmic contacts between the conductive substrate and the CNTs are obtained. The process developed in this study can be applied to form metal nanoparticles in regions that cannot be patterned using conventional catalyst deposition methods, for example at the bottom of deep holes or on vertical surfaces. This catalyst formation method is crucially important for the fabrication of vertical and horizontal interconnect devices based on CNTs. © 2012 American Institute of Physics.

Highly chiral-selective growth of single-walled carbon nanotubes with a simple monometallic Co catalyst

We report on the growth of single-walled carbon nanotubes from a monometallic Co catalyst on an oxidized Si wafer support by the most simple growth recipe (vacuum annealing, growth by undiluted C 2H 2). Nevertheless, multiwavelength Raman spectroscopy and transmission electron spectroscopy show a remarkable selectivity for chiral indices and thus, e.g., high abundance with a single chirality representing 58% of all semiconducting tubes. In situ x-ray photoelectron spectroscopy monitors the catalyst chemistry during carbon nanotube growth and shows interfacial Co-Si interactions that may help to stabilize the nanoparticle/nanotube diameter. We outline a two-mechanism model explaining the selective growth. © 2012 American Physical Society.

Plasma stabilisation of metallic nanoparticles on silicon for the growth of carbon nanotubes

Ammonia (NH 3) plasma pretreatment is used to form and temporarily reduce the mobility of Ni, Co, or Fe nanoparticles on boron-doped mono- and poly-crystalline silicon. X-ray photoemission spectroscopy proves that NH 3 plasma nitrides the Si supports during nanoparticle formation which prevents excessive nanoparticle sintering/diffusion into the bulk of Si during carbon nanotube growth by chemical vapour deposition. The nitridation of Si thus leads to nanotube vertical alignment and the growth of nanotube forests by root growth mechanism. © 2012 American Institute of Physics.

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Tantalum-oxide catalysed chemical vapour deposition of single- and multi-walled carbon nanotubes

Tantalum-oxide thin films are shown to catalyse single- and multi-walled carbon nanotube growth by chemical vapour deposition. A low film thickness, the nature of the support material (best results with SiO2) and an atmospheric process gas pressure are of key importance for successful nanotube nucleation. Strong material interactions, such as silicide formation, inhibit nanotube growth. In situ X-ray photoelectron spectroscopy indicates that no catalyst reduction to Ta-metal or Ta-carbide occurs during our nanotube growth conditions and that the catalytically active phase is the Ta-oxide phase. Such a reduction-free oxide catalyst can be technologically advantageous. © 2013 The Royal Society of Chemistry.