Plasma synthesis of semiconductor nanocrystals for nanoelectronics and luminescence applications

Functional nanocrystals are widely considered as novel building blocks for nanostructured materials and devices. Numerous synthesis approaches have been proposed in the solid, liquid and gas phase. Among the gas phase approaches, low pressure nonthermal plasmas offer some unique and beneficial features. Particles acquire a unipolar charge which reduces or eliminates agglomeration; particles can be electrostatically confined in a reactor based on their charge; strongly exothermic reactions at the particle surface heat particles to temperatures that significantly exceed the gas temperature and facilitate the formation of high quality crystals. This paper discusses two examples for the use of low pressure nonthermal plasmas. The first example is that of a constricted capacitive plasma for the formation of highly monodisperse, cubic-shaped silicon nanocrystals with an average size of 35 nm. The growth process of the particles is discussed. The silicon nanocubes have successfully been used as building blocks for nanoparticle-based transistors. The second example focuses on the synthesis of photoluminescent silicon crystals in the 3–6 nm size range. The synthesis approach described has enabled the synthesis of macroscopic quantities of quantum dots, with mass yields of several mg/hour. Quantum yields for photoluminescence as high as 67% have been achieved.     

Oriented growth of CoPt nanoparticles by pulsed laser deposition

The magnetic nanoparticles of Fe/FeCo/FePt, in the past, in a PLD system were grown by us using argon ambient gas pressure of about 0.1–75.0 mbar, as the ambient gas pressure can be used to tune the energy of the incident plasma plume species, the expansion volume, the growth duration, etc. which can control the particle size. In present paper, we report the direct synthesis of small-sized nanoparticles even when no ambient gas was used, with the experiments being done in higher vacuum of about 10^?5 mbar in PLD chamber. The deposition rate under vacuum condition is significantly higher than the deposition rate at high ambient pressure. The study of inplane and outplane magnetic properties, along with XRD results, confirmed that the as-deposited CoPt nanoparticles thin film has oriented growth. The as-deposited CoPt nanoparticles are in magnetically soft fcc phase and a post deposition annealing at 600°C resulted in phase transition to magnetically hard fct phase.     

Synthesis of Al–Cr decagonal quasicrystal nanoparticles and their temperature of phase transformation to stable crystal phase

The synthesis of Al–Cr single quasicrystal (QC) nanoparticles of the decagonal phase was achieved by introducing an advanced gas flow evaporation method. By obtaining successive electron diffraction patterns for single-QC nanoparticles, the phase transformation temperature of a single-QC nanoparticle was determined to be 700 °C. It was also determined that part of the QC nanoparticle decomposed into hex-Al₈Cr₅ and Al during the phase transformation. Since the grain growth did not occur during the phase transformation in the present experiment, the inherent phase transformation temperature could be measured.     

Fabrication of Nanostructured Composite Microspheres Based on the Self‐Assembly of Polymers and Functional Nanomaterials

This Review examines recent developments in the morphological control of polymer microspheres fabricated via the phase separation of polymers as well as the alignment of functional nanoparticles inside microspheres prepared by so‐called bottom‐up synthesis techniques. Several methods for adjusting the internal and surface morphologies of polymer microspheres based on the phase separation of polymer blends and block copolymers are discussed, and the effects of microsphere size on phase separated structures and theoretical simulations of morphologies are also reviewed. The alignment of functional nanoparticles in phase separated polymer microspheres and applications of nanostructured and hybrid polymer microspheres are summarized.     

In Situ Synchrotron X‐Ray Techniques for Real‐Time Probing of Colloidal Nanoparticle Synthesis

Solution‐phase synthesis of colloidal nanoparticles with precisely tailored properties is one of the fastest growing research topic and represents the most critical foundation to implant nanotechnology in a variety of areas to boost performance of traditional systems. Comprehensive understanding of the nucleation and growth mechanisms involved in the formation of colloidal nanoparticles is very important to realize rational design and synthesis of well‐tailored nanoparticles and requires appropriate in situ techniques to probe the kinetics of the synthetic reactions. Synchrotron hard X‐rays represent a class of promising probes for solution‐phase reactions due to their strong penetration in ambient environment and solutions. This review completely summarizes the in situ synchrotron X‐ray techniques emerged in the recent years for real‐time probing nanophase evolution of colloidal nanoparticles. Typical examples of colloidal nanoparticle syntheses are discussed in detail to shed the light on the advantages and disadvantages of individual techniques.     

