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Review

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

by
Marianna V. Kharlamova
1,* and
Christian Kramberger
2,*
1
Centre for Advanced Materials Application (CEMEA), Slovak Academy of Sciences, Dúbravská cesta 5807/9, 845 11 Bratislava, Slovakia
2
Faculty of Physics, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria
*
Authors to whom correspondence should be addressed.
Nanomaterials 2023, 13(1), 180; https://doi.org/10.3390/nano13010180
Submission received: 16 December 2022 / Revised: 28 December 2022 / Accepted: 28 December 2022 / Published: 30 December 2022
(This article belongs to the Special Issue Advanced Carbon Nanostructures: Synthesis, Properties and Applications)
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Abstract

:
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.

1. Introduction

The filling of single-walled carbon nanotubes (SWCNTs) [1,2,3,4,5,6,7,8,9,10] is made using a gas phase and liquid phase approach. Metals are introduced inside SWCNTs via a solution method, and metal halogenides are filled inside SWCNTs through the melt method [10]. These methods are very promising and allow high filling ratios to be obtained [10].
Significant progress has been made in the understanding of kinetics and the electronic properties of filled SWCNTs and the precise control of the Fermi level, which put SWCNTs a step forward toward their use in applications. The kinetics and electronic properties were analyzed using Raman spectroscopy, near edge X-ray absorption fine structure spectroscopy (NEXAFS), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and optical absorption spectroscopy (OAS) [11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67,68,69,70,71,72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89,90,91,92]. It is high time to review tremendous progress that has been made over the last five years [10]. There are five major achievements: Firstly, the kinetics of metal-filled SWCNTs were revealed with the precision of 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 previously been performed. The quantitative analysis allowed for the obtaining of quantitative data on charge transfer. Fifthly, the correlation between the physical properties, chemical properties, and electronic properties of SWCNTs were elucidated.
The goal of this review is to be the central reference for researchers aiming at a precise control of kinetics and electronic properties toward applications and to stimulate emerging applications utilizing the physical and chemical properties.
Kinetics and the electronic properties of filled SWCNTs and the engineering of their Fermi level are tailored for their use as applications. This review begins from the overview of metal and metal halogenide filled inside SWCNTs. Then, the kinetics of metal-filled SWCNT growth are discussed. After that, the review discusses the results of the investigation of doping and hybridization effects in SWCNTs filled with metals and metal halogenides using Raman spectroscopy, near edge X-ray absorption fine structure spectroscopy, photoemission spectroscopy, and optical absorption spectroscopy. The methods of the quantification of charge transfer are described, and a discussion of the influence of different metals and metal halogenides on the electronic properties is presented.

2. Overview of Substances Filled Inside SWCNTs

To date, more than 150 different substances have been succeeded [93,94,95,96,97,98,99]. The list includes metals and metal halogenides.
Metals are introduced inside SWCNTs, including alkali metals (potassium [100]), p-metals (bismuth [101]), transition metals (iron [102,102,103,104,105], cobalt [82,104], nickel [106], manganese [104], vanadium [104], molybdenum [104], ruthenium [107], palladium [108], silver [108,109,110,111,112,113,114], copper [109,115], rhenium [116,117,118], gold [108], platinum [108], tungsten [5,104,116,118], osmium [116,118]) and lanthanides (europium [119,120] and erbium [121]).
Chemical compounds are the largest group of substances introduced inside SWCNTs. The most popular among them are metal halogenides. SWCNTs were filled with metal fluorides (SnF2 [122]), metal chlorides (sodium/cesium/copper/silver/tantal)Cl [113,123,124,125,126,127,128,129,130,131,132,133], (manganese/iron/cobalt/nickel/zinc/cadmium/mercury/palladium/lead)Cl2 [108,126,127,134,135,136,137,138,139,140,141,142,143,144,145], (iron/yttrium/ruthenium/gold/lanthan/neodym/samarium/europium/gadolinium/terbium/thulium/praseodymium/holmium/erbium/ytterbium/luthetium)Cl3, Al2Cl6 [102,103,107,108,121,126,127,134,139,142,146,147,148,149,150,151,152], (zirkonium/hafnium/platinum/thorium)Cl4 [108,127,139,153,154,155,156], MoCl5 [126], WCl6 [126,127], (KCl)x(UCl4)y [113,157], metal bromides (cesium/copper/silver)Br [113,123,124,127], (manganese/iron/cobalt/nickel/zinc/cadmium/lead)Br2 [135,136,137,138,141,143,145,158,159]), TbBr3 [151], LuBr3 [152], metal iodides (lithium/sodium/potassium/rubidium/cesium/copper/silver)I [123,124,127,154,155,156,157,160,161,162,163,164,165,166,167,168], (calcium/strontium/barium/iron/cobalt/zinc/cadmium/lead)I2 [137,138,141,145,154,155,156,169,170,171], (lanthan/terbium/luthetium)I3, Al2I6 [139,151,152,172,173], SnI4 [126,127]), their mixtures [113,126,127,154,157,160,174,175], and other substances [176,177,178,179,180].

