7. Materials Characterization

Both flux and brightness are based on a measure of the number of photons per second in a narrow energy bandwidth and in a unit of solid angle in the horizontal and vertical directions. Flux is the number of photons per second passing through a defined area, and is the appropriate measure for experiments that use the entire, unfocused X-ray beam. Brightness is a measure of the intensity and directionality of an X-ray beam. It determines the smallest spot onto which an X-ray beam can be focused.

A listing of the energies and experimental techniques available from various beamlines at the APS in Argonne National Laboratory: https://​www1.​aps.​anl.​gov/​Beamlines/​Directory

Scattering from the nucleus does not contribute to coherent scattering due to its relatively large mass, precluding its oscillation from the impinging of incident X-rays.

The cosine of angle ϕ is simply the x component of a unit vector after it is rotated by ϕ around a unit circle. If the vector is rotated at some constant speed, then its x-value will trace out a cosine wave as a function of time, with amplitude of vector length. Waves of different wavelengths or periods would result in the vectors rotating at different speeds; however, X-ray crystallography uses monochromatic photons of a single wavelength.

http://​shelx.​uni-ac.​gwdg.​de/​tutorial/​english/​shelxs.​htm

Another way to state this is that for a single crystal, only a few lattice planes will be oriented at their Bragg angle at any one time.

http://​www.​fhi-berlin.​mpg.​de/​acnew/​department/​pages/​teaching/​pages/​teaching_​_​wintersemester_​_​2015_​2016/​frank_​girgsdies_​_​peak_​profile_​fitting_​in_​xrd_​_​151106.​pdf

For a discussion of the Scherrer constant, see: Langford, J. I.; Wilson, A. J. C. J. Appl. Cryst. 1978, 11, 102.

For more information on small-angle scattering, see:

a) http://​www.​eng.​uc.​edu/​~gbeaucag/​Classes/​XRD/​SAXS%20​Chapter/​SAXSforXRD.​htm

For a nice example that utilizes SAXS, WAXS, and SANS to determine the structural changes of polyethylene chains following annealing, see: Men, Y.; Rieger, J.; Lindner, P.; Enderle, H. -F.; Lilge, D.; Kristen, M. O.; Mihan, S.; Jiang, S. J. Phys. Chem. B 2005, 109, 16,650.

For an example of a quantitative SAXS study of a block copolymer-solvent system see: Soni, S. S.; Brotons, G.; Bellour, M.; Narayanan, T.; Gibaud, A. J. Phys. Chem. B 2006, 110, 15,157. An example of the use of SAXS to determine the particle size distribution of nanoparticles, see: Rieker, T.; Hanprasopwattana, A.; Datye, A.; Hubbard, P. Langmuir 1999, 15, 638.

More information on the components and operation of reflection microscopes may be obtained from http://​www.​microscopyu.​com/​articles/​dic/​reflecteddic.​html

Synge, E. H. Philos. Mag. 1928, 6, 356.

For a thorough review of NSOM, see: Dunn, R. C. Chem. Rev. 1999, 99, 2891.

Mass of a Golf Ball: http://​hypertextbook.​com/​facts/​1999/​ImranArif.​shtml

a) Cremer, J. T.; Piestrup, M. A.; Gary, C. K.; Pantell, R. H.; Glinka, C. J. Appl. Phys. Lett. 2004, 85, 494.b) https://​www.​nist.​gov/​programs-projects/​towards-neutron-microscopec) Liu, D.; Khaykovich, B.; Gubarev, M. V.; Robertson, J. L.; Crow, L.; Ramsey, B. D.; Moncton, D. E. Nat. Commun. 2013, 4, 2556.