Particle synthesis in flames

From the view point of combustion science, the fundamentals of particle formation in a flame environment are discussed. The principles of converting a gas phase precursor dopant into particles and also their growth are addressed. Various experimental methods and examples for the synthesis of particles of both single and mixed oxides are reviewed. First attempts to tune the stoichiometry of oxide particles by varying the combustion parameters of premixed flames are demonstrated. Some aspects of modelling and the problems which still need to be solved are illustrated by means of the particles’ population balance equation.     

PtPb nanoparticle electrocatalysts: control of activity through synthetic methods

Solution phase synthesis of intermetallic nanoparticles without using surfactants (for catalytic applications) and subsequent control of size distribution remains a challenge: of growing interest, but not widely explored yet. To understand the questions in the syntheses of Pt containing intermetallic nanoparticles (as electrocatalysts for direct fuel cells) by using sodium naphthalide as the reducing agent, the effects of the Pt precursors’ organic ligands were investigated. PtPb syntheses were studied as the model case. In particular, methods that lead to nanoparticles that are independent single crystals are desirable. Platinum acetylacetonate, which is soluble in many organic solvents, has ligands that may interfere less with nanoparticle growth and ordering. Interesting trends, contrary to expectations, were observed when precursors were injected into a reducing agent solution at high temperatures. The presence of acetylacetonate, from the precursor, on the nanoparticles was confirmed by ATR, while SEM imaging showed evidence of morphological changes in the nanoparticles with increasing reaction temperature. A definite relationship between domain size and extent of observed residue (organic material and sodium) present on the particles could be established. By varying post-reaction solvent removal techniques, room temperature crystallization of PtPb nanoparticles was also achieved. Electrochemical activity of the nanoparticles was also much higher than that of nanoparticles synthesized by previous reaction schemes using sodium naphthalide as the reducing agent. Along with the above mentioned techniques, BET, TEM, CBED, SAED, and XRD were used as characterization tools for the prepared nanoparticles.     

单一晶相氧化锰纳米颗粒的交换偏置效应

本文利用高温油相法制备出尺寸、形状均一的 MnO纳米颗粒, X射线衍射图 (XRD) 和透射电子显微镜 (TEM) 照片清晰表明MnO纳米颗粒为单一的面心立方岩盐晶体结构, 尺寸为15nm, 粒径分布很窄. 通过零场冷却 (ZFC) 和带场冷却 (FC)的磁滞回线发现MnO纳米颗粒具有明显的交换偏置效应, 而且磁滞回线同时表现出横向和纵向偏移. 横向偏移说明纳米颗粒中两相复合的存在, 纵向偏移说明了存在自旋玻璃相或者超顺磁相. 进而通过不同频率下随温度变化的交流磁化率的测定, 根据Mydosh的经验数值确认 MnO纳米颗粒表面层为自旋玻璃相, 并得到 MnO纳米颗粒表面自旋玻璃相的转变温度为T_SG=32K. 关键词： 纳米颗粒 氧化锰 交换偏置 自旋玻璃     

Nanoparticles-chemistry, new synthetic approaches, gas phase clustering and novel applications

In this paper, an overview of the synthesis, chemistry and applications of nanosystems carried out in our laboratory is presented. The discussion is divided into four sections, namely (a) chemistry of nanoparticles, (b) development of new synthetic approaches, (c) gas phase clusters and (d) device structures and applications. In ‘chemistry of nanoparticles’ we describe a novel reaction between nanoparticles of Ag and Au with halocarbons. The reactions lead to the formation of various carbonaceous materials and metal halides. In ‘development of new synthetic approaches’ our one-pot methodologies for the synthesis of core-shell nanosystems of Au, Ag and Cu protected with TiO₂ and ZrO₂ as well as various polymers are discussed. Some results on the interaction of nanoparticles with biomolecules are also detailed in this section. The third section covers the formation of gas phase aggregates/clusters of thiol-protected sub-nanoparticles. Laser desorption of H₂MoO₄, H2WO₄, MoS₂, and WS₂ giving novel clusters is discussed. The fourth section deals with the development of simple devices and technologies using nanomaterials described above.     

PECVD of Carbon Nanostructures in Hydrocarbon‐Based RF Plasmas

Different aspects of the plasma‐enhanced chemical vapor deposition of various carbon nanostructures in the ionized gas phase of high‐density, low‐temperature reactive plasmas of Ar+H₂+CH₄ gas mixtures are studied. The growth techniques, surface morphologies, densities and fluxes of major reactive species in the discharge, and effects of the transport of the plasma‐grown nanoparticles through the near‐substrate plasma sheath are examined. Possible growth precursors of the carbon nanostructures are also discussed. In particular, the experimental and numerical results indicate that it is likely that the aligned carbon nanotip structures are predominantly grown by the molecular and radical units, whereas the plasma‐grown nanoparticles are crucial components of polymorphous carbon films. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ru decorated Pt nanoparticles by a modified polyol process for enhanced catalytic activity for methanol oxidation