3. Kinetics

The kinetics of the growth of carbon nanotubes inside (C5H5)2Ni- and (C5H5)2Co-filled SWCNTs were investigated [98,99]. The growth rates were calculated, and the activation energies on nickel and cobalt clusters were measured to be between 0.5 and 2.7 eV. It was shown that metal clusters catalyze the growth of nanotubes that continue for long hours. Metal clusters grow in size with time and increasing annealing temperature. The investigations were performed at temperature between 480 and 640 °C for nickel- and cobalt-filled SWCNTs. The duration of growth was between 2 min and 5 days; however, it can continue for an even longer period of investigation. Figure 1 shows the initial metal clusters inside carbon nanotubes. They are seen as the dark contrast elements in the images.

4. Electronic Properties

4.1. Filling of SWCNTs with Metals

The encapsulation of metals inside SWCNTs was performed in a saturated solution of metal nitrate (AgNO3 [109,110,111,112,179] or Cu(NO3)2 [109,115]).

4.2. Filling of SWCNTs with Metal Halogenides

The embedding of metal halogenides inside SWCNTs was performed using the melt method. Sealed quartz ampoule was heated above the melting temperature (Table 1), kept at this temperature for some time, and then cooled down. The filling of the compound inside SWCNTs occurred via capillary forces. This filling method allowed nanocomposites with a large filling ratio (up to 90%) of SWCNTs to be obtained. The control of the cooling procedure of the ampoule allowed for the crystallization of the salt inside SWCNTs and for one-dimensional nanocrystals to be obtained.

4.3. Doping and Hybridization Effects

4.3.1. Optical Absorption Spectroscopy

The optical absorption spectroscopy (OAS) is an informative method used for the investigation of the electronic properties of filled SWCNTs. It provides data about charge transfer in filled SWCNTs. Many samples of filled SWCNTs can be investigated, and the method is simple and quick. A comparison of the spectra of pristine and filled SWCNTs reveals the modifications of the electronic structure of carbon nanotubes.
The OAS investigated SWCNTs filled with iron halogenides [138], cobalt bromide [158], zinc halogenides [137], silver halogenides [123], cadmium halogenides [141], CuCl [129], copper halogenides [124], PrCl3 [150], and TbCl3 [142]. In most cases, changes in the spectrum were attributed to the modification of the electronic properties of SWCNTs.
Figure 2 compares the OAS spectra of pristine and CuCl-filled SWCNTs with increasing exposure time [129]. There are E 11 S , E 22 S , E 33 S , and E 11 M absorption bands. The E 11 S absorption band vanishes after 5 h of exposure to CuCl gas; moreover, with increasing exposure time, other absorption bands are also slightly reduced. This was attributed to canceling optical transitions [129].
The suppression of the E 11 S absorption band was also revealed [123,124,129,135,136,137,138,141,142,158]. Taking into account these data, the authors made a conclusion about doping. For metal chalcogenide-filled SWCNTs, there are no noticeable changes [176,179,181,182,183,184,185,186,187,188].