For example, see: http://​accelconf.​web.​cern.​ch/​AccelConf/​p05/​PAPERS/​WOAC001.​PDF

For an image of the lattice structure and properties of LaB₆, see: http://​www.​kimphys.​com/​cathode/​catalog_​PDF/​LaB6_​cathode_​ES423.​pdf

Perkins, C. L.; Trenary, M.; Tanaka, T.; Otani, S. Surface Sci. 1999, 423, L222.

a) Nojeh, A.; Wong, W. K.; Baum, A. W.; Pease, R. F.; Dai, H. Appl. Phys. Lett. 2004, 85, 112.b) https://​alc.​surf.​nuqe.​nagoya-u.​ac.​jp/​alc11/​images/​Sample_​proc.​pdfc) Irita, M.; Homma, Y. Surf. Interf. Anal. 2014, 46, 1282.

Krauss, A. R.; Auciello, O.; Ding, M. Q.; Gruen, D. M.; Huang, Y.; Zhimov, V. V.; Givargizov, E. I.; Breskin, A.; Chechen, R.; Shefer, E.; Konov, V.; Pimenov, S.; Karabutov, A.; Rakhimov, A.; Suetin, N. J. Appl. Phys. 2001, 89, 2958, and references therein.

Chanana, R. K.; McDonald, K.; Di Ventra, M.; Pantelides, S. T.; Feldman, L. C.; Chung, G. Y.; Tin, C. C.; Williams, J. R. Appl. Phys. Lett. 2000, 77, 2560.

For a more detailed description of resolution and magnification of field-emission electron microscopes, see: a) Rose, D. J. J. Appl. Phys. 1956, 27, 215.b) O’Keefe, M. A. Ultramicroscopy 1992, 47, 282.

Unless otherwise stated, TEM micrographs are collected as bright-field images.

Formvar is a copolymer of polyvinyl alcohol, formaldehyde, and polyvinyl acetate.

The very same material obtained by reacting normal cotton with nitric acid and sulfuric acid to yield “gun cotton”—a highly explosive solid that burns with an extremely bright flash leaving behind no residue. Since the thickness is extremely small for the support material and the degree of nitration/sulfation is supposedly less than gun powder compositions, there are no explosion hazards in handling grids. However, the native resin used to make support films is a flammable solid and should be treated with caution.

Butvar B98 is a polyvinyl butyral resin containing 20% polyvinyl alcohol. These support films are hydrophilic, hence, they are useful for negative staining methods.

The FIB/lift-out technique yields cross sections of both the film and substrate, which maintains the integrity of the interface; in comparison, ultramicrotomy requires the removal of the polymer film and subsequent embedding/sectioning. For a detailed example, see: White, H.; Pu, Y.; Rafailovich, M.; Sokolov, J.; King, A. H.; Giannuzzi, L. A.; Urbanik-Shannon, C.; Kempshall, B. W.; Eisenberg, A.; Schwarz, S. A.; Strzhemechny, Y. M. Polymer 2001, 42, 1613.

Virgilio, N.; Favis, B. D.; Pepin, M. -F.; Desjardins, P. Macromolecules 2005, 38, 2368.

Morniroli, J. -P. “Introduction to Electron Diffraction” in NATO Series II: Mathematics, Physics and Chemistry 2006, 211, 61.

a) Steeds, J. W.; Morniroli, J. P. Rev. Mineralogy Geochem. 1992, 27, 37. b) Tsuda, K.; Mitsuishi, H.; Terauchi, M.; Kawamura, K. J. Electron Microsc. 2007, 56, 57.

https://​www1.​udel.​edu/​pchem/​C874/​LEED_​lecture.​pdf

http://​www.​chem.​qmul.​ac.​uk/​surfaces/​scc/​scat6_​3.​htm

It should be noted that EDS and WDS are often referred to as EDX and WDX, or XEDS and XWDS, respectively.

