等离子体增强热丝CVD生长碳纳米尖端的研究

用CH₄，NH₃和H₂为反应气体，利用等离子体增强热丝化学气相沉积系统在不同偏压电流的条件下制备了碳纳米尖端，并用扫描电子显微镜和显微Raman光谱仪对碳纳米尖端进行了研究.结果表明碳纳米尖端是石墨结构，随着偏压电流的增大，碳纳米尖端的顶角减小，生长速率增大.结合有关等离子体和溅射的理论，分析讨论了碳纳米尖端的形成和碳纳米尖端的生长随偏压电流的变化. 关键词： 碳纳米尖端 等离子体 化学气相沉积     

催化剂对纳米非晶碳膜场发射性能的影响

利用微波等离子体增强化学气相沉积(MPECVD)法,在经处理的单晶硅衬底上沉积了纳米非晶碳薄膜.通过Raman、SEM、XRD表征,研究了催化剂对纳米非晶碳膜的生长速率及场发射性能的影响.结果表明,在制备纳米非晶碳膜时使用FeC13,作为催化剂可大幅提高其生长速率.在相同的制备条件下,与未加FeCl3催化剂制备的纳米非...     

电子回旋共振等离子体增强化学气相沉积a-CFx薄膜的化学键结构

使用CHF₃和C₆H₆混合气体做气源,在一个电子回旋共振等离子体增强化学气相沉积装置中制备了氟化非晶碳(a-CF_x)薄膜.利用发射光谱研究了等离子体中形成的各种碳氟、碳氢基团随放电宏观参量的变化规律,对薄膜做了傅里叶变换红外光谱和X射线光电子能谱分析,证实等离子体中的CF₂,CF和CH基团是控制薄膜生长、碳/氟成分比和化学键结构的主要前驱物 关键词： 氟化非晶碳薄膜 电子回旋共振等离子体     

一种生长巴基洋葱的新方法—射频CVD法

在用射频ＣＶＤ法沉积碳的实验中，发现有较多量碳巴基洋葱生成。电镜观察表明，该方法只生成碳巴基洋葱，并无碳纳米管等们随生成，因而制得的巴其洋葱纯度较高。为制取纯净的碳巴基洋葱提供了一种可能的新途径。讨论了射频ＣＶＤ法中碳巴基洋葱的可能生长机理。认为在等离子作用下使甲烷的部分氢原子解离生成碳氢自由基，在催化剂的作下，生成的碳烯为了消除碳悬键而卷曲，而碳氢自由基则在表面不断沉积生长成碳巴基洋葱。     

石英衬底上生长的高光学质量的纳米金刚石薄膜

采用射频等离子体增强的热丝化学气相沉积(RFHFCVD)技术在石英玻璃衬底上制备了表面光滑、晶粒致密均匀的纳米金刚石薄膜.用扫描电子显微镜(SEM)和台阶仪观测薄膜的表面形貌和粗糙度,x射线衍射(XRD)和Raman光谱表征膜层的结构,并用紫外可见近红外光谱仪测量其光透过率.实验结果表明,衬底温度、反应气压及射频功率对金刚石膜的结晶习性、表面粗糙度及光透过率均有很大程度的影响,其最佳值分别为700℃,2×133Pa和200W.在该最佳参量下经1h的生长即获得连续、平滑的纳米金刚石膜,其平均晶粒尺寸为约25 关键词： 纳米金刚石薄膜 射频等离子体增强热丝化学气相沉积 光透过率     

氮对类金刚石薄膜的微观结构内应力与附着力的影响

采用原子力显微镜(AFM)、俄歇电子能谱(AES)和显微压痕分析等手段对射频等离子体增强化学气相沉积法制备的掺氮类金刚石(DLC：N)薄膜的微观结构和力学性能进行了研究.结果表明,随着含氮量的增加,DLC薄膜的AFM表面形貌中出现了几十纳米的颗粒,原子侧向力显微镜和AES分析表明这种纳米颗粒是x大于0.126的非晶氮化碳CN_x结构.这种非晶DLC/CN_x的纳米复合结构,减小了薄膜的内应力,从而提高了薄膜与衬底的附着力. 关键词： 类金刚石碳膜 微观结构 附着特性     

非晶空心碳球的制备及生长机制

采用射频等离子体增强化学气相沉积技术,在CH4/H2的气氛中合成了非晶空心碳球.利用SEM,TEM,拉曼光谱对样品的形貌、成分和结构进行了表征.非晶空心碳球的直径在100～800nm之间,分布在弯曲的碳纳米管丛中.非晶空心碳球的生长机制可能为膨胀生长.     