4.3.2. Raman Spectroscopy

Raman spectroscopy is a very useful method of investigation for examining the electronic properties of filled SWCNTs. It is a simple, nondestructive, and informative technique used to investigate the vibronic properties of carbon nanotubes upon filling. The nanotubes have a radial breathing mode (RBM) and D, G, 2D bands of Raman spectra, which are characteristic for a nanotube with a certain diameter, metallicity type, and chiral angle.
The Raman spectrum of pristine SWCNTs shows two dominant peaks in RBM (C1, and C2) [110]. They are located at 156 and 172 cm−1 (Figure 3a) and belong to main-diameter semiconducting and metallic SWCNTs, accordingly [189]. The G-line reveals three components at 1540, 1567, and 1591 cm−1 (Figure 3a). The positions of the individual peaks are very close to the predicted peak positions [190,191,192]. The G-band further backs up this interpretation, as this shape is reminiscent of metallic SWCNTs [190,193,194].
The Raman spectra of Ag-filled SWCNTs show differences (Figure 3b). In the RBM-band, there are just minuscule downshifts of the peaks by 3 cm−1. In the G-band, there are shifts from 2 to 6 cm−1. The relative strength of the metallic component increases from 0.70 to 0.79. There is the charge transfer between the SWCNTs and silver with a rigid band shift as the overall metallicity increases while the resonance conditions are preserved.
Besides silver [109,112,179], there are also similarities to copper [109,115]. This is in line with the n-doping of SWCNTs, which is expected from the lower work functions of metals as compared to nanotubes.
Raman spectroscopy was applied for manganese halogenides [136,143], iron halogenides [138], CoBr2 [158], nickel halogenides [135], ZnCl2 [142], zinc halogenides [137], silver halogenides [123], CuCl [129], CuI [161,165], copper halogenides [124], CdCl2 [142,144], cadmium halogenides [141], lead halogenides [145], SnF2 [122], RbI [168], RbAg4I5 [175], TbCl3 [142,149,151], TbBr3, TbI3 [151], TmCl3 [149,179], PrCl3 [149,150], luthetium halogenides [152], and HgCl2 [140].
The Raman spectra of pristine SWCNTs, electron acceptor PbCl2-filled SWCNTs [145], and electron donor RbI-filled SWCNTs [168] are shown in Figure 4. In the RBM-band, there are shifts in the peaks and an alteration in their relative intensities. In the D and 2D-bands, there are shifts in the peaks and changes in their intensities. The G-band shows changes in the peak positions and modifications inthe peak profiles [145,168].
An analysis of Raman modes allows the doping effects of the filled SWCNTs to be investigated in detail (Figure 5) [145,168]. In the RBM-band of the pristine SWCNTs (Figure 5a), there are peaks at 154, 171, 185, and 196 cm−1. In the G-band, there are three components, G−LO, G+TO, and G+LO, positioned at 1544, 1566, and 1592 cm−1 [168,190,193].
In the RBM-band of the PbCl2-filled SWCNTs (Figure 5b), there are peaks at 165 and 173 cm−1, and relative intensities are changed from 1:1.83 to 1.63:1. In the G-band, there are three peaks at 1554, 1575, and 1602. They are upshifted by 10, 9, and 10 cm−1 as compared to the pristine nanotubes. The relative intensity of the metallic component decreases from 0.40 to 0.06 because of the transition into a semiconducting state [159]. This is similar for other metal halogenides [122,123,124,129,135,136,137,138,140,141,142,143,144,149,150,151,158,161,165,179] and metal chalcogenides [176,180].
In the RBM-band of the RbI-filled SWCNTs (Figure 5c), peak positions are shifted by 5–10 cm−1. However, the intensities are slightly altered due to resonance conditions. In the G-band, peaks are upshifted by 9, 5, and 1 cm−1 as compared to the pristine nanotubes. This was consistent with the n-doping of SWCNTs observed using the encapsulated RbI.
Modifications were also found to depend on the p-doping level of nanotubes with CuCl [129]. The RBM-peaks were upshifted at low doping levels, and they were completely suppressed at high doping levels. In the G-band, there is a gradual upshift when the doping level increases.

4.3.3. Near Edge X-ray Absorption Fine Structure Spectroscopy

Near edge X-ray absorption fine structure spectroscopy (NEXAFS) is a synchrotron-based technique for the investigation of the electronic properties of filled SWCNTs. It provides information about hybridization in filled SWCNTs and the formation of new chemical bonds between the introduced substances and SWCNTs. It also reveals modifications in the band structure of SWCNTs upon filling; moreover, it can differ between chemical bonds for different substances and elements.
NEXAFS allows the formation of chemical bonds between nanotubes and encapsulated substances to be investigated. In the literature, the C 1s NEXAFS spectra of SWCNTs filled with iron halogenides [138], nickel halogenides [135], zinc halogenides [137], cadmium halogenides [141], silver halogenides [123], copper halogenides [124], ErCl3 [121], and HgCl2 [140] were reported.
Figure 6 compares the C 1s NEXAFS spectra of SWCNTs and HgCl2-filled SWCNTs [140]. There is also the π*-resonance at ~285 eV and the π*-resonance at ~292 eV. There is, however, an additional pre-edge peak in filled SWCNTs (see label A in Figure 6) before the π*-resonance at ~284.0 eV. This is due to the hybridization of the π-orbitals of SWCNTs with embedded mercury chloride.
There is an emergence of similar additional peaks for other metal halogenides [121,123,124,135,137,138,141], because chemical bonds are formed between SWCNTs and embedded substances.

