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While the power conversion efficiency (PCE) of colloidal quantum dot (CQD) solar cells can reach > 10%, the major obstacle for charge extraction and energy loss in such devices is the presence of surface trap sites within CQDs. In this work, highly trap-passivated PbS CQDs were developed using a novel iodide based ligand, 1-propyl-2,3-dimethylimidazolium iodide (PDMII). We examined the effects of PDMII on the surface quality of PbS-CQDs and compared them with TBAI, which is the best-selling iodide based ligand. By using PDMII, improved surface passivation with reduced sub-bandgap trap-states compared to TBAI was achieved. The reduced trap density resulted in enhanced charge extraction with diminished energy loss (0.447 eV) in the devices. Solar cell devices using our PDMII based CQDs displayed high PCE and air stability. The certified PCE of our PDMII based devices reached 10.89% and was maintained at 90% after 210 days of air storage. [ABSTRACT FROM AUTHOR]

Although various applications extensively utilize polymer-assisted graphene transfer step, the role of residual polymer on graphene was not well-understood. Here, we report the effect of poly (methyl methacrylate) (PMMA) on chemical vapor deposition-grown hexagonal graphene via Raman spectroscopy. Analysis of bare-, PMMA-covered supported, and PMMA-covered suspended graphene exhibits that their G and 2D band positions are progressively downshifted in that order. Mapping of spatial G and 2D band shifts into doping and strain contributions shows that PMMA residue exerts moderate 0.15% tensile strain on graphene/substrate, as compared to that of bare graphene. During this tensile strain, residual PMMA-covered graphene maintains its doping level as much as bare graphene does. [ABSTRACT FROM AUTHOR]

Twisted bilayer graphene (tBLG) provides an opportunity to control the optoelectronic properties of graphene owing to the relative orientation ( θ )-induced van Hove singularities (vHs). However, how different environments affect vHs behaviors of various tBLGs and their Raman resonance window is not clear. A study of the optical vHs properties of tBLGs on a quartz substrate, prepared by chemical vapor deposition, was carried out using simultaneous reflection and Raman imaging techniques according to the presence of ubiquitous residual amorphous carbon (RAC). The results show that the presence of RAC exhibits a narrower vHs peak width and resonance Raman windows of tBLG as compared to that without RAC, due to the absence of charge-inhomogeneous interactions from bare substrate. In addition, the background-subtracted vHs peak reflectances from various θ values at a specific laser energy are proportional to the measured G-band enhancement factor (GEF). The comparison reveals the detailed optical and Raman resonance windows of various tBLGs in both environments. Extension of the approach to twisted fewlayer graphenes reveals the different vHs peak behaviors including broadening, intensification, and splitting governed by θ- , along with layer number-dependent band structure hybridization. [ABSTRACT FROM AUTHOR]

Few atom thick, twisted bilayer graphene (tBLG) possesses a rotation angle (θ) dependent van Hove singularity (vHs). Fine-tuning vHs serves a potential method to enhance charge transfer (CT) in surface enhanced Raman spectroscopy. This study shows that tBLG having a specific θ promotes as high as a 1.7 times enhancement of the Raman signals of copper phthalocyanine (CuPc) as compared to that caused by single layer graphene (SLG). The results of a combination of reflection imaging spectroscopy and widefield Raman provide spatial and spectral information about both tBLG with θ ranging from 10.9 to 13.7° and the corresponding vHs. Comparison of Raman spectra of CuPc in presence and absence of tBLG demonstrates that a significant enhancement of certain CuPc vibrational modes occurs when the underlying tBLG possesses a θ = 12.2°, showing as high as 6.8 and 1.7 times enhancements of certain vibrational mode as compared to those of CuPc on bare and SLG substrates, respectively. Theoretical calculations indicate that a match between the energies of vHs of tBLG with those of frontier orbitals of CuPc facilitates CT from the distant SLG to CuPc. [Display omitted] [ABSTRACT FROM AUTHOR]

Although solvent governed stability, selection and optical behavior of single walled carbon nanotubes (SWNTs) brought about by using specialized surfactants have importance in relation to various optoelectronic and biological applications, their origins and solvatochromism have not been thoroughly explored owing to the lack of ideal surfactant dispersing SWNTs. We show that solvent driven SWNT selection and solvatochromism occurs in SWNTs wrapped by two flavin derivatives in solvents with dielectric constants (ε) ranging from 2.3 to 80.4. Flavin-SWNT nanocomposite dispersions exhibit near-armchair and chirality-specific enrichment in lower ε aromatic solvents, and those with broader chirality selectivity are formed in higher ε solvents. Those trends are also observed by controlling flavin concentration. Consideration of optical spectra provides relative quantum yields of flavin-SWNT in each solvent, showing toluene and p -xylene dispersions as best owing to highly individualized SWNT. The selectivities and relative stabilities of the flavin-SWNT nanoconjugates are associated with the solubility parameter (δ), which controls the respective morphology of the side chains and the relative Gibbs energies of the nanoconjugates relative to those of the free flavin and SWNTs. Differences between δ of side chains vs. the media results in extended and collapsed side chain conformations in respective lower and higher ε solvents, leading to diameters (d t) selection of SWNT owing to diameter modulation of the isoalloxazine assembly. In addition, with increasing ε optical transitions of flavin/SWNT exhibit lower bathochromic shifts owing to a passivating role played by the isoalloxazine that does not take place with other surfactants. The results suggest new guidelines for the design of good SWNT dispersions that take into consideration self-association of the surfactant, conformations of side chains and the nature of the solvent. [Display omitted] [ABSTRACT FROM AUTHOR]

