7. Materials Characterization

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

Cremer, J. T.; Piestrup, M. A.; Gary, C. K.; Pantell, R. H.; Glinka, C. J. Appl. Phys. Lett. 2004, 85, 494.

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

O’Dwyer, C.; Navas, D.; Lavayen, V.; Benavente, E.; Santa Ana, M. A.; Gonzalez, G.; Newcomb, S. B.; Sotomayor Torres, C. M. Chem. Mater. 2006, 18, 3016.

Hu, J.; Bando, Y.; Zhan, J.; Zhi, C.; Golberg, D. Nano Lett. 2006, 6, 1136.

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.

Nojeh, A.; Wong, W.-K.; Yieh, E.; Pease, R. F.; Dai, H. J. Vac. Sci. Technol. B 2004, 22, 3124.

(a) http://​anl.​gov/​techtransfer/​Available_​Technologies/​Chemistry/​uncd_​flc.​html (b) 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.

http://​www.​tedpella.​com/​aperfil_​html/​filament.​htm

The low-resolution SEM image was reproduced with permission from Li, F.; Zhang, L.; Metzger, R. M. Chem. Mater. 1998, 10, 2470. Copyright 1998 American Chemical Society.

The high-resolution SEM image was reproduced with permission from Moon, J. -M.; Wei, A. J. Phys. Chem. B 2005, 109, 23336. Copyright 2005 American Chemical Society.

Note: 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.

http://​www.​microstartech.​com/​index/​cryo.​htm

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.

Reproduced with permission from Fu, L.; Liu, Y.; Hu, P.; Xiao, K.; Yu, G.; Zhu, D. Chem. Mater. 2003, 15, 4287. Copyright 2003 American Chemical Society.

Reproduced with permission from Liu, Z.; Ohsuna, T.; Sato, K.; Mizuno, T.; Kyotani, T.; Nakane, T.; Terasaki, O. Chem. Mater. 2006, 18, 922. Copyright 2006 American Chemical Society.

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.

(c) http://​www.​emal.​engin.​umich.​edu/​courses/​CBEDMSE562/​index.​html (very nice online course for CBED, from the Univ. of Michigan).

Reproduced with permission from Sun, G.; Sun, L.; Wen, H.; Jia, Z.; Huang, K.; Hu, C. J. Phys. Chem. B 2006, 110, 13375. Copyright 2006 American Chemical Society.

Reproduced with permission from Liu, Y.; Xu, H.; Qian, Y. Cryst. Growth Design 2006, 6, 1304. Copyright 2006 American Chemical Society.

http://​www.​uksaf.​org/​tech/​leed.​html

http://​www.​uksaf.​org/​tech/​rheed.​html

The nomenclature for X-ray emission consists of the name of the shell in which the vacancy was created (K, L, M, N), and on the electronic shell that filled the vacancy. For instance, ejection of a K shell electron, filled with a L shell electron is denoted as K_α; if filled with an M shell electron, then K_β is used, and so on. Due to electronic subshells, nomenclature becomes significantly complex, as shown in Figure 7.17.

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

Fahlman, B. D., unpublished results.

Reproduced with permission from Harmer, M. A.; Farneth, W. E.; Sun, Q. J. Am. Chem. Soc. 1996, 118, 7708. Copyright 1996 American Chemical Society.

Reproduced with permission from Li, Y.; Xiang, J.; Qian, F.; Gradecak, S.; Wu, Y.; Yan, H.; Blom, D. A.; Lieber, C. M. Nano Lett. 2006, 6, 1468. Copyright 2006 American Chemical Society.

Note: 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 discussion of methods used for aberration correction in electron microscopy, see:

(a) http://​ncem.​lbl.​gov/​team/​TEAM%20​Report%20​2000.​pdf; (b) Tanaka, N.; Yamasaki, J.; Hirahara, K.; Yoshida, K.; Saitoh, K. Microscopy and Microanalysis 2006, 12, 158.

Specifications and information for TEAM 0.5 (TEAM = Transmission Electron Aberration-corrected Microscope) – the first ultra-high resolution TEM, located at the U.S. Department of Energy’s Lawrence Berkeley National Laboratory, may be found online at:

(a) http://​ncem.​lbl.​gov/​frames/​TEAM0.​5.​htm.

(b) http://​ncem.​lbl.​gov/​team/​TEAMpage/​TEAMpage.​html

(c) http://​ncem.​lbl.​gov/​team/​TEAM%20​publications.​html (publications that employ TEAM 0.5).

