Structural Tunability and Diversity of Two-Dimensional Lead Halide Benzenethiolate
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Chemistry↗
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Results for “BENZENETHIOL”
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Phenol as a Tethering Group to Gold Surfaces: Stark Response and Comparison to Benzenethiol
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Diffusion-Assisted Formation Mechanism of Molecular Break Junctions: A First-Principles Study of Benzenethiolate on Au(111)
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charge transport↗
Time Domain Simulations of Chemical Bonding Effects in Surface-Enhanced Spectroscopy
We employ the atom-centered density-matrix propagation method to illustrate how time-dependent structural and conformational changes affect the electronic structure and derived spectroscopic properties of a prototypical finite metal cluster-bound π-conjugated organic, namely the Ag7-benzenethiol complex. We find that the calculated spectroscopic properties are dictated by large amplitude motion which controls the coupling between the aromatic ring of the molecule and the metal cluster. The simulated vibrational spectra of Ag7-benzenethiol are in accord with previous experiments which probe Raman scattering from benzenethiol adsorbed on silver surfaces.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Understanding the chemical contribution to the enhancement mechanism in SERS: Connection with Hammett parameters
The enhancement mechanism due to the molecule-surface chemical interaction in surface-enhanced Raman scattering (SERS) has been characterized using a theoretical approach based on time dependent density functional theory. This includes a systematic study of the chemical mechanism (CM) to the SERS enhancement for halogen substituted benzenethiols interacting with a silver cluster. Changing the halogen on benzenethiol enables us to systematically modulate interactions between the benzenethiol ring and the metal cluster. We observe a decrease in the CM enhancement factor with an increase in atomic number of the halogen for para- substitutions. For meta- substitutions, there is no such trend. However, the results scale linearly with the Hammett parameters for both meta and para halogens, which provides an important predictive tool for interpreting chemical enhancements. We also study the effect of solvation on the CM, showing that there is a systematic increase in enhancement with increasing solvent dielectric constant. As a result, the correlation of CM with other properties, such as the amount of charge transfer between adsorbate and metal, or the excitation energies of charge transfer states, is much less predictive than the Hammett parameter correlation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation with a Ni(PS) 2 Complex
Tetra-coordinate Ni II and Zn II complexes employing the PS chelates 2-(diphenylphosphanyl)benzenethiol (HL 1 ) and 2-(diisopropylphosphanyl)benzenethiol (HL 2 ) have been synthesized and characterized by spectroscopic, structural, and electrochemical methods. All complexes were screened for electrocatalytic activity for hydrogen evolution with acetic acid and hydrochloric acid and hydrogen oxidation in the presence of triethylamine. The nickel complex Ni(L 1 ) 2 (1) was found to reduce protons from external acids to generate hydrogen with a turnover frequency of 140 s–1 at an overpotential of 1.1 V and cleave dihydrogen using redox active base triethylamine (Et 3 N) with a turnover frequency of 23 s–1 at an overpotential of 0.33 V. Ni(L 2 ) 2 (3) was also found to be an active catalyst for dihydrogen oxidation, but inefficient for proton reduction due to inaccessible Ni (II/I) reduction in the potential window. Zn(L 1 ) 2 (2) and Zn(L 2 ) 2 (4) complexes were found to be inadequate for their electrocatalytic behaviour towards both the reactions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electrocatalytic syngas generation with a redox non-innocent cobalt 2-phosphinobenzenethiolate complex
A cobalt complex supported by the 2-(diisopropylphosphaneyl)benzenethiol ligand was synthesized and its electronic structure and reactivity were explored.
Orchanian, Nicholas M.↗
Density functional theory approach to gold-ligand interactions: Separating true effects from artifacts
Donor-acceptor interactions are notoriously difficult and unpredictable for conventional density functional theory (DFT) methodologies. This work presents a reliable computational treatment of gold-ligand interactions of the donor-acceptor type within DFT. These interactions require a proper account of the ionization potential of the electron donor and electron affinity of the electron acceptor. This is accomplished in the Generalized Kohn Sham framework that allows one to relate these properties to the frontier orbitals in DFT via the tuning of range-separated functionals. A donor and an acceptor typically require different tuning schemes. This poses a problem when the binding energies are calculated using the supermolecular method. A two-parameter tuning for the monomer properties ensures that a common functional, optimal for both the donor and the acceptor, is found. A reliable DFT approach for these interactions also takes into account the dispersion contribution. The approach is validated using the water dimer and the (HAuPH{sub 3}){sub 2} aurophilic complex. Binding energies are computed for Au{sub 4} interacting with the following ligands: SCN{sup −}, benzenethiol, benzenethiolate anion, pyridine, and trimethylphosphine. The results agree for the right reasons with coupled-cluster reference values.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Vibrational Coupling
By homing in on the distribution patterns of electrons around an atom, a team of scientists with Berkeley Lab's Molecular Foundry showed how certain vibrations from benzenethiol cause electrical charge to "slosh" onto a gold surface (left), while others do not (right). The vibrations that cause this "sloshing" behavior yield a stronger SERS signal.
