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Graphene nanoribbons (GNRs), a quasi-one-dimensional form of graphene, have gained tremendous attention due to their potential for next-generation nanoelectronic devices. The chemical unzipping of carbon nanotubes is one of the attractive fabrication methods to obtain single-layered GNRs (sGNRs) with simple and large-scale production. The authors recently found that unzipping from double-walled carbon nanotubes (DWNTs), rather than single- or multi-walled, results in high-yield production of crystalline sGNRs. However, details of the resultant GNR structure, as well as the reaction mechanism, are not fully understood due to the necessity of nanoscale spectroscopy. In this regard, silver nanowire-based tip-enhanced Raman spectroscopy (TERS) is applied for single GNR analysis and investigated ribbon-to-ribbon heterogeneity in terms of defect density and edge structure generated through the unzipping process. The authors found that sGNRs originated from the inner walls of DWNTs showed lower defect densities than those from the outer walls. Furthermore, TERS spectra of sGNRs exhibit a large variety in graphitic Raman parameters, indicating a large variation in edge structures. This work at the single GNR level reveals, for the first time, ribbon-to-ribbon heterogeneity that can never be observed by diffraction-limited techniques and provides deeper insights into unzipped GNR structure as well as the DWNT unzipping reaction mechanism.

We report an efficient photo-induced covalent modification (PICM) of graphene by short-chain fatty acids (SCFAs) with an alkyl chain at the liquid-solid interface for spatially resolved chemical functionalization of graphene. Light irradiation on monolayer graphene under an aqueous solution of the SCFAs with an alkyl chain efficiently introduces sp(3)-hybridized defects, where the reaction rates of PICM are significantly higher than those in pure water. Raman and IR spectroscopy revealed that a high density of methyl, methoxy, and acetate groups is covalently attached to the graphene surface while it was partially oxidized by other oxygen-containing functional groups, such as OH and COOH. A greater downshift of the G-band in Raman spectra was observed upon the PICM with longer alkyl chains, suggesting that the charge doping effect can be controlled by the alkyl chain length of the SCFAs. The systematic research and exploration of covalent modification in SCFAs provide new insight and a potentially facile method for bandgap engineering of graphene.

We report an efficient photo-induced covalent modification (PICM) of graphene by short-chain fatty acids (SCFAs) with an alkyl chain at the liquid-solid interface for spatially resolved chemical functionalization of graphene. Light irradiation on monolayer graphene under an aqueous solution of the SCFAs with an alkyl chain efficiently introduces sp(3)-hybridized defects, where the reaction rates of PICM are significantly higher than those in pure water. Raman and IR spectroscopy revealed that a high density of methyl, methoxy, and acetate groups is covalently attached to the graphene surface while it was partially oxidized by other oxygen-containing functional groups, such as OH and COOH. A greater downshift of the G-band in Raman spectra was observed upon the PICM with longer alkyl chains, suggesting that the charge doping effect can be controlled by the alkyl chain length of the SCFAs. The systematic research and exploration of covalent modification in SCFAs provide new insight and a potentially facile method for bandgap engineering of graphene.

We report an efficient photo-induced covalent modification (PICM) of graphene by short-chain fatty acids (SCFAs) with an alkyl chain at the liquid-solid interface for spatially resolved chemical functionalization of graphene. Light irradiation on monolayer graphene under an aqueous solution of the SCFAs with an alkyl chain efficiently introduces sp(3)-hybridized defects, where the reaction rates of PICM are significantly higher than those in pure water. Raman and IR spectroscopy revealed that a high density of methyl, methoxy, and acetate groups is covalently attached to the graphene surface while it was partially oxidized by other oxygen-containing functional groups, such as OH and COOH. A greater downshift of the G-band in Raman spectra was observed upon the PICM with longer alkyl chains, suggesting that the charge doping effect can be controlled by the alkyl chain length of the SCFAs. The systematic research and exploration of covalent modification in SCFAs provide new insight and a potentially facile method for bandgap engineering of graphene.

