Tip-enhanced Raman spectroscopy (TERS) has been rapidly improved over the past decade and opened up opportunities to study phonon properties of materials at the nanometer scale. In this Letter, we ...report on TERS of an ultrathin MoS2 flake on a nanostructured Au on silicon surface forming a two-dimensional (2D) crystal/plasmonic heterostructure. Au nanostructures (shaped in triangles) are prepared by nanosphere lithography, and then MoS2 is mechanically exfoliated on top of them. The TERS spectra acquired under resonance conditions at 638 nm excitation wavelength evidence strain changes spatially localized to regions as small as 25 nm in TERS imaging. We observe the highest Raman intensity enhancement for MoS2 on top of Au nanotriangles due to the strong electromagnetic confinement between the tip and a single triangle. Our results enable us to determine the local strain in MoS2 induced during heterostructure formation. The maximum frequency shift of E2g mode is determined to be (4.2 ± 0.8) cm–1, corresponding to 1.4% of biaxial strain induced in the MoS2 layer. We find that the regions of maximum local strain correspond to the regions of maximum topographic curvature as extracted from atomic force microscopy measurements. This tip-enhanced Raman spectroscopy study allows us to determine the built-in strain that arises when 2D materials interact with other nanostructures.
In this work, the thermoelectric (TE) properties of poly(3,4-ethylenedioxylthiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films at room temperature are studied. Different methods have been ...applied for tuning the TE properties: 1 super(st) addition of polar solvent, dimethyl sulfoxide (DMSO), into the PEDOT:PSS solution; 2 super(nd) post-treatment of thin films with a mixture of DMSO and ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF sub(4)). It is verified that DMSO post-treatment is more efficient than DMSO addition in improving the electrical conductivity with a trivial change in the Seebeck coefficient. The power factor is increased up to 30.1 mu W mK super(-2) for the film with DMSO post-treatment, while the optimized power factor by DMSO addition is 18.2 mu W mK super(-2). It is shown that both DMSO addition and post-treatment induce morphological changes: an interconnected network of elongated PEDOT grains is generated, leading to higher electrical conductivity. In contrast, for those films post-treated in the presence of EMIMBF sub(4), an interconnected network of short and circular PEDOT grains with increased polaron density is created, resulting in the improvement in the Seebeck coefficient and a concomitant compromise in the electrical conductivity. An optimized power factor of 38.46 mu W mK super(-2) is achieved at 50 vol% of EMIMBF sub(4), which is the highest reported so far for PEDOT:PSS thin films to our knowledge. Assuming a thermal conductivity of 0.17 W mK super(-1), the corresponding ZT is 0.068 at 300 K. These results demonstrate that post-treatment is a promising approach to enhance the TE properties of PEDOT:PSS thin films. Furthermore, ionic liquid, EMIMBF sub(4), shows the potential for tuning the TE properties of PEDOT:PSS thin films viaa more environmentally benign process.
We provide a critical review of the current state of the synthesis and applications of nano- and micro-tubes of layered graphitic carbon nitride. This emerging material has a huge potential for ...light-harvesting applications, including light sensing, artificial photosynthesis, selective photocatalysis, hydrogen storage, light-induced motion, membrane technologies, and can become a major competitor for such established materials as carbon and titania dioxide nanotubes. Graphitic carbon nitride tubes (GCNTs) combine visible-light sensitivity, high charge carrier mobility, and exceptional chemical/photochemical stability, imparting this material with unrivaled photocatalytic activities in photosynthetic processes, such as water splitting and carbon dioxide reduction. The unique geometric GCNT structure and versatility of possible chemical modifications allow new photocatalytic applications of GCNTs to be envisaged including selective photocatalysts of multi-electron processes as well as light-induced and light-directed motion of GCNT-based microswimmers. Closely-packed arrays of aligned GCNTs show great promise as multifunctional membrane materials for the light energy conversion and storage, light-driven pumping of liquids, selective adsorption, and electrochemical applications. These emerging applications require synthetic routes to GCNTs with highly controlled morphological parameters and composition to be available. We recognize three major strategies for the GCNT synthesis including templating, supramolecular assembling of precursors, and scrolling of nano-/microsheets, and outline promising routes for further progress of these approaches in the light of the most important emerging applications of GCNTs.