4.3.4. Photoemission Spectroscopy

The X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) allow the electronic properties of filled SWCNTs to be investigated. In XPS, the modifications in the spectra of regions are observed. They are characteristic for different fillers. This includes shifts of peaks and alterations of spectral shapes. In UPS, the changes in the valence band spectra are revealed. These changes highlight the modifications of the band structure.
Using photoemission spectroscopy (XPS and UPS) SWCNTs filled with Ag [109,110,179], Cu [109,115], and Eu [120] were investigated, and more reports are expected.
In Figure 7, in the C 1s XPS spectrum, the first component is unchanged and is assigned to carbon in the unfilled nanotubes, whereas the other two components belong to the silver-filled SWCNTs, whose chemical composition is confirmed by the Ag 3d XPS spectrum (see inset in Figure 7b) [110]. The second component appears upshifted by +0.33 eV due to the raised Fermi level. The third component is not interpreted [110]. The same effects are observed for copper-filled SWCNTs [109,115].
The C 1s peak of the Eu-filled SWCNTs was upshifted by 0.1 eV due to the incorporated europium walls as well as the further modification of the electronic structure [120]. The UPS data of the Eu-filled SWCNTs demonstrated a uniform upshift of peaks. These peaks are the consequence of the equal Fermi level upshift. These changes in the spectra are a clear signature of metallic atomic wires [120].
XPS quantifies the Fermi level shift and reveals the direction of the charge transfer for SWCNTs filled with manganese halogenides [136,143], iron halogenides [138], CoBr2 [158], nickel halogenides [135], zinc halogenides [137], silver halogenides [123], lead halogenides [145], cadmium halogenides [141], ZnCl2, CdCl2, TbCl3 [142], copper halogenides [124], RbI [168], RbAg4I5 [175], TmCl3 [179], PrCl3 [150], and HgCl2 [140] that were reported. The authors observed the shift of components. These modifications were attributed to the alteration of the electronic properties.
The authors of Refs. [123,135,136,137,138,141,142,143,158] used the same interpretation of the components of the spectra as in the above-described case. They revealed the shift of the second component to lower binding energies, i.e., p-doping. The authors of Refs. [124,150] fitted the C 1s spectra with components of metallic and semiconducting SWCNTs. They showed larger p-doping for the metallic carbon nanotubes.
The determination of the Fermi level shift was conducted using the secondary electrons’ (SE) cutoff for the copper halogenide-filled SWCNTs [124]. This was reported to be −0.2, −0.6, and −0.65 eV for CuI, CuBr, and CuCl, accordingly. In [137], the SE cutoff spectra of SWCNTs and ZnBr2-filled SWCNTs allowed the Fermi level shift of −0.3 eV to be evaluated.
Additional valence band (VB) spectra measurements on copper halogenide- [124] and zinc bromide-filled [137] nanotubes were in line with the direct measurements of the work function in the SE cutoff spectra. Regarding the π -peaks in the VB spectra of SWCNTs, the copper halogenide-filled nanotubes originate from the photoemission from the π-band of SWCNTs, and the σ-peaks originate from the photoemission from the σ-band of SWCNTs [124]. The -peaks of filled SWCNTs are shifted to higher kinetic energies by 0.2–0.7 eV. This testifies to p-doping. The comparable effect was derived for ZnBr2 [137] and ErCl3 [121].