A cyanine dye (PIC) was occluded into two 1D-nanopoporus Mg-containing aluminophosphates with different pore size (MgAPO-5 and MgAPO-36 with AFI and ATS zeolitic structure types, with cylindrical channels of 7.3 Å diameter and elliptical channels of 6.7 Å × 7.5 Å, respectively) by crystallization inclusion method. Different J-aggregates are photophysically characterized as a consequence of the different pore size of the MgAPO frameworks, with emission bands at 565 nm and at 610 nm in MgAPO-5 and MgAPO-36, respectively. Computational results indicate a more linear geometry of the J-aggregates inside the nanochannels of the MgAPO-36 sample than those in MgAPO-5, which is as a consequence of the more constrained environment in the former. For the same reason, the fluorescence of the PIC monomers at 550 nm is also activated within the MgAPO-36 channels. Owing to the strategic distribution of the fluorescent PIC species in MgAPO-36 crystals (monomers at one edge and J-aggregates with intriguing emission properties at the other edge) an efficient and one-directional antenna system is obtained. The unidirectional energy transfer process from monomers to J-aggregates is demonstrated by remote excitation experiments along tens of microns of distance.

A cyanine dye (PIC) was occluded into two 1D-nanopoporus Mg-containing aluminophosphates with different pore size (MgAPO-5 and MgAPO-36 with AFI and ATS zeolitic structure types, with cylindrical channels of 7.3 Å diameter and elliptical channels of 6.7 Å × 7.5 Å, respectively) by crystallization inclusion method. Different J-aggregates are photophysically characterized as a consequence of the different pore size of the MgAPO frameworks, with emission bands at 565 nm and at 610 nm in MgAPO-5 and MgAPO-36, respectively. Computational results indicate a more linear geometry of the J-aggregates inside the nanochannels of the MgAPO-36 sample than those in MgAPO-5, which is as a consequence of the more constrained environment in the former. For the same reason, the fluorescence of the PIC monomers at 550 nm is also activated within the MgAPO-36 channels. Owing to the strategic distribution of the fluorescent PIC species in MgAPO-36 crystals (monomers at one edge and J-aggregates with intriguing emission properties at the other edge) an efficient and one-directional antenna system is obtained. The unidirectional energy transfer process from monomers to J-aggregates is demonstrated by remote excitation experiments along tens of microns of distance.

A cyanine dye (PIC) was occluded into two 1D-nanopoporus Mg-containing aluminophosphates with different pore size (MgAPO-5 and MgAPO-36 with AFI and ATS zeolitic structure types, with cylindrical channels of 7.3 Å diameter and elliptical channels of 6.7 Å × 7.5 Å, respectively) by crystallization inclusion method. Different J-aggregates are photophysically characterized as a consequence of the different pore size of the MgAPO frameworks, with emission bands at 565 nm and at 610 nm in MgAPO-5 and MgAPO-36, respectively. Computational results indicate a more linear geometry of the J-aggregates inside the nanochannels of the MgAPO-36 sample than those in MgAPO-5, which is as a consequence of the more constrained environment in the former. For the same reason, the fluorescence of the PIC monomers at 550 nm is also activated within the MgAPO-36 channels. Owing to the strategic distribution of the fluorescent PIC species in MgAPO-36 crystals (monomers at one edge and J-aggregates with intriguing emission properties at the other edge) an efficient and one-directional antenna system is obtained. The unidirectional energy transfer process from monomers to J-aggregates is demonstrated by remote excitation experiments along tens of microns of distance.

A cyanine dye (PIC) was occluded into two 1D-nanopoporus Mg-containing aluminophosphates with different pore size (MgAPO-5 and MgAPO-36 with AFI and ATS zeolitic structure types, with cylindrical channels of 7.3 Å diameter and elliptical channels of 6.7 Å × 7.5 Å, respectively) by crystallization inclusion method. Different J-aggregates are photophysically characterized as a consequence of the different pore size of the MgAPO frameworks, with emission bands at 565 nm and at 610 nm in MgAPO-5 and MgAPO-36, respectively. Computational results indicate a more linear geometry of the J-aggregates inside the nanochannels of the MgAPO-36 sample than those in MgAPO-5, which is as a consequence of the more constrained environment in the former. For the same reason, the fluorescence of the PIC monomers at 550 nm is also activated within the MgAPO-36 channels. Owing to the strategic distribution of the fluorescent PIC species in MgAPO-36 crystals (monomers at one edge and J-aggregates with intriguing emission properties at the other edge) an efficient and one-directional antenna system is obtained. The unidirectional energy transfer process from monomers to J-aggregates is demonstrated by remote excitation experiments along tens of microns of distance.

