HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY A Reference Book of Standard Data For Use In X-Ray Photoelectron Spectroscopy By C.D. Wagner WM. Riggs LE. Davis J.F, Moulder G.E. Muilenberg (Editor) Punlished By Perkin-Elmer Corporation Physical Electronics Division 8509 Flying Cloud Drive Eden Prairie, Minnesota 55344’ yy) y ) yy), ) ) ’ ,yyrvyY IY Copyright 1978 By Perkin-Elmer Corporation Physical Electronics Division Printed in U.S.A. All rights reserved ‘This book, of parts thereof, may not be reproduced in any form without permission of the publishers. y i) ) ve eey y )yX-Ray Photoelectron Spectroscopy (XPS), more Popularly known as Electron Spectroscopy for Chemical Analysis (ESCA), is now a widely-used analytical technique for investigating the chemical composition of solid surfaces. Much has already been written concerning the prin- ciples of the technique and the diverse range of applications for which it has been used. Until now, however, a concise reference work has not been available to the ESCA practitioner. Thus, we felt it desirable to assemble in a single, compact volume much of the information required by those persons using ESCA on a routine basis. Some users of this Handbook will recognize strong similarities between it and the Handbook of Auger Electron Spectroscopy, also published by Physical Electronics. This is natural since there are many similarities between ESCA and Auger spectroscopy and much was leamed from Publishing two editions of the Auger Handbook. As in the previous Handbook, we Include broad scan spectra of most of the elements, as well as, spectra from a number of oxides to indicate the differences between elemental states and ionic Preface forms. Also included is a lengthy discussion of the ESCA technique and its use. In many ways, ESCA is more complex than Auger spectroscopy. Both photoelectron lines and Auger lines are found in the spectra and a variety of satellite and other lines must be understood. In addition, more detailed chemical information can be obtained if exact line positions can be deter- mined. For these reasons, the Handbook of X-Ray Photoelectron Spectroscopy contains much precise spectroscopic energy information, in- cluding amplified Auger spectra and arrplified strong line photoelectron spectra. This Handbook is meant to serve as a guide and reference work for the long-time ESCA practi tioner as well as the newcomer to the ESCA field. We sincerely hope it serves this purpose and plays a useful role in the practice of x-ray photoelectron spectroscopy. PERKIN-ELMER, Physical Electronics Di December, 1978|. Xray Photoelectron Spectroscopy 1. Introduction 2, Principles of the Technique 3. Preparing and Mounting Samples \. Removal of Volatile Material . |. Removal of Non-volatile Organic Contaminants. s Surface Etching . Abrasion Fracture and Scraping Grinding to Powder . Mounting Powders for Analysis . |. Considerations of Mounting Angle XZO™mM90 wp 4, Experimental Procedure . A. Experimental Technique for Obtaining Spectra . : B. Instrument Calibration . Programming Scans for An Unknown. Sample .. (1) Survey Scans (2) Detail Scans 5, Data Interpretation : A. The Nature of the Spectrum .... (1) General Features (2) Kinds of Lines B. Line Identification .. 12 212 - 16 Contents ©. Chemical State Identification .........17 (1) Determination of Static Charge on Insulators (2) Photoelectron Line Chemical Shifts and Separations (9) Auger Line Chemical Shifts and the Auger Parameter (4) Satellite Lines and Peak Shapes D. Quantitative Analysis .. E, Determination of Element Location -...23 6. How To Use This Handbook ..... Il. Standard ESCA Spectra of the Elements and Line Energy Information... ..6eee0000 028 168 2, References for Line Energy Information ..174 1, Tables of Auger Parameter Data . UL Appendix . 179 Table 1. Line Positions from Mg X-rays (byelement)....... Table 2. Line Positions from Al X-rays (by element) . : Table 3. Line Positions from Mg Xrays (numerical order) . : Table 4, Line Positions trom Ai xrays. (numerical order) 187 Table 5. Atomic Sensitivity Factors ........188 Table 6. Periodic Table of the Elements... .. .189 Table 7. Alphabetical Index of the Spect'a. . 190 --182 184 +186eee a I. X-RAY PHOTOELECTRON SPECTROSCOPYSurface analysis by ESCA involves irradiation of the solid in vacuo with monoenergetic soft x-rays and sorting the emitted electrons, by energy. The spectrum obtained is a plot of the number of emit- ted electrons per energy interval versus their kinetic energy. Each element has a unique elemen- tal spectrum, and the spectral peaks from a mix- ture are approximately the sum of the elemental peaks from the individual constituents. Since the mean free path of the electrons is very small, the electrons which are detected originate from only the top few atomic layers. Quantitative data can be obtained from the peak heights or areas and iden- tification of chemical states often can be made from the exact positions and separations of the peaks, as well as from certain spectral contours. 1. Introduction This Handbook is designed to furnish the usar with much of the information necessary to use ESCA for diverse types of surface analysis. Information is, provided on methods of sample preparation, data gathering, identifying elements present, icentify- ing the chemical states of surface constituents, obtaining quantitative information on the elements present, and determining elemental distribution by depth and by phase. Survey spectra, strong line spectra, and Auger group spectra (x-ray excited) for most of the elements and some of their compounds are includ- ed, Plots and tables of spectroscopic energy data that will aid in the identification of chemical states, are also included with the spectral information, PERKINELVER 32. Principles of the Technique Surface analysis by xray photoelectron spec- troscopy (XPS), more commonly known as electron spectroscopy for chemical analysis (ESCA), is ac- complished by irradiating a sample with monoenergetic soft x-rays and energy analyzing the electrons emitted. MgKa x-rays (1253.6 eV) or AlKa x-rays (1486.6 eV) are ordinarily used. These photons have limited penetrating power in a solid, Of the order of 1-10 micrometers, They interact with atoms in this surface region by the photoelectric effect, causing electrons to be emitted. The emit- ted electrons have kinetic energies given by: KE = hy — BE - 4, o where hy is the energy of the photon, BE is the binding energy of the atomic orbital from which the electron originates, and 4, Is the spectrometer work, function. The binding energy may be regarded as an ioniza- tion energy of the atom for the particular shell in- volved. Since there is a variety of possible ions from each type of atom, there is a corresponding variety of kinetic energies of the emitted electrons. Moreover, there is a different probability, or cross- section, for each process. The variety of ionization processes for iron and uranium are shown schematically in Figure 1. The Fermi level cor- responds lo zero binding energy (by definition), and the depth beneath the Fermi level in the Figure in- dicates the relative energy of the ion remaining after electron emission, or the binding energy of the electron. The lengths of the lines indicate the relative probabilities of the various ionization pro- cesses. The p, d, and f levels'become split upon ionization, leading to vacancies in the Pye, Psa, Gan daa, fy) ANG fyp in the ratio 1:2 for p levels, 2:3 for d levels, and 3:4 for f levels, 4 PuysicaLetecrronics eam eve, au a ss ae ee eeeee cae energies for iron and uranium. (Line lengths are proportional to ionization cross-section and depths below Fermi level are proportional toIn addition to the photoelectrons emitted in the photoelectric process, Auger electrons are emitted due to relaxation of the energetic ions left after photoemission. This Auger electron emission oc- curs roughly 10" seconds after the photoelectric event. (The competing emission of a fluorescent x-ray photon Is a minor process in this energy range, occurring less than one percent of the time.) In the Auger process, shown in Figure 2, an outer electron falls into the inner orbital vacancy, and a second electron is emitted, carrying off the excess energy. The Auger electron possesses kinetic energy equal to the difference between the energy of the initial ion and the doubly-charged final lon, and is independent of the mode of the initial ioniza- tion. Thus, photoionization normally leads to two emitted electrons, a photoelectron and an Auger —eeeeee— sae a rE woraeLectRon PHoToN tee A AUGER ELECTRON se cone Figure 2. Diagram of the photoelectric process (top) and the Auger process (bottom). electron. Of course, the energies of the electrons emitted cannot exceed the energy of the icnizing photons. Probabilities of interaction of the electrons with matter far exceed those of the photons, sc while the path length of the photons Is of the order of micrometers, that of the electrons is of the order of tens of Angstroms. Thus, while ionization occurs to a depth of a few micrometers, only those elec- trons that originate within tens of Angstroms below the solid surface can leave the surface without energy loss. It is these electrons which produce the peaks in the spectra and are most useful. Those that undergo loss processes before emerging form the background. Experimental data 100 cs ® # vo eae vot . . 7 2 v oe 2 + Atos ‘a= caraon (oy LeCrRow escareoePTH rr a (EV ELECTRON ERGY, (ov) Figure 3. Electron mean tree paths in various materials, (com tabulation by C. J, Powell, Surface Science, 444 (1974) p. 289‘on mean free paths of electrons in various materials are shown in Figure 3. The electrons leaving the sample are detected by an electron spectrometer according to their kinetic energy. The analyzer normally is operated as an energy “window”, accepting only those electrons, having an eneray within the range of this fixed win- dow, referred to as the pass energy. Scanning for different energies is accomplished by applying a variable electrostatic field, before the analyzer is reached, This retardation voltage may be varied from zero up to the photon energy. Electrons are detected as discrete events, and the number of electrons for a given detection time and energy is, stored digitally or recorded using analog circuitry. 3. Preparing and Mounting Samples In the majority of ESCA applications, sample Preparation and mounting are not critical. Typical- ly, the sample can simply be mechanically attached to the specimen mount and analysis begun, with the sample in the ‘as-received’ condi tion, Sample preparation is even discouraged i many cases, especially where the natural surface is of interest, since almost any procedure will tend to modify surface composition. For those samples where special preparation or mounting procedures are necessary, the following techni- ques may be used. ‘A. REMOVAL OF VOLATILE MATERIAL. Ordinarily any volatile material must be removed from the sample before analysis, although in ex- ceptional cases, when the volatile layer is of in- terest, the sample may be cooled for analysis. Removal of volatile materials can be done by long-term pumping in a separate vacuum system or by washing with a suitable solvent. Sampies can be washed efficiently in a Soxhlett extractor with a suitable solvent sufficiently volatile that it quickly evaporates from the sam- ple after removal from the extractor. Choice of the solvent can be critical. Hexane or other light 6 prvsicat evectRonics hydrocarbon solvents are probably least likely to transform the surface, providing the solvent pro- perties are satistactory. It is desirable to do the extraction under a nitrogen atmosphere if the ‘sample is likely to be sensitive to‘oxygen. B. REMOVAL OF NON-VOLATILE ORGANIC CONTAMINANTS. When the nature of an organic contaminant is not of interest, or when a contaminant obscures underlying inorganic material that is of interest, it may be removed in a Soxhlett extractor as described above. Freshly distilled solvent should be used to avoid the possibility of con- tamination by high boiling point impurities within the solvent. C. SURFACE ETCHING. lon sputteretching or other erosion techniques, such as the use of oxygen atoms on organic materials (see Section |.5.E., p. 25), can also be used to remove surface contaminants. Argon ion etching is also commonly used to obtain i formation on composition as a function of depth into the specimen. It should be noted, however, that use of these methods for surface removalare likely to change the chemical nature of the surface. Thus, identification of the remaining chemical states may not accurately reflect the initial composition. D. ABRASION. Abrasion of a surface can be accomplished without significant contamination by using silicon carbide paper #600. This does cause local heating, so that reaction with environmen tal gases may occur (e.g. oxidation in air and for- mation of nitrides in nitrogen). The roughness produced will reduce the ESCA signal intensity relative to that of a smooth sample. Use of this technique usually provides intense spectra of metals along with a contribution from the oxides andior nitrides that form on the surface. Alkali and alkaline earth metals cannot be satistactori- ly prepared in this manner. Spectra of such samples can be obtained only with rigorous ultra-high vacuum preparation and measure- ment conditions. E, FRACTURE AND SCRAPING. With proper equipment, many materials can be fractured or scraped within the test chamber under ultra-high vacuum conditions. While this obviates contamination by reaction with at- mospheric gases, attention must nevertheless, be given to unexpected results that can occur. When fracturing, the fracture might occur along grain boundaries, for example, and scraping can cover hard material with soft material when the system is multi-phase. F. GRINDING TO POWDER. Spectra reasonably characteristic of bulk com- position are most frequently obtained on samples ground to a powder in an alumina mor- tar. Harder surfaces than alumina can be used, but they are expensive for general use. Again, protection of the fresh surfaces from the at- mosphere is required. When grinding samples, localized high temperatures can also be pro- duced, so grinding should be done slowly to minimize chemical change at the newly created surfaces. The alumina mortar should be well cleaned before re-use, preferably ending with a concentrated nitric acid cleaning, followed by rinsing with distilled water, and thorough drying, G. MOUNTING POWDERS FOR ANALYSIS. There are a number of methods that can be used to mount powders for analysis. Perhaps the most widely used method is to carefully and lightly dust the powder on polymer film based adhesive tape with a camel’s hair brush. The powder must be dusted on lightly, with no wip- ing strokes across the powder surface. Many researchers shun organic tape for UHV work, but certain types have been used successfully in the 10? Torr range. Alternative methods for mounting powders in- clude pressing the powder into an indium foil, supporting the powder on a metallic mesh, pressing the powder into pellets, and simply de- positing the powder by gravity. With the indium foil method, the powder is pressed between two pieces of pure foil. The pieces are :hen separated and one of them mounted for analysis. Success with this technique has been varied. Sometimes bare indium remains expos- ed and, if the sample is an insulator, parts of the powder can charge differently from other parts Differential charging can also be a problem when a metallic mesh is used to suppor: the powder. If a press is used to form the powder in- to a pellet of workable dimensions, a press with, hard and extremely clean working surfaces should be used. If a specimen holder with a horizontal sample surface is used, the powder can simply be deposited by gravity in a uniform layer. With this method, care must be taken in pumpdown to ensure that gas evolution does not disturb the powder. PERKIN-ELMER 7yyy vv dD DD H. CONSIDERATIONS OF MOUNTING ANGLE. In ESCA studies the sample mounting angle is not critical, but it does have some effect on the spectra. The use of a shallow electron take-off angle