5. Quantification of Charge Transfer in SWCNTs Filled with Inorganic Compounds

For the applications of filled nanotubes, one should quantify the charge transfer. In [132], the calculation was performed using the photoemission data. Alkali metals are very reactive, and the charge transfer is assumed to be practically one electron per K+ ion; thus, Fermi level shifts can be linked to charge transfer densities [195]. Using the calibration plot (Figure 8), the number of transferred electrons for AgCl-filled SWCNTs was calculated to be 0.0024 e− per carbon. The charge transfer density along the SWCNT amounted to 0.0406 e−/Å [132].
The crucial properties of fillers that influence the doping type and doping level of SWCNTs are the work function of inorganic compounds and elementary substances. There are three doping effect-defining parameters: metallicity type, diameter of SWCNTs, and filling ratio. The introduction of metals leads to a high-yield filling of the nanotubes. It was shown that metals result in n-doping, and the Fermi level shift amounted to ~+0.3 eV.
The encapsulation of inorganic compounds inside SWCNTs leads to a homogenous filling of SWCNTs with large filling ratios. The investigation of the filled SWCNTs, using OAS, Raman spectroscopy, XPS, UPS, and NEXAFS, proved that halogenides of 3d-metals (MX2, where M = manganese, iron, cobalt, nickel, copper, zinc, X = chlorine, bromine, iodine), 4d-metals (MX2, where M = silver, cadmium, X = chlorine, bromine, iodine), 5d-metals (MX2, where M = mercury, X = chlorine), 4f-metals (MX3, where M = praseodymium, terbium, erbium, thulium, X = chlorine, bromine, iodine), 5p-metals (MX2, where M = tin, X = fluorine), 6p-metals (MX2, where M = lead, X = chlorine, bromine, iodine), ternary halides (RbAg4I5), and gallium chalcogenides (GaX, X = selenium, tellurium) cause p-doping with a Fermi level shift of ~0.1–0.4 eV. For halogenides of 3d-, 4d- and 4f-metals, the Fermi level shift is the highest for chlorides and the smallest for iodides. Moreover, the hybridization of the π-orbitals of SWCNTs with introduced salts was revealed. The nanotubes of different diameters with arc-discharge and chemical vapor deposition synthesis methods have different doping levels. The introduced RbI leads to the Fermi level shift of ~+0.2 eV.

6. Conclusions

This review has demonstrated how filling leads to a precise control over their electronic properties and how it has widened the scope of possible applications, raising great interest in science and technology as a result. The ability to tailor the electronic properties according to the specific requirements of individual applications renders these fascinating materials viable in the advancement of cutting-edge and fundamental applied research.
Transparency, conductivity, and mechanical robustness are key challenges in the application of nanoelectronics. While the diameter is only 1 to 2 nm, the contact length and channel length can be reduced further. Filled SWCNTs can have better contacts, requiring shorter contact lengths and changes in mechanical stiffness. Thermoelectric applications based on filled SWCNTs have to aim at a higher conversion efficiency and a decreased thermal conductivity. Electrochemical energy storage in a filled SWCNT facilitates effective charge transfer throughout the bulk of composite material. In applications in catalysis, it is desirable to improve the lifetime of the catalytic particles. It is crucial to maximize the filling ratio and purity of the filled SWCNTs. For gas sensing, one aims to achieve sensitivity and selectivity. It is also required to determine the appropriate filling for spintronic applications. For magnetic recording, the filling might offer a way to shift the paramagnetic limit. Bioimaging applications of filled SWCNT will greatly benefit from higher spatial resolution as well as from the imaging of deeper layers of tissue. Reduced cytotoxicity and better biodegradability constitute the desired improved biocompability of filled SWCNTs. The targeting systems have to be specifically developed for the different use cases. The therapeutic options may be further expanded in combined therapies, where two or more therapeutics are co-delivered on a single platform. Filled SWCNTs are also a potential electrode material for solar cells.

Author Contributions

The paper is written solely by Marianna V. Kharlamova. She contributed to every work reviewed in paper. M.V.K.—writing—original draft preparation, C.K.—writing—review and editing. All authors have read and agreed to the published version of the manuscript.

Funding

These studies were partly performed during the implementation of the project Building-up Centre for advanced materials application of the Slovak Academy of Sciences, ITMS project code 313021T081 supported by Research & Innovation Operational Programme funded by the ERDF. The APC was funded by the University of Vienna.

Data Availability Statement

Data are available on request to first author (Marianna V. Kharlamova) of every reviewed paper.

Acknowledgments

Marianna V. Kharlamova acknowledges the coauthors of all reviewed paper. Open Access Funding by the University of Vienna.