Electromagnetic lenses suffer from three types of defects: astigmatism, spherical aberrations, and chromic aberrations. Astigmatism may be easily minimized by placing electromagnets, known as stigmator coils, around the column. The current in these coils may be varied, which will reform the distorted electron beam back into a round shape. Chromic aberrations may be reduced by using a field emission source that produces an electron beam with a sharper distribution of electron energies. However, the third type of defect, spherical aberrations (C _s), are not easily circumvented. In fact, this is the primary factor that limits the resolution of electron microscopes to values far below their theoretical values. Recently, techniques have been developed to correct for these defects, often involving the use of multipole lenses (e.g., quadrupole, octapole, etc.) with careful control of their fabrication and operation. For a description of techniques used to design a Cs-corrected HRTEM, see: http://​www.​superstem.​org/​cs-correctionA discussion of methods used for aberration correction in electron microscopy: https://​mrl.​illinois.​edu/​sites/​default/​files/​pdfs/​TEAMReport2000.​pdf

A collaborative research project between the Lawrence Berkeley National Laboratory, Argonne National Laboratory, Oak Ridge National Laboratory, and the Univ. of Illinois at Urbana-Champagne developed a transmission electron aberration-corrected microscope that achieved the 0.05 nm resolution target in 2009: a) http://​www.​ipd.​anl.​gov/​anlpubs/​2002/​03/​42224.​pdfb) http://​foundry.​lbl.​gov/​facilities/​ncem/​expertise.​html

Some important precedents that show the utility of Z-contrast imaging: (a) Arslan, I.; Yates, T. J. V.; Browning, N. D.; Midgley, P. A. Science 2005, 309, 2195. (b) Chisholm, M. F.; Kumar, S.; Hazzledine, P. Science 2005, 307, 701. (c) Nellist, P. D.; Pennycook, S. J. Science 1996, 274, 413.

The photon energies for the light elements are: Be (0.109 keV), B (0.185 keV), C (0.282 keV), N (0.392 keV), O (0.523 keV), and F (0.677 keV). Due to these low energies, the emitted X-rays are easily absorbed by the sample or the components of the detector.

Bremsstrahlung is from the German word bremsen (“to brake”), and Strahlung (“radiation”) – thus, “braking radiation.” This is characterized by a broad peak that results from deceleration of beam electrons due to scattering from atomic nuclei.

Pronounced: OH-zhā.

The energy-dispersing device at the heart of EDS is a semiconducting diode. As an incoming X-ray photon impinges the diode, electron-hole pairs are generated, which yields a measurable electrical current. In order to reduce background noise from photons not originating from the sample, the detector is operated at temperatures of ca. 140 K. A protective window comprising Be, or more recently, ultrathin windows of BN, diamond, or a supported polymer (paralene, norvar), is used to prevent the condensation of vapors (e.g., water, organics) onto the cooled diode. A “windowless” detector may also be used for EDS; with careful operation, this modification allows the detection of elements down as far as Be—with a maximum efficiency of only 2%. It should be noted that although UHV conditions are used in a TEM/SEM instrument, there will always be a low concentration of vapors—often originating from the rotary pump fluid, or the sample itself due to beam-induced volatilization/decomposition, residual solvent evaporation, etc. The buildup of such a coating on the detector window will reduce the energy of the incoming X-rays, which will drastically reduce the detection sensitivity—especially for low-Z elements.

It should be noted that reflection techniques are also possible through modifying the angle of approach of the incident electron beam of the TEM. Such analysis is referred to as reflection electron microscopy (REM), and accompanying characterizations such as reflection high-energy electron diffraction (RHEED) and reflection electron energy-loss spectroscopy (REELS) are also possible, grouped under the umbrella of reflection high-resolution analytical electron microscopy (RHRAEM). a) For an application of this multifaceted approach to study GaAs(110) surfaces, see: Wang, Z. L. J. Electron. Microsc. Tech. 1988, 10, 35 (citation found online at: http://​www.​osti.​gov/​energycitations/​product.​biblio.​jsp?​osti_​id=​6614173). b) Additional information may be found in Wang, Z. L. Reflection Electron Microscopy and Spectroscopy for Surface Analysis, Cambridge University Press: Cambridge, UK, 1996. (A book synopsis is found online at: http://​www.​nanoscience.​gatech.​edu/​zlwang/​book/​book2_​intro.​pdf)

For a thorough summary/examples of the details generated from EELS spectra, see: Thomas, J. M.; Williams, B. G.; Sparrow, T. G. Acc. Chem. Res. 1985, 18, 324.