The current state of the synthesis and applications of nano- and micro-tubes of graphitic carbon nitride is critically reviewed.
The engineering of acetylenic carbon-rich nanostructures has great potential in many applications, such as nanoelectronics, chemical sensors, energy storage, and conversion, etc. Here we show the ...synthesis of acetylenic carbon-rich nanofibers via copper-surface-mediated Glaser polycondensation of 1,3,5-triethynylbenzene on a variety of conducting (e.g., copper, graphite, fluorine-doped tin oxide, and titanium) and non-conducting (e.g., Kapton, glass, and silicon dioxide) substrates. The obtained nanofibers (with optical bandgap of 2.51 eV) exhibit photocatalytic activity in photoelectrochemical cells, yielding saturated cathodic photocurrent of ca. 10 µA cm
(0.3-0 V vs. reversible hydrogen electrode). By incorporating thieno3,2-bthiophene units into the nanofibers, a redshift (ca. 100 nm) of light absorption edge and twofold of the photocurrent are achieved, rivalling those of state-of-the-art metal-free photocathodes (e.g., graphitic carbon nitride of 0.1-1 µA cm
). This work highlights the promise of utilizing acetylenic carbon-rich materials as efficient and sustainable photocathodes for water reduction.
This Perspective provides a critical summary of the current state of the art in the synthesis and properties of polyheptazine single-layer carbon nitride (SLCN). The summary combines the authors' ...research and literature reports on SLCN concerning the synthesis of single-layer polyheptazine sheets, light absorption and emission by SLCN, photochemical and photocatalytic properties of SLCN as well as examples of applications of SLCN sheets as "building blocks" in heterostructures with nanocrystalline semiconductors and metals. The Perspective is concluded with an outlook discussing the most promising directions for further studies and applications of SLCN and related composites.
This Perspective provides a critical summary of the current state of the art in the synthesis and properties of polyheptazine single-layer carbon nitride (SLCN).
It is believed that plasmon-excited electrons from Ag and Au nanostructures can induce photochemical reactions. However, the influence of heat generated by nanoparticle (NP) hotspots during light ...irradiation was not systematically studied yet. To evaluate the role of plasmonic heating, we performed a surface-enhanced Raman spectroscopy study of the photocatalytic conversion of 4-nitrobenzenthiol to 4-aminobenzenthiol by metal NPs with different compositions and shapes having localized surface plasmon resonances (LSPRs) spanning the whole visible range. Our collective results based on temperature-dependent studies and multiwavelength analyses show that contrary to the previous reports, the photocatalytic reaction is not only determined by the excitation of LSPRs or by the NP material (Ag or Au) but also drastically dependent on the plasmon-induced heating. This work has strong implications for the development and engineering of novel plasmonic and photonic applications where the role of localized temperature must be considered.
Abstract
Stability is one of the most important challenges facing material research for organic solar cells (OSC) on their path to further commercialization. In the high-performance material system ...PM6:Y6 studied here, we investigate degradation mechanisms of inverted photovoltaic devices. We have identified two distinct degradation pathways: one requires the presence of both illumination and oxygen and features a short-circuit current reduction, the other one is induced thermally and marked by severe losses of open-circuit voltage and fill factor. We focus our investigation on the thermally accelerated degradation. Our findings show that bulk material properties and interfaces remain remarkably stable, however, aging-induced defect state formation in the active layer remains the primary cause of thermal degradation. The increased trap density leads to higher non-radiative recombination, which limits the open-circuit voltage and lowers the charge carrier mobility in the photoactive layer. Furthermore, we find the trap-induced transport resistance to be the major reason for the drop in fill factor. Our results suggest that device lifetimes could be significantly increased by marginally suppressing trap formation, leading to a bright future for OSC.
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