Conflicts of Interest

Author may have the conflict of interest with Andrei Eliseev (Lomonosov Moscow State University). The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

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Figure 1. Transmission electron microscopy of cobalt clusters annealed at 550 °C for 2 h: (a,b) an inner tube; (c,d) metal clusters with graphitic structures. Scale bars, 2 nm. Reprinted from Kharlamova, M.V., et al. Chiral vector and metal catalyst-dependent growth kinetics of single-walled carbon nanotube, Carbon. 2018. V. 133. P. 283-292, Copyright (2018), with permission from Elsevier [98].
Figure 1. Transmission electron microscopy of cobalt clusters annealed at 550 °C for 2 h: (a,b) an inner tube; (c,d) metal clusters with graphitic structures. Scale bars, 2 nm. Reprinted from Kharlamova, M.V., et al. Chiral vector and metal catalyst-dependent growth kinetics of single-walled carbon nanotube, Carbon. 2018. V. 133. P. 283-292, Copyright (2018), with permission from Elsevier [98].
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Figure 2. The OAS spectra evolution upon exposure to CuCl gas. Reprinted with permission from [129], copyright 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Figure 2. The OAS spectra evolution upon exposure to CuCl gas. Reprinted with permission from [129], copyright 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Figure 3. Raman spectra of the pristine SWCNTs (a) and silver-filled SWCNTs (b) recorded at 1.96 eV (λex = 633 nm). The peak positions are indicated. Reproduced from M. V. Kharlamova et al. Donor doping of single-walled carbon nanotubes by filling of channels with silver, Journal of Experimental and Theoretical Physics, V. 115, № 3, p. 485–491, 2012, Springer Nature [110].
Figure 3. Raman spectra of the pristine SWCNTs (a) and silver-filled SWCNTs (b) recorded at 1.96 eV (λex = 633 nm). The peak positions are indicated. Reproduced from M. V. Kharlamova et al. Donor doping of single-walled carbon nanotubes by filling of channels with silver, Journal of Experimental and Theoretical Physics, V. 115, № 3, p. 485–491, 2012, Springer Nature [110].
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Figure 4. The Raman spectra of the pristine SWCNTs (a) [168] (reprinted with permission from [168], copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim), PbCl2@SWCNT (b) (reproduced from M. V. Kharlamova et al. Revealing the doping effect of encapsulated lead halogenides on single-walled carbon nanotubes, Appled Physics A, V. 125, article number 320, 2019, Springer Nature [145]) and RbI@SWCNT (c) [168] (reprinted with permission from [168], copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
Figure 4. The Raman spectra of the pristine SWCNTs (a) [168] (reprinted with permission from [168], copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim), PbCl2@SWCNT (b) (reproduced from M. V. Kharlamova et al. Revealing the doping effect of encapsulated lead halogenides on single-walled carbon nanotubes, Appled Physics A, V. 125, article number 320, 2019, Springer Nature [145]) and RbI@SWCNT (c) [168] (reprinted with permission from [168], copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
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Figure 5. Raman spectra of pristine SWCNTs (a) (reproduced from M. V. Kharlamova et al. Revealing the doping effect of encapsulated lead halogenides on single-walled carbon nanotubes, Appled Physics A, V. 125, article number 320, 2019, Springer Nature [145]) and the PbCl2-filled SWCNTs (b) (reproduced from M. V. Kharlamova et al. Revealing the doping effect of encapsulated lead halogenides on single-walled carbon nanotubes, Appled Physics A, V. 125, article number 320, 2019, Springer Nature [145]) and RbI (c) (reprinted with permission from [168], copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) acquired at 1.96 eV-laser. The positions of the components are denoted.
Figure 5. Raman spectra of pristine SWCNTs (a) (reproduced from M. V. Kharlamova et al. Revealing the doping effect of encapsulated lead halogenides on single-walled carbon nanotubes, Appled Physics A, V. 125, article number 320, 2019, Springer Nature [145]) and the PbCl2-filled SWCNTs (b) (reproduced from M. V. Kharlamova et al. Revealing the doping effect of encapsulated lead halogenides on single-walled carbon nanotubes, Appled Physics A, V. 125, article number 320, 2019, Springer Nature [145]) and RbI (c) (reprinted with permission from [168], copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) acquired at 1.96 eV-laser. The positions of the components are denoted.