(a) Williams, B. G.; Sparrow, T. G.; Egerton, R. F. Proc. R. Soc. Lond. Ser. A 1984, 393, 409. (b) Sparrow, T. G.; Williams, B. G.; Thomas, J. M.; Jones, W.; Herley, P. J.; Jefferson, D. A. J. Chem. Soc., Chem. Commun. 1983, 1432. (c) Ferrell, R. A. Phys. Rev. 1956, 101, 554.

For example, see: Goris, B.; Guzzinati, G.; Fernandez-Lopez, C.; Perez-Juste, J.; Liz-Marzan, L.; Trugler, A.; Hohenester, U.; Verbeeck, J.; Bals, S.; Van Tendeloo, G. J. Phys. Chem. C Nanomater. Interfaces 2014, 118, 15,356.

For a comparison between ELNES, XANES, and the basics of X-ray absorption spectroscopy, see: a) http://​susi.​theochem.​tuwien.​ac.​at/​reg_​user/​textbooks/​WIEN2k_​lecture-notes_​2011/​Blaha_​xas_​eels.​pdfb) http://​www.​iucr.​org/​_​_​data/​assets/​pdf_​file/​0004/​60637/​IUCr2011-XAFS-Tutorial_​-Ascone.​pdf

For an application of EELS in determining the nature of C bonding in amorphous carbon nanotubes see: Hu, Z. D.; Hu, Y. F.; Chen, Q.; Duan, X. F.; Peng, L.-M. J. Phys. Chem. B. 2006, 110, 8263.

a) For a comprehensive list of tutorials related to XAFS, see: http://​xafs.​org/​Tutorialsb) For a thorough summary/examples of the details generated from EELS spectra, see: Thomas, J. M.; Williams, B. G.; Sparrow, T. G. Acc. Chem. Res. 1985, 18, 324.

For information on the analysis of surfaces by IR radiation instead of electrons, there exists a complimentary technique known as reflection absorption infrared spectroscopy (RAIRS). For instance, see: a) Bolina, A. S.; Wolff, A. J.; Brown, W. A. J. Phys. Chem. B 2005, 109, 16,836.b) Wang, X. D.; Tysoe, W. T.; Greenler, R. G.; Truszkowska, K. Surf. Sci. 1991, 258, 335.c) http://​www.​annualreviews.​org/​doi/​10.​1146/​annurev.​physchem.​51.​1.​381

For example, the development of fibers/fabrics that will actively adsorb and surface deactivate chemical and biological warfare agents, of increasing importance as new modes of terrorist activity continue to emerge. For more information, see: a) http://​web.​mit.​edu/​isn/​ (Institute of Soldier Nanotechnologies at M.I.T.). b) Richards, V. N.; Vohs, J. K.; Williams, G. L.; Fahlman, B. D. J. Am. Ceram. Soc. 2005, 88, 1973.

Wang, Z. L.; Bentley, J.; Evans, N. D. J. Phys. Chem. B 1999, 103, 751.

Some of the (potential) energy of the incident electrons is required to release an outer electron from its valence or conduction band, with the remaining being transferred into the kinetic energy of the ejected secondary electron.

https://​serc.​carleton.​edu/​research_​education/​geochemsheets/​ebsd.​html

For example, see: a) https://​www.​bruker.​com/​products/​x-ray-diffraction-and-elemental-analysis/​eds-wds-ebsd-sem-micro-xrf-and-sem-micro-ct/​esprit-dynamics/​overview.​htmlb) https://​www.​oxford-instruments.​com/​products/​microanalysis/​ebsd/​ebsd-post-processing-software

Both carbon and gold coating are performed using a sputter-coating PVD method. The film of choice is most often C since it is less costly and is transparent to X-rays (for EDS). Gold is used to coat very uneven surfaces, and is only useful when EDS is not being performed (strong Au signal would mask other elements present in the sample).

