Synthesis and Properties of Single-Walled Carbon Nanotubes Filled with Metal Halogenides and Metallocenes

This chapter reviews the current status of the research on the electronic properties of single-walled carbon nanotubes (SWCNTs) filled with metal halogenides and metallocenes and growth kinetics of inner SWCNTs inside metallocene-filled nanotubes. The chapter starts with the description of the peculiarities of the synthesis of metal halogenide-filled SWCNTs, comparison of different filling methods, their advantages, disadvantages, and restrictions. Then, we comprehensively summarize, compare, and critically discuss the recent studies on the electronic properties of metal halogenide-filled SWCNTs. After that, the synthesis methods of metallocene-filled SWCNTs are described and the results of the investigation of the growth kinetics of inner SWCNTs inside the filled nanotubes are summarized. Then, the reports dedicated to the investigation of the electronic properties of metallocene-filled SWCNTs are reviewed. Finally, potentials for future research, development, and application of filled SWCNTs are highlighted

Metal and Metal Halogenide-Filled Single-Walled Carbon Nanotubes: Kinetics, Electronic Properties, Engineering the Fermi Level

Here, we present a review of the major achievements in kinetics, electronic properties, and engineering in the Fermi level of single-walled carbon nanotubes (SWCNTs). Firstly, the kinetics of metal-filled SWCNTs were revealed with precision over several minutes. Secondly, the growth rates of nanotubes were calculated. Thirdly, the activation energies of nanotubes were measured. Fourthly, the methods of the quantitative analysis of the doping level were developed. Indeed, only qualitative analysis has been previously performed. The quantitative analysis allowed us to obtain quantitative data on charge transfer. Fifthly, the correlation between the physical properties, chemical properties, electronic properties of SWCNTs was elucidated

Metal Cluster Size-Dependent Activation Energies of Growth of Single-Chirality Single-Walled Carbon Nanotubes inside Metallocene-Filled Single-Walled Carbon Nanotubes

By combining in situ annealing and Raman spectroscopy measurements, the growth dynamics of nine individual-chirality inner tubes (8,8), (12,3), (13,1), (9,6), (10,4), (11,2), (11,1), (9,3) and (9,2) with diameters from ~0.8 to 1.1 nm are monitored using a time resolution of several minutes. The growth mechanism of inner tubes implies two successive stages of the growth on the carburized and purely metallic catalytic particles, respectively, which are formed as a result of the thermally induced decomposition of metallocenes inside the outer SWCNTs. The activation energies of the growth on carburized Ni and Co catalytic particles amount to 1.85–2.57 eV and 1.80–2.71 eV, respectively. They decrease monotonically as the tube diameter decreases, independent of the metal type. The activation energies of the growth on purely metallic Ni and Co particles equal 1.49–1.91 eV and 0.77–1.79 eV, respectively. They increase as the tube diameter decreases. The activation energies of the growth of large-diameter tubes (dt = ~0.95–1.10 nm) on Ni catalyst are significantly larger than on Co catalyst, whereas the values of small-diameter tubes (dt = ~0.80–0.95 nm) are similar. For both metals, no dependence of the activation energies on the chirality of inner tubes is observed

Investigation of growth dynamics of carbon nanotubes

The synthesis of single-walled carbon nanotubes (SWCNTs) with defined properties is required for both fundamental investigations and practical applications. The revealing and thorough understanding of the growth mechanism of SWCNTs is the key to the synthesis of nanotubes with required properties. This paper reviews the current status of the research on the investigation of growth dynamics of carbon nanotubes. The review starts with the consideration of the peculiarities of the growth mechanism of carbon nanotubes. The physical and chemical states of the catalyst during the nanotube growth are discussed. The chirality selective growth of nanotubes is described. The main part of the review is dedicated to the analysis and systematization of the reported results on the investigation of growth dynamics of nanotubes. The studies on the revealing of the dependence of the growth rate of nanotubes on the synthesis parameters are reviewed. The correlation between the lifetime of catalyst and growth rate of nanotubes is discussed. The reports on the calculation of the activation energy of the nanotube growth are summarized. Finally, the growth properties of inner tubes inside SWCNTs are considered

Kinetics, Electronic Properties of Filled Carbon Nanotubes Investigated with Spectroscopy for Applications