Ru decorated Pt nanoparticles on carbon nanotubes (MWCNTs) were prepared by a modified polyol synthesis method for enhanced catalytic activity for methanol oxidation. The characterizations for the electrocatalysts were carried out by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV) and chronoamperometry (CA). The modified polyol synthesis method promoted position-controlled nucleation and growth of Ru atoms near Pt, and resulted in improved durability against catalyst poisoning compared to PtRu/MWCNTs prepared by common polyol method. This concept also allowed a high loading and dispersion of the catalyst on the carbon supports with few agglomerations of catalyst nanoparticles, resulting in high catalytic activity.     

Carbon nanotubes as nanoparticles collector

This communication reports on a new method for the collection of nanoparticles using carbon nanotubes (CNT) as collecting surfaces, by which the problem of agglomeration of nanoparticles can be circumvented. CNT (10–50 nm in diameter, 1–10 μm in length) were grown by thermal CVD at 923 K in a 7 v/v% C₂H₂ in N₂ mixture on electroless nickel-plated copper transmission electron microscopy (TEM) grids and Monel coupons. These samples were then placed downstream of an arc plasma reactor to collect individual copper nanoparticles (5–30 nm in diameter). It was observed that the Cu nanoparticles preferentially adhere onto CNT and that the macro-particles (diameter >1 μm), a usual co-product obtained with metal nanoparticles in the arc plasma synthesis, are not collected. Cu–Ni nanoparticles, a catalyst for CNT growth, were deposited on CNT to grow multibranched CNT. CNT-embedded thin films were produced by re-melting the deposited nanoparticles.     

人造金刚石低压气相生长的相图计算

用非平衡热力学耦合模型计算了由CH₄/H₂，CO/H₂和乙炔火焰等气相体系生长金刚石的相图．与经典平衡热力学理论计算结果不同的是这些相图都有一个金刚石生长区存在．相图中的金刚石生长区是实现金刚石气相生长的热力学基础，它的存在体现了超平衡氢原子等激活粒子对石墨的激活和对金刚石的稳定作用．计算的相图与报道的实验结果基本相符，因而对金刚石气相生长的理论和实验研究具有重要的指导意义 关键词：     

Buoyancy induced limits for nanoparticle synthesis experiments in horizontal premixed low-pressure flat-flame reactors

Premixed low-pressure flat-flame reactors can be used to investigate the synthesis of nanoparticles. The present work examines the flow field inside such a reactor during the formation of carbon (soot) and iron oxide (from Fe(CO)₅) nanoparticles, and how it affects the measurements of nanoparticle size distribution. The symmetry of the flow and the impact of buoyancy were analysed by three-dimensional simulations and the nanoparticle size distribution was obtained by particle mass spectrometry (PMS) via molecular beam sampling at different distances from the burner. The PMS measurements showed a striking, sudden increase in particle size at a critical distance from the burner, which could be explained by the flow field predicted in the simulations. The simulation results illustrate different fluid mechanical phenomena which have caused this sudden rise in the measured particle growth. Up to the critical distance, buoyancy does not affect the flow, and an (almost) linear growth is observed in the PMS experiments. Downstream of this critical distance, buoyancy deflects the hot gas stream and leads to an asymmetric flow field with strong recirculation. These recirculation zones increase the particle residence time, inducing very large particle sizes as measured by PMS. This deviation from the assumed symmetric, one-dimensional flow field prevents the correct interpretation of the PMS results. To overcome this problem, modifications to the reactor were investigated; their suitability to reduce the flow asymmetry was analysed. Furthermore, ‘safe’ operating conditions were identified for which accurate measurements are feasible in premixed low-pressure flat-flame reactors that are transferrable to other experiments in this type of reactor. The present work supports experimentalists to find the best setup and operating conditions for their purpose.     

Influence of the oxygen concentration on the formation of crystalline phases of TiO<Subscript>2</Subscript> during the low-pressure arc-discharge plasma synthesis

The synthesis of titanium dioxide (TiO₂) nanoparticles with different percentage of anatase and rutile phases is investigated. The synthesis is performed by controlling the oxygen percentage in the gas mixture in the plasmachemical evaporation–condensation process employing a low-pressure arc discharge. In all our experiments, the pressure in the plasmachemical reactor and the average size of particles remain constant and are 60 Pa and 6 nm, respectively. The crystal structure of synthesized TiO₂ is studied using X-ray diffraction; the morphology of the particles is analyzed employing transmission electron microscopy. Using X-ray phase analysis, it is established that the concentration of the TiO₂ anatase phase decreases upon a decrease in the oxygen concentration in the gas mixture. It is shown that the TiO₂ anatase phase is more efficient for photocatalytic decomposition of methylene blue than the rutile phase.     