Rades, S.; Hodoroaba, V. D.; Salge, T.; Wirth, T.; Lobera, M. P.; Labrador, R. H.; Natte, K.; Behnke, T.; Gross, T.; Unger, W. E. S. RSC Adv. 2014, 4, 49,577.

The effect of charging can be controlled by either altering the position of the sample with regard to the incident electron beam, or using an argon ion (Ar⁺) gun to neutralize the charge.

A recent issue of the MRS Bulletin was devoted to in situ TEM: MRS Bull. 2008, 33.

For a historical background of ESEM development, see: http://​www.​danilatos.​com/​

For instance, see: https://​www.​researchgate.​net/​profile/​Marek_​Uncovsky/​publication/​268271525_​High_​resolution_​in_​situ_​STEM_​in_​SEM/​links/​556d980308aeab77​722362cd/​High-resolution-in-situ-STEM-in-SEM.​pdf?​origin=​publication_​detail

For instance, see: van Huis, M. A.; Kunneman, L. T.; Overgaag, K.; Xu, Q.; Pandraud, G.; Zandbergen, H. W.; Vanmaekelbergh, D. Nano Lett. 2008, 8, 3959.

For example, in situ growth of carbon nanotubes: Lin, M.; Tan, J. P. Y.; Boothroyd, C.; Loh, K. P.; Tok, E. S.; Foo, Y. -L. Nano Lett. 2007, 7, 2234.

For an example of a TEM PicoIndenter®, see: https://​www.​hysitron.​com/​media/​1579/​pi95ss_​sam-0073-a.​pdf

http://​mcff.​mtu.​edu/​acmal/​wp-content/​uploads/​2013/​01/​Data_​Sheet_​-STM-TEM.​pdf

For instance, see: Wang, Z. L.; Poncharal, P.; de Heer, W. A. Pure Appl. Chem. 2000, 72, 209. May be accessed online at: http://​www.​iupac.​org/​publications/​pac/​2000/​pdf/​7201x0209.​pdf

http://​hummingbirdscien​tific.​com/​products/​tomography/​

Chiaramonti, A. N.; Schreiber, D. K.; Egelhoff, W. F.; Seidman, D. N.; Petford-Long, A. K. 2008, 93, 103,113.

Klein, K. L.; Anderson, I. M.; De Jonge, N. J. Microsc. 2011, 242, 117.

Zheng, H.; Smith, R. K.; Jun, Y. -W.; Kisielowski, C.; Dahmen, U.; Alivisatos, A. P. Science 2009, 324, 1309.

A very detailed example of XPS to distinguish among Li salts for Li-ion battery applications is: Dedryvere, R.; Leroy, S.; Martinez, H.; Blanchard, R.; Lemordant, D.; Gonbeau, D. J. Phys. Chem. B 2006, 110, 12,986.

For instance, see:a) Seah, M. P.; White, R. Surf. Interf. Anal. 2002, 33, 960.b) Libra, J.; Matolin, V. Surf. Sci. 2006, 600, 2317.c) https://​core.​ac.​uk/​download/​pdf/​34898173.​pdfd) In addition to angle-resolved PES, photoluminescence spectroscopy is typically used as a nondestructive means to delineate the electronic properties of materials. For more information, see: (i) Glinka, Y. D.; Lin, S.-H.; Hwang, L.-P.; Chen, Y.-T. J. Phys. Chem. B 2000, 104, 8652. (ii) Wu, J.; Han, W.-Q.; Walukiewicz, W.; Ager, J. W.; Shan, W.; Haller, E. E.; Zettl, A. Nano Lett. 2004, 4, 647.

For an application example of EXAFS, see: Borgna, A.; Stagg, S. M.; Resasco, D. E. J. Phys. Chem. B 1998, 102, 5077. An example of XPS and XAFS (XANES and EXAFS), see: Chakroune, N.; Viau, G.; Ammar, S.; Poul, L.; Veautier, D.; Chehimi, M. M.; Mangeney, C.; Villain, F.; Fievet, F. Langmuir 2005, 21, 6788.