Note: another group at Argonne National Laboratory is also working on aberration correction for electron microscopy: http://​www.​ipd.​anl.​gov/​anlpubs/​2002/​03/​42224.​pdf – the NTEAM project, for aberration-corrected standard and in situ TEM.

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.

For a study that shows the influence of focus, sample thickness, and inner detector angle on the image, Klenov, D. O.; Stemmer, S. Ultramicroscopy 2006, 106, 889.

Note: 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.

Note: 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.

Note: 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: http://​ipn2.​epfl.​ch/​CHBU/​papers/​ourpapers/​Stockli_​ZPD97.​pdf

(top) Reproduced with permission from Gerald Kothleitner (http://​www.​felmi-zfe.​at), Electron Energy-Loss Spectroscopy (EELS) for the Hitachi HD-2000, found online at: www.​cs.​duke.​edu/​courses/​spring04/​cps296.​4/​papers/​EELS.​method.​pdf (bottom) Reproduced with permission from Brydson, R. Electron Energy Loss Spectroscopy, BIOS Scientific Publishers: Oxford, UK. Copyright 2001 Taylor & Francis Group.

A very nice tutorial on XANES and XAFS is found online at: http://​cars9.​uchicago.​edu/​xafs/​xas_​fun/​xas_​fundamentals.​pdf

For a recent 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.

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, a complimentary technique known as reflection absorption infrared spectroscopy (RAIRS), see: (a) http://​www.​uksaf.​org/​tech/​rairs.​html (b) http://​www.​cem.​msu.​edu/​~cem924sg/​Topic11.​pdf

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.

Note: Monte Carlo simulations performed by the author using the program CASINO (“monte CArlo SImulation of electroN trajectory in sOlids”), available free-of-charge on the Internet: http://​www.​gel.​usherbrooke.​ca/​casino/​What.​html

Note: 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.

For example, see: http://​www.​edax.​com/​products

Note: 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).

The SEM image of charging was taken from unpublished work by the author. The gold-coated SEM image is also from the author’s research: Vohs, J. K.; Raymond, J. E.; Brege, J. J.; Williams, G. L.; LeCaptain, D. L.; Roseveld, S.; Fahlman, B. D. Polym. News 2005, 30(10), 330.

Richards, V. N.; Vohs, J. K.; Williams, G. L.; Fahlman, B. D. J. Am. Ceram. Soc. 2005, 88(7), 1973.

(a) Spectrum reproduced with permission from Zhu, Z.; Srivastava, A.; Osgood, R. M. J. Phys. Chem. B 2003, 107, 13939. Copyright 2003 American Chemical Society. (b) Auger depth profile reproduced with permission from Zhang, Y. W.; Yang, Y.; Jin, S.; Tian, S. J.; Li, G. B.; Jia, J. T.; Liao, C. S.; Yan, C. H. Chem. Mater. 2001, 13, 372. Copyright 2001 American Chemical Society.

An example of a tandem SEM/SAM instrument is the Thermo Microlab 350: http://​www.​thermo.​com/​

Note: 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:

http://​www.​fei.​com

Schematic reproduced with permission from Miller, A. F.; Cooper, S. J. Langmuir 2002, 18, 1310. Copyright 2002 American Chemical Society.

Reproduced with permission from Rossi, M. P.; Ye, H.; Gogotsi, Y.; Babu, S.; Ndungu, P.; Bradley, J. -C. Nano Lett. 2004, 4, 989. Copyright 2004 American Chemical Society.

For example, see: Wang, Z. L.; Poncharal, P.; de Heer, W. A. J. Phys. Chem. Solids 2000, 61, 1025.

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: http://​www.​hysitron.​com/​products/​pi-series-tem-picoindenter/​

http://​nanosci.​co.​kr/​p_​img/​TEMSTM.​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://​www.​fischione.​com/​products/​model_​2000.​asp

Chiaramonti, A. N.; Schreiber, D. K.; Egelhoff, W. F.; Seidman, D. N.; Petford-Long, A. K. 2008, 93, 103113.

http://​www.​hummingbirdscien​tific.​com

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

Note: XPS is generally less damaging to beam-sensitive samples relative to SEM, EDS, and AES due to its use of “soft” X-rays, of much less energy (1–1.5 keV).

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, 12986.