accentuates the spectrum of any layer segregated on the surface, whereas a sample mounting angle normal to the analyzer axis minimizes the contribution from such a layer. This effect can be utilized in estimating the depth of atoms contributing to the spectrum. It is not limited to planar surtaces, but is even observed with powders, though the effects are muted. The geometry of the double pass cylindrical-mirror analyzer used to obtain the spectra presented in this Handbook effectively integrates over a large range of take-off angles when used in the normal configuration. This reduces the effect of variations in sample geometry and mounting angle to an insignifi- cant level in most cases. However, use of a 50° sample mounting angle in conjunction with the angle-resolved aperture inside the analyzer allows the take-off angle to be varied without changing the sample mounting angle. Thus, take-off angle effects can be minimized for routine work, or emphasized when desired (see Section 1.5.E., p. 25) 4. Experimental Procedure A. EXPERIMENTAL TECHNIQUE FOR OBTAINING. SPECTRA. All spectra in this Handbook were obtained us- ing a PHI Model 550 ESCA/SAM system. A schematic diagram of the apparatus, shown in Figure 4, indicates the relationship of major ‘components, including the electron energy analyzer, the xray source, and the fon gun used for sputter-etching. The Model 25-260, Precision Electron Energy Analyzer, incorporated in the ESCAISAM is a double pass, oylindrical-mirror type analyzer (CMA) with a retarding grid input stage. The xray source is a standard flange- mounted Physical Electronics source which can be configured with a magnesium or an aluminum anode. All of the spectra in the Hand- book were taken with an x-ray source power of 600 watts (10Kv-60 ma).As shown in Figure 4, the specimens were mounted on the end of the sam- ple introduction probe at an angle of 50° with 8 PHysicaL eLecrRonics respect to the analyzer axis. The x-ray source is located perpendicular to the analyzer axis and the ion beam is nearly normal to the sample surface. In the ESCA/SAM System, energy distribution, energy resolution and the size of the analysis area are strictly a function of the analyzer. For all of the spectra in the Handbook the analyzer ‘was operated in the retarding mode. This gives an eneray distribution function with intensity proportional to E". The retarding grids are used to scan the spectrum while the CMA is operated at a constant pass energy. This results in con- stant resolution (AE) across the entire energy spectrum. The size of the analysis area is de- fined by the size of the circular apertures at the output of the CMA stages. Analyzer energy resolution (AE/E) is also determined by these apertures. In the Precision Electron Energykan since, f MAREN. 5 “aR HORE iY mae cones wa a at PULSE COUNTING Sean ves | cour, | sue ett, | cata | “aR sxc Sa rciyacsoweo eo site a Figure 4, Schematic representation of the PHI Model $50, ESCA'SAM system. Analyzer, three different aperture sizes are available. All spectra in the Handbook were ob- tained using the largest apertures. Use of the large apertures results in maximum signal inten- sity, a circular analysis area approximately Smm in diameter, and energy resolution which is 2% of the pass energy. All spectra obtained while compiling the data for the Handbook were recorded and stored us- ing a PHI Multiple-technique Analytical Com- puter System. The instrument was calibrated Weekly and the calibration was checked several times each day during data acquisition. The ana- lyzer work function was determined assuming the binding energy of the gold 4f,, peak to be 838 eV. All survey spectra, scans of 1000 eV or more, were taken at a pass energy of 50 eV, pro- viding an instrumental resolution of 1 eV. The narrow scans of strong lines are, in most cases, just wide enough to encompass the peak(s) of interest and were obtained with a pass energy of 25 eV. The narrow spectra are necessary to determine accurately the energy and shape of the strong lines. On insulating samples, a high resolution spectrum of the adventitious hydrocarbon on the surface of the sample was taken to use as a reference for charge correc- tion. It has been experimentally determined that the binding energy for the adventitious carbon peak is approximately 284.6 eV. The samples analyzed to obtain the spectra in the handbook were standard materials of known composition. Metal foils and polycrystalline materials with large surface areas were mechanically held to the specimen probe. Powder samples were ground with a mortar and pestle to expose fresh surfaces and dusted onto adhesive tape. Most elemental standards were sputteretched immediately prior to analysis to remove surface contaminants. Most com- PERKINELMER 9Pounds, however, were ground and the freshly exposed surface was analyzed without etching in order to avoid possible changes in surtace chemistry. Several materials, for example mer- cury, were cooled for the analysis, and xenon and argon were imbedded in graphite via ion im- plantation just prior to analysis. INSTRUMENT CALIBRATION. To ensure the accuracy of the data presented in the Handbook, the instrument used to obtain the data was calibrated regularly throughout the data gathering process. The energy scale was periodically calibrated using a high precision digital voltmeter. Then, several times each day, the calibration was checked for accuracy. ‘The best way to check the calibration, and the method used here, is to record suitable lines from a known, conducting specimen. Typically, the Audf or Cu2p and 3p lines are used. The lines should be recorded with a narrow sweep width in the range of 5-10 eV, and a pass energy of 25 eV or less, corresponding to the pass energy normally used for high resolution scans, should be used. The peak position is determined ac- curately by drawing cords parallel to the baseline and drawing the best straight line or simple monotonic curve through the midpoints, as shown in Figure . The peaks should occur at exactly the correct position in the spectrum, Figure 5, Method for accurately locating the peak position from a narrow scan. 10 PaysicaL eLecTRoNics There is not as yet general agreement on ac- curate values of any standard line energies, but at this point the following is recommended for clean gold and copper (on a binding energy scale): Curp ae 932.4 eV Cu(LjM,M,) 567.9 eV (Al radiation) 334.9 eV (Mg radiation) Cusp ae 749 eV Aualya 83.8 eV Since the 2py, and 3py, photoelectron peak energies of copper are widely separated in energy, measurement of these peak binding energies provides a quick and simple means of checking the magnitude of the binding energy scale. Utilizing all of the above standard energies establishes the magnitude and lineari- ty of the energy scale and its position, ie. the location of the Fermi level. PROGRAMMING SCANS FOR AN UNKNOWN SAMPLE. For a typical ESCA investigation where the sur- face composition is unknown, a broad scan survey spectrum should be obtained first to identity the elements present. Once the elemen- tal composition has been determined, narrower detailed scans of selected peaks can be used for a more comprehensive picture of the chemical composition. This is the procedure that has been followed in compiling data for the Handbook, even though specimen composition was known prior to analysis. (1)Survey Scans. Ordinarily, a scan range from 1000-0 eV binding energy is sufficient for the identification of all detectable elements. In a few cases, such as with Zn, Mg, and Na, the strongest lines may occur at a binding eneray above this range. Most spectra in this Hand- book were recorded with scan ranges of 1000-0 or 1100-0 eV binding energy. There area few, especially where AlKe xrays were used, that cover a wider range. In an unknown sample, if specific elements are suspected at low concentrations, their standard spectra should be consulted before programming the survey scan. If the strongest line occurs above 1000 eV binding energy, the scan range can be modified accordingly. An analyzer pass energy of 100 eV, in conjunc tion with the normal ESCA aperture settings, is recommended for survey scans with the ESCA/SAM system. These settings result in adequate resolution (AE = 2eV) for elemental identification and produce very high signal in: tensities, minimizing data acquisition time and maximizing elemental detectability (2)Detail Scans. For purposes of chemical state identification, for quantitative analysis of minor components and for peak deconvolu- tion and other mathematical manipulations of the data, detail scans must be obtained for precise peak location and for accurate registration of line shapes. There are some logical rules for this programming: i.Scans should be wide enough to encom- pass the background on both sides of the region of interest, yet narrow enough, less than 25 eV, to permit determination of the exact position of the peaks. If these re- quirements cannot be met in one region, two regions of the spectrum must be pro- grammed. Sufficient scanning must be done, within the time limitations of the i analysis, to obtain good counting statistics and clear spectra. |.Peaks from any species thought to be radiation-sensitive or transient should be tun first. Otherwise any convenient order may be chosen. If the Cts line is to be used for charge referencing, it should preferably be run ear- ly and again late in the sequence or, alter- natively, run at a time closest to the region of greatest interest. This is because there is occasionally a slight change in steady- state static charge with time (cf Section 18.C., p.17) No clear guidelines can be given on the maximum duration of data gathering on any one sample, It should be recognized, however, that chemical states have vastly varying degrees of radiation sensitivity, and for any one set of irradiation condi- tions there exists for many samples a period beyond which itis impractical to at tempt to gather data. With the ESCAISAM, an analyzer pass energy of 25 eV (AE = 0.5 eV) is normally adequate for routine detail scans. Where higher resolution is needed, lower pass energies can be utilized with correspon- ding loss of signal intensity. For the ultimate in resolution, the smaller aper- tures should be used in conjunction with an analyzer pass energy of 10 or 15 eV. PERKIN-ELMER 115. Data Interpretation A. THE NATURE OF THE SPECTRUM (1) General Features, The spectrum is displayed a8 a plot of electron binding energy versus the number of electrons in a fixed, small energy interval. The position on the kinetic eneray scale equal to the photon energy minus the spectrometer work function corresponds to a binding energy of zero with reference to the Fermi level (equation 1). Therefore, a binding energy scale beginning at that paint and in- creasing to the left is customarily used. ‘The spectra in this Handbook are typical for the various elements. The well-defined peaks are due to electrons that have not lost energy in emerging from the sample. Electrons that have lost energy form the raised background at binding energies higher than the peaks. The background is continuous because the energy loss processes are random and multiple, The “noise” in the spectrum is not instrumen- tal, but is the consequence of the collection of single electrons as counts randomly spaced in time. The standard deviation for counts collected in any channel is equal to the square root of the counts, so that the per- cent standard deviation is 100/ (counts)"®, The signal/noise ratio is then proportional to the square root of the counting time. The background level upon which the peak is superimposed is a characteristic of the specimen and the transmission charac- teristics of the instrument. (2)Kinds of Lines. Several types of peaks are observed in ESCA spectra. Some are fun- PHYSICAL ELECTRONICS damental to the technique, and are always observed. Others are dependent upon the ex- act physical and chemical nature of the sam- ple. The following describes the various spec: tral features that are likely to be encountered. i.Photoelectron Lines. The most intense of the photoelectron lines are usually relative- ly symmetrical and are typically the nar- rowest lines observed in the spectrum. Photoelectron lines of pure metals can, however, exhibit considerable asymmetry due to coupling with conduction electrons. Peak width is a convolution of the natural line width, the width of the x-ray line and the instrumental contribution to the line width, Less intense photoelectron lines at higher binding energies are usually wider by 1-4 eV than the lines at lower binding energies. All of the photoelectron lines of insulating solids are of the order of 0.5 eV wider than photoelectron lines of conduc- tors. The approximate binding energies of all photoelectron lines detectable are catalogued in Tables 1-4 of the Appendix. Auger Lines, These are, more properly, groups of lines in rather complex patterns. There are four main Auger series obser- vable in ESCA. They are the KLL, LMM, MINN, and NOO series, identified by speci- fying the initial and final vacancies in the Auger transition, The KLL series, for exam- ple, includes those processes with an in- itial vacancy in the K shell and final double vacancy in the L shell. The symbol V, e.g. KVV, indicates that the final vacancies are in valence levels. The KL series has, theoretically, nine lines and others havestill more, Since Auger lines have kinetic energies that are independent of the ioniz- ing radiation they appear on a binding energy plot to be in different positions when ionizing photons of different eneray (Le. different x-ray sources) are used. Core- type Auger lines (with final vacancies deeper than the valence levels) usually have at least one component of intensity and width similar to the most intense photoelectron line. Positions of the more prominent Auger components are catalogued along with the photoelectron peaks in Tables 1 through 4 in the Appendix. ji, Xway Satellites, The x-tay emission spec- trum used for irradiation exhibits not only the characteristic xay, but some minor x-fay components at higher photon energies. For each photoelectron peak that results from the Ka x-ray photons, there is a family of minor peaks at lower binding energies, with intensity and spacing characteristic of the x-ray anode material. The pattem of such satellites for Mg and Al is shown in Figure 6 and Table 1. Wen si coun pen seconD Fen UNIT ENERGY INTER) mao wa aie Fi ts0 zo 200. 