74 ATOMIC AND MOLECULAR PHYSICS↗
Self-assembled large Au nanoparticle arrays with regular hot spots for SERS.
The cost-effective self-assembly of 80 nm Au nanoparticles (NPs) into large-domain, hexagonally close-packed arrays for high-sensitivity and high-fidelity surface-enhanced Raman spectroscopy (SERS) is demonstrated. These arrays exhibit specific optical resonances due to strong interparticle coupling, which are well reproduced by finite-difference time-domain (FDTD) simulations. The gaps between NPs form a regular lattice of hot spots that enable a large amplification of both photoluminescence and Raman signals. At smaller wavelengths the hot spots are extended away from the minimum-gap positions, which allows SERS of larger analytes that do not fit into small gaps. Using CdSe quantum dots (QDs) a 3-5 times larger photoluminescence enhancement than previously reported is experimentally demonstrated and an unambiguous estimate of the electromagnetic SERS enhancement factor of {approx}10{sup 4} is obtained by direct scanning electron microscopy imaging of QDs responsible for the Raman signal. Much stronger enhancement of {approx}10{sup 8} is obtained at larger wavelengths for benzenethiol molecules penetrating the NP gaps.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Plasmonic hybrid core-shell (HyCoS) AgPt NP template hybridized with GQDs for SERS enhancement of 4-MBA and BT
Surface-enhanced Raman spectroscopy (SERS) is an attractive vibrational spectroscopic technique that can enable a non-destructive and ultra-sensitive detection down to the single-molecule level. Herein, a novel hybrid SERS platform is developed based on hybrid core-shell (HyCoS) AgPt nanoparticles (NPs) and graphene quantum dots (GQDs) for the enhancement of Raman vibration of 4-mercaptobenzoic acid (4-MBA) and benzenethiol (BT). The unique design of HyCoS AgPt NPs induces strong electromagnetic mechanism (EM) enhancement through the amplification of electromagnetic fields by the excitation of high-density surface plasmons and hot spots. Superior localized surface plasmon resonance (LSPR) is generated by the AgPt core-shell and background Ag NP coupling, which is systematically investigated by the optical properties and FDTD simulations. The background Ag NPs can further increase the coverage of metallic NPs, leading to higher-density hot spots and enhanced SERS response. At the same time, GQDs can provide plentiful accessible edges for the charge transfer to the HOMO and LUMO of 4-MBA and BT based on the chemical mechanism (CM) enhancement. The mixing approach of GQDs and target molecules on the HyCoS AgPt NPs can significantly amplify the Raman signals via the strong adsorption of probe molecules by the π – π interaction. The enhancement factors of proposed SERS platform can reach ~107 and ~105 for the 4-MBA and BT respectively.
36 MATERIALS SCIENCE↗
Near IR Scanning Angle Total Internal Reflection Raman Spectroscopy at Smooth Gold Films
Total internal reflection (TIR) Raman and reflectivity spectra were collected for nonresonant analytes as a function of incident angle at sapphire or sapphire/smooth 50 nm gold interfaces using 785 nm excitation. For both interfaces, the Raman signal as a function of incident angle is well-modeled by the calculated interfacial mean square electric field (MSEF) relative to the incident field times the thickness of the layer being probed in the Raman measurement (D{sub RS}). The Raman scatter was reproducibly enhanced at the interface containing a gold film relative to the sapphire interface by a factor of 4.3–4.6 for aqueous pyridine or 2.2–3.7 for neat nitrobenzene, depending on the analyzed vibrational mode. The mechanism for the increased Raman signal is the enhanced MSEF at incident angles where propagating surface plasmons are excited in the metal film. The background from the TIR prism was reduced by 89–95% with the addition of the gold film, and the percent relative uncertainty in peak area was reduced from 15 to 1.7% for the 1347 cm–1 mode of nitrobenzene. Single monolayers of benzenethiol (S/N = 6.8) and 4-mercaptopyridine (S/N = 16.5) on gold films were measured by TIR Raman spectroscopy with 785 nm excitation (210 mW) without resonant enhancement in 1 min.