For an application example of REFLEXAFS, see: d’Acapito, F.; Emelianov, I.; Relini, A.; Cavotorta, P.; Gliozzi, A.; Minicozzi, V.; Morante, S.; Solari, P. L.; Rolandi, R. Langmuir 2002, 18, 5277.

Gervasini, A.; Manzoli, M.; Martra, G.; Ponti, A.; Ravasio, N.; Sordelli, L.; Zaccheria, F. J. Phys. Chem. B 2006, 110, 7851.

Data analysis represents the most essential and time-consuming aspects of these techniques (as well as EELS). Typically, sample spectra are compared to reference samples that contain the probed element with similar valences and bonding motifs. In this example, Cu metal foil was used for the Cu-Cu interactions, and CuO/Cu₂O were used for the Cu-O contributions. A variety of software programs are used for detailed curve-fitting, in order to obtain information regarding the chemical environment of the sample. For example, see: a) http://​www.​dragon.​lv/​eda/​b) http://​www.​xsi.​nl/​software.​htmlc) http://​www.​xpsdata.​com/​

For information regarding the quantum mechanical description of spin–orbit splitting, see: a) http://​hyperphysics.​phy-astr.​gsu.​edu/​hbase/​quantum/​sodzee.​html#clb) http://​www.​technology.​niagarac.​on.​ca/​people/​mcsele/​lasers/​Quantum.​htm

The presence of these satellites are indicative of Cu²⁺. For instance, see: (a) Espinos, J. P.; Morales, J.; Barranco A.; Caballero, A.; Holgado, J. P.; Gonzalez-Elipe, A. R. J. Phys. Chem. B 2002, 106, 6921. (b) Morales, J.; Caballero, A.; Holgado, J. P.; Espinos, J. P.; Gonzalez-Elipe, A. R. J. Phys. Chem. B 2002, 106, 10,185. (c) Fuggle, J. C.; Alvarado, S. F. Phys. Rev. A 1980, 22, 1615 (describes the cause of peak broadening in XPS spectra, related to core-level lifetimes).

In an excited 2s¹ state, with an energy of 19.8 eV and a lifetime of ca. 4000 s.

Many references exist for MIES studies of surfaces, most often carried out in tandem with UPS (to gain information for both the surface and immediate subsurface of the sample). For example, see: (a) Johnson, M. A.; Stefanovich, E. V.; Truong, T. N.; Gunster, J.; Goodman, D. W. J. Phys. Chem. B 1999, 103, 3391. (b) Kim, Y. D.; Wei, T.; Stulz, J.; Goodman, D. W. Langmuir 2003, 19, 1140 (very nice work that describes the shortfall of UPS alone, and the utility of a tandem UPS/MIES approach).

Note: though conventional RBS is carried out with He⁺ ions (which will backscatter from any atom with a greater Z ), heavier ions such as C, O, Si, or Cl may be used in order to prevent background backscattering interactions with the matrix. For example, use of incident O ions to eliminate backscattering from lattice O atoms for the RBS analysis of ceramic oxides.

Simulations for ion scattering techniques such as RBS are typically compared with actual spectra in order to characterize the surface features. There are many such algorithms; for example: (a) Kido, Y.; Koshikawa, T. J. Appl. Phys. 1990, 67, 187. (b) Doolittle, L. R. Nucl. Instrum. Methods 1986, B15, 227 (RUMP program).

Many such systems exist; some examples include: a) Brookhaven National Laboratory (https://​www.​bnl.​gov/​tandem/​) b) Western Michigan University (https://​wmich.​edu/​physics/​accelerator)c) University of Kentucky (http://​www.​pa.​uky.​edu/​accelerator/​)

Also known as forward recoil scattering (FRS) or hydrogen forward scattering (HFS).

