Supplemental Material
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Introduction: Supplemental Material

Surface science underpins much of the science behind heterogeneous catalysis and nanotechnology. The purpose of these supplemental pages is to explore further some of the applications of surface science as well as some of the web-based resources that exist. Hopefully you will find that this material enhances the learning experience of my textbook as well as providing you the opportunity to delve further into those topics that you find of interest.

A good place to start is to surf some of the sites of organization involved in Catalysis and Nanoscience. This is why I've created a page of useful links to societies involved in these areas.

You can learn about the history of catalysis from the North American Catalysis Society. You might also like to check out the very fine Introduction to Heterogeneous Catalysis site of Per Stoltze.

Or maybe you would like to Explore the Nanoworld with the help of this U of Wisconsin-Madison website. Oder nimm doch ein NanoReisen auf Deutsch or in English. Learn how to build your own scanning tunneling microscope.

An introduction to nanoscience from Prof. Vicki Colvin can be found here.

There's lots more to discover under these links:

Educational Sites in Surface Science, Nanotechnology and Catalysis

Web Resources in Surface Science, Nanotechnology and Catalysis

Journals covering Surface Science, Nanotechnology and Catalysis

Labs working in Surface Science, Nanotechnology and Catalysis

Chemistry, Physics and Catalysis Societies

Dynamics of Gas-Surface Interactions

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Chapter 1. Bulk & Surface Structure

Interest in graphene is generated mainly by its structure: a single layer thick, so strong, what's a Dirac point? The 2010 Nobel Prize in Physics honors the work of Andre Geim and Konstantin Novoselov for "for groundbreaking experiments regarding the two-dimensional material graphene."

Here is more information on the crystal planes of semiconductors.

3D solid-state crystal models.

Porous solids can be formed by etching. Learn more about etching to produce porous silicon.

Center for Atomic-scale Material Design The Lundbeck Foundation's Center for Atomic-scale Materials Design aims at developing electronic structure theory to understand the properties of materials and use the insight to design new functional nanostructures.

The Open Surface Structure Database (oSSD) (an open access version of the NIST Surface Structure Database) is available here.

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Chapter 2. Experimental Probes of Surface & Adsorbate Structure

The scanning tunnelling microscope or STM has lead to a revolution in surface science. Indeed, it has ushered in the age of nanoscience and nanotechnology. Nonetheless this remarkable instrument is amazingly simple and you can even find instructions on how to build your own. However, it probably will be difficult to achieve atomic resolution on your kitchen table.

The STM was invented by Gerd Binnig and Heinrich Rohrer who won the Physics Nobel Prize in 1986 for this achievement. You can learn more about Binning and Rohrer by visiting the Nobel Prize Archive. They shared the Nobel Prize with Ernst Ruscka, who designed the first electron microscope. Two important types of electron microscope are the transmission electron microscope (TEM) and the scanning electron microscope (SEM). I don't talk much about TEM & SEM in the book but they are two of the most important tools for imaging on the micro- and nano-scales.

The Nobel Prize in Chemistry 2014 was awarded jointly to Eric Betzig, Stefan W. Hell and William E. Moerner "for the development of super-resolved fluorescence microscopy". Their achievements open up the field of nanoscopy - imaging with visible light below the diffraction limit to < 200 nm. Their work has made possible the imaging of single molecules, proteins and living cells.

Lots of STM image galleries exist. For instance, here's one from the Technische Universität Wien.

Here's another from RHK Technologies.

And, of course, IBM since they invented it and also scientists at IBM (Manoharan, Lutz & Eigler) produced one of the images that was on the cover of the first edition of this textbook. IBM has also produced A Boy and His Atom, and the more interesting Moving Atoms: Making A Boy and His Atom. These are YouTube videos made by moving CO molecules with an STM .

A more venerable technique of surface structure determination is low energy electron diffraction (LEED). Clinton J Davisson shared the 1937 Physics Nobel Prize with George P Thomson for demonstrating that the wavelike characteristics of the electron. Thomson was the son of Sir JJ Thomson, who won his Nobel Prize for showing that the electron was a particle. Davidson and Germer are credited with discovering LEED.

Karl Manne Georg Siegbahn won the 1924 Nobel Prize in Physics for his discoveries and research in the field of X-ray spectroscopy. His son Kai developed X-ray spectroscopy further to create electron spectroscopy for chemical analysis (ESCA), which is also known as the surface sensitive spectroscopy XPS. For this he won a share of the 1981 Nobel Prize in Physics. Afterward he visited the University of Pittsburgh and became the first Nobel Prize winner I ever met. It didn't make a big impression on him but it was a big deal to me at the time.

