Charge transfer in steam purified arc discharge single walled carbon nanotubes filled with lutetium halides.

In the present work, the effect of doping on electronic properties in bulk purified and filled arc-discharge single-walled carbon nanotubes samples is studied for the first time by in situ Raman spectroelectrochemical method. A major challenge to turn the potential of SWCNTs into customer applications is to reduce or eliminate their contaminants by means of purification techniques. Besides, the endohedral functionalization of SWCNTs with organic and inorganic materials (i.e. metal halides) allows the development of tailored functional hybrids. Here, we report the purification and endohedral functionalization of SWCNTs with doping affecting the SWCNTs. Steam-purified SWCNTs have been filled with selected lutetium(iii) halides, LuCl3, LuBr3, LuI3, and sealed using high-temperature treatment, yielding closed-ended SWCNTs with the filling material confined in the inner cavity. The purified SWCNTs were studied using TGA, EDX, STEM and Raman spectroscopy. The lutetium(iii) halide-filled SWCNTs (LuX3@SWCNTs) were characterized using STEM, EDX, Raman spectroscopy and in situ Raman spectroelectrochemistry. It was found that there is a charge transfer between the SWCNTs and the encapsulated LuX3 (X = Cl, Br, I). The obtained data testify to the acceptor doping effect of lutetium(iii) halides incorporated into the SWCNT channels, which is accompanied by the charge transfer from nanotube walls to the introduced substances.

Chemical Postdeposition Treatments To Improve the Adhesion of Carbon Nanotube Films on Plastic Substrates.

The robust adhesion of single-walled carbon nanotubes (SWCNTs) to plastic substrates is a key issue toward their use in flexible electronic devices. In this work, semitransparent SWCNT films were prepared by spray-coating on two different plastic substrates, specifically poly(ethylene terephthalate) and poly(vinylidene fluoride). The deposited SWCNT films were treated by dipping in suitable solvents separately, namely, 53% nitric acid (HNO3) and N-methyl pyrrolidone. Direct evidence of SWCNT adhesion to the substrate was obtained by a peel-off test carried out with an adhesive tape. Moreover, these treatments caused enhanced film transparency and electrical conductivity. Electron microscopy images suggested that SWCNTs were embedded in the plastic substrates, forming a thin layer of conductive composite materials. Raman spectroscopy detected a certain level of doping in the SWCNTs after the chemical treatments, which particularly affected metallic nanotubes in the case of the HNO3 treatment. The microscopic adhesion and hardness of the SWCNT films were studied through a nanoscratch test. Overall, the efficiency of selected chemical postdeposition treatments for improving the SWCNT adhesion and the robustness of the resulting SWCNT films are demonstrated on flexible substrates of different chemical compositions.

A tool box to ascertain the nature of doping and photoresponse in single-walled carbon nanotubes.

The effect of doping on the electronic properties in bulk single-walled carbon nanotube (SWCNT) samples is studied for the first time using a new in situ Raman spectroelectrochemical method, and further verified by DFT calculations and photoresponse. We use p-/n-doped SWCNTs prepared by diazonium reactions as a versatile chemical strategy to control the SWCNT behavior. The measured and calculated data testify an acceptor effect of 4-aminobenzenesulfonic acid (p-doping), and a donor effect (n-doping) in the case of benzyl alcohol. In addition, pristine and covalently functionalized SWCNTs were used for the preparation of photoactive film electrodes. The photocathodic current in the photoelectrochemical cell is consistently modulated by the doping group. These results validate the in situ Raman spectroelectrochemistry as a unique tool box for predicting the electronic properties of functionalized SWCNTs in the form of thin films and their operational functionality in thin film devices for future optoelectronic applications.

Multipurpose Nature of Rapid Covalent Functionalization on Carbon Nanotubes.

In the vast field of functionalization routes to carbon nanoforms, the fulfillment of such critical requirements as quick and nonharsh methods, good dispersibility, introduction of reactive groups, short reaction time, and low cost can be quite challenging. Traditional thermally induced diazonium chemistry on single-walled carbon nanotubes (SWCNTs) is revisited by using commercial anilines and providing useful insight into the versatility of this approach. Functionalized SWCNTs with multiple controllable features, such as degree (and ratio) of coverage, orthogonalization, doping, and high water dispersibility, are obtained by introducing benzenesulfonic acid and benzylamine moieties. The scenario opens up an avenue to address relevant applications in which most functionalization methods could not be applied in a straightforward way.