20202100 NDI ENERGY, ev Figure 6. Mg xray satellites (Cts graphite spectrum, Table 1 — Xray satelite energies and intensities a2[ ae [es | | a displacement, ev| 0 [a4 102|17.5 [200 [aes relative height | 100/80] 41] 0.55] 0.45] 05, 1 displacement, ev] o [9.8 |118| 20.1 |23.4 feo7, relative heignt [100 }64| 32] 04) °03 | 055 iv. Xtay_ "Ghosts", Occasionally x-adiation from an element other than the xray source anode material impinges upon the sample, resulting in small peaks cor- responding to the most intense spectral peaks, but displaced by a characteristic energy interval. These lines can be due to Mg impurity in the Al anode, or vice versa, Cu from the anode base structure or generation of x-ray photons in the aluminum foil x-ray window. On occasion, such lines can originate via generation of x-rays within the sample itself. This last possibility is rare, because the probability of xray emission is low relative to the ‘Auger transition. Nevertheless, such minor lines can be puzzling. Table 2 indicates where such peaks are most likely to occur, relative to the most intense photoelectron lines. Since the appearance of “ghost” lines is a rare occurrence, they should not be considered in line identification until all other possibilities are excluded. Tablo 2 — Displacements of xay “ghost” lines (Apparent binding energy of the “ghost line minus that of the parent photoelectron line) Contaminating Radiation © (Ka) Cu (La) 556.9 Mg (Ke) 233.0 A (Ka) - PERKIN-ELMER 13Ip_Lines, Not all photoelectric pro- Gesses are simple ones, leading to the for- mation of ions in the ground state. Rather often, there is a finite probability that the ion will be left in an excited state, a few electron volts above the ground state. In this event, the Kinetic energy of the emitted photoelectron is reduced, with the dif ference corresponding to the energy dit- ference between the ground state and the excited state. This results in the formation of a satellite peak a few electron volts lower in Kinetic energy (higher in binding energy) than the main peak. As an example, the characteristic shake-up line for carbon in unsaturated compounds, a shake-up pro- cess involving the energy of the nen" tran- sition, is shown in Figure 7. | oe 0 Figure 7. The rbond shakeup satelite for the Cis line in polystyren In some cases, most often with paramagnetic compounds, the intensity of the shake-up satellite may approach that of the main line. More than one satellite of a principal photoelectron tine can also be observed, as shown in Figure 8. The occur- rence of such lines is sometimes more ap- parent in Auger spectral contours, of which PHYSICAL ELECTRONICS a a) ‘ING ENERGY, ov Figure 8. Examples of shakoup lines observed with the ‘copper 2p spectrum. an example is presented in Figure 9. The displacements and relative intensities of shake-up satellites can sometimes be useful in identifying the chemical state of an element, as discussed in Section I.5.C., p. 20. vi, Multiplet Splitting. Emission of an electron from a core level of an atom that itself has a spin (unpaired electrons in valence levels)ee et me : wel 9) we na a 04 SBS Se SS asa Sas ‘INDING ENERGY, ev oa Figure 9. Some effects of chemical state on Auger ine sivas even, ev shapes, can create a vacancy in two or more ways. The coupling of the new unpaired electron left after photoemission from an s-type or- bital with other unpaired electrons in the atom can create an ion with either of two configurations and two energies. This results in a photoelectron line that is split asymmetrically into two components similar to the one shown in Figure 10. Splitting also occurs in the ionization of p levels, but the result is more complex and subtle. In favorable cases, it results in an apparent slight increase in the spin doublet separation, evidenced in the separation of the 2Pxe and 2pyq lines in first row transi- tion metals, and the generation of a less easily noticed asymmetry in the line shape of the components. Often such effects on the p doublet are obscured by shake-up lines. Figure 10, Multiplt splitting n the Cr 3 line, vii. Energy Loss Lines. With some materials, there is an enhanced probability for loss of a specific amount of energy due to interac- tion between the photoelectron and other electrons in the surface region of the sam- ple. An example of this is shown in Figure 11. The enhanced probability of energy loss produced a distinct and rather sharp hump at an energy about 21 eV above the binding energy of the parent line. Under certain conditions of spectral display, energy loss lines can cause confusion. Such phenomena in insulators are rarely sharper than that shown in Figure 11, and are usually much more muted. They are, of course, different in each solid medium. With metals, the effect is often much more dramatic, as indicated by the loss lines for PERKIN-ELMER 15aw—— Figure 11, |. Energy loss envelope trom the O15 line in SiO, aluminum shown in Figure 12, Energy loss to the conduction electrons occurs in well- defined quanta characteristic of each metal. The photoelectron line, or the Auger line, is successively mirrored at intervals of higher binding energy, with reduced inten- sity. The energy interval between the primary peak and the loss peak is called the plasmon energy. The so-called “bulk [tet te a a a ‘Nowa Evenot Figure 12, Energy loss (plasmon) lines associated with the 2s ling of aluminum (8 plasmon at b). 15.32 rote surlace 16 PhysicacetectRonics plasmons" are the more prominent of these lines. A second series, the “surface plasmons”, exists at energy intervals deter- mined by dividing the bulk plasmon energy by V2, The effect is not easily observable in non-conductors, nor is it prominent in all conduetors. vili, Valence Lines and Bands, Lines of low in- tensity occur in the low binding energy region of the spectrum between the Fermi level and about 10-15 eV binding energy. These lines are produced by photoelectron emission from molecular orbitals and from solid state energy bands. Differences be- tween insulators and conductors are especially noted by the absence or presence of electrons from conduction bands at the Fermi level. B. LINE IDENTIFICATION : In general, interpretation of the ESCA spectrum is most readily accomplished by first identifying the lines that are almost always present, specifically those of carbon and oxygen, then identifying major lines and associated weaker lines and, lastly, identifying the remaining weak lines. The following step-by-step procedure generally simplifies the data interpretation task and minimizes data ambiguities. Step 1, The Cts, Ots, C(KLL) and O(KLL) lines are usually prominent in any spectrum. Iden- tity these lines first along with all derived x-fay Satellites and energy loss envelopes. Step 2, Identify other intense lines (of Appen- Tables) present in the spectrum. Then label any related satellites and other less in- tense spectral lines associated with those elements. Keep in mind that some lines may be interfered with by more intense, overlap- ping lines from other elements. The mostserious interferences by the carbon and oxy- gen lines, for example, are Rudd by Cis, V2p and Sb3d by Ots, I(MNN) and Cr(LMM) by O(KLL), and Ru(MNN) by C(KLL). Step 3, Identify any remaining minor lines. In doing this, assume they are the most intense lines of an unknown element. If not, they should already have been identified in previous steps. Again, possible line in- terterences should be kept in mind. Small lines that seem unidentifiable can be ghost lines. This possibility can be checked for the more intense parent photoelectron lines us- ing Table 2 (p. 13). Step 4, Check the conclusions by noting the spin doublets for p, d, and f lines. They should have the right separation (cf Appendix Tables 11 and 2, pp. 182 and 184) and should be in the correct intensity ratio. The ratio for p lines should be about 1:2, d lines 2:3, and flines 3:4, except that p lines, especially 4p lines, may be less than 1:2, C. CHEMICAL STATE IDENTIFICATION The identification of chemical states depends primarily upon the accurate determination of line energies. To determine line energies ac- curately, the voltage scale of the instrument must be precisely calibrated (cf Section 1.4.8., p. 10), a line with a narrow sweep range must be recorded with good statistics (of the order of several thousand counts per channel above background), and accurate correction must be made for static charge if the sample is an insulator. (1) Determination of Static Charge on Insulators. During analysis, insulating samples tend to acquire a steady-state charge of as much as several volts. This steady-state charge is a balance between electron loss from the sur- face by emission and electron gain by con. duction or by acquisition of slow or thermal electrons from the vacuum space. The steady. state charge, usually positive, can be minimized by adding slow electrons to the vacuum space with an adjacent neutralizer or flood gun. It is often advantageous to de this to reduce differential charging and to sherpen the spectral lines. A serious problem is the exact determination of the extent of charging. Any positive charg: ing adds to the retardation and tends to make the peaks appear at higher binding energy, whereas excessive compensation can make the peaks shift to lower binding energy. The following are five methods that are usually valid for charge correction on insulating samples: i.Measurement of the position of the Cts line from adventitious hydrocarbon nearly always present on samples introduced from the laboratory environment or from a glove box. This line, on unsputtered inert metals such as gold or copper, appears at 284.6 eV, so any shift from this value can be taken as a measure of the static charge. (Much of the literature uses the more ap- proximate value of 286). At this time, it is not known whether a reproducible line position exists for carbon remaining on the surface after ion beam etching. iiEvaporation of a trace of gold ontc the sample after the spectra have been record- ed. The Au4f doublet is then recorded as well as a repetition of the most important line in the sample spectrum. It is then assumed that the potential of the gold islands reflects the new steady-state charge of the surface of the sample. Care PERKIN-ELMER 1718 ‘must be taken to ensure that the gold is present in trace quantities so that the original spectrum js little affected. In this procedure there may well be a double cor- rection. The steady-state potential after gold is deposited may well be different from the steady-state potential in the original sample before gold deposition. The use of an internal standard, such as a hydrocarbon moiety in the sample, The value of 284.6 eV for the Cts line is recommended, iv.The use of an insulating sample so thin that it effectively does not insulate. This can be assumed if the spectrum of the underlying conductor appears in good in- tensity and line positions are not affected by changes in electron flux from the charge neutralizer. v.For the study of supported catalysts or similar materials, one can adopt a suitable value for a constituent of the support and Use that to interrelate binding energies of different samples. One must be certain that treatments of the various samples are not so different that the inherent binding energies of support constituents are changed. ‘Some precautions should be borne in mind, If the sample is heterogeneous on even a micrometer scale, particles of different materials can charge to different extents, and interpretation of the spectrum Is complicated accordingly. One cannot physically mix a con- ducting standard like gold or graphite of micron dimensions with a powder and validly Use the goid or graphite line in order to cor- rect for static charge. Puvsicac eLecTRowics ’ voy yy (2)Photoelectron_Line Chemical Shifts and Separations. An important advantage of ESCA is the ability to obtain information on chemical states from the variations in binding energies, or chemical shifts, of the photoelec- tron lines. This has been extremely useful in many studies. While many attempts have been made to caiculate chemical shifts and absolute binding energies, the factors in- volved, especially in the solid state, are im- Perfectly understood and one must rely on ex- perimental data on standard materials, The tables accompanying the spectra in this Handbook record considerable data from the literature as well as data obtained specifically for this Handbook. All literature data have been carefully evaluated and corrected, and are believed reliable These data have been adjusted to the instrumental calibration and static charge reference values given above, and are, therefore, directly compatable. Since occasional line interferences do occur, it is sometimes necessary to use a line other than the most intense one in the spectrum, Chemical shifts are very uniform among the photoelectron lines of an element, so that line separations rarely vary by more than 0.2 eV. However, exceptional separations can occur in paramagnetic materials because of multiplet spiitting. Separations of photoelec- tron lines can be determined approximately from Tables 1 and 2 in the Appendix (pp. 182 and 184). @)Auger Line Chemical Shifts and the Auger ameter. Core-type Auger lines (transitions (tn sme cases, erent binding enray valves appaning in the erature for he same materi! eoulo not be recone! ec, Bund no grounds could be ound Yor enoosing One over te ‘tre. such eases, moro than One value i included to Inaleate the degre of uncertainty.ending with double vacancies below the valence levels) usually have at least one com ponent that is narrow and intense, often near. ly as intense as the strongest photoelectron (ct. spectra for F, Na, As, In, Te, and Pb). There are four core Auger groups that can be generated by Mg or Al xrays: the KLL (Na, Mg): the LMM (Cu, Zn, Ga, Ge, As, and Se} the MNN (Ag, Cd, in, Sn, 8b, Te, |, Xe, Cs, and Ba; and the NOO (Au, Hg, Tl, Po, and Bi). The MNN lines in the rare earths, while accessi- ble, are very broad because of multiplet split- ting and shake-up phenomena with most of the compounds. Valence-type Auger lines (final states with vacancies in valence levels), such as those for O and F (KL); Mn, Fe, Co, and Ni (LMM); and Ru, Rh, and Pd (MNN), can be intense and are, therefore, also useful. Chemical shifts occur with Auger lines as well as with photoelectron lines. The chemical shifts are different from those of the photoelectron lines, however, and usually are Considerably more pronounced. This can be very useful for identification of chemical states, especially in combination with photoelectron chemical shift data. If data for the various chemical states of an element are plotted, with the kinetic energy of the photoelectron line on the abscissa and that of the Auger line on the ordinate, a two- dimensional chemical state plot is obtained. Such plots accompany the spectra for F, Na, Cu, Zn, As, Ag, Cd, In, and Te. With chemical states dispiayed in two dimen- sions, the method becomes more powerful as @ tool for identifying the chemical com: ponents. in the format adopted for the Hand- ook, the Kinetic energy of the Auger line is plotted against the binding energy of the photoelectron line, with the latter plotted in the -x direction {kinetic energy is still, im- plicitly, +x). the kinetic energy of the Auger electron, referred to the Fermi level, is easily calculated by subtracting from the photon energy the position of the Auger line on the binding energy scale. With this arrangement, each diagonal line represents all values of equal sums of Auger kinetic energy and photoelectron binding energy. A quantity called the Auger parameter, a, is defined as, KE, — KE, = BE, BE or, the difference in binding energy between the photoelectron and Auger lines. This dif- ference can be accurately determned because static charge corrections cancel. Then, with all kinetic energies and binding energies referenced to the Fermi level, KE, = hv - BE, ° KE, + BE, = hy te « or, the sum of the kinetic energy of the Auger line and the binding energy of the photosiec- tron line equals the Auger parameter plus the photon energy. A plot showing Auger kinetic energy versus photoelectron binding energy then becomes Independent of the energy of the photon, In general, polarizable materials, especially conductive materials, have @ high Auger parameter, while insulating compounds fall lower on the grid. The points on the two- dimensional plot are drawn as rectancular boxes at 45°, reflecting the expected error of measurement in the two perpendicular direc- tions. At present, sufficient data for the two- dimensional chemical state plots are available only for the nine elements listed above. PERKINELMER 19(4)Chemical_information From Satellite Lines and Peak Shapes, i,Shake-up Lines. These satellite lines have intensities and separations from the parent, photoelectron line that are unique to each chemical state (Figure 8). Some Auger lines also exhibit radical changes with chemical state that reflect these processes (Figure 9). With transition elements and rare earths the absence of shake-up satellites is usual- ly characteristic of the elemental or Table 3 — General guide to paramagnetic species, Maltiotet spiiting and shake-up lines are generally expected in the paramagnetic states below. diamagnetic states. Prominent shake-up patterns typically occur with paramagnetic states. Table 3 has been included as a guide to some expected paramagnetic states. Multiplet Splitting. On occasion, the ‘multiplet splitting phenomenon can’ also be helpful in identitying chemical states. The 3s lines in the first series of transition metals, for example, exhibit separations characteristic of each paramagneti Atomic No. Paramagnetic States, Diamagnatic States 22 Tit? 1199 ue = vit yt3 yee ves 24 crt2, crt8, crt 4, ort ort 3 Mn*2, Mn*3, Mn*4, Mn*8 Mat? 6 Fet?,Fe*® KaFe (CN)g, Fe (COMBr: 27 o*?, Got? CoB, Co(NOa(NHs). KCO(CN}e, COtNHalCls 8 