NIST provides a number of databases with information pertinent to electron spectroscopy.

The NIST X-ray Photoelectron Spectroscopy online database has been a valuable source of binding-energy and related data for the surface analysis of a wide range of materials by x-ray photoelectron spectroscopy.

The NIST Electron Elastic-Scattering Cross-Section Database provides values of differential elastic-scattering cross sections, total elastic-scattering cross sections, phase shifts, and transport cross sections for elements with atomic numbers from 1 to 96 and for electron energies between 50 eV and 300 keV (in steps of 1 eV). These data can be used in simulations of electron transport in Auger-electron spectroscopy, x-ray photoelectron spectroscopy, electron-probe microanalysis, and analytical electron microscopy.

The NIST Surface Structure Database provides 3-dimensional graphics to allow researchers to visualize the structures of crystal surfaces on the atomic scale.

The NIST Electron Inelastic-Mean-Free-Path Database provides values of electron inelastic mean free paths (IMFPs) for use in quantitative surface analyses by AES and XPS.

The NIST Electron Effective-Attenuation-Length Database provides values of electron effective attenuation lengths (EALs) for applications in AES and XPS.

The NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA) provides data for many parameters needed in quantitative Auger electron spectroscopy and X-ray photoelectron spectroscopy (differential inverse inelastic mean free paths, total inelastic mean free paths, differential and total elastic-scattering cross sections, transport cross sections, photoionization cross sections, photoionization asymmetry parameters, electron-impact ionization cross sections, photoelectron lineshapes, Auger-electron lineshapes, fluorescence yields, and Auger-electron backscattering factors). SESSA can also simulate Auger-electron and X-ray-photoelectron spectra of mulitlayered samples with compositions and thicknesses specified by the user. The simulated spectra can then be compared with measured spectra (for specified measurement conditions), and the layer compositions and thicknesses adjusted to find maximum consistency between simulated and measured spectra.

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Chapter 3. Chemisorption, Physisorption & Dynamics

Fritz-Haber-Institut

What is now called the Fritz-Haber-Institute of the Max-Planck-Society was founded in 1911 as the Kaiser-Wilhelm Institute for Physical Chemistry and Electrochemistry. Fritz Haber, who was awarded the 1918 Nobel Prize in Chemistry, was its first director. In 1986 Gerhard Ertl succeeded Heinz Gerischer as director of the Department of Physical Chemistry and was appointed Scientific Fellow at the institute. His research interests focus on structure and chemical reactions at solid surfaces, for which he was awarded the 2007 Nobel Prize in Chemistry. In 2008 Ertl was succeeded by Martin Wolf. A joint Computer Center (Gemeinsames Rechenzentrum, GRZ) for the Fritz-Haber Institute and the Max-Planck Institute for Molecular Genetics was opened in 1986. In July 1988 Matthias Scheffler was appointed Scientific Fellow of the institute and director of the Theory Department. The department specializes in surface theory as well as solid state research, quantum chemistry, and computational physics. In 1995Robert Schloegl was appointed Scientific Fellow of the institute and the Department of Inorganic Chemistry was established. This department concentrates on heterogeneous reactions on inorganic surfaces. Oxidation reactions of carbons and metals are studied as well as a range of heterogeneous catalytic processes involving partial oxidation and dehydrogenation steps. The goal of this experimental research is to bridge the gap between surface physics and surface chemistry. In 1995, Hans-Joachim Freund became director of the Department of Chemical Physics, its objectives being studies of adsorption and reaction on solids, in particular, on oxide surfaces. In 2002 Gerard Meijer was appointed as a new director at the institute, and he installed the new Department of Molecular Physics. Respective renovations and rebuilding started in autumn 2002, and the new department is expected to be operational in autumn 2003.

Max von Laue, winner of the 1914 Nobel Prize in Physics, was elected director of the Fritz-Haber-Institut in 1951.

Otto Stern won the 1943 Nobel Prize in Physics for his contribution to the development of the molecular ray method and his discovery of the magnetic moment of the proton. Now we call them molecular beams and his use of H and He beams demonstrated that wavelike behavior is not limited to subatomic particles and photons.

Here is more information on some of my interests in adsorption and desorption dynamics.

The University of Liverpool Surface Science Center is a hotbed of activity in surface dynamics.