微波等离子体化学气相沉积方法在Si衬底上生长SiC纳米线

应用微波等离子体化学气相沉积方法,在单晶Si(100)衬底上生长出SiC纳米线.应用扫描电子显微镜、透射电子显微镜、能量损失谱(EDS)和选区电子衍射(SAD)等方法对纳米线化学组成和结构进行了分析和表征.给出该纳米线的生长机理 关键词： 微波等离子体化学气相沉积 SiC纳米线 生长机理     

等离子体增强化学气相沉积法实现硅纳米线掺硼

用等离子体增强化学气相沉积(PECVD)方法成功实现硅纳米线的掺B.选用Si片作衬底，硅烷 （SiH4）作硅源，硼烷（B2H6）作掺杂气体， Au作催化剂，生长温度440℃.基于气-液-固(VLS)机制，探讨了掺B硅纳米线可能的生长机制.PECVD法化学成分配比更灵活，更容易实现纳米线掺杂，进一步有望生长硅纳米线pn结，为研制纳米量级器件提供技术基础. 关键词： 硅纳米线 化学气相沉积 纳米器件     

螺旋波等离子体化学气相沉积纳米硅薄膜的光学发射谱研究

利用光学发射谱技术对螺旋波等离子体化学气相沉积纳米硅薄膜的等离子体内活性粒子的光发射特征进行了原位测量.研究了薄膜沉积过程中各实验参量对活性基团SiH^*， H^β以及H^α的发射谱强度的影响.实验结果表明，静态磁场的加入可显著提高反应气体 的解离效率 ；适当的氢稀释可以提高氢活性粒子的浓度，而过高的氢稀释比将使含硅活性基团浓度显著 减小；提高射频馈入功率整体上可以使各活性粒子的浓度增加，并有利于提高到达衬底表面 氢活性粒子的相对比例.结合螺旋波等离子体色散关系和等离子体特点对以上结果进行了分 析.该结果为螺旋波等离子体沉积纳米硅薄膜过程的理解及制备工艺参数的调整提供了基础 数据. 关键词： 光学发射谱 螺旋波等离子体化学气相沉积 纳米硅薄膜     

Degree of chemical reaction of carbon and oxygen to ferromagnetic grains for Co-based alloy-oxide granular structure

The saturation magnetization factor, M_s, was investigated for a Co-based alloy-oxide granular film through the quantitative analysis of film composition and phase formation. Using a carbon cap layer deposited directly onto the Co-SiO₂ film, both oxidation and carbonization of cobalt caused a reduction in M_s. The composition of the granular film strongly affects M_s, because the Ar gas pressure and discharge power during Co-SiO₂ sputtering alters the Co and oxygen content in the film. In particular, for a film fabricated under a high Ar gas pressure such as 8.0 Pa, M_s was significantly decreased, due to the formation of the antiferromagnetic CoO phase.     

Laser-Induced Graphitic Carbon with Ultrasmall Nickel Nanoparticles for Efficient Overall Water Splitting

Metal nanoparticles encapsulated in graphitic carbon can show high catalytic efficiency and stability, yet the production method remains improved. Herein, it is demonstrated that a Ni-based metal–organic framework [EG-MOF-74(Ni)] can be rapidly transformed into ultrasmall Ni-nanoparticles with different sizes (4–11 nm) encapsulated in graphitic carbon via the laser-scribing method. The synthesized sample shows the best electrocatalytic performances with excellent stability in alkaline electrolyte for oxygen/hydrogen evolution reactions with overpotentials of 0.35/0.18 V at a current density of 10 mA cm⁻² when the Ni particle size is ≈6 nm. This is because of its well-developed micro/mesoporous structure, high electronic transport, and large electrochemical active surface area. An electrolyzer with Ni-nanoparticles encapsulated in the graphitic carbon shows a current density of 10 mA cm⁻² at a voltage of 1.6 V, which is comparable to the Pt/C and RuO₂ counterparts. The laser-based synthesis can serve as a powerful tool for the size-controlled synthesis of various catalysts out of MOFs.     