Nit? KaNW(CN\s, square planar complexes Ey cut? cut? 2 Mo*4, Mo*® Mo*8, MoS2, KeMO(CN)g 44 Rut, Rut, Ruts Rut? a Agt? Agtt 58 cet? cet* 5970 | Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb compounds 7 wetwes 15 Ret? Ret? Ret4Re*® Rete 6 os*9,0s*4,0s*8 7 ut 92 utiute PHYSICAL ELECTRONICS W*S, Wop, WOls, WC, KeWICNIa Re*?, Re, 0s*?,08*6,0s*® 3 usschemical state. The 3s line, however, is weak and therefore is not often useful analytically. The 2p doublet separation is also affected by multiplet splitting and the lines are more intense, The effect becomes very evident with cobalt compounds where the separation varies up to one electron volt. Little utilization of this effect has yet been made. However, when first row transi- tion metal compounds are under study, it may prove useful to record accurately these line separations and make com- parisons with mode! compounds. Auger Line Shape. Valence type Auger tran- sitions form final-state ions with vacancies in molecular orbitals, The distribution of the group of lines is strongly affected, therefore, by the nature of the molecular or- bitals in the different chemical states. Although little has yet been published on this subject, the spectroscopist should bear in mind the possible utility of Auger line shapes of oxygen, fluorine, the first row transition metals (So-Ni), and Ru, Rh, and Pd, D. QUANTITATIVE ANALYSIS For many ESCA investigations, it is important to determine the relative concentrations of the various constituents. Methods for quantifying the ESCA measurement utilizing peak area sen- sitivity factors and peak height sensitivity fac- tors have been developed. The method which utilizes peak area sensitivity factors typically is the more accurate and is discussed below. The method for determining peak height and peak area is shown in Figure 13. This approach is satisfactory for quantitative work except with transition metal spectra with prominent shake- up lines. For these, it is often better to include the entire 2p region when measuring peak area, VesrcaL Heit, PEAR TO BASLE wom oxnaute 10 BASELINE AT HALE Weg 7 vanceniasxseune Benen ac Figure 13. Method for determining height, width, and area of 2 photoelectron peak. For a sample that is homogeneous in the analysis volume, the number of photoelectrons in a specific spectral peak is given foyAAT 6 where n is the number of atoms of the element per cm? of sample, f is the x-ray flux in Photonsicm*-sec, o is the photoelectric cross- section for the atomic orbital of interest in om’, @ is an angular efficiency factor for the In: strumental arrangement based on the angle bet- ween the photon path and detected electron, y is the efficiency in the photoelectric process for formation of photoelectrons of the normal photoelectron energy, iis the mean free path of the photoelectrons in the sample, A is the area of the sample from which photoelectrons are detected, and T is the detection efficiency for electrons emitted from the sample. From (5): = IfogyAAT © PERKIN-ELMER 2122 The denominator in equation 6 can be assigned the symbol S, defined as the atomic sensitivity factor. If we consider a strong line from each of two elements, then: my This expression may be used for all homogeneous samples if the ratio S,/S, is matrix independent for all materials. It is certainly true that such quantities as o and A vary somewhat from material to material (especially 2), but the ratio of each of the two quantities ojo, and d/h, remains nearly constant. Thus, for any spec- trometer, we may develop a set of relative values of S for all of the elements. A generalized expression for determination of the atom fraction of any constituent in a sample, G,, can be written as an extension of equation 7: WS, ® Zus, Values of S based on peak area measurements are indicated in Table § of the Appendix. These values are presentedrelative to the F's intensity, which has been used as a standard. The values of Sin the Appendix are based upon calculated values of o” which have been corrected for the Kinetic energy dependence of the spectrometer detection efficiency and an average value for the dependence of Aon kinetic energy of E™75(Figure 3). The values in the Appendix are only valid for, land should only be applied, when the electron energy analyzer used has the transmis: a) JH, Seotiels J Geet, Spectr. 8 129 (1976) PHYSICAL ELECTRONICS characteristics of the double pass cylindrical- mirror type analyzer supplied by Physical Elec- tronics, An example of the application of equa- tion 8 to analysis of a nearly ideal sample, polytetrafluoroethylene, is shown in Figure 14, ‘caMosiion: atom reacent THEORETICAL EXPERIMENTAL cma mz Fu? a Figure 14. Quantitative analysis of polytetratiuorosthylene (by peak area of F's and Cis). The use of atomic sensitivity factors in the man- ner described will normally furnish semiquan- titative results (within 10-20%) except in the following situations. (1) The technique cannot be applied rigorously to heterogeneous samples. It can be useful with heterogeneous samples in obtaining results in terms of the relative number of atoms detected, but one must be conscious that the microscopic character of the heterogeneous system influences the quantitative results. Moreover, an overlying contamination layer has the effect of diminishing high binding energy peaks more than those with low binding energies. (Q)Transition metals, especially of the first series, have widely varying and low values of y, whereas y for the other elements is ratheruniform at about 0.8. Thus, a value of S deter- mined on one chemical state for a transition metal may not be valid for another chemical state. (When peak interferences occur, alternative lines must sometimes be used. The ratios of spin doublets (except 4p) are rather uniform and the weaker of the pair can often be substituted, Figure 15 is a general guide to the relative peak height of the minor lines. However, with the minor lines, there is much variation in relative peak heights and widths, so the figure should be regarded as a semi- quantitative guide, of the order of +30%, The sample spectra of the elements may also be consulted, but caution must be exercised, since the spectra of the elements themselves can be somewhat different, quantitatively, from the spectra of their compounds. Occasionally an x-ray satellite from an in- tense photoelectron line interferes with measurement of a weak component. A mathematical approach can then be used to subtract the x-ray satellite before the measurement. For quantitative work it is advisable to check the spectrometer operation frequently to ensure that analyzer response is constant and op- timum, A useful test Is the recording of the three widely-spaced spectral lines from copper. Measurement of peak height in counts per se- cond should be made on 20 volt wide scans of the 2p5,, LMM Auger, and 3p lines, and the peak width of the 2pyq line should be measured as, shown in Figure 13. Maintenance of such records makes it easily noticeable if an in- strumental change occurs that would affect quantitative analysis. E, DETERMINATION OF ELEMENT LOCATION (1) Depth. There are four methods of obtaining in- formation on the depth of an element in the sample. The first two methods below utilize the characteristics of the spectrum itself, but provide limited information. The third, depth profiling by erosion of the surface, provides more detailed information but is attended by certain problems. The fourth utilizes measurements at two or more electron escape angles. i.The presence or absence of an energy loss peak or envelope indicates whether the emitting atoms are in the bulk or at the sur- face. Since electrons from surface atoms do not traverse the bulk, peaks due to the surface atoms are symmetrical above level baselines on both sides and the energy loss peak is absent. I.Elements whose spectra exhibit photo- electron lines widely spaced in kinetic energy can be approximately located by noting the intensity ratio of the lines. in the energy range above approximately 100 eV, electrons moving through a solid with lower kinetic energy are attenuated more strongly than those with higher kinetic energy. Thus, for a surface species, the low kinetic energy component will be relatively stronger than the high kinetic energy com- Ponent, compared to that observed in the pure material. The data in Figure 15 for homogeneous bulk solids can be com- pared with intensity ratios observed on unknowns to determine qualitatively the distribution of the element in the sample. Suitable elements include Na and Mg (1s and 2s); Zn, Ga, Ge, and As (2P3 and 3c); and Gd, in, Sn, Sb, Te, I, Cs, and Ba (3px and 4d, oF 3¢gz_ and 4d), PERKIN-ELMER 23ey, ’ ’ y y ,) one . aya = 18 AELIIVE weg OF otNeR SPECTRAL LES 5 emg] 8 |S | ie y= 00 alulie)alo)elalslalolefa[a fale lol alalalals|elsle| sa | sla ca] | tf re] wf mf oe | ae {Se |e | S| 2 | Mo] a | ev | co | se] | xe] a | oe |B PINs Te nase saan sT woo soe ns s 7 2 ee v Figure 15. Peak heights of minor lines relative to strong lines (based on survey spectra contained he 24 pwvsicar evecrRonics ) yFor the situation where the element is ina bulk homogeneous layer beneath a thin contaminating layer the characteristic in tensity ratio is modified in the opposite direction. Thus, for a pair of tines due to subsurface species, the low kinetic energy Tine will be attenuated more than the high kinetic energy line, distorting the characteristic intensity ratio. By observing such intensity ratios and comparing them with the values for pure bulk elements (Figure 15), itis possible to deduce whether the observed lines are due to predominant- ly surface, subsurface, or homogeneously distributed material. Depth profiling can be accomplished by controlied erosion of the surface by ion sputtering. In Table 4 are presented some data on sputter rates as a general guide. One can use this technique on organic materials, but few data are avaliable for calibration. Chemical states are usually changed by the sputter technique, but useful information on elemental distribu- tion still can be obtained. Table 4 — Some representative sputter rates, (2 keV argon ion beam with 100 yampslem* impinging on Sputter Rate, Amin’) Ta205 700 si 90 iQ. ca Pt 220 cr 140 Al 95 Au 410 3) = 20%, Another method of controlled erosion that is useful, especially with organic materials, is reaction with oxygen atoms from a plasma. This technique may also change the chemical states in the affected surface, Further, since the elements differ in their rates of reaction with oxygen atoms, the rate of removal of surtace materials will be somewhat sample dependent. iv.One may alter the angle between the plane of the sample surface and the angle of en- trance to the analyzer. At 90°, with respect to the surface plane, the signal from the bulk is maximized relative to that from the surface layer. At small angles, the signal from the surface becomes greatly en- hanced, relative to that from the bulk. The location of an element can thus be deduc- ed by noting how the magnitude of its spectral peaks change with sample orien- tation in relation to those from other elements. The electron energy analyzer used in the ESCAISAM incorporates a special aperture arrangement that permits angular resolved studies. An example of the information that can be gained through the use of this capability is shown in Figure 16. Data were obtained at high (near 90°) and low (near 15°) exit angles from a silicon sample with a thin silicon oxide overlayer. The observed intensity ratio of oxidized to elemental silicon is much greater at the small exit angle. (Insulating Domains on a Conductor, The oc- currence of steady-state charging of an in- sulator during analysis sometimes has useful consequences. Microscopic insulating do- mains on a conductor reach their own steady: PERKIN-ELMER 25ewer, we € No sretiMen NEbTRALEER i a a a Nowe even, ev specie weureazea on Figure 16. Use of aifferent electron escape angles to det depth distribution (Si 2p line from sample with approximately one monolayer overlayer) Angles indicated are electron take-oll specimen t angles relative to specimen surface. nuraautzen 1 on WITH Hines hs VOLAGE ‘ state charge, while the conductor remains at spectrometer potential. Thus, an element in ae ! the same chemical state in both phases will gnowsteacia Te exhibit two peaks. If a change is made in the supply of low energy electrons which stabilize the charge, as from the neutralizer filament, Figure 17. Use of specimen neutralizer to shitt the p: spectrum from insulating domains (Al 25, or if a bias is applied to the conductor, the foe aroser sista scape spectral peaks from the insulating phase will move relative to those from the conducting (@)Surface Distribution, ESCA is not ordinarily phase, as shown in Figure 17. For such used to obtain information on X-Y distribution heterogeneous systems, this is an extremely because a large analysis area is required for useful technique. It makes it possible to good signal intensity. With the PHI double determine whether the elements that con- ass cylindrical-mirror analyzer used in the tribute to the overall spectrum are in the con- ESCA/SAM, however, a circular area of 2-5 ducting of the insulating phase, or in both mm diameter can be imaged, depending upon phases. the apertures in use and the retarding condi- 26 PrvsicaLetectRoNicstions. This area is expressed as the full width at half maximum of the photoelectron intensi ty observed as a function of distance from the center of the imaged area. Thus, the effective 6. How to Full utilization of this Handbook can best be ac- complished by following these procedures. A. FOR QUALITATIVE ANALYSIS The elemental and chemical identification of sample constituents can be performed most readily by combining the information in the stan- dard survey spectra in Section Il with the binding energy tables (Tables 1-4) presented in the Appendix (1) First identify all major photoelectron peaks utilizing the line position tables (Tables 1-4, pages 182-187). (\Check to see that the determinations made in step 1 are consistent with the standard survey spectra. @)ldentify the Auger electron peaks by the life positions listed in Tables 1-4 in the Ap- pendix (these are different for Mg and Al x-ray sources) and the expanded spectra provided for many of the elements in Section Il (4)Review section 1.5.4. (p. 12) to account for fine structure such as energy loss lines, shake-up peaks, satellite lines, etc. not identi- fied in Handbook spectra or energy tables. sample area is not large. It is often possible to analyze different positions on the same sam- ple when the surface is heterogeneous on a scale larger than two millimeters. Use This Handbook {6)identity any remaining small peaks, assuming they are intense photoelectron or Auger lines of minor constituents using Tables 3 and 4, (@)Chemical state identification can be deduced from high eneray resolution (E,,, = 25 eV) spectra of the strongest photoéléctron tines and sharpest Auger lines. i,Review Section 1.5.C. (p. 17) to correct binding energies for static charging of in- sulators. When applicable, charge reference the binding energy scale to the hydrocarbon Cts photoelectron peak (BE =2846 eV). Use the tabulated experimental data and standard high energy resolution spectra to determine the chemical state from measured shifts in the photoelectron binding energies (cf section 1.5.C., p. 18) For the elements F, Na, Cu, Zn, AS, Cd, In, and Te, convert corrected Auger line posi- tions to Kinetic energies by subtracting from the photon energy (Mg = 1253.6, Al 1486.6 eV). Note the location of the points for Auger kinetic energy and photoelectron binding energy on the respective elemental plot. Proximity of experimental points to PERKIN-ELMER 27those of recorded chemical states should be considered probable identification, if consistent with other elemental findings and with calculated stoichiometry (see below). Note that experimental error in point location is much greater along the Auger parameter grid than normal to the grid lines. iv.As suggested in the text (Section 1.5.C., p. 20), much can be determined about the chemical state from the magnitude and Position of shake-up lines as well as the energy and shape of valence Auger elec- tron lines. B. FOR QUANTITATIVE ANALYSIS The atomic sensitivity factors (S,) presented in Table 5 of the Appendix (p. 188) were calculated according to theoretical photoelectron cross sections, the kinetic eneray dependence of the PHI Precision Electron Energy Analyzer and an average value for the dependence of the elec- tron escape depth on kinetic energy. A simplified expression to determine the atomic 28 puysicaLeLecraonics concentration (C,) of any element x is given in equation 8: WS. Zys, a where I, is the relative peak area of photoelec- trons from element x. However, it must be pointed out that the method is limited in ac- curacy by the assumptions made (cf Section 1.5.D., p. 21). The spectrum should be examined with a view to finding information on the depth of the element (ie., by peak intensity ratios, or the presence or absence of ioss lines). Further scans with variable take-off angle, or by erosion of the sur- face, can be made if this point needs further elucidation, FOR A FINAL CHECK A concluding effort should be made to ensure that quantitative data and the conclusions on chemical state are consistent. This includes quantitative apportionment of an element among two or more chemical states, where that is indicated.