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Chapter 4. Thermodynamics & Kinetics of Surface Processes

The NIST Thermophysical Properties Division is one of the oldest data research centers in the United States. For over 60 years, it has produced a great number of the periodical compilations and electronic databases that have become a major source of recommended data for scientific research and industrial process design, for both pure materials and mixtures.

The NIST Chemistry WebBook provides access to data compiled and distributed by NIST under the Standard Reference Data Program.

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Chapter 5. Liquid Interfaces

Believe it or not, somebody else is trying to teach science with Sumi Nagashi. And now it seems everybody wants to get on the bandwagon. Try this for example. And here's another example of touchable digital painting. And if you would like to organize a workshop in it, I'm sure Frederica Marshall will help you out, though this offer may only pertain if you live in Maine or the Gulf Coast of Florida.

This from GE's web site: Non-reflecting glass - “Invisible Glass” (1918): A non-reflective glass that is the prototype for coatings used today on virtually all camera lenses and optical devices. It was invented by Katherine Blodgett, the first female scientist to join GE's Research Center. She, of course, is the same Blodgett of Langmuir-Blodgett films. Some of the first work on monomolecular films on water was performed by Agnes Pockels. (Noch mehr auf Deutsch) This fascinating story was brought to the scientific community's attention with the helpf of Lord Rayleigh, who transmitted some of her results to the journal Nature.

"I shall be obliged if you can find space for the accompanying translation of an interesting letter which I have received from a German lady, who with very homely appliances has arrived at valuable results respecting the behavior of contaminated water surfaces. The earlier part of Miss Pockel's letter covers nearly the same ground as some of my own recent work, and in the main harmonizes with it. The later sections seem to me very suggestive, raising, if they do not fully answer, many important questions. I hope soon to find opportunity for repeating some of Miss Pockels' experiments." Lord Rayleigh, March 1891.

Much of electrochemistry occurs as the liquid/solid interface. In chapter 8, there is more focus on charge transfer and photovoltaics. Here we focus more on an introduction to the electrified interface. You can find basic refresher course in electrochemistry here. For more on the nomenclature, definitions and standards of electrochemistry, visit this site. You can find a application notes on electrochemical instrumentation and methods at this site maintained by Princeton Applied Research.

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Chapter 6. Complex Surface Reactions: Catalysis & Etching

Wilhelm Ostwald won his 1909 Nobel Prize in Chemistry in recognition of his work on catalysis and for his investigations into the fundamental principles governing chemical equilibria and rates of reaction.

Heterogeneous catalysis was greatly advanced by the work of Paul Sabatier, who shared the 1912 Nobel Prize in Chemistry for, as stated by the Committee, "his method of hydrogenating organic compounds in the presence of finely disintegrated metals whereby the progress of organic chemistry has been greatly advanced in recent years." His work laid the basis of what would be developed into Fischer-Tropsch chemistry.

Fritz Haber won his Nobel Prize in Chemistry in 1918 for the synthesis of ammonia from its elements.

Carl Bosch, who commercialized the catalyst shared the 1931 Nobel Prize in Chemistry in recognition of his contributions to the invention and development of chemical high pressure methods. Haber is an interesting character, perhaps very much so in the sense of the Chinese proverb that it is a curse to be born in interesting times. Perhaps no scientific achievement has had more impact than the discovery of the nanostructured material that is the iron-based ammonia catalyst. It is estimated by Smil in his fascinating book Enriching the Earth: Fritz Haber, Carl Bosch, and the Transformation of World Food Production that 2.5 billion more people survive on the planet than would be possible without the iron catalyst. Yet in 1918 World War I was still being fought and Haber, who was an ardent nationalist, sought to help his country's war effort by introducing chemical weapons to the battlefield. This was a less admirable gift (pardon the pun in German) from Haber to mankind. Later, disgusted by Nazi Germany he would leave the country that he had long tried to serve, recognizing that this was not a regime that he could follow and that they were the ruin of his ideal of the German state. He died in exile. The Fritz-Haber-Institut in Berlin would later be named for him. Fritz's story has had an impact on me. Two tangible ways are that my grandfather was gassed in WWI. He survived but suffered lingering effects. Later, I took up a post doc at the FHI and worked in the very lab that Fritz had once used.

One of the most profound influences of the field of surface science was Irving Langmuir, who essentially established surface chemistry from a molecular perspective and was awarded the 1932 Nobel Prize in Chemistry. His research at the General Electric research labs were wide ranging. He sought literally to make a better ligh bulb and the pursuit (and achievement) of that goal lead him to fundamental studies of the interactions of gases with solid surfaces.