Facile construction of graphene nanostructures are potentially important for fundamental studies and various applications owing to its transparency and mechanical strength. Here we found that focused laser irradiation of a graphene/entrapped water/hydrophobic substrate leads to vaporization of entrapped water and consequent formation of graphene nanostructures. Graphene mechanically exfoliated on a hydrophobicized Si substrate was served as a transformable and impermeable nanocontainer in which water anisotropically and slowly diffuses from the weak edges into the van der Waals (vdW)-coupled interstitial volume between graphene and the substrate. Time-lapsed Raman mappings show that water entrapment promotes progressive lowering of the frequencies of the G and 2D bands of graphene and exhibits slower diffusion owing to vdW decoupling of substrate-induced doping and biaxial strain of graphene with hydrophobic substrate. Moreover, vaporized entrapped water promotes nanostructures by graphene sliding and bulging actions. This methodology represents viable approach to produce nanostructures from two dimensional materials. [Display omitted] [ABSTRACT FROM AUTHOR]

Despite the many advances that have been made in using anionic surfactants to disperse and sort single-walled carbon nanotubes (SWNTs) for optoelectronic applications, one-pot methods for deposition of SWNTs in a diameter (d t) and position controlled manner from as-dispersed sample are essential. Here, we designed and prepared flavin-containing self-assembled monolayers (flavin-SAMs) that can be used to assemble d t -selective individualized SWNT networks directly from SWNT dispersions by using the widely-used anionic surfactant. For a given glass substrate, the dimethallylsilane-linked azide, along with surface immobilization was employed to have Click reaction with terminal acetylene tethered to flavin group known to have strong affinity with SWNT. As demonstrated by atomic force microscopy and other methods, along successful assembly of individualized networks, the SWNTs are either fully or partially wrapped in a d t selective manner by isoalloxazine moieties tethered to the surface, displaying Langmuir isotherm adsorption behaviors in a dipping method dependent manner. The assembled SWNT network secures photoluminescence and electrical conductivity albeit its intimacy to underlying substrate and near monolayer coverage of SWNT network, respectively, and, furthermore, preferentially takes place on flavin-SAM over hydrophobic surface. Functional self-assembled monolayer captures single-walled carbon nanotube network with diameter selectivity from as-dispersed suspension. Image 1 [ABSTRACT FROM AUTHOR]

Abstract High-end applications of single-walled carbon nanotube (SWNT) require detailed understanding of their binding affinity (K d) with surfactants. Here, we quantitatively determined the comprehensive K d and aggregation number (γ) of nine nonionic and anionic surfactants according to SWNT chirality. Photoluminescence (PL)-based titration using flavin mononucleotide (FMN)-SWNT complexes showing the largest redshifted optical transition enabled quantitative comparison of the surfactants and displayed distinct first and second regimes which correspond to partial and full replacements of FMN, respectively. Especially, the second transition exhibited sigmoidal PL change whose middle point denoted by the inverse of K d slightly differs from critical micelle concentration of surfactant alone, depending on its functional groups. Moreover, nonionic surfactants displayed larger K d and lower γ values than the anionic did. Specifically, K d values between Pluronic F108 and sodium dodecyl sulfonate differ by four orders of magnitude. Such differences were rationalized in terms of the occupied volume of the micelle based on the hydrodynamic volume and γ. During the replacement, K d and γ were affected by the degree of surfactant rearrangement induced by aging process, leading to more stable complex. Scaling the interactions between surfactant and SWNT provides useful guidelines to design novel SWNT sorting method using more than two surfactants. Graphical abstract Image 1 [ABSTRACT FROM AUTHOR]

When the width of a graphene nanoribbon (GNR) is only a few nanometers, it possesses semiconducting properties that enable various high-end electronic applications. In this study, we report that the dense and stable dispersion of a natural graphite formed using flavin mononucleotide (FMN) as a surfactant produces GNRs as small as 10 nm in width. High-resolution transmission electron microscopy reveals GNRs with various widths, along with a graphene flake containing straight-edged GNRs and cuts, depending on substrate treatments. Such nanoribbon formation originates from sonochemical graphene unzipping with a one-dimensional FMN supramolecular ribbon as a template. Raman spectroscopy demonstrates the universal intensity ratio of D over D′ bands near 4, supporting formation of continuous edge defect. Thermal annealing enhances the optical contrast and van der Waals interactions of the graphene film, resulting in increased conductivity compared to the as-prepared graphene film, which is also better than that of reduced graphene oxide. [ABSTRACT FROM AUTHOR]