(o¢ Ce i | | Il. STANDARD ESCA SPECTRA OF THE | ELEMENTS AND LINE ENERGY INFORMATION PERKINELMER 29This section of the Handbook contains survey (broad scan) spectra of sixty-eight elements, detail spectra of the strongest photoelectron lines, and a photoelectron binding energy chart or a two- dimensional Auger parameter plot for each of the sixty-eight elements. Used in combination with the Tables in the Appendix, the survey spectra facilitate element identification. The detail spectra and charts aid in the identification of chemical states. SURVEY SPECTRA The broad scans include all of the lines that are normally useful. The photoelectron and more pro- minent Auger lines for the element of interest are identified. Lines that occur due to other elements are only designated by the elemental symbol, and x-ray satellites and energy loss lines are not noted. Many elements exhibit xray generated Auger lines which have sufficient sharpness and structure to be useful. For these elements, the Auger region is displayed in expanded form. Exact energies of the sharper Auger lines are noted. The energies of those that are less sharp are recorded to the nearest electron volt. The instrumental contribu- tion to the line width is 1.0 eV (60 volts pass energy) for the broad scans, ‘The Y scale has been left undesignated because it was not possible to control the surface roughness of the standards. However, the general contours and relative intensity ratios in the spectra should be typical of measurements made with the PHI Precision Electron Energy Analyzer in the retard mode. DETAIL SPECTRA ‘The detail spectra of the strongest photoelectron lines are presented opposite the survey spectra. In all cases, the binding energy of the main line is in- 30 PuYsicaL eLectRONics dicated and, where appropriate, the spin doublet separation is noted, When necessary, checks were made to ensure that chemical states were un- changed by the radiation. The lines from insulators have been charge-corrected to the adventitious hydrocarbon Cis line at 284.6 eV. The instrument was, in all cases, calibrated to place the Aust, line at 83.8, Cups, line at 74.9, and the Cu2ps. line at 932.4 eV. The instrumental contribution to the line width for the detail spectra is 0.5 eV (25 volts pass energy). PHOTOELECTRON BINDING ENERGY AND TWO-DIMENSIONAL AUGER, PARAMETER CHARTS. The photoelectron binding energy charts have been constructed utilizing data available in the literature up to 1978. Data from the experimental work contained in this section have been included and denoted by the symbol ®. Data from literature references have not been included if the method of charge referencing is unknown or of questionable validity. Data included are all referred to a binding energy scale with Audf,, = 83.8 and Cis = 284,6eV, although it is recognized at this time that general agreement has not been reached and that the values 84.0 and 284.8 could have been chosen with equal justification. It is likely that the values ultimately agreed upon will be within these limits. Line positions have been shown as bars 0.2 eV wide, although with insulating materials the error may be somewhat larger. Data available for C, N, ©, P, 8, Cl, K. Cr, Mn, Fe, Co, Ni, Mo, Rh, Pd, Sn and Pt were numerous, and selection was made of those chemical states deemed most useful, Multi- ple data on the same chemical state are frequently included to indicate reproducibility in different laboratories. Data that are obviously outlying have been rejected, but where some doubt existed on the selection, disagreeing values were included.Two-dimensional chemical state plots accompany the spectra for F, Na, Cu, Zn, As, Ag, Cd, In and Te, In the format adopted, the kinetic energy of the ‘Auger line is plotted against the binding energy of the photoelectron line, with the latter plotted in the ~x direction (kinetic eneray is stil, implicitly. +). The points on the two-dimensional plot are drawn as rectangular boxes at 45°, reflecting the ex: pected error of measurement in the two perpen- dicular directions. References for the one and two-dimensional plots were catalogued by initials of the first three authors. Where two or more identical symbols for references would have resulted, a final differen tiating number was added. The entire reference list is presented in Section II-2(p. 174).Those in the list that are marked with an asterisk have many more data besides those listed here, Abbreviations used in the tables and plots include the following: R= alkyl acac = acetylacetonate Me = methyl ox = surface oxidized in air Et =ethy! —sulf = surface treated with H,S Pr = propyl p- = para Bu = butyl aq = hydrate Am =amyl tu = thiourea Ph = phenyl tm = tetramethyithiourea Ac =acetyl cp = cyclopentadiene Bz = benzyl bae = ethylenediamine + acetylacetone (condensation product) ethylenediamine + 2 salicylaldehyde {condensation product) salen PERKINELMER 31ee) Lithium, Li 25 Pe y WaNoBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY omPOUND 1s BINDING ENERGY, eV 50 55 REF. Bow KL SGR MVS. Act ACT Mvs. Mvs. Mvs. ® 32 puvsicat evectaonics LiF 555 35 BINDING ENERGY, ev 45 ’ 1gb [ene [eta YaNo900K OF XAAY PHOTOELECTRON SPECTROSCOPY Lithium, Li t2:3 T T 7 1 r T T . LiF e Mg Ka | Ne 4 E L F 4 FE 4 . © uits 1 1 i 1 i & 1000 ‘900 800 700 600 500) 400 300 200 100 BINDING ENERGY, eV PERKINELMER 33iy oe ia el : MD esse teeta tee Beryllium, Be 2:4 : comPouND 15 BINDING ENERGY, ev ner. 110 5 120 Be Be © fa Be HIG is. Be B1 Be0° Neo BeO HJG NaBeF, | e NKB Naber, NKB BeF, NKB BeF; 1 HIG ® 34 puysicaL evectaonics 12 112 BINDING ENERGY. eV «voz Co Ct ce eee ee CE oF nay PHoTOFLECTHON SPECTROSCOPY Beryllium, Be 2:4 1 T 7 7 1 1 4 Mg Ka | 1000 1800 700 L 600 1 500) BINDING ENERGY, eV 1 400 300) 1 700 0 PERKINELMER 35Yedrod dats PEPPY VPP DDD DD Wd Denbrorbcednartinaten DMD Boron, Biss We ‘COMPOUND 1s BINDING ENERGY, eV REF. 7 1 ‘s = : BN B.C. T HHJ an ind, mec TiB, 1 MEG ! ‘CoB . MEC i L vB, ire MEC Ht Hid, mee Mod, Meo Fe,B MEC AIBy MEC i NaBH, 7 HHJ Fs y B HHJ Me.NB;Hy L HHJ NaBPh, 1 HHJ Bache I HHJ B,,H,.PUPPh), a 1 R | wey eH PUPEt ef 1 R ; MeL i 1 oe =) 70 BN abe a I HHJ . BINDING ENERGY, eV BN " HG. p-CIC,H.B(OH), 1 HHA NaBH(OMe); HHJ Nae.or : HH F Ph,POBB), HW ‘Na,B.0;-10H,0; ed _| He B(OH); | HHJ B,0, NGD Post Aw ‘Me.NBF; | HHS i Ph,POBF,” : : LHW GHNBR, Sg ® 7 Bc2 EINH,BF, L | 8cz NH,BF, BC2 NaBF, I HHJ L 1100 36 PHYSICAL ELECTRONICS fCt ( ed Ce ( ( eee ¢ viano900K OF x.nay PHOTOELECTRON SPECTROSCOPY Boron, B x: T T T T T T T BN L Mg Ka | N Ne) 1100 ek) 1000 ‘200 800 700 L L 600 500 BINDING ENERGY, eV “400 300 200 700 PERKIN-ELMER aLoimictitgh PP PNT NY » Vadecdvenactucttinten? 9 Pau Carbon, C sss6 * ‘COMPOUND 1s BINDING ENERGY, eV REF, : 280 284 288 292 296 Polyethylene iG RHI a Tic RHI ne we RHI C (graphite) i HJG fi (CH), ° MavCyHol scp SaPhy BAL MeCH.NH, GHH CHCH ae PFD : MeCH,Cl GHH MeCH,OH GHH MeCH,OEt 1 GHH MeCH,OOCMe GHH cs, GHH Fe(CO), act NEL Meco. * ae GHH \ . (NH,),CO GHH —a9¢ 288 2 CF wie GHH BINDING ENERGY, eV MeCOONa 1 GHH MeCOOEt GHH _MeCOOH. 2 GHH h, 'Na,CO, GHH ‘ NaHCO, GHH | ‘co | BC1 co, | GHH i (CHFCH,), I cFK | ACHECHF), | cFK | ‘(CHFCF,), CFK ACF.CH)y > CFK (CF,CHF), ~ CFK (CF)o CFK GF,COONa GHH 1 Col, GHH : ie {CF,come = GHH CF,COOEt GHH @ 1100 38 puvsicat evecrronicsteen eee EEE EEE EEE EEE EE TE hnoacbs oF Saar euovoetecrnon specrnoscorr Capen cle T La T ff T T T r Polyethylene crKLLy r kw Mg Ka | e790 1100 1000 900 ‘800 700 600 500 400 300 200 100 0 BINDING ENERGY, eV PERKINELMER 39’ Wikode Naty? PPP PP PHY DvD des Jon Means Morden de seanostony COMPOUND 15 BINDING ENERGY, eV REF. 394 398 402 408 410 BN Bony, NAB ts PhNH, 1 NAB 3979 pyridine 1 NAB HaNCAH.NO, NAB HANSOeNNO, \ nas tetracyanoquinodimethane KSP Phen NAB PhNHCSNHPh PNS guanidine HC! LR phthalocyanine NKT PhNNPR NAB H,N*CHRCOO - NAB EINH,C! NAB Me.NBr sGc Me,NCI NAB D-NH,*C,H,SO;- ~~ I NAB i chloranit-pyridine NHI agp 398) 388 Me,NO : ‘| | NAB SINDING ENERGY. ev ‘AmONO i NAB MeNO, BMG PhNO, | NAB WN I cR BN ® NaSCN Oe F K,Fe(CN), YN1 KCN F SIN, Add ql SOI Co(NH Ch TTS N NiH,SO, 5 I F (NH.OH)*CIn. 2 1 F NH.NO, F NaNO, SF NaN, I F Nano, Hy | F NaNO, IL F @ 40 puvsicat evectAoNics88 reegpessnaanciee BINDING ENERGY. eV | (1 Ce Cr oo ( Ce HANOWOOK OF X-RAY PHOTOELECTION SPECTROSCOPY ii Atomic. Nitrogen, N ss 1 7 T 1 NeW) BN L Mg Ke | Nas 3 4 Ne) we | 4 c 220 280 340 8 7 ° | ¢ 4 1 L 1 L \ \ \ 1 I 1100 1000 900 800 700 600 500 400 300 200 100 0 PERKIN-ELMER 41ey) yyy) xygen, O iter " ‘COMPOUND. 1s BINDING ENERGY, eV REF. i ie 525 530 595 ALO; RUD, KBA 1s NiO 1 KBA sa Fe,0, KI uo, a I KA : L wo, oR : Cr,05 ACT i Cu,0 RBO Ni,O, KBA Ni(OH),. KBA KOH ~ ~ ~ KI =H ALO, ® Na zeolite. I Mwd SiO, gel MW 1 AM(OH), I FWF Caco, ‘$4 i Naso; q-} \ th \ Sr ‘Na,SO, LHJ 542 532 522 Na,SO,_ 3" 2 eee LHJ BINDING ENERGY. eV CsClO, I MVS” Li,CrO, ACT CuCrO, ACI cb ~] ACT AlAMoOds Al(WO,)s RSO,Na poly (methyl methacrylate) ' Et,0 * meee et] | | PnocooPh i I | 1 42. puvsicaL evectRonics 1006Pee eee EEE EEE EE EEE EE EEE EEE EE LENS : HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Oxygen, O as 1 1 + 1 + 1 + 1 1 ors Al,O, : Mg Ke | oy) we | 522 1 1 1 L 1 1 1 L L 1000 ‘900 ‘800 700 600 500 400 ‘300 200 700 0 BINDING ENERGY, eV PERKIN-ELMER 43vy) ‘i “Atomic. HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Fluorine, F ss 1344 T i sso 120 3 ts LiF 659, raz & 8 Sj 5 Shy e 657 1340 = q 1300 & _ § 3 2 Bess 7 ! o 5 695, é 685 675 = ess 653 & Kid ost ! eco 609668687 60668860002 1 BINOING ENERGY, ev ® 44° puvsicat eLecTRONicsers (eee t (eet Oe ae Fluorine, F tes 9 T 7 1 T T T T T Fis FeKuL) KLates LiF 588.7 Mak le GKa | 688 o18 a5 r ‘FiKUL) ) 7 re oO j ° 1 1 1 < 300 200 700 300 500 400 300 200 700 ° 1000 BINDING ENERGY, ev PERKINELMER 45’ yy) Sodium, Na iss 11 eee ’ yey y vy HANDBOOK OF K:NAY PHOTOELECTRON SPECTROSCOPY 2067 2086 Tw on 208s sons Na.HPO, 996 2066 995 2053 2 2 oe oon g 3 E & 8 5 we aw § 5 v0 vor Eom 2080 BR Ps on on os ss tore rere OVO eds 18 BINDING ENERGY, eV ® 46 PHYsicaLevectaonics 1082 y NEE)TT rac 4 banDu00x OF Kay PHOTOELECTRON SPECTROSCOPY Sodium, Na 42:11 T T T T : i ¥ : Na.HPO, NatkuLy [ re Mg Ka 2635 [Nats NE) 082 350 300 250 1100 1000 900 800 700 600 500 +400 300 200 100 0 BINDING ENERGY, eV PERKINELMER 47by) Magnesium, Mg ed sere 12 , Deedee eee eave HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY COMPOUND. 4s ‘2p BINDING ENERGY, eV 55 h ® 48 prvsicaLetectnoNics REF. uMK HEY FWr FWF FWF FWF FWE Mg 2p 4975 1 30 AINDING ENERGY, eV “0go HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Magnesium, Mg 7:12 1400 1300 Mg(KLL) 1100 1000 ‘900 L 1 1 800 700 600 BINDING ENERGY, eV 500) Al Ka Mg2s Mg2p 1 ak 400 300 200 700 PERKIN-ELMERPe Y codon orca norotccrntnsilrnostor * . HANDBOOK OF X-nay PHOTOELECTRON SPECTROSCOPY Aluminum, Al és13 ‘COMPOUND 2p BINDING ENERGY, eV ‘REF. : 79 75 80 2 Al nN ° 72085 Al 1 msc Al cceeeae \ 52 al LM AlB, 1 Mec Alox ee 1 _| .|82 Al,O; 1 2 ALLO; NSL ALLO, eee Msc Al, I NGD -A1,0, ow 7-AL0, WLEEES MW 7-Al,0; NH2 Na zeolite 1 MWS 1 PCa 76 8 q ip NH2 BINDING ENERGY, ev Al,(WOd)s NH2 Al,(MoO,)s I PCL eat el ela ee Msc aE Hl z | Msc AlO; MSC 2 = [23 eee e Msc 147 1 Msc MSC MSC @ ; 86 76 co 50 PHYSICAL ELECTRONICS BINDING ENERGY, ev 1000Er ee ee et sry © | © Bondar otk mar troroftecrnbn seetrosdony Aluminum, Al 13 T T T T T T T T T L Mg Ka | Al 2s 2 1 L L L 1 L L 1 L 65 j 1000 900 800 700 600 500) 400 300 200 100 0 BINDING ENERGY, eV PERKINELMER 51*sikcdn, Si eadtg? 2 9 2 9? yy snidbor Yaa’ ys Mormon ¥ Suicon, $i stone 2p Mee bee en compound 2p BINDING ENERGY, eV REF ee 193 108 = si | 99.15. cos MV ee HBB I mv : NBA GCH NBA GCH Me,SiSiMe, CH Me,SiNHSiMe, a Me,SiO! GCH Ph,Si(OH), a Ph,SiOH NBA Ph,SiOSiPh, a Et,SiCl FE GCH f (Me,Sio), | GCH 4g fod ae (Me,Si0)y -f NBA BINDING ENERGY, ov EI,SiE GcH Et,SiCl, GCH ESIC... I GcH T it " NBA 2 ‘1 Ne zeolite 4 ili Da} ae sio, Silicates, “y= te | ele} }oos Sis, l mv SiO, 1 o NSL “| MV cos Si0, gel Rival Na,bir, Se nat K.SIF, i ® 52. puvsicat evectaoNics 14 104 BINDING ENERGY. eV Cree) 4 NE)elt ( i MANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Silicon, Si sine 14, Mey T Mg Ka Si2p L L 1 1 L L L L ‘800 700 00 500) 400 300 200 700 0 BINDING ENERGY, ev PERKIN-ELMER 53Vee ee a ionic HANDBOOK OF X-nay PHOTOELECTRON SPECTROSCOPY Phosphorus, P cs 15 COMPOUND 2p BINDING ENERGY, eV ‘REF. y 128 133 138 Na,HPO, or, T PHH MnP PHH GaP o BP PHH P PHH PhP PHH 2 Pt(PPh,), | R 132.9 PICl,(PPh,), R PACI,IPPh,), KBM PdBr(PPh,), KBM Pal (PPh), KBM PLOAPPhgy ee R PICl,(PMePh,), LB Ph,PS PHH Bu,PC] is i | PHH Ph PBr ll SRH 1 Ph,PO 1 PHH aq 1 (Pns),Ps Job MSA BINDING ENERGY. ev (Phs),P PHH PAN, PHH Ph,POOH| = |_| NK BaHPO, PHH KHPO, PHH Na,HPO, = ' Lf fe] o KH,PO, 1 PHH POBr, PHH \Na,PO, 1 e | MVS. Na,P,0; MVS (NaPO,)s 1 PHH NaPO, os 2 PHH (PhO},PO q PHH P.O, N@D NHPFy | [lf | PHH KPF, 1] sma PBrs PHH ® 54 PHYSICALELECTAONICS 724 a! mn‘nANODUUK OF X-RAY PHOTOELECYRON SPECTROSCOPY a eet @@ € € € 4 Phosphorus, P t:2:45 ME) T T T T T T 1 1 Na,HPO, Mg Ka | 1100 700 600 500 400 300 200 100 0 BINDING ENERGY, ev PERKIN-ELMER 55yr, DYDD DYDD DD DDD DDD > Sulfur, S ss16 ‘COMPOUND 2p BINDING ENERGY, eV REF. \ 160 165 0 s 2» NaS LHJ p-NaSC,H,NO, A LHJ ect Pbs. 1 SFS FeS B4 KFes, Be ws, 1 NH2 MoS; 1 PCL Na,SSO, 1 LHJ PhNHCSNHPh | PNS ns PhSCMe, 7 PLB Ph,PS MSA tetrahydrothiophene _ MMP PhSH LHJ LHJ ny NUE) a LHJ i o 173 163 153 dl LH : BINDING ENERGY, ov I SOL LHJ LHJ - yo ~ LHJ 5 ML : . LHJ LHJ Na,SSO, I LHJ B2MeSO, ML so, “7 . 7 LHJ PhSO,Na eet Wt p-HNC,H,SO.NH, yi LHJ PhSO,Me LHJ Na,SO, LHS Fes0, LH FeSO), LHJ x 56 puysicaLeLectronies153 ead: cet Ct (et ( ( eeceeaee anthivox Se xan puotoEvectnon sPecrnoscory Ao T T T 7 ; : ~ | Mg Ka | 1000 1 600 L 500 BINDING ENERGY, ev L 400 200 2p 1 100 0 PERKINELMER 57ohiodi A 47? ee Chlorine, Cl es 7 COMPOUND 2p BINDING ENERGY, eV REF. : 195, 199 203 207 an Poly (Vinyl Chloride) scr NSM 2» ROC! NSM 1999 KCI MVS: Neca: mvs uc 1 MVS. guanidine HCI }| LR AgCl I Kit cuci KIT Nicl, KI HCl, es I N ZnCl, * I N CdCl, { N FeCl, KIT FeCl, KIN CuCl, KI K,MoCl, 7 TEs cHt Ll K,SnCl, CHt oop 200 K,ReCl,_ : cHt : BINDING ENERGY. eV K.PICl, Ht K,PICl, R PUPPHY,Cl | a PAPEL). Cle Fy ¥ a R “CO(NH) Cl 2s | N poly (vinyl chloride) } | jo chioranil OYK tetrachlorohydroquinone OYK chloranit-pyridine NHt 3 alt FE HW f KM als day CKA KA KM MVS 1 7 MVS mvs @ 58 PHYSICALELECTAONICSi0 (CoN HANDBOOK OF x-RaY PHOTOELECTAON SPECTROSCOPY 1400 T T KO T cum) 1100 L 7000 900) L L L 800 700 600 BINDING ENERGY, ev eee (eat Chlorine, Cl 254 Poly (Vinyl Chloride) Al Ka | 200 100 geaRsreeepeatgalaayepeeee 7 59.Vee) 2) ye) Argon, Ar 2218 Hano8OOx OF X-RAY PHOTOELECTRON SPECTROSCOPY GomPouND 2p», BINDING ENERGY, eV _REF. ; 235 240 245, Arinc Ar (in G) T ® Ar (in C) KW Ax (in Fe) t wa ) Af (in Cu) : cH2 ! ‘Ar (ing) KW. ‘Ar (in Ag) : _ cH2 Ar (in PA) KW Ar (in Au) cH2 Ar (in Au) KW 4 i Ne ae 2 : 28 2 | BINDING ENERGY. eV { 60. puysicaL evectRONics 11¢232 NCE) Ce ( eee ( ( (( ANOBOOX OF x:Aa¥ PHOTOELECTRON SPECTROSCOPY Argon, Ar 18 u : T T T T i T 7 Arinc is Mg Ka ¢ 1100 ArtLaMaMza) c 1000 ‘900 00 700 L L 600 500 BINDING ENERGY, ev 200 100 PERKIN-ELMER 61’ yr» ”D Potassium, K ’ vee), 19 ey ) ) HANDUOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY ‘COMPOUND 220 2py, BINDING ENERGY, eV 295, REF, 300 KSnCl. NSM NSM NSL wt SGR | NSM NSL cH CHT CHI CHI CHI wi oO 62. PrvsicaLetectRonics ery, 228 1 KBr 206 BINDING ENERGY, ev 284 ’ NEbeta sees ee ceru cases eee euaeeie es CC (eee e ee € € E CC 4 qt HANDBOOK OF XRAY PHOTOELECTRON SPECTROSCOPY Potassium, K 19 y T T T T : r ; : (uM ' KBr 1005-1 so02.7 Mg Ke | NE) K(LWM) 1100 1000 900 ‘800 700 600 500 BINDING ENERGY, eV 400 ‘300 200 100 0 PERKINELMER 63yy) yr DY Ova yy yy Calcium, Ca 2:20 ee ‘COMPOUND 2py, BINDING ENERGY, eV REF. l ‘ 345 350, 355, caco, CaO o Caco, ° Caso, ule wi CaCl] BRT ee = ae wt Cary : Nst CaF, ° os : 363 9 ® 64 prvsicaLeLectronics BINDING ENERGY, eV «HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY 6 Calcium, Ca sss 20 ca(LMM) Nite) Ca(LMM) 339 1 1 L 1 L L LaMaMas Caco, Mg Ka | 1000 300 800 700 600 500) 400) 300 ' BINDING ENERGY, eV 200 700 0 PERKIN-ELMER 65heyy eee) Scandium, Sc ies 21 On OFT ene COMPOUND Zpo, BINDING ENERGY, eV REF. 25 400 49s | Sc,0; Se wn wort CiH,SCC.H, we {CsHy),ScC! 1 WM SCN BE = iB Fine aan it “| STA Sagi Bae ! $ $20; eg ae cee eee eee _.