Naab, F. U.; Holland, O. W.; Duggan, J. L.; McDaniel, F. D. J. Phys. Chem. B 2005, 109, 1415, and references therein.

For a very thorough tutorial regarding SIMS, see: http://​www.​geology.​wisc.​edu/​~wiscsims/​HiRes2015/​pdfs/​talks/​HiRes2015_​06010920_​Kita.​pdf

For background information regarding polymer characterization using MALDI, see:a) Montaudo, G.; Samperi, F.; Montaudo, M. S. Prog. Polym. Sci. 2006, 31, 277.b) http://​ws680.​nist.​gov/​publication/​get_​pdf.​cfm?​pub_​id=​852404

For a thesis that has a nice background on ESI, see: http://​uu.​diva-portal.​org/​smash/​record.​jsf?​pid=​diva2%3A161937&​dswid=​7454

Typically, the majority of secondary ions are ejected from the top two or three monolayers (10–20 Å) of the sample.

For instance, the ion concentration of the impinging ion beam must be <1% of the number of surface molecules. If this “static limit” is breached, a residue from molecular fragmentation will build up on the surface, which depletes the signal.

The use of fullerene ion sources represents an area of increasing interest. For example, see: Cheng, J.; Winograd, N. Anal. Chem. 2005, 77, 3651, and references therein.

Winograd, N. Anal. Chem. 2005, 77, 142A.

For example, see: (a) Delcorte, A.; Medard, N.; Bertrand, P. Anal. Chem. 2002, 74, 4955. (b) Delcorte, A.; Bour, J.; Aubriet, F.; Muller, J. -F.; Bertrand, P. Anal. Chem. 2003, 75, 6875.

Marcus, A.; Winograd, N. Anal. Chem. 2006, 78, 141.

For instance, see:a) Chandra, S. Appl. Surf. Sci. 2003, 203–204, 679.b) Allen, G. C.; Brown, I. T. Eur. Mass Spectrom. 1995, 1, 493.c) Chandra, S.; Lorey, D. R. Int. J. Mass Spectrom. 2007, 260, 90.

For example, see:a) Groner, E.; Hoppe, P. Appl. Surf. Sci. 2006, 252, 7148. b) http://​www.​minersoc.​org/​pages/​Archive-MM/​Volume_​53/​53-369-3.​pdfc) http://​www.​minersoc.​org/​pages/​Archive-MM/​Volume_​55/​55-380-347.​pdfd) https://​shrimprg.​stanford.​edu/​intro-sims

http://​www.​cameca.​com/​products/​lexes/​technique

http://​www.​geology.​wisc.​edu/​~johnf/​g777/​MM/​Staub-LEXES.​pdf

Hombourger, C.; Staub, P. F.; Schuhmacher, M.; Desse, F.; de Chambost, E.; Hitzman, C. Appl. Surf. Sci. 2003, 203–204, 383.

Seidman, D. N. Annu. Rev. Mater. Res. 2007, 37, 127, and references therein.

For example, see:a) Larson, D. J.; Petford-Long, A. K.; Ma, Y. Q.; Cerezo, A. Acta. Mater. 2004, 52, 2847.b) Gault, B.; Menand, A.; de Geuser, F.; Deconihout, B.; Danoix, F. Appl. Phys. Lett. 2006, 88, 114,101.

A recent issue of MRS Bulletin is focused on APT: MRS Bull. 2009, 34 (Oct. 2009).

Seidman, D. N.; Stiller, K. MRS Bull. 2009, 34, 717.

Perea, D. E.; Hemesath, E. R.; Schwalbach, E. J.; Lensch-Falk, J. L.; Voorhees, P. W.; Lauhon, L. J. Nature Nanotechnol. 2009, 4, 315.

Perea, D. E.; Arslan, I.; Liu, J.; Ristanovic, Z.; Kovarik, L.; Arey, B. W.; Lercher, J. A.; Bare, S. R.; Weckhuysen, B. M. Nat. Commun. 2015, 6, 7589.