Fabrication of amine-functionalized magnetite nanoparticles for water treatment processes

The anatase phase of titania (TiO₂) nano-photocatalysts was prepared using a modified sol gel process and thereafter embedded on carbon-covered alumina supports. The carbon-covered alumina (CCA) supports were prepared via the adsorption of toluene 2,4-diisocyanate (TDI) on the surface of the alumina. TDI was used as the carbon source for the first time for the carbon-covered alumina support system. The adsorption of TDI on alumina is irreversible; hence, the resulting organic moiety can undergo pyrolysis at high temperatures resulting in the formation of a carbon coating on the surface of the alumina. The TiO₂ catalysts were impregnated on the CCA supports. X-ray diffraction analysis indicated that the carbon deposited on the alumina was not crystalline and also showed the successful impregnation of TiO₂ on the CCA supports. In the Raman spectra, it could be deduced that the carbon was rather a conjugated olefinic or polycyclic hydrocarbons which can be considered as molecular units of a graphitic plane. The Raman analysis of the catalysed CCAs showed the presence of both the anatase titania and D and G band associated with the carbon of the CCAs. The scanning electron microscope micrographs indicated that the alumina was coated by a carbon layer and the energy dispersive X-ray spectra showed the presence of Al, O and C in the CCA samples, with the addition of Ti for the catalyst impregnated supports. The Brunauer Emmet and Teller surface area analysis showed that the incorporating of carbon on the alumina surface resulted in an increase in surface area, while the impregnation with TiO₂ resulted in a further increase in surface area. However, a decrease in the pore volume and diameter was observed. The photocatalytic activity of the nanocatalysts was studied for the degradation of Rhodamine B dye. The CCA-TiO₂ nanocatalysts were found to be more photocatalytically active under both visible and UV light irradiation compared to the free TIO₂ nanocatalysts.     

The behaviour of carbon species produced by CO disproportionation on Ru(1, 1, 10) and Ru(001) surfaces

The behaviour of adsorbed CO on Ru(001) flat and Ru(l,1,10) stepped surfaces in the CO pressure range between 10^?6 and 10¹ Pa has been investigated by TDS, AES, LEED and UPS. The disproportionation of CO proceeds rapidly on the stepped surface and its apparent activation energy was obtained to be 20 kJ mol^?1 at nearly zero coverage. The carbon species produced by CO disproportionation show non-uniform reactivity with ¹⁸O₂ and provide four CO desorption peaks in TPR spectra, which are assigned to α-C¹⁸O,ß-C¹⁸O and those derived from carbidic and graphitic carbons. At smaller carbon coverage, only α-CO and β-CO were observed, but with increasing coverage the amount of ß-CO reaches a maximum and carbidic carbon is newly formed. Further increase of carbon deposition gives graphitic carbon. The conversion from carbidic to graphitic carbon and the dissolution into the bulk took place upon heating to 1000 K. It is remarkable that very active carbon species are converted to molecular CO through the reaction with O₂ even at low temperature such as 200 K. It was also confirmed that active carbon species are formed on Ru surface during COH₂ reaction.     

Catalytic activity of Fe, Co and Fe-Co-MCM-41 for the growth of carbon nanotubes by chemical vapour deposition method

Iron, cobalt and a mixture of iron and cobalt incorporated mesoporous MCM-41 molecular sieves were synthesised by hydrothermal method and used to investigate the rules governing their nanotube producing activity. The catalysts were characterised by XRD and N₂ sorption studies. The effect of the catalysts has been investigated for the production of carbon nanotubes at an optimised temperature 750 °C with flow rate of N₂ and C₂H₂ is 140 and 60 ml/min, respectively for a reaction time 10 min. Fe-Co-MCM-41 catalyst was selective for carbon nanotubes with low amount of amorphous carbon with increase in single-walled carbon nanotubes (SWNTs) yield at 750 °C. Formation of nanotubes was studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Transmission electron microscope and Raman spectrum was used to follow the quality and nature of carbon nanotubes formed and the graphitic layers and disordered band, which shows the clear evidence for the formation of SWNTs, respectively. The result propose that the diameter of the nanotubes in the range of 0.78-1.35 nm. Using our optimised conditions for this system, Fe-Co-MCM-41 showed the best results for selective SWNTs with high yield when compared with Fe-MCM-41 and Co-MCM-41.     