| NGD 80,0, 1 WM ScCl, wi pa ScF, wi _— ! a 75 es ® 66. Puvsicar etecrRonics BINDING ENERGY, 2 y NED 10| } WANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Scandium, Sc ss 21 ‘Se(LMM) NE) 1000 900 800 700 1 600) T T T ‘se(LMM) Sc,0, Mg Ke | 1 1 L rl 500 400) 300 200 100 BINDING ENERGY, ev PERKIN-ELMER 67oy ee) Titanium, Ti tex: 22 HANDBOOK OF X-AaY PHOTOELEC COMPOUND 2py, BINDING ENERGY, eV REF, : 433 458 463 Dy, Ti i eo 4598 Ti RHI Ti Nsc Ti PJH Tit, NSC TiB, A I | RHA 20% Tie, Mec Ts | a Tic RH1 Tic IK1 TIN 1 RHI SiN = i I STA Tio I FUM CsH.TIC,H, GSM Feces ersemeeerereeeecee (C.Hy),TIC! I GsM ‘BaTiO, F MW : PbTIO, - MWI ao 480 450 SITIO, - | dA MW BINDING ENERGY. eV CaTiO; MWI Tid, RHi i NSC T . pated Baas oO 20x, Mwt 585 ne 23 1 _.| GSM GSM Na,TiF. wi 204 82 a0 7160 750 68 puysicaceLecTRonics BINDING ENERGY, eV ’ NE) rT‘350 HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Titanium, Ti a: 22 Mey Ti(LMM) Ti(LMM) Mg Ka | Ti3p 00 700 600 500) BINDING ENERGY, ev 400 100 0 PERKIN-ELMER 69Ve ee ed, Vanadium, V ss: 23 HaNowooK oF x ‘COMPOUND 2p, BINDING ENERGY, eV REF. a 510 15 520 511.95 v v ® v Il He v AA v LFS v NSC v Gsm wy, af FS v SA v HVB vB, MEC ve’ ~|—|-] | eum vs RHe VN RR VN STA |--—__—_——— 7. —__—__+| {CHV _ ! BCD (CHV EF " Gsm ! (CHINE! I GSM gas 3s ms Vacacs Wisin: 2. LES BINDING ENERGY, eV VO acac, LFS Les es pat ed 1 SA v.05 GSM Hy |) pues © 1 SA V:05 I NSC V.05 o V0; NGD 70 Pavsicavetectaonics : or Py ray % stele 533 328 513 BINDING ENERGY, ev 106Ce Cat Cd | HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY ii Atomic. “ Vanadium, V sz: 23 7 T T T T T T T T T a Vp, | view : Mg Ka | 7 7 vem 4 SEL « 4 ae | 1 1 \ ! 1 L L ae 1000 soe 00 700 300 300 7200 306 200 700 ° BINDING ENERGY. ev PERON-ELMER 71eo ’ ’ ’ eee Oo 7 HaNOBOOK OF X-RAY PHOTOELECTRON SPEC: ROSCUPY Chromium, Cr as: 24 : ! COMPOUND 2py, BINDING ENERGY, eV REF. r T J 2 8 3 Cr I P% Cr 1 o 874.1 f ce, MEG CaS, I csc ClCH CDH CHC HNC.H.) OH | Cr(CsHas I COH cn : RR 2% | cn STA | Cr{CO).NH, Bc3 4 Cr(CO),CyHe PFD ¢ Cr(CO), l PFD Gren. 1 Gen | Cracac, 1 ZH K,Cr(CN), i 2H |. 53 __-| | K,Cr(CN), 1 csc : j ‘roOH oe 1 “| pik Ll Ll Ll L Cre + : us 598 500 585 380) 375 370 ‘C0, a | }ii« BINDING ENERGY. eV Cr,0. Att | Cucro, AT | Licro, Am T T T T hs ATT 4 csc wy, CFOs csc 5786 csc crcl, att Cr(NH3)Cl, an 2% K,CrC,00, “ol tpr} an Grurea),Cl, I att 1 ACI aGt ACt ACI Po] ‘jan csc |}+———s: ___+| ® ; ' ; | 598 590) 385 380 378 o70 72 prvsicaL evecTRONICs BINDING ENERGY, evget eaceeceecece eee Cee eee eee Cet } HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Chromium, Cr e224 L T T T T T T T T 4 I Mg Ka crummy criLmM) a0 770 720 670 Crap eal 1 1 i 1 1 1 1 1 1 Fae 1000 ‘900 800 700 600 500 400 300 200 100 o*mangantse’ Mn ee Yan box ra vor Meee. Bs. Brn Bows 9 ‘COMPOUND 635 2p, BINDING ENERGY, eV 610 Min Mn(CsH.), Mo(CsH,)(CO), MAS. 2 Mns a@-MnS B-MnS Mn(COjs BrMn(CO), [BrMa(CO}4, BrMin(CO}){PPh,), Mng(CO)(PPh.) Mal, K,Mn(CN). MnBr, MnBr, MnCl; MnCl, 2 Mno MnO Mno Mno 7-MnOOH Ms,0; Mn,05 Mn,0, MnO, nO, MnO, MnO, KMno, Mak, Mn, MnF; REF. 645 © CDH OH csc FUM A A vw vw vw vw vw A csc csc A csc A FUM OHI A csc OHI OHI any Mn seb 2 |}+————11.2s —_—_+| 1 1 1 55 650 es 40 BINDING ENERGY, eV 535 660 655 T T T orp 642.2 MnO, 650 65 60 BINDING ENERGY. eV 63535 Ce HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Manganese, Mn _ tz: 25 Ma(Lain L. Ma 2py, Mg Ka Mo(LMM) Mn 3p L 1000 800) 800 700 600 500) BINDING ENERGY, ev 400 700 PERKIN-ELMER 15Deep peepee pea erep eee Peer Pee arene Dee Ree Pte Detap en ecu D ics Dare Racemeg Pacer PaO re, NANOBOOK OF KAY PHOTOELECTRON SPECTROSCOPY Iron, Fe a: 26 . : ‘COMPOUND, 2p, BINDING ENERGY, eV REF. \ i 705 710 ns 2p, Fe Fe © 708.75 Fe.B Mec FeB MEC Fes, f a4 2py Fe(CsH.), 1 CDH Ye Fe(CsH)ts ! - a Zn,Fe(CN), I csc K,Fe(CN), csc K,Fe(CN),, Vv NayFe(CN),Na . 1 YN2 Na,Fe(CN),NO I YN2 |——— 13.2 + K,Fe(CN), 1 v Fe.P.S, Ba KFes, Ba Fes csc Fe(CO, FF | B01 ! : tl Fe(CO),(NO), + i | BCI 70 730 720 T10 700 Fe(CsH,)(CO),BPh 1 CDH 2 BINDING ENERGY, ov Feo Mz FeO Ac2 Fe,0, o T T T Fe.0, : WS Fe.0, AC2 Fe,0, FeOOH AC2 FeoOH Mz Fe,0, AC2 ee NaFeO, Ac2 Pte ee Mz FeBr, csc Febr, csc FeCl, csc FeCl, esc Fer, ose Fer, esc Pace eae] KFeF, esc 10 720 720 710 700 76 PavsicaL ELECTRONICS BINDING ENERGY, eV )(ete e Ct Ct rt | (Gt Cd vianoW0oK OF xRay PHOTOELECTRON SPECTROSCOPY Iron, Fe es 26 : T T T Te T T T T T Fe(LMM) ' Mg Ka | 05 Fe3p = Pm Feas | 1000 ‘800 700 600 500) BINDING ENERGY, ev i 400 200 L 100 0 PERKIN-ELMER 77Pe ee Cobalt, Co sss 27 COMPOUND. 2p, BINDING ENERGY, eV REF. r ! an 75 790 785 a Co Co oO Co;B MEC CoB 1 MEC ColGsHiss LF I BCD Co(salen)*”* BOT 2% Colbae) : aot Co(CO},NO I BC1 Co0,0, o 0,0, OH 00 ‘ Il mec |-~——15 0s CoO / K CoO Hee OH Co(OH), 1 Mc ‘CoOOH Mc 60,0; EE MC CoFe,0, © Jes te ie Mc 1 L : CoCr,0, fa 4 OH 810 800 790 720 770 GoM, 2 oH : BINDING ENERGY. eV ZnCo,0, OH CoAI,O, = Mc CoAI,0, OH Goal, FEE : PCL Cs,CoCl,*” | NBM 20% a GoMod, | a PCL 720.0 Co(NH,),Cl NBM Co(NH,).Cls NBM Co(NH,).C! osc 2by K.Co(Cn)y" OH % HCol, (aimethyigivexime) BF HCoBr, (dimethylgiyoxime) Hf. BF HCoCI, (dimethyigi ve) BF K,Co(NO.). i NeM CoF, csc Cor, RE csc CoF,-4H,0 ae NBM |-————— 15s ———_+| © ' evo 00 790 700 70 78 Prvsicat ELECTRONICS BINDING ENEAGY, ev770 i WANOBOOK OF X:RAY PHOTOELECTRON SPECTROSCOPY Tet et tt ee Cobalt, Co ts: 27 + ‘800 T T T T T T ‘ColLMM) UaMesMay 605 MgKa | 700 eee L 600 500 400 300 200 100 0 BINDING ENERGY, eV PERKIN-ELMER 79Cee ev Oe ee Pa, Nickel, Ni is 28 : ‘COMPOUND 2py, BINDING ENERGY, eV REF. i ‘ 7 ' es ese ee Ni i Wi T o Nil, 1 MYG Ni(CsHy), BCD 7 Ni(PPh),~ : TRL NiS : NH2 : Nis NH2 Ni(CO), BCI NiBr, MYG Ni (dimethylglyoxime) MyG NiCl{NBU), STH ‘ Nicl(PBu), Mya NiCI,(PPh,)2 MYG Niacac, TRL i Me,NNiCI;, MYG Ni(CN), I MYG NE) KNICN)S OTL - MyG L 1 L Znnic TRL age we wee we Mya : BINDING ENERGY, ev i MRC : | KO i | MyG 7 T 7 | “-| MAC Nio : KBA KBA 2pm ne ess KD NiCl, TRL 2% NiFe,0, - Jo MC Ni(NOs)s 2) TAL ae NisO. mye i NiAl,O. NH : Niwo, 1 NH2 NiF, MyG (NHN fe 1 a MYG KNB, aye |+ 1, + ee oe 88 ose a8 BINDING ENERGY, ov 80 PHvsicaLetectRonicsBINDING ENERGY, ev eee te Nickel, Ni a: 28 T T 1 1 1 T T 1 1 - 7 T 7 nice uw Maes Mal tae tora M gKa Ne fe ae i 1100 1000 900 800 700 600 500, 400 300 200 100 0 PERKIN-ELMER 81Pd ed Copper, Cu sss 29 T 1 T ox 2035 soa CU wa 1080 at vse 8 8 8 ag 1850 3 2 5 8 “Ly wo 3 g Zs e ba td y g BINDING ENERGY, eV Eo reas 8 z chalang ; : 316 wa 1867 Ccuo by 20 ay ais % a wags ou ona fee 938 937, 936 995. 934 933 932 931 eee 2p SINDING ENERGY, eV or 3 35 ae we ms 82 PHYSICAL ELECTRONICS BINDING ENERGY. eVBs Poet et eee cect MANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Cae Copper, Cu iss 29 1 1 NED 1000 za T T T T T uw 335.0 ‘cu(LMM) cure, cul) L ‘300 800 700 600 500) 400 300) BINDING ENERGY, eV Mg Ka | 200 100 0 PERKINELMER 83Dee i oie ANDGOOK OF K.8aY PHOTOELECTRON SPECTROSCOPY | Zinc, Zn iss 30 1 T T T 298 6 ove an roars oe aon & 993 2012 © 2 Y a ose aor 3 01 wo 2 ecu = | _____—s: ____- 90 2o0 oneae Ze 3 L \ n 1 ee 1065 7055 045; 7038 1025 701s & L ° BINDING ENERGY, eV 909 ‘iG 2008 z Kb yy 3 Vo ‘pours T T T 908 Ls 20% ZNO Sp Ky; 1021.7 204 87 % 986 w ses E 02s 1025024 ~—~t0e3”~=«teee—ta2i=—« aad «a18 | 2p, SINDING ENERGY, eV @O * 230 1 1 1 ie 1085 5088 104s 1095; 1025; 015 BINDING ENERGY. eV 84 PuvsicaL eLectRONicsee ee ee aes (eee Ge Gates (eeeGaed i ° Zinc, Zn srs 30 | T T T T T T T Zn 2p, 2niLMM) Mats Mg Ka NEY L 1100 600 500 BINDING ENERGY, ev 0 PERKIN-ELMER 85be », rv > yyy dD DDD YD Gallium, Ga iss 31 ° ‘COMPOUND 3¢ BINDING ENERGY, eV REF. f 15, 20 25 Ga Ga o Ga St es Ga = _ |. LBH Gaas f *| L8H GaP "*» o GaP | i 1 ;] BH GaSb LBH Ga,0, 1 LBH ! Fr 2 70 ® 86 Prvsicat evecTRoNics BINDING ENERGY, ev ’ 2(Coon d (et Gallium, Ga wx 34 T T 7 7 7 1 T T T T T T T LM | S22, 4183, AlKa | N(E) X 4 7 1 n 1200 1000 800) 800 700 600 500 400 300) 200 100 0 BINDING ENERGY, ev | PERKIN-ELMER 87’ Se i ee wordaccon sernaboors Germanium, Ge 2%: 32 OPA ONS COMPOUND ‘3d BINDING ENERGY, eV REF. i 25 20 38 Ge Ge o 30 Ge HKM 28.85 Ge I SFS Gele [GR zi HKM cere | ors Gere, : ad] J ain Ges, 1 HKM. GeSe I SFS Ges I HKM Ges Scere “| SFS Ges, HKM PhGe 2s? Es __| Hw Ph,Gel HW Ph,GeBr Hwy Ph,GeCi HWV Geo, 1 HKM L “ 38 2 SINDINGENERGY, ev Ge Ge Gel, PhGe aS GeS Ges, Na,GeO, Geo GeO, Ger, Gere ® 8B puvsicat eLecTRonics Ne)CCC Ct Ct tt er HANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY. i Atomic Germanium, Ge 125 32 T T T T T T 7 1 1 7 T i co(uam) LaMasMes oe [ Al Ka LMM Lia piven 4s 1300 433.0 LaMaMuy LiMaMas 3100 “aici Geas xd Geap Gead | 800 700 600 BINDING ENERGY, ev 300 200 300 0 PERKIN-ELMER 89ey Arsenic, AS Number dee) 33 py dv Dd Y QroodorMrenbocdinonbrcibscut b » 1268) 127 1228 1228 1204 1208 222 221 LiMaMes KINETIC ENERGY 120 219 1218 117 a a? @ 90 puysicatevecraonics 48 44 a 2 4 ‘3d BINDING ENERGY, ov “0 267 1266 1264 1263, 1262 AUGER PARAMETER PLUS PHOTON ENERGY so GaAs 38 407 “0 BINDING ENERGY, ev ‘208 cots Cet © CC eed ( 4 c sianon00% oF r-aay enOTOSLECTHON EPECTMOSCoPr A : : T T T T T T T : 1 ; T r : : stun a LaMasMag L ero Ape LaMat 7a Lalla 1400 AS 2py As 2p, 1300 359.2 LiMesMas 334.5 225.4 385 1200 1100 335 1000 900 285 235 1 L L 800 700 600 BINDING ENERGY, eV 185 x4 Asap As 200 100 PERKIN-ELMER 0 aee 7 sate HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY : " Selenium, Se ss: 34 ‘comPouND 34 BINDING ENERGY, eV REF. r 82 El 62 36 Se PbSe T SFS oN PbSe wsP SnSe ' l SFS SnSe i] wsP ig Bi,Se, I oR NbSe, 83 Nb,Se, 83 GeSe 1 SFS As,Se, wsP Se “| ses Ae Se 83 Se : ® Se wsp Se MTH CyyH,SeSeCigHss MTH : BrC,H,SeC.H,8r yf oe] wa L E HOC,H,SSeSC,H.OH ~+<]"l" lwse gs 5 “5 Na,SeS.0, x 1 : BINDING ENERGY, eV (PnCH,),S20 L (BrC,H.),Se0 MTH [HOOCICH,),Se0 MTH CiwH,,S20(OH) ale “| wth , k ‘PnSeO(OH) MTH PhSeCh, 3) SE MTH ' Na,Se0, wi Na,Se0; wsp CIC.H,Se0(0H) l MTH b 1H,Se0, ae MTH Seo, MTH : ‘S20, wa : | wsP CIC,H.Se0,(04) MTH Na,Se0, 1. fw : Na,Seo, L| wse : 100 92. puvsicat evectnowicsHANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Selenium, Se “2: 34 T T T T T ¥ t L Al Ka Se(LsMaMus) L Se(L MaMa) Se(LyMaMss) ‘So(LeMzsMas) Seas Se Spy, Se3py, Se(L2MuMa) L L L 1 1 L L 1 L 1000 900 00 700 600 500) +400 300 200 100) 0 BINDING ENERGY, eV PERKIN-ELMER 93yyy vv YoY DD yy oe rete ee Bromine, Br. iz 35 COMPOUND: 3d BINDING ENERGY, eV REF. T ad @ 2 7 = KBr ier ° KBr I Mvs CsBr MVS oer MVS Nasr mvs Lier MVS HgBr; N CdBr, N ZnBr, 1 N (CygHs:MesNBr Oy wi CyH.Ni(PPH,)Br i 1 TRL PaPPh, Br, a N Pd(NH,):8r N Pt(NH,)Br, N Pt(NH,).Br, N Co(NHshSbBr 7 1 T L Rb,Sb,B8r, T 70 Cs,Sb.8r, I ajc] of..|7 einoic enency, ev KPdBr. N KPtBr. N Kt, N bromanil 7 Ee i ryd sz] OYK bromphenol bluese : 1 | )f} wi KBrO, . + I wi @ 94 puvsicat eLecTaoNics ’ ’ NE)eC Ge NANOBOOK OF X.AaY PHOTOELECTRON SPECTROSCOPY T T T T T T Br3py, Br 3p, 8r3s 1 L L 1 1 L L L L 1100 1000 900 800 700 600 500 400 300 200 BINDING ENERGY. ev Bromine, Br 25 35 T KBr Mg Ka arsa 100 0 PERKIN-ELMER 95yy) rey eee , o> ee Strontium, Sr S238 T GomPouND ay, BINDING ENERGY, eV REF. 130 138 140 ae SrF, Sh ° Sirs wi 2g 1 16 139 ® 96 puvsicat eLecTRONICs BINDING ENERGY, eV 123 xfe ee ee naNoB0OK OF ¥-naY PHOTOELECTRON sPecTROSCOPY Strontium, Sr is: 38 T T T 7 1 1 : SrF, Mg Ka | 72a 1 L L 1 L L L L i 1000 ‘900 800 700 600 500 400 300 200 100 0 BINDING ENERGY, eV PERKIN-ELMER 97ee) Yttrium, Y iss 39 Ve ANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY COMPOUND dy, BINDING ENERGY, eV REF. 155 160 165 YO, T © Y:03 1 NGD t YF, I wi | 98 puvsicat eLecTAoNics see eee ee 17 187 “a7 : BINDING ENERGY, ev( WANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY 0 Yttrium, Y iss 39 1000 T T T 1 1 1 1 L 1 L 1 ‘300 ‘800 700 600 500 400 300) 200 BINDING ENERGY, ev 1 Y,0, Mg Ka L 700 PERKIN-ELMER 0 99) yt ad PD boa) De see cate teneno seernetccees Zirconium, Zr iss 40 ‘COMPOUND 3d), BINDING ENERGY, eV REF. : 1 180 1s dag Zr Zr o v8? fy NSC ale Nsc ay NSC * Ned Zr(OH)alanine,Cl:12H.0 | _ | KNP K,ZrF, NKB K,ZrF, NKB Na,ZrF, wi KZrF,“H;O NKB ZF, NKB | 2.4—>| 1 13 73 7 @ 100 PHvsicaLeLectronics BINDING ENERGY, eV NED 10eee eee ee ee EEE EEE EEE ECTEEES t ANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Zirconium, Zr 2: 40 ' T T T T T Mg Ke | MaNeaNes 20304 1135 173 L L 1 1 1 1 L L L 1000 900) 800 700 600 500) 400 300) 200 700 0 1 BINDING ENERGY, eV PERKIN-ELMER 101ee Niobium, Nb az44 HANODOOK OF K.RAY PHOTOELECTRON SPECTROSCOPY fl COMPOUND 3dy, BINDING ENERGY, eV REF. 200 208 20 Bey, Nb No © 20202 Nb t RH2 SPB BS. Msc Buy FOF NSC Ne Nsc RH2 1 SPB I FCF FCF SPB —20—+| Msc SP5 Nee Msc : SP [FOR any 207 197 NGD BINDINGENERGY, ev MSC Msc L Msc ® 102 Puvsicat evectaonics 110087 Cor OOO Ce tt (0 4 cpr iy HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Niobium, Nb 37:44 T T T T T T : T Nb(MNN) vecMInny Ne) Mg Ka 1080 1040 i Nb Sd, L L L L 1 1100 1000 900 800 700 600 500 400 300) 200 100 0 BINDING ENERGY, eV PERKINELMER 103,a Molybdenum diay , Mo ’ 42 > oo MANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY COMPOUND 225 230 ‘dy, BINDING ENERGY, eV REF. 235 Mo Mo{CO), bipyridy! IC,H.Mo(CO},}s Mo(CO)PBus): Mo(CO),PPh, MoB, Mose, C,H,Mo(CO}, C,H,Mo(CO),” BF. MoCI,{CO).APPA)s MoS, MoS, MoCl,(PMe,Ph); MoCl,(CsH;N)s MoO; MoO, MoCl,, MoCl, Mocl, MoGI,(NO)(PPh,), MoCli(PPh)e MoOCl,(CsHsN). 7 MoOCI,(PPh,), MOC, (CsHsN), _ MoCl, bipyridyl MoO,Cl, bipyridy! MoO, acac, ‘Na,Mo0, NajMoO,-2H,0 AlsMoO,)s CoMoO, MoO, MoO, Meo, : (NH,)sMo;0,4°4H,0 MEC co) 104 pHvsicat evectRonies: 2044 Mo ard Say |—3.15—>| 230 220 BINDING ENERGY. ev 240 dey J-—a.2—+| MoO, Byy 0265 230 220 BINDING ENERGY, ev U Lu Ne) ce 1100Ct Ct ec. IMANOUOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Molybdenum, Mo ts 42 T T T T x T T T ; t — T ‘Mo(MNN) Mg Ka | }_Mo(MNN) 1100 7000 ‘300 1 L 1 1 1 L i 800 700 600 500 400 300 200 700 0 BINDING ENERGY, eV PERKIN-ELMER 105eee el a rundaoon de ead mubereePon Jecrndbcor Ruthenium, Ru ssc44 ‘COMPOUND 3d,, BINDING ENERGY, eV REF. 7 a5 290 285 Ru co Aa © 220 Ru KW Fu 2 _|_lF Ei BHH Hake F Ru(NH)).N.Br =] =f] = RU(NHL)sN:Cly F e RU(NH,)MeGN)Brs erm BFM I “} >) Kw F = joe kw KW a 1 292 382 ® 106 PHYSICAL ELECTRONICS BINDING ENERGY. 