Surface Studies by Scanning Tunneling Microscopy

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Surface Studies by Scanning Tunneling Microscopy G. Binnig, H. Rohrer, Ch. Gerber, and E. Weibel IBM Zurich Research Laboratory, 8803 Ruschlikon-ZH, Switzerland (Received by Phys. Rev. Lett. on 30th April, 1982) DOI: https://doi.org/10.1103/physrevlett.49.57 Presented by Tyler Salners, Preetha Sarkar, Devyn Shafer, and Jiayu Shen Physics 596 December 1st, 2017 University of Illinois at Urbana-Champaign Cover picture taken from the video: https://www.youtube.com/watch?v=excqxuwr1pi

Significance of Surface Science Characterization of surface structures is essential for the development of new materials Surface characteristics are typically different from bulk characteristics A few applications: Semiconductors: As electronic components get smaller, it becomes more important to understand nanoscale characteristics Quantum dots: Applications in solar energy, transistors, LEDs, medical imaging Solar Panels: Surface properties are paramount to optimizing efficiency https://www.sciencedaily.com/relea ses/2016/09/160928151119.htm Scanning tunneling microscope (STM) STM image of the image of Si(111)5x5 GaAs(110) surface. reconstructed surface http://www.andrew.cmu.edu/user/feenstra/stm/ Catalysis: Determining how and why catalytic reactions occur and designing surfaces for specific outcomes http://jqi.umd.edu/news/quantumbit/2014/01/20/quantum-dotsnanocrystals-packed-potential Graphene: Strong, light, flexible, transparent, and conductive; possible applications in electronics, energy, and medicine http://www.spaceflight.esa.int/impress/text/education/cata lysis/commercial.html https://phys.org/news/2016-10-scientistsgraphene-high-resistance-ozonation.html

Invented in 1982, Scanning Tunneling Microscopy offered scanned images of atoms on the surface of a sample at unprecedented levels of resolution (~2A horizontal and ~0.1A vertical) with an instrument much less susceptible to vibrational noise than its predecessor, the Topografiner. Binning and Rohrer won the Nobel Prize for STM in 1986. Surface Characterization Techniques, 1920s-1970s Technique Year Features Auger Electron Spectroscopy 1922 Composition Low-Energy Electron Diffraction (LEED) 1927 Surface lattice structure and its level of regularity/perfection Transmission Electron Microscopy 1931 Requires an ultrathin section of the material Field Emission Microscopy 1936 Requires a needle-shaped sample X-Ray Photoemission Spectroscopy 1954 Composition Scanning Probe Microscopy (Topografiner) 1972 Surface features with vertical resolution of ~30A and horizontal resolution of ~4000A

Principle of Operation of a Scanning Tunneling Microscope (STM) Metal tip scanning the surface at a constant tunnel current J T exp(-aφ 1/2 s) A=(4π/h)(2m) ½ =1.025A -1 ev -½ φ: average barrier height (work function) s: width of barrier (z-distance) Voltages applied to piezo elements P x,p y and P z map the surface topography directly R. H. Fowler and L. Nordheim, Proc. Roy. Soc. London, Ser. A 119,173 (1928); J. Frenkel, Phys. Rev. 36, 1604 (1930)

Principle of Operation of a Scanning Tunneling Microscope Theoretically, lateral resolution < 100A require tip radius ~100A Solid metal rods of 1mm diameter and ground 90 o tips. Overall tip radii ~1000A - 1μm Minitips and mini-spot-welding increase lateral resolution to up to 10A New feature: A highly sensitive tip Separation of true structures and work function mimicked structures, although can be done in principle, was not studied in detail

Resolution Capability of STM: CaIrSn 4 (110) Surfaces The Ir layers are very inert after solvent etching: good for the STM at moderate vacuum Data of its crystal structure were available in literature Weak and homogeneous contamination Height of steps: a few atoms Average spacing 6.7Å: consistent with crystallography (Mater. Res. Bull. 15, 799)

Resolution Capability of STM: Au (110) Surfaces Reconstruction of Au (110) surfaces was of interest Scanned at room temperature and 300, both after annealing at 600 a) Room temperature: smooth corrugation b) 300 : more abundant steps Reconstruction of Au (110) was controversial 2 1 reconstruction: favored by LEED (Surf. Sci. 77, 265, 283), but NOT observed by STM Distorted hexagonal topmost layer model? (Verh. Dtsch. Phys. Ges. 1, 278) Future study: combination of LEED and STM

Early Implications of Scanning Tunneling Microscopy The STM technique developed in this paper has orders of magnitude better resolution than previous scanning techniques (e.g., scanning electron microscopy). The method is non-destructive. The method has potential use in any field that uses microscopy. STM technique can, in principle, separate true structural features from work function-mimicked features. Work function profiles, however, weren t studied in detail, and rather were used to get an overall picture of the surface condition.

Critiques: Scientific Validity Developed better-suited tip to suppress vibrations Recognized possibility of work-function-mimicked structures and took measures to attenuate them Used smooth-surfaced materials for tests where results confirmed previous measurements (Ir(110) plane spacing and SEM-located growth spirals) and also demonstrated the ability to rule out theories of surface reconstruction in Au Did not really explain the details of modulating signals to rule out the variation in work function

Critiques: Importance This was the first paper with surface topography using STM. The authors verified that tunnel current depends strongly on barrier width. It was possible to see monoatomic step resolution. Precise measurement of corrugation resulted in better understanding of surface reconstructions. Broad impacts: the technique enables Detailed understanding of the microscopy of adsorbed molecules, Study of crystal growth, Confirmation of the fundamental aspects of tunneling, and Space-resolved tunneling spectroscopy.

Number of Citations 3189 Citations Year

Critiques: Accessibility Although it was probably necessary, the paper heavily referenced other literature, which at times made it a difficult read. The paper did not explicitly include some technical details, but it was in general easy even for non-experts to read to get a big picture of STM. Some terms were used without a clear definition or reference: work-functionmimicked, work function profile, etc. The reasons why Au was used were not explained in detail by the paper.

Summary The paper reports the first experimental results on surface topography in high resolution using STM, a technique that revolutionized the field of surface science, particularly with respect to the study of surface reconstruction. The introduction of a new type of scanning tip improved the resolution by several orders of magnitude, reduced vibrational impacts, and presented a non-destructive method of surface determination. The STM technique can, in principle, be used to separate true surface structures from those introduced by changes in work function. Topographies of CaIrSn 4 (110) surfaces and Au (110) surfaces were shown to demonstrate the capabilities of STM.