(a) As you may recall from Chapter 4, the energy bands of crystalline solids (e.g., semiconductors) are denoted as parabolas in an E–k diagram. Interactive E–k diagrams for SiGe and AlGaAs are found online (respectively) at:

(i) http://​jas.​eng.​buffalo.​edu/​education/​semicon/​SiGe/​index.​html

(ii) http://​jas.​eng.​buffalo.​edu/​education/​semicon/​AlGaAs/​ternary.​html

(b) In addition to angle-resolve PES, photoluminescence spectroscopy is typically used as a nondestructive means to delineate the electronic properties of materials. For more information, see: (i) http://​www.​nrel.​gov/​measurements/​photo.​html (ii) Glinka, Y. D.; Lin, S.-H.; Hwang, L.-P.; Chen, Y.-T. J. Phys. Chem. B 2000, 104, 8652. (iii) 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://​cars9.​uchicago.​edu/​~ravel/​software/​Welcome.​html (b) http://​www.​dragon.​lv/​eda/​ (c) http://​www.​aecom.​yu.​edu/​home/​csb/​exafs.​htm (d) http://​www.​xsi.​nl/​software.​html (e) http://​www.​xpsdata.​com/​

For information regarding the quantum mechanical description of spin–orbit splitting, see: http://​ hyperphysics.​phy-astr.​gsu.​edu/​hbase/​quantum/​sodzee.​html#cl; http://​gardenofdestiny.​com/​Physics%20​of%20​Destiny.​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, 10185. (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).

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). (c) http://​www.​surrey.​ac.​uk/​ati/​ibc/​research/​ion_​beam_​analysis/​ (d) http://​www.​ee.​surrey.​ac.​uk/​SCRIBA/​ndf/​publist.​html (publications re RBS simulations). (e) http://​www-iba.​bo.​imm.​cnr.​it/​(a nice compilation of software for ion-beam analyses).

Many such systems exist; some examples include: (a) Western Michigan University (http://​tesla.​physics.​wmich.​edu/​AcceleratorFacil​ity.​php?​PG=​1). (b) Brookhaven National Laboratory (http://​tvdg10.​phy.​bnl.​gov/​index.​html). (c) National Institute of Standards and Technology (NIST, http://​physics.​nist.​gov/​Divisions/​Div846/​Gp2/​graaff.​html). (d) Yale University (http://​wnsl.​physics.​yale.​edu/​).

Note: 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 web presentation regarding SIMS see: (a) http://​www.​eaglabs.​com/​en-US/​presentations/​TOFSIMS/​Presentation_​Files/​index.​html (b) http://​www.​eaglabs.​com/​en-US/​research/​research.​html (other links to SIMS theory, applications, presentations).

For background information and recipes to study a variety of polymers using MALDI, see: http://​polymers.​msel.​nist.​gov/​maldirecipes/​maldi.​html

For a nice background on ESE, see: http://​www.​magnet.​fsu.​edu/​education/​tutorials/​tools/​ionization_​esi.​html

Note: 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.

Images reproduced with permission from Kim, Y. -P.; Oh, E.; Hong, M. -Y.; Lee, D.; Han, M. -K.; Shon, H. K.; Moon, D. W.; Kim, H. -S.; Lee, T. G. Anal. Chem. 2006, 78, 1913. Copyright 2006 American Chemical Society.

Images reproduced with permission from Verlinden, G.; Janssens, G.; Gijbels, R.; Van Espen, P. Anal. Chem. 1997, 69, 3772. Copyright 1997 American Chemical Society.

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, 114101.

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.

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, 10527. (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 a more sophisticated commercial liquid cell AFM system, see: http://​www.​veeco.​com/​escope

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) Takamura, Y.; Chopdekar, R. V.; Scholl, A.; Doran, A.; Liddle, J. A.; Harteneck, B.; Suzuji, Y. Nano Lett. 2006, 6, 1287. (b) 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.​veecoprobes.​com/​probes.​asp

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

Nanotube-terminated tips: Reproduced with permission from Hafner, J. H.; Cheung, C. -L.; Oosterkamp, T. H.; Lieber, C. M. J. Phys. Chem. B 2001, 105, 743. Copyright 2001 American Chemical Society.

Nanoparticle-terminated tips: Reproduced with permission from Vakarelski, I. U.; Higashitani, K. Langmuir 2006, 22, 2931. Copyright 2006 American Chemical Society.

Named after Brunauer, Emmett, and Teller.

Tandem TGA/DSC instruments are commercially available, for example: http://​www.​tainst.​com/​

For more information on small-angle scattering, see: (a) http://​www.​ncnr.​nist.​gov/​programs/​sans (b) 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, 16650.

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, 15157. 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.