0 22Pet Cee : HaNOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Ruthenium, Ru x44 Ru(MNN) con Mg Ka | Ru(MNN) a2 L 1 1 L L L 1 L 1100 1000 ‘900 200 700 600 500 400 300 200 400 0 BINDING ENERGY, eV PERKINELMER 107Vevey eee Dee ec y ced) », > yy) Rhodium, Rh fs 45 ‘COMPOUND dy, BINDING ENERGY, eV REF. v 305 0 318 3d yy, Rh = . wre Rh I HKN Ah(PPh,),Br NSK Rh(PPh,),1 sat NSK Rh(PPh,JNO NSK 30; Rh(PPh,),COCI NSK ve Rh(PPh,),COBr NSK Rh(PPh,),COL NSK Rh(PPh,),CIC,H, NSK Rh(PPh,),CIC,H, ! MMA Rhl; NSK Rh(PPh)),Cl N NSK Rh(PPh,),Cl MMR Rh,(PPh,),(OAc): NSM a Rh,(OAc),*2H,0 NSM Rh,(OAc),-(NHs) 7 NSM fi Bh,(OAc),(HzNCSNHz)2 NSM 320 ‘310 300 Bh(PMe,Ph),Cl, meee | ig LB BINDING ENERGY. eV Rh(PMe;Ph)Cl;, N Rh(PPh,),COCI[CCN),] 1 MMR Rh(PPh,),Cl(C NSK AREINCI, ~ id NSK Rh(PPh,)HCI, NSK Bh(NH))sI5 |e NSK Rh(PPh,),Cl, NSK Rh(C.HN),Cl, NSK K,RhCl, NSK Na,Rhcl, : wt Rhacac, t Wi Rh(NH,),Cl, £/-: NSK RA(NHS)Cl;, NSK R(NO,),, Wt ARNO. NSK KRHICN), KRh(NO,), NSK © 108 puysicarecectaonics ’ alZCC CC ts HANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Rhodium, Rh ss 45 Rh(MNN) MaNiV 1031 ERn(MNN) L 1 T Mg Ka T 1100 1000 ‘900 800 700 00 500 BINDING ENERGY, eV “400 300 200 100) PERKIN-ELMER 109y yy vy DD ey) ’ yyy > DD DD DD 7 ome HANOBOOK OF x-nay PHOTOELECTRON SPECTROSCOPY Palladium, Pd 2s: 46 ‘COMPOUND 3d, BINDING ENERGY, eV REF, 330 335 40 Pd Pa ® 9 Pd 1 Kem Pao KGW Pal, KBM Boy [Pac,Hy8n, NzM Pd(CH,PPh,)C! 1 NZM [PdIC,HICI]s lt NZM PdBr, KeM K,PdBr, I NZM K.PdBr KBM Pd,(PBU),.Cl, CAB PdCl, Soa KBM Paci, NZM PatPPh.). Be, NZM Pd0; KGW |+——5. | Pd(PPh,).Cls 7 om = ae KBM L Pd(PPh,).Cly 1 sola eater NSH ey ary an Pa{PPh;},CO, aoa TU) NZM BINDING ENERGY. eV Pd(C.H.N),Cl, NZM Pd(NH,),Br, NZM Pd(NH;):Cl, NZM Ba(PPh,), (CN), 7 “| KBM K,PdCl, 3 KBM KPC” x NZM PaPOPA) LET, : NZM Pd(NH,).Cl NZM Pd(OAc), NZM Pd(NH,),(NO}); 7 = . NzM K,PAINO), NZM K,Pd(NO,), KBM K,PA(CN), ™ "| NZM K,Pd(CN), KBM PA(CN: KEM K,PdCl, SPetoel” NZM K,PdCl, i w wef nf KBM © 110 puvsicat etectRONics:ee ‘ ANOBOOK OF w.NAY PHOTOELECTRON SPECTROSCOPY Palladium, Pd 2:46 T T T = T T T T T 4 1 Pen) c Mg Ka | Peaiiny 1 1 11080 700 360 S00 PS, 4 i 1 1 1 1 1 1 1 1 00 0 700 se zo0 “00 300 700 708 0 1000 BINDING ENERGY. eV PERKIN-ELMER 11tyy vy DvD Silver, Ag yy dD aes 47 »y ) ’ WANDB0OK OF X:RAY PHOTOELECTRON SPECTROSCOPY T 2 ae ne 4 > 2678 Ag 2 361 nso Boy, e 5 260 ma & g as rma § zg 358, GLY re = 2 57 a ra [+00 : 1 2 260 370 30 2 BINDING ENERGY. ev = a6 2 3 ah YE 2 oe ass 7 ast 236 ase an aoa ata 8S 112 puysicatetectaonics 3dyg BINDING ENERGY, eV yfe te ’y HANDBOOK OF X.AAY PHOTOELECTRON SPECTROSCOPY Silver, Ag “2:47 ' : F T T T T Ag(MNN) Ag 34, Mw 9 35 : oor Mg Ke | Ag(MNN) Ag Sd, 360 x4 Ag 4p Ag 4s L L L 1 L L L r 1 1000 900 00) 700 600 500) 400 ‘300 200 700 0 BINDING ENERGY, ev PERKINELMER 119’ y 1) y yr) Cadmium, Cd 222548 yy) HANDBOOK OF X-RAY aa) PHGTOELECTRON spEcrRoscoPY MiNgNap KINETIC ENERGY 7 386 be 788 ans ta one Z, 706 aa ves b awe 78 ty ae: 2x0 me ‘ wm an oe 4090840740608 aa 008 a0 ® 114 PHYSICAL ELECTRONICS dg, BINDING ENERGY, AUGER PARAMETER PLUS PHOTON ENERGY Ody, |-_——s. 76 | 38, 4048 Cd 408 BINDING ENERGY, eV 398 NEei re i Sa 1 Oo Baal montetstnon seernctcor Ste ey T T T T T T T T T \ caqMnny MiNaNes | Mg Ka | Cd3dy, 995 245: 895 345, ) | caren 388 BINDING ENERGY, eV | L 1 r 1000 300 ‘800 700 600 500 400 300 200 100 0 PERKIN-ELMER 115Sead) », yr) Indium, In ts 49 ’ Ve yar den) aya) HANDBOOK OF X.RAY PHOTOELECTRON SPECTROSCOPY Bigg 4436 Bdyy |}+———71. >| In es ee ase 5 an as 4 g 5 410 ase & 9 es § z 408 eso & 5 & & g @ 407 Kye uo - a : g G 1 Zz oy = 405 i se oa wa “eats aa dy, BINDING ENERGY, eV O 116 Prvsicat evectnonics 48 BINDING ENERGY, eV 28 yo? i Me NE) 1000aye ( A } ANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY T Indium, In Number 49 BINDING ENERGY, ev PERKIN-ELMER, T T n(n) MNarNes asi.0 E Mg Ka | Indy, (35) Ne) i ca L Indy 1 910 360 B10 aH Inad Indpy, Ingpy, b x 4 Ings Ind L L L L L r n i i 1000) 300 00 700 600 500 “400 300 200 700 0 7ee ) Tin, Sn ss 50 . comPouND ‘3dy, BINDING ENERGY, eV REF. : 2 40 ‘65 «0 a sn 7 : atts Sn FHE Sa : LAK Sn . SFS Seg Aus FHP SnSe . SFS Sate SFS SnPh, MV SaPh, I BAL _ ‘SnPh, ‘ 1 HW fi sns Mv Sns oe ee 1 ‘ SFS SnS, I Mv ‘Sni; MV Sno, : I _|wy, pees Me.NSnCl, 1 GzF ji Najsno, SPO) gop 70 70 snd st ° : eINoING ENERGY. ev SnO GZF Sn0, ° ‘$n0, LAK = Sno, GZF Sk (NH.)Sn1 GZF a Sn0. (CcHAN)SAL i GZF Ph,SnCl He “| Mv SnCl, GZzF SnCl-2+,0 GzF ‘Me.Sn aeagy Ele BAL ‘(pnP).Snors HW (Ph,P).SnF, . “| Hwy SnF, GZF SnF, MV ‘SnF. GZF KSnF, "FE eel “| GzF K,SaFy ‘J MV |.___—.;___ ® : 00 70 70 BINDING ENERGY, ev ME rsemetcrnoes(eCeCOCOCCECOCECECECECECOCEE Cl Tin, Sn 2250 T T So(MNN) MyNasNes 828.4 Mg Ka Sn 4s Sn 4p | 1 1 L L 1 80 000) ‘800 ‘800 700 600 500) “400 300) 200 | BINDING ENERGY, eV r 700 0 PERKIN-ELMER 119c. Ws, Mine Door DD y Yaw htintony, db Yoo 5) De Nae hae he COMPOUND ‘dy, BINDING ENERGY, eV REF. T , 595 530 535 Sy Sb i i . 52005 Sb sv i Sb SFS | Alsb Msv Bey, ; Bu,Sb BCs | Ph,sb BCs Ph,SbS BC4 Ph,SbO BC4 Sb,S, Msv ' 8,8, ce 1 Msv i 80,5, 1 8C4 Ph,SbBy | Bc4 Me,SbBr, I BC4 BuNH,Sbl, I BC4 ee | $b,0, Msv Pease aera 80,0, { “| | aca L NaSbo, MSV sa 3 323 SdS(Catte)s 22" z ale | msv BINDING ENERGY, 6V ‘Sb(OAC), Msv 80,0, L 84 jr Sb,0, 1 BCs (i Cs,Sbily SRE alll ~ “|7 | C4 \ Cs,Sb,Ci,' 1 =| BC4 Gs,Sb.8n'5" 2 ae #)"] 8) pea i Gs, SbF, \ BCs 1 CsSbF, 1 BC4 CsSbF, BC4 K,H.Sb,0/4H OER | "7 fp] msv Msv i se] S| =.=). MSV 4 msv i KSOF, Msv ! NaSbF, BC4 : | \ | Et.NSbF, ll BCs i O 120 puvsicaL eLecraoNicsWANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Antimony, Sb as 51 S23 T Sb(MNN) MyNaNus 798.7 Mg Ka || 1000 200 700 600 500 400 300 200 100 0 BINDING ENERGY, eV PERKIN-ELMER 11ev) ’ ) Vy Tellurium, Te sts 52 ’ . 8 E : 2 24 Te 2 SF soee 3 b 8 dey, 431 1063 3 ’ 490, 1062 3 i ie 7 5 Z é g S 2 5 és Base +10, —_____- 8 Fr 1 g P Np ] se wre ze a . Aeseeres : BINDING ENERGY, eV 3 ‘ 485 i 4 1 i saa ata Sy, BINDING ENERGY, ov @ 122 puvsicat evectRoNics| —_ ™ HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Tellurium, Te tz: 52 Te(MNN) ae m3 L i MgKa | Teddy, 761.2 800 770 740 4 388 TelMNNy L L fi 1 L T 1000 ‘200 800 700) 600 500 400 300) 200 700 0 BINDING ENERGY, eV PERKIN-ELMER 123Mov) foaine, 1 =; 53 Maroudoc or Lan horedectnds srudinoscber ‘COMPOUND 3dy, BINDING ENERGY, eV 61s 620 REF. 625 ni ees] © 124 PHYSICALELECTRONICS o Mvs. Mvs. MVS. Mvs. Mvs. N N N oYK T wi Bay, By, 6195 4152——__———+| 637 exe x7 622 BINDING ENERGY, ev air B12 Ne 0( HANDBOOK OF X-Ray PHOTOELECTRON SPECTROSCOPY Iodine, I sina 53 NED 1100 900 800 MeNucNas 748.1 (MINN) MNuNes 736.4 700 L L 600 500 ‘400 BINDING ENERGY, ev Lil Mg Ka 100 ipa eee 128yyy) yr» .) bo Xenon, Xe is54 ce COMPOUND ‘d,, BINDING ENERGY, eV REF. uy : 7 iy oss 70 es Xe inc Ke Gn O) 1T o oe Xe (in Fe) wi esas Me (iniGu) eae as | cH2 3 CH2 cH2 yg wi : |_$_—_ a __ 1 1 L 1 eee ee 78 es ee8 es ® 126 pHysicaLeLectRonics BINDING ENERGY, ev Ne) =Haseeno tant rioron cesta teecrncteaey Xenon, Xe 2s 54 1 t 1 1 r 1 1 emnny t Xe inc Mat L m5 aa Mg Ka | 092 Xe 3d, Xe(MNI IN) | xe ads, | L 1 1 L L L L 1000 ‘900 ‘800 700 600 500) 400 300 200 100 0 BINDING ENERGY, eV PERKIN-ELMER 127Vevey ev) Cesium, Cs iss55 HaNOBGOK OF X-Ray PHOTOEL: COMPOUND, 3dy, BINDING ENERGY, eV REF. 720 728 m0 CsOH MVS 723.95 Mvs SGR Bay mvs mvs mvs |}+—__1ss_______-| NE) L L L 1 163 738 733 728 723 718 . BINDING ENERGY. eV ® 128 puvsicat evectRoNics 16Ce ee ee | rr CC Cesium, Cs sx 5:, r r T T T T T T | . | waka ca(hnn) CsOH | Mg Ka _| | —| wie) | 1100 7000 900 L 1 1 L L L L 600 500) BINDING ENERGY, eV 100 PERKIN-ELMER r 12577s 1 yb ye Cb ed Barium, Ba «56 ano80OK OF -AAY PMOTOELECTHON SPECTROSCOPY ‘COMPOUND ‘dy, BINDING ENERGY, eV REF. : : l 78 753 78 acy BaO uo i. gs Ba erucate ws 1 ws 304 a I See w3 l ws See eae 1 1 1 1 200 785 700 708 780 O 130 puysicat eLecTaonics BINDING ENERGY. ov775 Cot (tC Barium, Ba 2: 56 Badpy, T T T T T Ba(MNN) BaO Mg Ka | MNaNas 668.7 MaNasV 1000) 900 ‘800 700 600 500) 400 300 200 100 0 BINDING ENERGY, eV PERKIN-ELMER 131ON ntantim La dete PPP PPD DD dd OL H , ’ Lahtrantim’ Ld tes 87 wamdoor Prantrordticcibonstersctory® 9, comPouNs 36, SINOING ENERGY, AER 0 oes 7 Ge aa vn : i i iF ’ (( i t | ee ® 132 paysicacetectrowies: 870 ‘360 350 a0 330 320 BINDING ENERGY, evcs (ee Ceres (tC CC Cee HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Lanthanum, La diac 57 T T a T T T La,O, Mg Ka | 183g La dey La(MNN) La ddyy Lass Lap, \ 1 1 L 1 1 1 J 1000 200 BINDING ENERGY, eV 500) “400 300 200 100 PERKIN-ELMER 0 133Pe eee i Atomic HANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Cerium, Ce .tz:58 ‘COMPOUND ‘34y, BINDING ENERGY, eV REF, r Tea as 60 as ay, CeO, Ge TT [82 CeO, NGD Ce0, o s Bde, s 8 e816 @ 134 puvsicaL evectrowics S=Satalite ines 925 aS 305 295 BINDING ENERGY, eV 385 875, 1ers 'WANODUOK OF X-RAY PHOTOELECTRON SPECTROSCOPY 700 Ce(MaNusNs) Co(MaNaV) L 600 1 500) BINDING ENERGY, eV 400 Cerium, Ce .ts:58 CeO, Mg Ka x Cedp con 700 PERKIN-ELMER al 135Mobndndm sin dcdgh 2 PPP ver dD sadron tecradsco) V4) somber ‘COMPOUND ‘Sdy, BINDING ENERGY, eV AEF. f y : z 1080 1085 1090 sm,0, sm KM Sm,0, KM Sm,0, ® 264, |+__—_____»7,2—____| ae 1106 1096 7086 1078 1086 BINDING ENERGY, eV ® 136 PuYSicaL ELECTRONICSCome eee OO EOE EE EEE EEE EEE EEE a WANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Samarium, Sm ses 62 T T T T T T T T Sm,0, | sine) Mg Ke MasNesNas 7066 1 i i 1 1 1 1 z 1 z 1 1100 1000) 900 800 700 600 300 400 300 200 100 ° BINDING ENERGY, eV { PERKINELMER 137y nANDROUK OF x:RAY PHOTOELECTRON SPECTROSCOPY vy ey yyy yD?DD Terbium, Tb “x= 65 COMPOUND “dy, BINDING ENERGY, eV AEF. us 190 155 7 ° om) 198 PHysicaL etectronics 180 370 7 BINDING ENERGY. 60 wv 150Cee eee eC EEEEE EEE EEE EEE EEE CECE ' HANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Terbium, Tb 32z< , Th sees T T T T 1 T T T T T "b | roa Al Ka ' tI) te 2% 140 To(MaNsNs) a) To(M.vV) £ rexnaavyy ® 1300 1200 1100 1000 9200) ‘800 700 600 ‘500 400 300 200 100 BINDING ENERGY, ev PERKINELMER 13, NANDBOGK OF X-RAY PHOTOELECTRON SPECTROSCOPY ee) py ’ Erbium, Er omMPOUND “4d,, BINDING ENERGY, eV AEF, 165 170 1s & r © E10, Neo E10, I ® 140. Pavsicacevectaonics: T 43 Er 1692 L 100 70 160 BINDING ENERGY. eV T Er,0; 4 1625 180 170 160 BINDING ENERGY, ev160 ie 'NANDBOOK OF x-naY PHOTOELECTRON sPECTROSCOY Erbium, Er tz: 68 1000 T 900) 800 700 L 600 Er4s and En(MigNuNas) L 500) BINDING ENEAGY, ev L 400 Er Any, 300 Er(MaNaV) T Al Ka Er(Mavv) Er(Mav¥) L 100 PERKIN-ELMER 0 441») Pe Hafnium, Hf 22:72 (OTOELECTRON spectRoscoPY ‘COMPOUND 4fy, BINDING ENERGY, eV REF. " rT 10 6 2 ty, Ht A © HIF. I] Ady, BINDING ENERGY, eV i 210 as 20 HO, Neo HE(OH),alanine,Cly:12H,0 KNP Ne) we) | BINDING ENERGY, ev 1000 142 pavsicat ecectRoNicsNe) NANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY 1000 900 00 700 600 500) BINDING ENERGY, ev L 400 1 100 0 PERKIN-ELMER 143cob ed Tantalum, Ta is: yy vy dD 73 MANDBOOK OF X-RAY PHOTCELECTRON SPECTROSCOPY ‘COMPOUND 20 4%, BINDING ENERGY, eV 25 REF. 30 © RH2 Msc RH MSC Msc Msc MSC Msc “| msc NGD Msc Msc Msc Msc ® 144 puysicacevectaonics 4 % —+| 18 L Ta 35 2 BINDING ENERGY, eV ySee eee eee eee Peet pea r HANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Tantalum, Ta 2:73 T T T T T 1 7 ok Al Ka | Tat 1 L 1 L 1 L L L L 1000 900 800 700 600 500 400 300) 200 700 0 BINDING ENERGY, ev PERKINELMER 145ey ’ ee Tungsten, W ise 74 GomPouno iy, BINDING ENERGY, eV REF. 30 35 40 sty WwW a o 10 Ww I BP . w - 1 NH2 fe Ww i cR we cR wo ae 1 cR we Msc ws, I NH2 WN . I cr wo, sie et NH2 wo, cR WCL(PMe:Ph): = LB WCI(PEt,); I LB 2.15%] K.WCl, I LB wo, NGD Wo 1 NSL \ wo, Ty. fisfee]MSC as 35 25 wo, fee fom | Pa bs al BiNoING ENERGY. ev Wo, NH2 cR Ee NGD 3 = /F2)"| BP = Msc off | a]nee BP NH ep fata MSC Msc 1 Msc MSC 145 pwysicavetectaonicsCe ee ee ee wy : HANDBOOK OF X-RAY PHOTOELECTHON SPECTROSCOPY Tungsten, W ss 74 T T T T T T AlKa wet, : ‘* 1 1 1 1 L L L 1 1 1000 200) 800 700 600 500) 400 300 200 700 0 4 BINDING ENERGY, eV PERKINELMER 147See Rhenium, Re stsns 75 omPOUND Wy, BINDING ENERGY, eV REF. ay Fy ‘9 8 wo Re Re ® Re F ReCIN,(Ph,PCH,PPh,} He ReCIN,PMe;Ph), ae Bie Beer eae ReOCI (PPh Il F ReCiNsPMe,Ph). | eles) Jeattenlies eee ce) ReCi,(PMe,Ph), 1 Ls ReCl,(PMe,Ph), I iB ReCl,(PMe,Ph); I LB ReCi{Et,P) ale | | . ee LB K,ReCh, | LB K.ReCi, t CHI ‘KReO, i] fs wi 54 a 34 BINDING ENERGY, eV 148 prvsicat eLectRoNicsHANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY ce Ce Rhenium, Re ts: 75 1000 800 700 600 1 500 BINDING ENERGY, eV 400 Al Ka L L 300) 200 100) 0 PERKIN-ELMER 149) Iridium, Ir 4s 77 Pepe ve HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY compound 41,, BINDING ENERGY, eV Tr ie ir InPPhy)CIN, In(PPh;)C10,(CO) A(PPh)CKCO), In(PPh,);103(CO) I(PPh,),C(COVCF.) In(PMe,Ph),Cl, InPPh,),CI[C(CN).) Kirs{CO)Cly K,lr(CO).Cly In(PMe,Ph),Cl, IPEL).Cl. Ich, Ir(CO),C1 Ir (ethylenediamine), ‘Ir (ethylenediamine),(SCN),” Ir (ethylenediamine),(NO3), Ir (ethylenediamine),Cl, ic (ethylenediamin: Kier, KIrCl, Kren, KaIn(CN), KyleCi, KylrCiy Karch "K.I(NO,), ANH,)IrCl, (NHoalCiy KirCl(NO) ® 180. puysicat eLecraonics REF, BHH LC MMR MMR, MMR, MMA, LB MMA, KSP KSP LB Ls KsP NB NB NB NB NB NBP NBP NBP NBP CHI LB NBP NBP EPC EPC NSB 4h te 606 Ir My, |-2.25—| 4 3 BINDING ENEAGY, eV NE) 10¢( WANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY 1000 800 600 1 500) BINDING ENERGY, eV L 400 300) Ce ee eet Iridium, Ir 32577 suber i T L L 200 100 0 PERKIN-ELMER 151biatindm,'Pr e787) * P compound 41y, BINDING ENERGY, eV 70 75 20 Pr PUPPA,), PUPP). PUPBU).Cl, * PUPPh,):Cl, PUPPh,):Cls PUPPh,).Me, PUPPh,),Phs PUPPh,)als PUPPh,), HCI : PA(OH); PUPPh): CH, PUPPh): CH, PUPPh):C.F, PLPPhy):Gx(CN), PUPPh,),0; PUPEt),Cly K,PtCh, KPtCl, * PIC, K,PLCN). PO URSEE PHPEt),Cl, PHPEL):Cl K;PLCN). Cl," SHORE? PH(ERNH,).Cl.4H,0 3. © 182 Paysicatetectronics REF. SS oo DD DDDAQDDS 4h, 708 sty, —s.35—| Pt 85 75 BINDING ENERGY, eV 65 + NE) 1000eee ¢ Wawon0ox oF XRAY eHOTOELECTRON SPECTROSCOPY Platinum, Pt 22:78 T T T T T T 5 Mg Ka 1 L 1 1 L 1 1 L L 200 100 0 900 800 700 600 500) +400 300 BINDING ENERGY, eV PERKIN-ELMER 153Po ee 1 , Yam Doon Ba nathvo Dees Ron selernudbor Gold, Au 22579 2 % 85 %0 shy Au Au I JHB a8 Au FKW we : I FKW. a WHP : WHP. " FHP Sees I Ki2 KI2 NaAuCl, KI2 | | ; © 154 PHYSICAL ELECTRONICS BINDING ENERGY, eV NE) 1Pe ee : NANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Gold, Au 2:79 T T T T T T T T T 5 Mg Ka Aust, "wet L L L 1 1 L L 1 1 1000 ‘900 ‘800 700 600 500 400 300 200 700 0 BINDING ENERGY, eV PERKINELMER 155Dey ee pa Mercury, Hg ise: 80 ComPOUND. 41, BINDING ENERGY, eV REF. : : 98 193, 108 Hg Hg T © Hg SMB Hg L BM na 102 3 BINDING ENERGY, ev ® 156 puvsicat eLectaonicsCw ANOBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Mercury, Hg css 80 T T T T Mg Ka 1000 L 1 1 1 L L L 1 L 500 400 300 200 100 ° BINDING ENERGY, eV 900 800 700 600 PERKIN-ELMER 157eel! DDD DD DD Den iP aarProraiscn tn setmostonr Thalium, V1 es 81 comPoUND 4ty, BINDING ENERGY, eV REF. ' 4h ns 120 13s wits TI TT T ° Ti I MWwM TL Msc re MSC Msc 1 Msc MSC Tier MSC TIF MSC @ 188 PHysicat etecraowics 12 122 72 BINDING ENERGY. eV 10(eee tt HANDBOOK OF X-RAY PHOTOELECTRON SPECTROSCOPY Ce Ce Thallium, TI 22: 84 Ne) € 1000 900 T T T T T T T Mg Ka Titty L 1 L L 1 1 L 700 600) ‘500 400 300 200 700 0 BINDING ENERGY, ev PERKIN-ELMER 159ee be dD omic NaNOBOOX OF X-RAY PHOTOELECTRON SPECTROSCOPY Lead, Pb sims 82 COMPOUND 4ty, BINDING ENERGY, eV REF. ‘ thy 135 0 us aed Pb Pb T © Pb LkM yy Pb . BM Po wwe Pb SFS Pb . . KOW PoTe SFS PbSe SFS PbS SFS Pes uv PhP mv Pb - I MV PbO KOW PbO o Pbo a mv |+——4.9s_—_+| PbO ms Bee L PbO, ‘ Mv 150 140. 130 Bb,0, EES Ele KOW BINDINGENERGY, eV Poo, kOW PbO; MV Ph,PbCl MV T 7 Ph,Pociy oop) av " ‘Pb, “3 ede] BY wis PbO Ay, ® eae 150 a0 130 160 puysicaLetecrnowics: BINDING ENERGY, evte ae ory NanoB0OK OF X-RAY PHOTOELECTRON SPECTROSCOPY Lead, Pb se:82 T T T T T T T T T Paty, eeinee) Ni0us0u, 1160.45 Mg Ka | Neus 1157.15 NED a] E 130 A L ou L 1 L 1 1 L 1 130 1000 900 00 700 600 500) 400 300 200 100 0 BINDING ENERGY, eV PERKIN-ELMER 161VV DVD DD DD DDD DD DD DD MMe Meal mortacchonsterdcon? 9? Bismuth, Bi: 83 cae ‘ ‘COMPOUND 4t), BINDING ENERGY, eV REF. ' Ahy 155 160 185 1568 Bi | a ° Bi eM Bi mw i | elas SFS i Lk : _| |usv | ~“ DR I DR DR : 1 ~| | msv > | msv i . a] of ff MSV. “| NGD. Bi0, oR Bi,0,-2H,O MSV ' Bim | Mw MS Yeas t70) 160 180 msv BINDING ENERGY, ev BiT10; MSV BiOcI Msv Bi(SO,),-H:0 MSV BiF, I MSV t 162 PHYSICAL ELECTRONICS || 0 | |150 {| oC C4 (0 000 Bismuth, Bi =x: 83 T T T T 7 aa Bist, L Mg Ka | L i 4, S40, 4 Bisd | @O Bisp 1 ! 1 \ L L 300 700 300 500 700 Ev 200 700 0 1000 BINDING ENERGY, ev PERKIN-ELMER 163ee ’ ee) Thorium, Th 90 omPOUND “iy, BINDING ENERGY, eV REF. 330 305 240 “% Th ; re anas Th o ve Th Few Thox wi Bho # 1 vio onise onde, Thr, wi ThE, o Sdy, BINDING ENERGY, eV #0 ¢s 0 Th 1 Few Thox Few (Securit eee Thox vib iThO; EE “|>-)NGD sThO,, NMS Tach =< Seb Ty). |) | us ! Th(OAc,) 1 NMS 4355 340, 330 ThlPO. NMS BINDING ENERGY. eV ThBr,-10H,O NMS prn'urea, Cl ea alo) [75] nus FTn(NO,)25H.0 Soe | gata] NMS : Fhe, 2 eee | | NMS ThF, thn sags ue 0 164 paysicat evectRonics 350 BINDING ENERGY, ev Nee) 100:— Thorium, Th tx: 99 i i 1 1 1 T 1 T 1 1 : | | Thaty ft I Mg Ka I | ; Ne |e | | i = | L 1 n 1 1 L 1 000 300 300 700 00 500 700 300 200 70 0 j BINDING ENERGY. ev PERKIN-ELMER 165ee te Ce te ee nee Uranium, U te: 92 COMPOUND. 