Image of the Month

Image of the Month
posted May 1, 2016
may-iom

Figure 1: Atomic positions obtained by density functional calculations overlaid on an image created by a scanning tunneling microscope of D2O-covered step edges on Pt(553). STM image of D2O-covered step edges on Pt(553) [Tip type: cut and pull Pt/Ir; 4.5×4.5nm2; TSTM=25K; V=−1V , I= −9pA (Phys. Rev. Lett. 116, 136101)

The interaction of platinum with water plays a key role in (electro)catalysis. Herein, we describe a combined theoretical and experimental study that resolves the preferred adsorption structure of water wetting the Pt(111)-step type with adjacent (111) terraces. Double stranded lines wet the step edge forming water tetragons with dissimilar hydrogen bonds within and between the lines. Our results qualitatively explain experimental observations of water desorption and impact our thinking of solvation at the Pt electrochemical interface.

Credits:
Manuel J. Kolb1, Rachael G. Farber2, Jonathan Derouin2, Cansin Badan1, Federico Calle-Vallejo1, Ludo B. F. Juurlink1, Daniel R. Killelea2, and Marc T. M. Koper1 (Phys. Rev. Lett. 116, 136101)

1 Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA, Leiden, The Netherlands

2 Department of Chemistry and Biochemistry, Loyola University Chicago, Chicago, Illinois 60660, USA

Images and data graciously provided by Dan Killelea, Loyola University Chicago, Chicago, Illinois.

Microscope:
RHK PanScan Freedom Microscope

Control System:
RHK R9 Control System

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Image of the Month
posted April 1, 2016
iotm-apr2016

Figure 1: Adsorption of DDQT molecules on Au(111) in the intermediate coverage regime. STM image [set point 100 mV, 5 pA] of a large areafeaturing a finite-sized 2D crystal of DDQT with individual DDQT dimers in the vicinity (J. Phys. Chem. C 2015, 119, 26959−26967)

Charge transport in electronic applications involving molecular semiconductor materials strongly depends on the electronic properties of molecular-scale layers interfacing with external electrodes. In particular, local variations in molecular environments can have a significant impact on the interfacial electronic properties. In this study, we use scanning tunneling microscopy and spectroscopy to investigate the self-assembly regimes and resulting electronic structures of alkyl-substituted quaterthiophenes adsorbed on the Au(111) surface. We find that at dilute molecular concentrations, dimerized cis conformers were formed, while at higher concentrations corresponding to small fractions of a submonolayer, the molecular conformation converted to trans, with the molecules self-assembled into ordered islands. At approximately half-monolayer concentrations, the structure of the self-assembled islands transformed again showing a different type of the trans conformation and qualitatively different registry with the Au(111) lattice structure. Molecular distributions are observed to vary significantly due to variations in local molecular environments, as well as due to variations in the Au(111) surface reactivity. While the observed conformational diversity suggests the existence of local variations in the molecular electronic structure, significant electronic differences are found even with molecules of identical apparent adsorption configurations. Our results show that a significant degree of electronic disorder may be expected even in a relatively simple system composed of conformationally flexible molecules adsorbed on a metal surface, even in structurally well-defined self-assembled molecular layers.

Credits:
Dmitry A. Kislitsyn, Benjamen N. Taber, Christian F. Gervasi, Stefan C. B. Mannsfeld, Lei Zhang,
Alejandro L. Briseno, and George V. Nazin (J. Phys. Chem. C 2015, 119, 26959−26967)
Images and data graciously provided by George Nazin, University of Oregon, Eugene, Oregon.

Microscope:
RHK PanScan Freedom Microscope

Control System:
RHK Technology Control System

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Image of the Month
posted January 1, 2016
iotm-jan2016

Non-contact AFM images showing metal-organic coordination chains of platinum(II)dipyridinyl-tetrazine on the reconstructed Au(100) surface.  The model in the lower right panel is based on the molecular resolution image shown in the lower left.

Credits:
Daniel Skomski, Christopher D. Tempas, Kevin A. Smith, and Steven L. Tait*
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States

Microscope:
RHK Technology AFM/STM UHV 7500

Control System:
RHK Technology SPM 1000 Control System

Reference:
D. Skomski, C. D. Tempas, K. A. Smith, and S. L. Tait

“Redox-Active On-Surface Assembly of Metal-Organic Chains with Single-Site Pt(II),”
Journal of the American Chemical Society136, 9862-9865 (2014).
DOI: 10.1021/ja504850f

Abstract:
The formation and stabilization of well-defined transition-metal single sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts. Organic ligand coordination to produce a well-defined oxidation state in weakly reducing metal sites at surfaces, desirable for selective catalysis, has not been achieved. Here, we address this using metallic platinum interacting with a dipyridyl tetrazine ligand on a single crystal gold surface. X-ray photoelectron spectroscopy measurements demonstrate the metal−ligand redox activity and are paired with molecular-resolution scanning probe microscopy to elucidate the structure of the metal−organic network. Comparison to the redox-inactive diphenyl tetrazine ligand as a control experiment illustrates that the redox activity and molecular-level ordering at the surface rely on two key elements of the metal complexes: (i) bidentate binding sites providing a suitable square-planar coordination geometry when paired around each Pt, and (ii) redox-active functional groups to enable charge transfer to a well-defined Pt(II) oxidation state. Ligand-mediated control over the oxidation state and structure of single-site metal centers that are in contact with a metal surface may enable advances in higher selectivity for next generation heterogeneous catalysts.

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Image of the Month
posted December 1, 2015
iotm-dec2015

Figure 1: Clean H terminated Si 100 surface 100nm*100nm
Scanning parameters:
Sample bias: -3V;   Current:-0.45nA;  Scanning angle:45 deg; Integral gain: 200 m/As; Pixel: 1024*1024; Scanning speed: 476 nm/s

Preparing atomically clean samples are a primary requirement for developing patterned dopant devices based on hydrogen resist lithography.  The samples from this study are used to develop moderately low temperature silicon overgrowth to ensure epitaxial Si on Si growth.  The overall process involves, hydrogen lithography, phosphine dosing and subsequent dopant activation, and then silicon overgrowth to encapsulate the patterned devices.  Quality Si epitaxial overgrowth is essential to good local electronic properties for the encased atomic-scale phosphor-based donor devices.  The silicon (100) samples ( 4 mm x 10 mm ) were first chemically cleaned using  an RCA Piranha recipe and HF dipped to passivate the surface. The samples were then load locked into a UHV system for thermal processing. Thermal processing includes a couple of 1200 °C flashes (maintaining low -10 Torr pressure all the time) and a 1050 °C anneal for a few hours. The samples were then hydrogen terminated in situ with an atomic hydrogen source and moved to the Pan Scan STM chamber for RT imaging using the recent new design RHK all metal tip holder.  W polycrystalline tips were used.

Credits:
Images and data graciously provided by Richard Silver, NIST.

Microscope:
RHK PanScan Microscope

Control System:
RHK Technology Control System

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