A cyanine dye (PIC) was occluded into two 1D-nanopoporus Mg-containing aluminophosphates with different pore size (MgAPO-5 and MgAPO-36 with AFI and ATS zeolitic structure types, with cylindrical channels of 7.3 Å diameter and elliptical channels of 6.7 Å × 7.5 Å, respectively) by crystallization inclusion method. Different J-aggregates are photophysically characterized as a consequence of the different pore size of the MgAPO frameworks, with emission bands at 565 nm and at 610 nm in MgAPO-5 and MgAPO-36, respectively. Computational results indicate a more linear geometry of the J-aggregates inside the nanochannels of the MgAPO-36 sample than those in MgAPO-5, which is as a consequence of the more constrained environment in the former. For the same reason, the fluorescence of the PIC monomers at 550 nm is also activated within the MgAPO-36 channels. Owing to the strategic distribution of the fluorescent PIC species in MgAPO-36 crystals (monomers at one edge and J-aggregates with intriguing emission properties at the other edge) an efficient and one-directional antenna system is obtained. The unidirectional energy transfer process from monomers to J-aggregates is demonstrated by remote excitation experiments along tens of microns of distance.

Tip-enhanced Raman scattering (TERS) microscopy is a promising technique for use in surface analysis, allowing both topographic and spectroscopic information to be obtained simultaneously at a scale below 10 nm. One proposed method to further improve spatial resolution is the use of propagating surface plasmons as an excitation light source (i.e.,remote excitation). However, this requires a specialized tip that can only be fabricated via expensive procedures, such as electron-beam lithography. Here, we propose a new method for fabricating silver nanowire-based tips that are suitable for remote excitation-TERS, removing the need for such techniques. A silver nanowire was fixed onto a tungsten-tip using a micromanipulator, before gold nanoparticles were attached in a site-specific manner using AC-dielectrophoresis. All the processes were completed using an optical microscope in the ambient. The background intensities in TERS spectra were suppressed with remote excitation relative to the conventional excitation configuration, indicating an increase in TERS sensitivity.

Tip-enhanced Raman scattering (TERS) microscopy is a promising technique for use in surface analysis, allowing both topographic and spectroscopic information to be obtained simultaneously at a scale below 10 nm. One proposed method to further improve spatial resolution is the use of propagating surface plasmons as an excitation light source (i.e.,remote excitation). However, this requires a specialized tip that can only be fabricated via expensive procedures, such as electron-beam lithography. Here, we propose a new method for fabricating silver nanowire-based tips that are suitable for remote excitation-TERS, removing the need for such techniques. A silver nanowire was fixed onto a tungsten-tip using a micromanipulator, before gold nanoparticles were attached in a site-specific manner using AC-dielectrophoresis. All the processes were completed using an optical microscope in the ambient. The background intensities in TERS spectra were suppressed with remote excitation relative to the conventional excitation configuration, indicating an increase in TERS sensitivity.

Tip-enhanced Raman scattering (TERS) microscopy is a promising technique for use in surface analysis, allowing both topographic and spectroscopic information to be obtained simultaneously at a scale below 10 nm. One proposed method to further improve spatial resolution is the use of propagating surface plasmons as an excitation light source (i.e.,remote excitation). However, this requires a specialized tip that can only be fabricated via expensive procedures, such as electron-beam lithography. Here, we propose a new method for fabricating silver nanowire-based tips that are suitable for remote excitation-TERS, removing the need for such techniques. A silver nanowire was fixed onto a tungsten-tip using a micromanipulator, before gold nanoparticles were attached in a site-specific manner using AC-dielectrophoresis. All the processes were completed using an optical microscope in the ambient. The background intensities in TERS spectra were suppressed with remote excitation relative to the conventional excitation configuration, indicating an increase in TERS sensitivity.