What is a catalytic converter? Engelhard has a site dedicated to their industrial engine emission control catalysts. Here's a link to catalysis at Johnson Matthey.

BASF has a site dedicated to Milestones In Catalyst Development of BASF.

Franz Fischer and Hans Tropsch reported using Co, Fe & Ni catalysts to make liquid hydrocarbons from syngas (CO+H2) in 1926. There is a tremendous wealth of information on FT synthesis at the Fischer-Tropsch Archive. The site is a bit difficult to navigate but if you're interested, it's worth the effort. For instance, you can find a shed load of presentations.

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Chapter 7. Growth & Epitaxy

The 2014 Nobel Prize in physics was awarded to Isamu Akasaki, Hiroshi Amano and Shuji Nakamura “for the invention of efficient blue light-emitting diodes which has enabled bright and energy-saving white light sources”. Paraphrasing from Nobelprize.org, the first LEDs were studied and constructed during the 1950s and 1960s. They emitted light at different wavelengths, from the infrared to the green. However, emitting blue light proved to be a difficult task, which took three more decades to achieve. It required the development of techniques such as MBE and MOVPE for the growth of high-quality crystals as well as the ability to control p-doping of semiconductors with high bandgap, which was achieved with GaN only at the end of the 1980s. The development of efficient blue LEDs also required the production of GaN-based alloys with different compositions (such as AlGaN and InGaN) and their integration into multilayer structures such as heterojunctions and quantum wells. The development of efficient blue LEDs is a fascinating story at the intersection of surface science, materials science and solid state physics. The history of development for gallium-nitride-based light-emitting diodes (LEDs) is reviewed by Nakamura and Krames.

The 2014 Nobel Prize in physics built on the foundation laid by Zhores I. Alferov and Herbert Kroemer, who won the 2000 Nobel Prize in physics "for developing semiconductor heterostructures used in high-speed- and opto-electronics" and to Jack S. Kilby "for his part in the invention of the integrated circuit". Kroemer described his work in this paper. Alferov's address is found here. These papers contain short reviews of the physics, technology of preparation and applications of quantum wells and superlattices.

Etching can be performed with either a liquid phase or a gas phase in contact with the solid. I do a lot of work on etching silicon in aqueous solutions to form porous silicon. You can read more about etching silicon in aqueous solutions to form porous silicon.

Laser induced processes with a reactive gas phase can also be used to modify the structure of solids.

You can learn more about surface structure modification and corrosion from the Surface Science and Corrosion Group in Erlangen.

Integrated circuits (as well as many micromachines and nanoscale devices) are fabricated in cleanrooms. The technology behind this fundamental application of surface science is complex and well developed.

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Chapter 8. Laser and Nonthermal Chemistry

The transformation of one kind of energy into another accompanies all processes in our world, and frequently also propels them. Many of these transformations - like the chemical reactions on catalysts or in sensors, or the mechanical friction or dispersion of charge carriers in microprocessors - take place at surfaces, or at the interfaces of solid materials.

SFB616 targets the clarification of these elementary procedures through the energy dissipation at surfaces. The program of the SFB616 is broadly designed and comprises the whole spectrum of stimulation and relaxation from the eV regime (particle interaction, laser stimulation, reactions and surfaces) through phonons and frictions losses in the meV regime to the meV area (electromigration)

Here is a short introduction to ultrafast surface photochemistry in the VUV.

The STM was invented by Gerd Binnig and Heinrich Rohrer who won the Physics Nobel Prize in 1986 for this achievement. You can learn more about Binning and Rohrer by visiting the Nobel Prize Archive

Lots of STM image galleries exist. For instance, here's one from the Technische Universität Wien.

Here's another from RHK Technologies.

And, of course, IBM since they invented it and also scientists at IBM (Manoharan, Lutz & Eigler) produced one of the images that is on the cover of the textbook.

Electrochemistry is also a part of this chapter. Much of electrochemistry occurs as the liquid/solid interface (Chapter 5) but in this chapter we focus on the charge transfer aspect of electrochemical reactions. Here's a basic refresher course in electrochemistry. You can find application notes on electrochemical instrumentation and methods at this site maintained by Princeton Applied Research.

CCI Solar has an education page that provides links to lectures on electrochemistry, photoelectrochemistry and solar energy topics.

Find out more on hydrogen and fuel cells from the National Renewable Energy Laboratory (NREL). They also have a big program in solar energy.

Walther Nernst was not only the discoverer of the third law of thermodynamics and the Nernst equation of electrode potentials, but also he was the winner of the Nobel Prize in 1920 for his many discoveries in physical chemistry.