The paper is dedicated to the discussion of kinetics of growth, and electronic properties of filled carbon nanotubes investigated by spectroscopy for applications. The paper starts with discussion of growth of carbon nanotubes inside metallocene-filled carbon nanotubes. Nickelocene, cobaltocene are considered for growth of carbon nanotubes. Then, the investigations of filled carbon nanotubes by four spectroscopic techniques are discussed. Among them are Raman spectroscopy, near edge X-ray absorption fine-structure spectroscopy, photoemission spectroscopy, optical absorption spectroscopy. It is discussed that metal halogenides, metal chalcogenides, metals lead to changes in electronic structure of nanotubes with n- or p-doping. The filling of carbon nanotubes with different organic and inorganic substances results in many promising applications. This review adds significant contribution to understanding of the kinetics and electronic properties of filled SWCNTs with considering new results of recent investigations. Challenges in various fields are analyzed and summarized, which shows the author’s viewpoint of progress in the spectroscopy of filled SWCNTs. This is a valuable step toward applications of filled SWCNTs and transfer of existing ideas from lab to industrial scale

Spectroscopy of Filled Single-Walled Carbon Nanotubes

Many envisaged applications, such as nanoelectronics, photovoltaics, thermoelectric power generation, light-emission devices, energy storage and biomedicine, necessitate single-walled carbon nanotube (SWCNT) samples with specific uniform electronic properties. The precise investigation of the electronic properties of filled SWCNTs on a qualitative and quantitative level is conducted by optical absorption spectroscopy, Raman spectroscopy, photoemission spectroscopy and X-ray absorption spectroscopy. This review is dedicated to the description of the spectroscopic methods for the analysis of the electronic properties of filled SWCNTs. The basic principle and main features of SWCNTs as well as signatures of doping-induced modifications of the spectra of filled SWCNTs are discussed

Phemenology of Filling, Investigation of Growth Kinetics and Electronic Properties for Applications of Filled Single-Walled Carbon Nanotubes

This review discusses the phemenology of filling, the investigation of kinetics, and the electronic properties for applications of filled single-walled carbon nanotubes (SWCNTs), and summarizes five main achievements that were obtained in processing the spectroscopic data of SWCNTs filled with metal halogenide, metal chalcogenide, metal and metallocenes. First, the methods of processing kinetic data were developed to reveal precise trends in growth rates and activation energies of the growth of SWCNTs. Second, the metal-dependence of kinetics was revealed. Third, metallicity-sorted (metallic and semiconducting) SWCNTs were filled with a range of substances and the electronic properties were investigated. Fourth, new approaches to processing the data of spectroscopic investigations of filled SWCNTs were developed, which allowed more reliable and precise analysis of the experimental results. Fifth, the correlation between the physical and chemical properties of encapsulated substances and the electronic properties of SWCNTs were elucidated. These points are highlighted in the review

Raman Spectroscopy Study of the Doping Effect of the Encapsulated Iron, Cobalt, and Nickel Bromides on Single-Walled Carbon Nanotubes

In this contribution the modification of the electronic properties of single-walled carbon nanotubes (SWCNTs) filled with nickel bromide, cobalt bromide, and iron bromide was studied by Raman spectroscopy. The doping-induced alterations of the radial breathing mode (RBM) and G-mode in the Raman spectra of the filled SWCNTs were analyzed in detail. The observed shifts of the components of the Raman modes and changes of their profiles allowed concluding that the embedded compounds have an acceptor doping effect on the SWCNTs, and the doping level increases in the line with nickel bromide-cobalt bromide-iron bromide

Applications of Filled Single-Walled Carbon Nanotubes: Progress, Challenges, and Perspectives

Single-walled carbon nanotubes (SWCNTs), which possess electrical and thermal conductivity, mechanical strength, and flexibility, and are ultra-light weight, are an outstanding material for applications in nanoelectronics, photovoltaics, thermoelectric power generation, light emission, electrochemical energy storage, catalysis, sensors, spintronics, magnetic recording, and biomedicine. Applications of SWCNTs require nanotube samples with precisely controlled and customized electronic properties. The filling of SWCNTs is a promising approach in the fine-tuning of their electronic properties because a large variety of substances with appropriate physical and chemical properties can be introduced inside SWCNTs. The encapsulation of electron donor or acceptor substances inside SWCNTs opens the way for the Fermi-level engineering of SWCNTs for specific applications. This paper reviews the recent progress in applications of filled SWCNTs and highlights challenges that exist in the field

Metal and Metal Halogenide-Filled Single-Walled Carbon Nanotubes: Kinetics, Electronic Properties, Engineering the Fermi Level

Here, we present a review of the major achievements in kinetics, electronic properties, and engineering in the Fermi level of single-walled carbon nanotubes (SWCNTs). Firstly, the kinetics of metal-filled SWCNTs were revealed with precision over several minutes. Secondly, the growth rates of nanotubes were calculated. Thirdly, the activation energies of nanotubes were measured. Fourthly, the methods of the quantitative analysis of the doping level were developed. Indeed, only qualitative analysis has been previously performed. The quantitative analysis allowed us to obtain quantitative data on charge transfer. Fifthly, the correlation between the physical properties, chemical properties, electronic properties of SWCNTs was elucidated