Particle size prediction of magnesium nanoparticle produced by inert gas condensation method

Properties of nanoparticles are normally depending on particle size; therefore, developing a model to predict particle size is of vital importance. This paper established an energy analysis model to predict average particle size of magnesium nanoparticles fabricated by inert gas condensation method. Predictions of average particle size ranging from 20 to 50 nm by energy analysis model have relative errors of less than 10% compared with experimental research. Further, the model is applied to investigate operation conditions to decrease the average particle size of magnesium nanoparticles. It is found that decreasing the absolute pressure in the condensation room and increasing the temperature rise of the inert gas can both produce nanoparticles with smaller average particle sizes. Temperature rise of the inert gas plays a more important role in effect on average nanoparticle size than the absolute pressure in the condensation room. Energy transformed by collision bonding and dissipated by convection are the dominant processes for particle growth when number of atoms in one particle is greater than 2000 atoms.     

Amorphous nanoparticles — Experiments and computer simulations

The data obtained by both experiments and computer simulations concerning the amorphous nanoparticles for decades including methods of synthesis, characterization, structural properties, atomic mechanism of a glass formation in nanoparticles, crystallization of the amorphous nanoparticles, physico-chemical properties (i.e. catalytic, optical, thermodynamic, magnetic, bioactivity and other properties) and various applications in science and technology have been reviewed. Amorphous nanoparticles coated with different surfactants are also reviewed as an extension in this direction. Much attention is paid to the pressure-induced polyamorphism of the amorphous nanoparticles or amorphization of the nanocrystalline counterparts. We also introduce here nanocomposites and nanofluids containing amorphous nanoparticles. Overall, amorphous nanoparticles exhibit a disordered structure different from that of corresponding bulks or from that of the nanocrystalline counterparts. Therefore, amorphous nanoparticles can have unique physico-chemical properties differed from those of the crystalline counterparts leading to their potential applications in science and technology.     

Cadmium (II) pyrrolidine dithiocarbamate complex as single source precursor for the preparation of CdS nanocrystals by microwave irradiation and conventional heating process

The complex of cadmium with pyrrolidine dithiocarbamate Cd(pdtc)₂ has been used as single source precursor for the synthesis of CdS nanoparticles. The formation of CdS nanostructures was achieved by thermal decomposition of the complex under microwave irradiation and conventional heating in presence of hexadecylamine. The CdS nanoparticles with disordered close-packed structure were obtained under microwave irradiation, whereas wurtzite hexagonal phase CdS nanorods were obtained by conventional heating method (up to 150 °C). Scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and high resolution transmission electron microscopy (HRTEM) studies also were carried out to study the structure and morphology of nanoparticles. The optical property of the CdS nanoparticles was studied by UV-visible and fluorescence emission spectral studies. Fluorescence measurements on the CdS nanoparticles show a strong emission spectrum with two sub bands that are attributed to band-edge and surface-defect emissions. The reduction of a suitable cadmium metal complex is considered to be one of the single pot methods to generate CdS semiconductor nanoparticles with different shapes and high yield.     

Synthesis and self-assembly of magnetic nanoparticles

We report the synthesis and self-assembly of different shapes and sizes of FePt nanoparticles. Our study shows that surfactants and solvent play an important role in the synthesis of different shapes and sizes of FePt nanoparticles. Higher boiling point solvents lead to the formation of spherical nanoparticles and low boiling point solvents form cubic nanoparticles. Our studies also indicate that self-assembly of FePt nanoparticles on substrates is a complex process that is sensitive to the concentration of excess surfactant in the nanoparticle solution.     

Recent advances in the research of inorganic nanotubes and fullerene-like nanoparticles

This minireview outlines the main scientific directions in tile research of inorganic nanotubes （1NT） and fullerene-like （IF） nanoparticles from layered compounds, in recent years. In particular, this review describes to some detail the progress in the synthesis of new nanotubes, including those from misfit compounds; core-shell and the successful efforts to scale-up the synthesis of WS2 multiwalt nanotubes. The high-temperature catalytic growth of nanotubes, via solar ablation is discussed as well. Furthermore, the doping of the 1F-MoS2 nanoparticles and its influence on the physiochemical properties of the nanoparticles, including their interesting tribological properties are briefly discussed. Finally, the numerous applications of these nanoparticles as superior solid lubricants and for reinforcing variety of polymers are discussed in brief.