36 MATERIALS SCIENCE↗
Crystalline 1D Coordination Polymer Inhibitor Layer Leads to Vertical Sidewalls in Selectively Deposited ZnO on Nanoscale Patterns
Area-selective atomic layer deposition (AS-ALD) is a promising technique for the fabrication of next-generation nanoelectronics. There are two main challenges in AS-ALD: (1) achieving high selectivity of deposition on the growth regions, and (2) preventing mushrooming of the growth material onto the nongrowth regions and achieving well-defined interfaces. In this work, we use benzenethiol (BT) as an inhibitor in the selective deposition of ZnO on SiO 2 in the presence of copper with and without a native oxide (Cu/CuO x ). We observe that BT forms a monolayer on the Cu surface and a Cu-thiolate multilayer structure on CuO x . Using grazing incidence X-ray diffraction combined with simulations, we find that the multilayer structure is crystalline and composed of 1D coordination polymers of Cu-thiolate. Here, using ellipsometry and X-ray photoelectron spectroscopy, we show that the BT consumes the entirety of the CuO x during multilayer formation, allowing the multilayer thickness to be tuned by the thickness of the original oxide. Both the monolayer BT and the multilayer BT prove to be effective inhibitors of ZnO ALD, blocking nearly 500 ALD cycles, which is more than twice that achieved with other thiol inhibitors. Finally, we demonstrate that the multilayer structure can prevent mushrooming of the ALD material onto the nongrowth surface of nanoscale patterns, creating vertical sidewalls with well-defined material interfaces and providing excellent pattern transfer, even for a relatively thick deposited film. As such, these results demonstrate that BT is not only an effective inhibitor but also that its ability to form tunable multilayers makes it well-suited for highly precise nanopatterning applications.
Layers↗
Lithography-free approach to highly efficient, scalable SERS substrates based on disordered clusters of disc on pillar structures
We present a lithography-free technological strategy that enables fabrication of large area substrates for surface-enhanced Raman spectroscopy (SERS) with excellent performance in the red to NIR spectral range. Our approach takes advantage of metal dewetting as a facile means to create stochastic arrays of circular patterns suitable for subsequent fabrication of plasmonic disc-on-pillar (DOP) structures using a combination of anisotropic reactive ion etching (RIE) and thin film deposition. Consistent with our previous studies of individual DOP structures, pillar height which, in turn, is defined by the RIE processing time, has a dramatic effect on the SERS performance of stochastic arrays of DOP structures. Our computational analysis of model DOP systems confirms the strong effect of the pillar height and also explains the broadband sensitivity of the implemented SERS substrates. Our Raman mapping data combined with SEM structural analysis of the substrates exposed to benzenethiol solutions indicates that clustering of shorter DOP structures and bundling of taller ones is a likely mechanism contributing to higher SERS activity. Nonetheless, bundled DOP structures appeared to be consistently less SERS-active than vertically aligned clusters of DOPs with optimized parameters. The latter are characterized by average SERS enhancement factors above 10^7.
field enhancement↗
Modulating the optoelectronic properties of hybrid Mo-thiolate thin films
In this study, hybrid MoS 2 -based molybdenum thiolate thin films with selected organic motifs are grown using molecular layer deposition (MLD), allowing for tunable optoelectronic film properties. The thin films are deposited at 170°C using the metal precursor molybdenum hexacarbonyl and one of the three organic precursors: 1,2-ethanedithiol, 1,4-butanedithiol, and 1,4-benzenedithiol. The resulting Mo-ethanethiolate, Mo-butanethiolate, and Mo-benzenethiolate films show saturating growth with a growth per cycle of 1.2, 1.0, and 1.5 Å/cycle, respectively. Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy, Raman spectroscopy, x-ray absorption spectroscopy, and x-ray diffraction are used to characterize the as-deposited films. Results show that by changing the organic precursor, the film composition as well as the optical and electronic properties can be tuned. The Mo-thiolate films grown with benzenedithiol exhibit the lowest resistivity, which at 12 mΩ cm is ~400 times more conductive than Mo-thiolates grown with aliphatic organic linkers. All three backbone chemistries of the Mo-thiolates show an optical bandgap between 2.3 and 2.4 eV and mild photoconductivity response. The MLD of these Mo-thiolate films demonstrates the synthesis of transition metal-organosulfur thin films with tunable properties.
