The extreme instability and strong chemical activity of carbyne, the infinite sp 1 hybridized carbon chain, are responsible for its low possibility to survive at ambient conditions. Therefore, much less has been possible to explore about carbyne as compared to other novel carbon allotropes like fullerenes, nanotubes and graphene. Although end-capping groups can be used to stabilize a carbon chain, length limitation is still a barrier for its actual production, and even more for applications. Here, we report on a novel route for bulk production of record long acethylenic linear carbon chains protected by thin double-walled carbon nanotubes. A corresponding extremely high Raman band is the first proof of a truly bulk yield formation of very long arrangements, which is unambiguously confirmed by transmission electron microscopy. Our production establishes a way to exceptionally long stable carbon chains, and an elegant forerunner towards the final goal of a bulk production of essentially infinite carbyne.Different kinds of allotropes can be formed from elemental carbon due to its sp n hybridization 1 . 1 arXiv:1507.04896v2 [cond-mat.mtrl-sci]
Ultra long linear carbon chains of more than 6000 carbon atoms have recently been synthesized within doublewalled carbon nanotubes, and they show a promising new route to one-atom-wide semiconductors with a direct band gap. Theoretical studies predicted that this band gap can be tuned by the length of the chains, the end groups, and their interactions with the environment. However, different density functionals lead to very different values of the band gap of infinitely long carbyne. In this work, we applied resonant Raman excitation spectroscopy with more than 50 laser wavelengths to determine for the first time the band gap of long carbon chains encapsulated inside DWCNTs. The experimentally determined band gaps ranging from 2.253 to 1.848 eV follow a linear relation with Raman frequency. This lower bound is the smallest band gap of linear carbon chains observed so far. The comparison with experimental data obtained for short chains in gas phase or in solution demonstrates the effect of the DWCNT encapsulation, leading to an essential downshift of the band gap. This is explained by the interaction between the carbon chain and the host tube, which greatly modifies the chain's bond length alternation. arXiv:1705.02259v2 [cond-mat.mtrl-sci]
Recently the novel system of linear carbon chains inside double-walled carbon nanotubes has extended the length of sp1 hybridized carbon chains from 44 to thousands of atoms [Shi et al., Nat. Mater. 15, 634 (2016)]. The optoelectronic properties of these ultralong chains are poorly described by current theoretical models, which are based on short chain experimental data and assume a constant environment. As such, a physical understanding of the system in terms of charge transfer and van der Waals interactions is widely missing. We provide a reference for the intrinsic Raman frequency of polyynes in vacuo and explicitly describe the interactions between polyynes and carbon nanotubes. We find that van der Waals interactions strongly shift this frequency, which has been neither expected nor described for other intramolecular C-C stretching vibrations. As a consequence of charge transfer from the tube to the chain, the Raman response of long chains is qualitatively different from the known phonon dispersion of polymers close to the Γ point. Based on these findings we show how to correctly interpret the Raman data, considering the nanotube's properties. This is essential for its use as an analytical tool to optimize the growth process for future applications
We studied the effect of varying sonication and centrifugation parameters on double-walled carbon nanotubes (DWCNT) by measuring optical absorption and photoluminescence (PL) of the samples. We found that by using a low sonication intensity before applying density gradient ultracentrifugation (DGU), only inner tube species with a diameter ⩽0.8 nm can be identified in absorption measurements. This is in stark contrast to the result after sonicating at higher intensities, where also bigger inner tubes can be found. Furthermore, by comparing PL properties of samples centrifugated either with or without a gradient medium, we found that applying DGU greatly enhances the PL intensity, whereas centrifugation at even higher speeds but without a gradient medium results in lower intensities. This can be explained by extraction of inner tubes from their host outer tubes in a two-stage process: the different shearing forces from the sonication treatments result in some DWCNT to be opened, whereas others stay uncut. A subsequent application of DGU leads to the extraction of the inner tubes or not if the host nanotube stayed uncut or no gradient medium was used. This work shows a pathway to avoid this phenomenon to unravel the intrinsic PL from inner tubes of DWCNT.
A highly selective enhancement of the optical response of the inner tubes of double‐walled carbon nanotubes has been identified upon transformation of the residual C atoms inside the hollow core to linear carbon chains (LCC). By varying the growth conditions and using standardized suspensions, it has been observed that this optical response depends sensitively on the tube diameter and LCC growth yield. It is reported how the formation of LCC by postsynthesis annealing at 1400 °C leads to an increase of the photoluminescence (PL) signal of the inner tubes up to a factor of 6 for tubes with (8,3) chirality. This behavior can be attributed to a local charge transfer from the inner tubes to the carbon chains, counterbalancing quenching mechanisms induced by the outer tubes. These findings provide a viable pathway to enhance the low PL quantum yield of double‐walled carbon nanotubes and proof the capability of inner tubes to exhibit photoluminescence.
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