Record players are once again rising in popularity, as audiophiles believe the sound quality far surpasses that of digital media.

For a recent review of atomic manipulation using AFM, see: Custance, O.; Perez, R.; Morita, S. Nature Nanotechnol. 2009, 4, 803.

For example, see: Zhang, J.; Chi, Q.; Ulstrup, J. Langmuir 2006, 22, 6203.

For example, see: (a) France, C. B.; Frame, F. A.; Parkinson, B. A. Langmuir 2006, 22, 7507. (b) Li, W.-S.; Kim, K. S.; Jiang, D. -L.; Tanaka, H.; Kawai, T.; Kwon, J. H.; Kim, D.; Aida, T. J. Am. Chem. Soc. 2006, 128, 10,527. (c) Namai, Y.; Matsuoka, O. J. Phys. Chem. B 2006, 110, 6451.

For a recent precedent, see: Park, J. B.; Jaeckel, B.; Parkinson, B. A. Langmuir 2006, 22, 5334, and references therein. For a thorough recent review, see: Wan, L. -J. Acc. Chem. Res. 2006, 39, 334.

For example, see: Alam, M. S.; Dremov, V.; Muller, P.; Postnikov, A. V.; Mal, S. S.; Hussain, F.; Kortz, U. Inorg. Chem. 2006, 45, 2866.

Examples of some common forces that may exist between a surface and an AFM tip are Van der Waal, electrostatic, covalent bonding, capillary, and magnetic. In addition to providing information regarding the topography of the surface (constant force mode), forces may be applied to understand the morphology of a surface – for example, to determine the frictional force between the tip and surface, or the elasticity/hardness of a surface feature. For instance, see: Tranchida, D.; Piccarolo, S.; Soliman, M. Macromolecules 2006, 39, 4547, and references therein.

For example, see: O’Dwyer, C.; Gay, G.; Viaris de Lesegno, B.; Weiner, J. Langmuir 2004, 20, 8172, and references therein.

For example, see: a) Cho, Y.; Ivanisevic, A. Langmuir 2006, 22, 1768. b) Poggi, M. A.; Lillehei, P. T.; Bottomley, L. A. Chem. Mater. 2005, 17, 4289. c) Gourianova, S.; Willenbacher, N.; Kutschera, M. Langmuir 2005, 21, 5429.

For example, see: a) Polking, M.; Huan, M. G.; Yourdkhani, A.; Petkov, V.; Kisielowski, C. F.; Volkov, V.; Zhu, Y.; Caruntu, G.; Alivisatos, P. A.; Ramesh, R. Nat. Mater. 2012, 11, 700.b) Takamura, Y.; Chopdekar, R. V.; Scholl, A.; Doran, A.; Liddle, J. A.; Harteneck, B.; Suzuji, Y. Nano Lett. 2006, 6, 1287. c) Li, Y.; Tevaarwerk, E.; Chang, R. P. H. Chem. Mater. 2006, 18, 2552.

For example, see: Zhang, J.; Roberts, C. J.; Shakesheff, K. M.; Davies, M. C.; Tendler, S. J. B. Macromolecules 2003, 36, 1215, and references therein.

For a thorough description of SECM, see: Gardner, C. E.; Macpherson, J. V. Anal. Chem. 2002, 74, 576A.

For instance, see: https://​www.​brukerafmprobes.​com

a) Nanoparticle-terminated tips: Vakarelski, I. U.; Higashitani, K. Langmuir 2006, 22, 2931.b) Nanotube-terminated tips: Hafner, J. H.; Cheung, C. -L.; Oosterkamp, T. H.; Lieber, C. M. J. Phys. Chem. B 2001, 105, 743. c) Nanotube-terminated tips: Wilson, N. R.; Macpherson, J. V. Nano Lett. 2003, 3, 1365.

Named after Brunauer, Emmett, and Teller.

Tandem TGA/DSC instruments are commercially available, for example: http://​www.​tainstruments.​com/​simultaneous-tgadsc/​