36 MATERIALS SCIENCE↗
Surface-Enhanced Raman Scattering (SERS) Studies of Disc-on-Pillar (DOP) Arrays: Contrasting Enhancement Factor with Analytical Performance
The use of nanomachining methods capable of reproducible construction of nano-arrayed devices have revolutionized the field of plasmonic sensing by the introduction of a diversity of rationally engineered designs. Significant strides have been made to fabricate plasmonic platforms with tailored interparticle gaps to improve their performance for surface-enhanced Raman scattering (SERS) applications. Over time, a dichotomy has emerged in the implementation of SERS for analytical applications, the construction of substrates, optimization of interparticle spacing as a means to optimize electromagnetic field enhancement at the localized surface plasmon level, and the substrate sensitivity over extended areas to achieve quantitative performance. Here, we assessed the enhancement factor of plasmonic Ag/SiO 2 /Si disc-on-pillar (DOP) arrays of variable pitch with its analytical performance for quantitative applications. Experimental data were compared with those from finite-difference time-domain (FDTD) simulations used in the optimization of the array dimensions. A self-assembled monolayer (SAM) of benzenethiol rendered highly reproducible signals (RSD ~4–10%) and SERS substrate enhancement factor (SSEF) values in the orders of 10 6 –10 8 for all pitches. Furthermore, spectra corresponding to rhodamine 6G (R6G) and 4-aminobenzoic acid demonstrated the advantages of using the more densely packed DOP arrays with a 160 nm pitch (gap= 40 nm) for quantitation in spite of the strongest SSEF was attained for a pitch of 520 nm corresponding to a 400 nm gap.
36 MATERIALS SCIENCE↗
Plasmonic hybrid core-shell (HyCoS) AgPt NP template hybridized with GQDs for SERS enhancement of 4-MBA and BT
Surface-enhanced Raman spectroscopy (SERS) is an attractive vibrational spectroscopic technique that can enable a non-destructive and ultra-sensitive detection down to the single-molecule level. Herein, a novel hybrid SERS platform is developed based on hybrid core-shell (HyCoS) AgPt nanoparticles (NPs) and graphene quantum dots (GQDs) for the enhancement of Raman vibration of 4-mercaptobenzoic acid (4-MBA) and benzenethiol (BT). The unique design of HyCoS AgPt NPs induces strong electromagnetic mechanism (EM) enhancement through the amplification of electromagnetic fields by the excitation of high-density surface plasmons and hot spots. Superior localized surface plasmon resonance (LSPR) is generated by the AgPt core-shell and background Ag NP coupling, which is systematically investigated by the optical properties and FDTD simulations. The background Ag NPs can further increase the coverage of metallic NPs, leading to higher-density hot spots and enhanced SERS response. At the same time, GQDs can provide plentiful accessible edges for the charge transfer to the HOMO and LUMO of 4-MBA and BT based on the chemical mechanism (CM) enhancement. The mixing approach of GQDs and target molecules on the HyCoS AgPt NPs can significantly amplify the Raman signals via the strong adsorption of probe molecules by the π–π interaction. The enhancement factors of proposed SERS platform can reach ~10 7 and ~10 5 for the 4-MBA and BT respectively.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Nanopillars array for surface enhanced Raman scattering
The authors present a new class of surface-enhanced Raman scattering (SERS) substrates based on lithographically-defined two-dimensional rectangular array of nanopillars. Two types of nanopillars within this class are discussed: vertical pillars and tapered pillars. For the vertical pillars, the gap between each pair of nanopillars is small enough (< 50 nm) such that highly confined plasmonic cavity resonances are supported between the pillars when light is incident upon them, and the anti-nodes of these resonances act as three-dimensional hotspots for SERS. For the tapered pillars, SERS enhancement arises from the nanofocusing effect due to the sharp tip on top. SERS experiments were carried out on these substrates using various concentrations of 1,2 bis-(4-pyridyl)-ethylene (BPE), benzenethiol (BT) monolayer and toluene vapor. The results show that SERS enhancement factor of over 0.5 x 10{sup 9} can be achieved, and BPE can be detected down to femto-molar concentration level. The results also show promising potential for the use of these substrates in environmental monitoring of gases and vapors such as volatile organic compounds.
36 MATERIALS SCIENCE↗