A Facile Strategy to Synthesize Cobalt‐Based Self‐Supported Material for Electrocatalytic Water Splitting

Designing and developing active, robust, and noble‐metal‐free catalysts with superior stability for electrocatalytic water splitting is of critical importance but remains a grand challenge. Here, a facile strategy is provided to synthesize a series of Co‐based self‐supported electrode materials by combining electrospinning and chemical vapor deposition (CVD) technologies. The Co, Co₃O₄, Co₉S₈ nanoparticles (NPs) are formed in situ simultaneously with the formation of carbon nanofibers (CNFs) during the CVD process, respectively. The Co‐based NPs are uniformly distributed through the CNFs and they can be directly used as the electrode materials for hydrogen evolution reaction (HER) in acid and oxygen evolution reaction (OER) in alkaline. The Co₉S₈/CNFs membrane exhibits the best HER activity with overpotential of 165 mV at j = 10 mA cm^?2 and Tafel slope of 83 mV dec^?1 and OER activity with overpotential of 230 mV at j = 10 mA cm^?2 and Tafel slope of 72 mV dec^?1. The onion‐like graphitic layers formed around the NPs not only improve the electrical conductivity of the electrode but also prevent the separation of the NPs from the carbon matrix as well as the aggregation.     

Enhancement of field emission properties of graphite flakes by producing carbon nanotubes on above using thermal chemical vapor deposition

In order to improve the field emission properties of the graphite flakes, the carbon nanotubes (CNTs) are produced on above without the metallic catalyst using mixtures of C₂H₂ and H₂ gases by thermal chemical vapor deposition. We spin the graphite solution on the silicon wafer and dry it, then synthesize the CNTs on the graphite flakes. We change the synthetic time to obtain the optimal conditions for enhancement of field emission properties of graphite flakes. The experimental results show that the density and quality of the CNTs could be controlled significantly by the synthetic time. Besides, the field emission properties of the treated graphite flakes are also affected greatly by it. The emission current density of the treated graphite flakes reaches to 0.5 mA/cm² at 3 V/μm, and the turn-on field is decreased from 7.7 to 1.9 V/μm after producing the CNTs on above.     

Low‐temperature photoluminescence of oxide‐covered single‐layer MoS2

We present a photoluminescence study of single‐layer MoS₂ flakes on SiO₂ surfaces. We demonstrate that the luminescence peak position of flakes prepared from natural MoS₂, which varies by up to 25 meV between individual flakes, can be homogenized by annealing in vacuum. We use HfO₂ and Al₂O₃ layers prepared by atomic layer deposition to cover some of our flakes. In these flakes, we observe a suppression of the low‐energy luminescence peak which appears in asprepared flakes at low temperatures. We infer that this peak originates from excitons bound to surface adsorbates. We also observe different temperature‐induced shifts of the luminescence peaks for the oxide‐covered flakes. This effect stems from the different thermal expansion coefficients of the oxide layers and the MoS₂ flakes. It indicates that the single‐layer MoS₂ flakes strongly adhere to the oxide layers and are therefore strained. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Yolk–Shell‐Structured Cu/Fe@γ‐Fe2O3 Nanoparticles Loaded Graphitic Porous Carbon for the Oxygen Reduction Reaction

Core–shell Cu/γ‐Fe₂O₃@C and yolk–shell‐structured Cu/Fe@γ‐Fe₂O₃@C particles are prepared by a facile synthesis method using copper oxide as template particles, resorcinol‐formaldehyde as the carbon precursor, and iron nitrate solution as the iron source via pyrolysis. With increasing carbonization temperature and time, solid γ‐Fe₂O₃ cores are formed and then transformed into Fe@γ‐Fe₂O₃ yolk–shell‐structured particles via Ostwald ripening under nitrogen gas flow. The composition variations are studied, and the formation mechanism is proposed for the generation of the hollow and yolk–shell‐structured metal and metal oxides. Moreover, highly graphitic carbons can be obtained by etching the metal and metal oxide nanoparticles through an acid treatment. The electrocatalytic activity for oxygen reduction reaction is investigated on Cu/γ‐Fe₂O₃@C, Cu/Fe@γ‐Fe₂O₃@C, and graphitic carbons, indicating comparable or even superior performance to other Fe‐based nanocatalysts.     

Graphitic encapsulation of micron- and nano-sized Ni particles using ethylene as precursor

This work deals with the catalytic decomposition of carbon-containing gases (ethylene) over nickel catalysts to grow graphitic capsules at relatively low temperatures (853 K). The influence of different experimental conditions, such as catalyst size, reactant flow ratio (C₂H₄:O₂), gas flow rate and temperature, is studied. The size of the nickel particles determines the type of structures; while nano-sized nickel particles favor the growth of nanofilaments, graphitic capsules occur over nickel microparticles. The use of reducing and oxidizing environments in the growth of graphitic structures over microparticles are compared, the latter being more appropriate for growing nanofilaments. Below 853 K, no graphitic structures are formed. Moreover, a new model is proposed for the encapsulation of the catalyst metal particles by graphite layers.