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Figure 6. The C 1s NEXAFS spectra of SWCNTs and HgCl2-filled SWCNTs. The label A marks a new feature. Reprinted with permission from Fedoseeva Y.V. et al. Single-walled carbon nanotube reactor for redox transformation of mercury dichloride, ACS Nano. 2017. V.11. N.9. P.8643-8649. Copyright 2017 American Chemical Society [140].
Figure 6. The C 1s NEXAFS spectra of SWCNTs and HgCl2-filled SWCNTs. The label A marks a new feature. Reprinted with permission from Fedoseeva Y.V. et al. Single-walled carbon nanotube reactor for redox transformation of mercury dichloride, ACS Nano. 2017. V.11. N.9. P.8643-8649. Copyright 2017 American Chemical Society [140].
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Figure 7. The C 1s XPS spectra of SWCNTs (a) and Ag-filled SWCNTs (b). The inset in (b) shows the Ag 3d XPS spectrum. Reproduced from M. V. Kharlamova et al. Donor doping of single-walled carbon nanotubes by filling of channels with silver, Journal of Experimental and Theoretical Physics, V. 115, № 3, p. 485-491, 2012, Springer Nature [110].
Figure 7. The C 1s XPS spectra of SWCNTs (a) and Ag-filled SWCNTs (b). The inset in (b) shows the Ag 3d XPS spectrum. Reproduced from M. V. Kharlamova et al. Donor doping of single-walled carbon nanotubes by filling of channels with silver, Journal of Experimental and Theoretical Physics, V. 115, № 3, p. 485-491, 2012, Springer Nature [110].
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Figure 8. The calibration plot for potassium. The data are from Ref. [195] are plotted.
Figure 8. The calibration plot for potassium. The data are from Ref. [195] are plotted.
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Table
Table 1. Synthesis temperatures of nanocomposites X@SWCNT using the melt filling method.
Table 1. Synthesis temperatures of nanocomposites X@SWCNT using the melt filling method.
Filled SubstanceTfilling, °CReferenceFilled SubstanceTfilling, °CReference
manganese (II) chloride750[136,143]cadmium (II) bromide669[141]
manganese (II) bromide798[136,143]cadmium (II) iodide488[141]
iron (II) chloride774[138]lead (II) chloride601[145]
iron (II) bromide784[138]lead (II) bromide471[145]
iron (II) iodide687[138]lead (II) iodide 502[145]
cobalt (II) bromide778[158]terbium (III) chloride688[142,149,151]
nickel (II) chloride1101[135]terbium (III) bromide927[151]
nickel (II) bromide1063[135,159]terbium (III) iodide1057[151]
copper (I) chloride530[124]praseodymium(III) chloride886[149,150]
copper (I) bromide600[124]erbium (III) chloride900[121]
copper (I) iodide705[124]thulium (III) chloride924[149,179]
zinc (II) chloride400[137,142]luthetium (III) chloride940[152]
zinc (II) bromide494[137]luthetium (III) bromide1050[152]
zinc (II) iodide546[137]luthetium (III) iodide1100[152]
rubidium (I) iodide756[168,175]mercury (II) chloride290[140]
rubidium-silver iodide756[175]silver (I) chloride555[123]
tin (II) fluoride300[122]silver (I) bromide530[123]
cadmium (II) chloride668[141,142,144]silver (I) iodide660[123]
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Kharlamova, M.V.; Kramberger, C. Metal and Metal Halogenide-Filled Single-Walled Carbon Nanotubes: Kinetics, Electronic Properties, Engineering the Fermi Level. Nanomaterials 2023, 13, 180. https://doi.org/10.3390/nano13010180

AMA Style

Kharlamova MV, Kramberger C. Metal and Metal Halogenide-Filled Single-Walled Carbon Nanotubes: Kinetics, Electronic Properties, Engineering the Fermi Level. Nanomaterials. 2023; 13(1):180. https://doi.org/10.3390/nano13010180

Chicago/Turabian Style

Kharlamova, Marianna V., and Christian Kramberger. 2023. "Metal and Metal Halogenide-Filled Single-Walled Carbon Nanotubes: Kinetics, Electronic Properties, Engineering the Fermi Level" Nanomaterials 13, no. 1: 180. https://doi.org/10.3390/nano13010180

APA Style

Kharlamova, M. V., & Kramberger, C. (2023). Metal and Metal Halogenide-Filled Single-Walled Carbon Nanotubes: Kinetics, Electronic Properties, Engineering the Fermi Level. Nanomaterials, 13(1), 180. https://doi.org/10.3390/nano13010180

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