4ly, BINDING ENERGY, eV REF. J as 20 es - '% g i oe 165 PHysicAL eLectRONics |+ 10s —_____-| 398 388 BINDING ENERGY, ev a74 NEare .NOBOOK OF X-AAY PHOTOELECTRON SPECTROSCOPY Uranium, U singe QQ 1000 UNO.) 700 1 500) BINDING ENERGY, ev Udtey ‘400 200 Mg Ka 1 100 PERKIN-ELMER 1671. Tables of Auger Parameter Data Line position data from the literature that are in- cluded along with the elemental spectra for F, Na, Cu, Zn, As, Ag, Cd, In, and Te in Section Il are presented as two-dimensional plots, rather than the one-dimensional binding energy charts in- cluded with the rest of the elements. While these two-dimensional plots are more useful for chemical state identification, they lack the necessary space for inclusion of some chemical states, and references cannot be included. The tabulations presented in this section are the basis for the two-dimensional charts in Section Il. It should be noted that a number of chemical states included here were not incorporated in the piots. ACKNOWLEDGEMENTS Gratitude is expressed to Snell Development Gom- pany for the use of some unpublished energy data, and especially for permission to publish several two-dirensional chemical state plots in a form similar ‘0 that in the comprehensive paper by C. 0. Wagner, L. H. Gale, and A. H. Raymond, submitted for publication, 168 pysicat eLecTRONICsqe € € OE (eer tt Cece qe Fluorine, F sss Compound ts Kal, athy Ret. ‘Compound 1s Katy athv Ref, uF 684.9 ©6549 13398 ZnF 6558 13003 GW LiF* 6846 «655.8 1340.4 WI ZnFy" 6558 13808 = W3 NaBF, 6868 6530 13398 WI Na,GeF," 6542 13399 wi C.F 7" 97.2 °° 656.7 1943.9 “Wi } Si, T 656.5°°" 13613 ° wi cr ea2 653.1 13423 wt | YF, 656.0 13411 Wt (CF, 689.1 6521 1341.2, ws Na,ZiFy 6553 13401 Wi Ni(QOCCF,), 688.2 653.1 1341.3 WI K.NDF, 655.4 13408 = Wi NaF 6342 © 655.2 © 1339.4 WS AQF 659.5 13420 Gw MgF, 685.3 654.3 13398 WS CaF, 6560 13404 GW (NH,.AIF, 6845 "655.4" 13399 "WI cor, “I 7 656.4 "713406 Wt Na,AIFe 6853 654.3 13398 | Wt InF, 656.6 1341.6 Wi K AIFS | 6851 6544 013305 wt} NaSnFy" 654.6 1338.7. WI Na,SIF. 6858 6532 © 1339.0” WS KSbF, 654.1 1339.5 CoSiF, 685.8 ©6545 = 1340.3 WI 6540 1339.7 CaF; 6846 655.6 1340.2 656.4 1340.0 =NaTiF, 685.1 777655.9° 7 71340.4 ~ TH325 ATIF," 6848/6559” 1340.7 "Wi 4 887.4 13418 tMnF? 6846) 655.7 | 13403 Wt 057.2 1341.8 K,FeF, 6838” 656.2 © 1340.07 Wt 657.2 "1341.6 Fe(MPT)PF,” 686.1 654.9 1340.4 Wt 655.5 1340.7 NiF 6849 655.6 13405 GW K,TaF,* 685.0 655.2 1340.2 NIE," : 6848 655.8” 13406 "Wt PDF, TT gaa. 658.7 1342.1 uF, 6841 657.2 13413 GW ThE, 6847 657.2 1341.9 uF, 6845 656.4 1340.9 Wt Omitie tom plot because of crowing a) MPT = C.-M; a ligand with three methylprisine rings. D)G¥F ane GF ate tuorinated graphite samples ® PERKIN-E naeSodium, Na “s11 Compound 1s Klaly ath Ref. ‘Compound 1s Katy @hy Ret. Na 10715 994.4 2065.9 Nazir, v071.4 $888 2060.2 WS Na 40718 904.5 2066.3 Na zeolite 1071.6 989.0 2060.6 «= W3 Na ox 10725 990.0 2062.5 NaPo, 1071.6 989.4 2061.0 W3 NaF 2 4071.1 988.8 2059.9 Na,HPO, 3071.4 $901 2061.5 ® Naci 1071.4 990.4 2061.8 Na,SO;* 1071.2 990.4 2061.6 W3 NaBr woaist) 107146 9908 _ 2062.4 Na,S.0," 2. w0714 990.3 2061.7 W3 Nal 1071.5 991.4 2082.9 Na,S.0. 1071.0 990.8 20818 = W3 NaOAc 10708 © 980.2 2061.0 Na,SO, 1071.0 990.0 206.0 W3 Na,CO, 1071.3 $90.0 2061.3. Na benzenesulfonate’ 1071.1 989.9 2061.0 Wi NaHCO," “ES 4071.1 990.0 2061.1 Chloramine-T"* 1071.6 © 989.2 20608) WI NaQOCH*. "4070.9 990.0 2060.9 Na,CrO, - 1071.0 991.1 2062.1 W3 2NaC,0." 20°. 40706 990.7 | 2061.3. NaCrO,* |.) 1074.4 990.6 | 20620 Wi Na thiogiy 1071.0” $90.6 * 2061.6 NaAsO, 1070.7 990.8 © 2061.5 °° W3 Na EDTA™™ 10706 © 980.6 2081.2 Na,Se0, 10706 © 991.1 2061.7 W3 NaNO," w071.4 $80.0 2061.4 NasMoO; 1070.7 990.2 2080.9 W3 NaNO, £ "4071.2-' 989.6 2060.8 'Na,PdCl 1071.6 990.4 20820 W3 NAB, eh oo 1072.5 987.3 2059.8 : Na,Sn0,, 1070.9... 990.5», 2081.4 WI ‘Na, AIF, GR Bees 1071.7 988.4. 3 2060.1 iNa,TeO,* 1070.9 8 “5. 2061.5 | W3. Na,SiF, 4071.5 987.9" 2059.4 Na,WO," w07i.t 2061.7" W3 Na,TiF? 4071.4 988.7 2060.1 NazIrCly+6H,0° 1071.7 2081.1 W3 Na,GeF, 1071.5 988.3 2059.8 NaBi0," 3071.1 20622 WI “Omites trom pot bacause a crowding 8) NAEOTA =Na salt of eihylenedaminetatacetic ale 1H .C.H,SO,NNaGl ® 170. puvsica. ELECTRONICS(CeCe CeCe Ce eee ts t Copper, Cu iss 29 Zinc, Zn 285 30 ‘Compound 2pm_ — LyMaMay thu Ret. Compound 2py —LiMagMy @ehy — Ref, cu 9324 9188 «= 18510 Zn w021.4 9924 20138 cur $320 9192 1851283 zn* wwe; eyez UTS cur 9324 9190 1851.4 GW Zn" 40215 992.7 = 2014.2 St cur 9022 9192 1851.4 = MR Zn* 10217 © 9926 © 20143 CE cur 9028 9182 © 18508: KPM Zn" 1021.8 © 9920 2013.8 = KL2 cur 9025 «918818513 FKW Zn" 1021.6 992.0 20136 KPM cur 9324 9188 1851.2 Zn" 1022.1 992.0 20141 GW Al,Cu 9336 9183 1851.9 Zn 1021.9 992.3 2014.2 -HF2 Cu,0 9322 917.4 1849.6 Zn" 1021.4 © 9925 20189 MD Chr: 9322 9176 1849.8 ZnO 10217 ° 9888 20105 Cu,0° 932.2 9169 = 1849.1 ZnO 10225 © 987.7 20102 GW CUCN 992.9. 9147 1847.6 Zn0* 10225 © 987.6 20100 sHF2 uct 9322 9158 1848.0 Zn ox 1021.8 988.2 2010.0 «= W3 CuCl 9324 ©9152 1847.8 Zn ox 4021.9 989.1 2011.0 CE Cus 9323 917.6 1849.9 Zn acacy jo2t.2 9879 2008.1 W3 ‘CuCo, 934.8 ~ 916.5 "77 1851.3 Zak, ee 4022.4 7° 986.7 0 cuo 993.5... 917.9 1851.4 © ZnF; je. 1022.2°° . 986.2 cuo* 933.4 9183 1851.7 ZnS "\922.4 988.2 ‘cuo* 9330 9179 18509 ZnS 10220 989.7 Cur, 9388 9150 18518 Zn8r, 1023.2 987.5 Cur, 9359 9162 18521 Zl, 1022.9 988.7 cusio, 934.7 915.4 1850.1 ZnPT(BF,);" 1021.7 ~~ 988.5, wt CuSO, aq 935.3 se 916.1, 55 1851.4 ZnTe iT geks | 10220 991.93." 2011.3 52 HF2 cuci,* 934.2 °° 915.7" 1849.9 uci," $350 9153 18503 CuPT(PF,).” 933.8 916.1 1849.9 “Caitted rom plot because of crowding 2) PT =ligand, C,H, containing thea pyriaine rings. @ PERKIN-ELMER m1» rr? eee Ne Arsenic, As 42s 33 Silver, Ag 3547 Compound Sd LMM, = thu Ret. Compound 3dy = MNaNa a+hv — Ref. re aia 125.4 12667 a 378 3581 7260 ~~ As 4131026312678 age 9680 35847284 WO As 418 12252 12608 AQ" 3681 958.2 7263 $2 NbAS, See 1226.2, 1266.8 ages + 968.0 357.89 725.8 Gw GaAs 40.7 1225.6 1266.3. Ag” 367.9 358.0 725.9 As,Se, fat 42.8 | 12235 1266.3 AlAg, __ : 368.4 358.0 726.4 1223.1 1266.4 ‘Ag.0 367.6 356.9% ~ 724.5 12225 1265.8 9,0 3677 35687248 1222.2 © 1265.5 AgO . 367.2 356.8 724.0 1222.9 1265.8 ‘AgO ~ (367.4 357.4 724.8 1221.3 1263.5 AgO ff 967.8 5 355.7 723.5 2. 1220.2 | 1264.1 Agt 2g SR ss 967.8 25 356.99 327041 1219.5” 1263.3 AgOOCCF, 368.6 355.3 723.9 1218.3 1263.4 Ag,SO, (368.1 354.4 722.5 1219.1 1263.3 Ag:SO, 367.7 355.3" 23.0 1219.0 - 1263.8 Wor oe 7 355.5" 9723.0 ‘AaFe Boss." ae 722.9 | Ph,AsO” 44.1 1219.7 1263.8 Ph,AsO(OH)* 44.2 1219.2 1263.4 FPhASO(OH), BITES 0 9218.6 1263.6 _BUASOIOH EE 48.9 4 ‘i HCH) ASQ(OH) Ha 43.8 Cadmium, Cd «48 Me,AsO(OH) 44.4 KASF," 47.6 Compound 3d, MANgNas thu Ref. Ca wad 089 7887 @ ca 404738397888 WS Gd i: 404.7 | 984.2" 7889 GW ‘CdTe 404.8 382.7% 787.5 Gw CdSe 405.1 381.7) 786.8 Gw *Omitied tom plot because of crowding (oe 405.1 381.4 786.5 GW. Btn castes ey eae ee eeer ae (oH 4052 “gens” "7055 GW 1) CAO believed hydrated. Penn eee cdo 404.0 382.5" 786.5 Gw Ca(OH), 404.9 380.2 785.1 Wi ® 172. puysicat etecrrowicsIndium, In xs MsNasNes 52 M.NeNe thu Ret, ‘Compound Sdy, in 443.6 in 4440 tn 443.6 InTe ~ 444.1 Inte, 4443 Ine 4448 In,Se, 4446 Ins 4443 In,Sy 444.5 Ink, E Indr, inGliaeee : 484.6 incl, 4458 In,O 444.1 In,0, 1,0; Inox -In(OH), In (NHa3inF, “Omitted tom plot because of crowcing Raine) ® 410.6 410.8 410.9 409.4 409.1 408.2 408.5 408.5 407.5 406.0 * 405.0 405.9 404.8 407.0 “404.2 404.3 (eee Tellurium, Te sss Compound 3dy, Te 572.7 te 579.2 Te 5728 Ph,Te, 573.7 Pniel, 575.6 PhTel, 575.2 Et, Tel, 575.1 Me,Tel,” 875.4 TeBr, 576.5 PhTeBr, 576.4 RB ® ‘575.0 (FH TERK," 576.1 MeC,H,TeBr,” 575.8 BuTeBr," 576.4 Ph,TeBr* 576.0 ‘TeQ, 575.9 i: ‘TeO, 877.15 Te(OH). if 576.5 Te ox: 576.9 NaTeO, 576.8 Tel, 576.7 Ph,TeCl, So” S760 (p-MeOC,H,)TeCl, 876.5 Tetu, Cl, 23%. 574.1 Tetum ci* 576.1 (NH).Tecl; 576.3 (p-MeC,H,)TeOOH 575.9 * 496.5 492.4 1065.1 4917 © 1088.9 WO. 492.0 1064.9 BWI 498.7 1062.4 BWI 498.4 1064.0 BWI 497.8 © 10629 BWI 4978 © 10629 BWI 497.8 497.5 497.0 497.3 497.2 496.8 496.7 496.9 497.3 498.7 495.7 496.5 496.5 496.3 496.1 498.9 496.8 497.0 496.8 PERKIN-ELMER 1732. References for Line Energy Information Line position data from the literature that are Presented with the elemental spectra in Section Il were obtained from the following references, The references are listed according to the first letters of the authors' names, to a maximum of three authors. In cases of ambiguity, concluding 174 puysicat eLecTaoNics numbers have been used. An asterisk by a reference indicates that it contains many data that were not used in this Handbook. All data have been charge referenced to a C1s binding energy Of 284.6 eV or a Au4t,, binding energy of 83.8 eV.A ‘ act 1 ace i an ara 81 82 83 ed “BAL, ec1 sca 803 ecs eco ecw oT ar FM Bap BHH aM 5MG ens oP ES aw! aww ez cas cos ‘A. Aoki, Japan J. App. Phys. 15, 905 (1976) G.C. Allen, M. T. Curtis, A.J. Hooper, and P. M. Tucker, J. Chem. Soc. (alton) 1979 1675 G. C. Allen, M. Curtis, A. J. Hooper, and P. M. Tucker, J. Chem. Soc. (Galton) 1974 1528 G.G. Allen and P. M. Tucker. Inorg. Chim. Acta, 16 41 (1976) G.C. Allen and P.M. Tucker, J. Chem. Soe. (Dalton) 1973 470 TL Barr, Chem. Phys, Lett. 49, 89 (1976) ‘A. Barrie, Chem. Phys. Lett. 19,1 (1973) M.K. Bahi, J. Phys, Chem. Solids 26, 485 (1975) H. Binder, 2 fer Natirforsch. B28 5, 256 (1973) G. M, Bancroft, | Adams, H. Lampe, and T. K. Sham, J. Elect, Speciros. 9,191 (1976) M. Barber, J. A. Connor, M.F. Guest, M. B. Hall, H. Hillier, ang W. N. E. Meredith J. Chem. Soc. Far. Disc. 4, 220 (1972) M. Barber, J. A. Connor, M. F. Guest, IH. Hillier, M. Schwarz, and M, Stacey, J’ Gher. Soc. Far, 1, $8, 551 (1973) M. Barber, J. A. Connor, |. H. Hillier, and W. N. . Meredith, J. Elect. Spectros. 3,110 (1972), T. Birchall, J. A. Connor, and I. H. Hillis 2003 M, Barber, J. A. Connor, L. M.R. Derrick, M. B. Hall, and I. H, Hiller, J Chem. Soe. Far. I, 69.559 (1979) Y. Baer, P.H. Citrin, and G. K, Werthelr, Phys. Rev. Lett. 37, 51 (1976) J. H. Burnes, J. G. Dillard, and L.T. Taylor, J. Am. Chem. Soc. 97, 080 (1875) K. Burger and &. Fluck, Z. Anorg. Algem. Chem. 408, 304 (1874), ©. Battistoni C. Furlani, G. Mattogno, and G. Tom, Inorg. Chim. Acta 24, L25 (1977) J. P. Bonnelle, J Grimblot, A. 0. D'Huysser, J. Elect. Spectros. 7, 151 (i975) Y. Baer, P. F. Heden, J. Hedman, M. Klason, C. Nordling, and K. Siegbah, Phys. Ser. 3, 85 (1970) 4J.S. Brinen and J. €. McClure, Anal, Lett. 5, 737 (1972) P. Baybutt, W.N.E. Meredith, M. . Guest, V-R: Saunders, lH. 5, and J. A. Connor, Molec, Phys. 25, 1011 (1973) {LR Bact Fe NewdberaF StowoE &. bridge, and MM ‘ones, Inorg. Chem. 9. 2374 (1970) P. Biloen and G. T. Pot, J. Catal. 30, 169 (1973) A. Barrie and F. J. Stret, J. Elect. Spectros. 7, 1 (1975) 'M. K. Bahl, RL. Watson, and K. J. rgoli, J. Chem. Phys, 68 5526 (1977), 68, $272 (1978) M. K. Bahl, R.D. Woodall, A. L. Watson, and K. J. Irgoic, J. Chem. Phys. 64 1210 (1976) Y, Baer and Ch. Zurcher, Phys. Rev, lett. 38, 956 (1977), D.T, Clark, Adams, and . Briggs, Chem. Comm. 1971, 603, B, Carrere, J.P. Deville, D. Brion, and J. Escard, J. Elect. Spectres. 30, 85 (1977) 4. Chem. Soc. (Dalton) 1975 “Many data not used con ce set rk cs cH cue ka km cu. ca ese cr Km pa ec EPC Few For FHP FKW FS FUM FWe “cc “cHH “om osm J.A Connor, L. M.A. Derrick, and | H. Hier, J. Chem. Soc. Far. 70, ‘341 (1974) J. E, Castle and 0. Epler, Proc. Ray. Soe. A333, 49 (1974) J. Chat, C, M. Elson, G. J. Leigh, and J. A. Connor, J. Chem. Soe, (alton) 1976 4952 D.T. Clark, W.. Feast, 0. Kileast, and W.K A Musgrave, Palyen, Sei. 17, 389 (1975) 1D. Chadwick and J, Graham, Nature Phys. Sci. 237, 127 (1972) LE. Cox and 0. M. Hercules, J. Elect. Specttos. 1. 197 (1972) P. H. Citra and D. R, Hamann, Phys, Rev. B10, 4948 (1974) .T. Clark, 0. Kilcast, 0. 8, Adams, and W. K. R, Musgrave, J. Elect, Spectros. 6 117 (1978) 0. Clark, D. Kileast, end W. K. A. Musgrave, Chem. Comm, 1971, 516 1. Cahen and J. E. Lester, Chem, Phys. Lett. 18, 109 (1973) . J. Colton and J. W. Rabalais, Inorg. Chem. 15, 297 (1876) J. Carver, G. K. Schweitzer, and T. A, Carlson, J. Chem. Phys. 57 ‘360 (1972) D.T. lark and H.R. Thomas, J. Polym. Scl. Polym. Chem. 18, 791 (37a) . Dufour, RC. Karnatak, et. 42, 439 (1978) T.P, Debies and J. W. Rabalais, Chem. Phys. 20, 277 (1977) J. Escard, G. Leclere, and J. P. Contour, Compt. rendu. 274C, 1645 sr) 4J. Escard, 8. Pontvianne, and J.P. Contour, J. Elect. Spectros, §, 17 Gers) B. Folkesson, Acta Chem. Scand. 27, 287 (1973) J.C. Fuggle, A. F. Burr, LM. Watson, 0. J, Fablan, and W. Lang, J, Phys. F Metal Phys. 4, 395 (1374) A. Fontaine, A. Caillat, L. Feve, and M. J, Guittet, J. Elect. Spectros, 19, 349 (1977), RM. Friedman, J. Hudis, M. L. Perlman, and R. E. Watson, Phys. Rev Ba, 2484 (1973) J.C. Fuggle, E. Kline, L. M. Watson, & D. J. Fablan, Phys. Rev. B16, 750 (1977) H. F. Franzen and G. A. Sawatzky, J. Solid State Chem. 15, 29 (1875) HF. Franzen, M. X, Umana, J. A, McCreary, and R. J. Thorn, J. Solid State Chem. 18, 363 (1878) J.C. Fuggle, L, M, Watson, D. J, Fabian, and S. Aflrossman, J. Phys. Fa Metal Phys. §, 375 (1978) LC. Gray, J.C, Carver, and D. M. Hercules, J. Elect. Specttos. 8, 343 (976) U, Gels, P. F. Hedén, J. Hadman, B. J. Lindberg, A. Manno, R. Nordberg, C. Nordling, and K. Siegbahn, Phys. Ser. 2, 70 (1870), 8.0. Grim and L. J, Matienzo, Inorg. Chem, 14, 1015 (1973) C. J, Groenenboom, G. Sawatzky, H. J. deL. Melje, and F. Jelinek, J Organometall chem. 26, C4, (1974) /M. Marlot, and ©. Bonnelte, Crem, Phys. PERKIN-ELMER 175cw oar Ho Hee HY Fe oH Hus KM HKN Hs. HW Hv Hw uk IKI 8 JHB, Kea ken ko Kew Kir Kia Kut 176 3, W. Gaarenstroom and N. Winograd. J. Chem. Phys. 67, 3500 (1977) P. A, Grutsch, MLV, Zeller, and T. P. Fehiner, Inorg, Chem, 12, 1492 (973) W. B, Hughes, and 8. A. Baldwin, org. Chem. 13, 1591 (1974) 4J.Heaman, ¥. Baer, A. Berndtsson, M. Klasson, G. Leonhardt, R. Wileson, and C. Novaling, J Elect, Spectros. 1, 10% (1972) R, Hoogewigs, L. Fiermans, and J. Vernik, J. Elect. Spectros. 11, 171 (arn FR. Hoogeuijs, L. Fiermans, and J. Ventik, J. Microse. & Spectros. Electron. 1, 109 (1976) D. N. Hendrickson, J. M, Hollander, and W. L. Joly, Inorg. Chem. 9, 8121970), . Hamria, G. Johansson, U, Gelius, C. Nordling, ard K. Siegbahn, Phys. Ser. 1, 277 (1970) G. Hollinger, P. Kumurdjian, J. M. Mackowskl P. Pertosa, L. Porte, and Tran Minh Duc, J. Elect. Spectros. 8, 287 (1574) J. Hedman, M. Klason, R. Nilsson, C. Norling, M. F. Sorokina, D. kijushnikov, S. A. Nemnonoy, V. A. Trepeznikov, and V. G. Zyryanoy, Phys. Scr. , 195 (1971) H. Harker and P.M. A. Sherwood, Phil, Mag. 27, 124 (1973) 4.S. Hammond and N. Winograd, J, Electroanal. Chem. Interfacial Electrochem. 80, 123 (1977) 4J.M, Honig, L.L. VanZandt, R, D, Board, and H. E, Weaver, Phys. Rev. 1325 (1872) 5. Hoste, H. Willeman, D. Van de Vondel, and G. P. Van der Kelen, J Elect. Speciros. 5, 227 (1978) I. Ikemoto,K. Ishi S. Kinoshita, H. Kuroda, M. A. A. Franco, and J. M. ‘Thomas, J Solid State Chem, 17, 428 (1976) H, Ihara, ¥, Kumashiro, A. Itoh, and K. Maeda, Japan J, Appl. Phys. 12, 1482 (1973) C.K. Jérgensen and H. Berthou, “Photoelectron Spectra Induced by X-Rays of Above 600 NonMetallic Compounds Containing 77 Elements,” Det Kongelige Danske Videnskabernes Selskab Matematisk-lysiske Meddelelser 38, 15(1972) Kebennavn G. Johansson, J. Hedman, &. Berndteson, M. Klasson, and A, Nilsson, J: Elect. Speciras. 2, 295 (1973) KS. Kim, Phys. Rev. B11, 2177 (1975) KS. Kim, W. E, Baitinger, J. W. Amy, and N. Winograd, J, Elect. Spectroa'5, 351 (1974). G. Kumar, J. Blackburn, W. E, Moddeman, R.G. Albridge, snes, Indig. Chem. 13, 296 (1972) K.-S. Kim and R, E, Davis, J. Elect, Spectros. 1, 254 (1972) K.S. Kim, AF. Gossmann, and N. Winograd, Anal. Chem. 46, 197 ciara) K. Kish and S. ikeda, Bull, Chem, Soc. Japan 46, 242 (1973) K. Kishi and S. Ikeda, J. Phys. Chem. 78,107 (1974) SP. Kowalczyk, L. Ley, F. R, McFeely,R. A. Pollak, and O. A, Shirley, Phys, Rev, 88, 3665 (1973) 1nd. M PHYSICAL ELECTRONICS Kw KNe kow KPM ksP kw Kwo aK ts LeH LFS Hy LK KM um Ly La mc MO Mec ML. ML MMP ner MRC ssa Msc sv *MTH 5. P. Kowalczyk, L. Ley, F, Ru McFeely, R.A. Pollak, and D. A. Shirley, Phys. Rev. 89, 981 (1974) LG. Kharitonova, V. |. Nefedoy, L. N. Pankratova, and V. L. Pershin, Zh. Neorg. KR. 19, 860'(1978) K.S. Kim, T. J. O'Leary, and N. Winograd, Anal. Chem. 45, 2214 1973) 5. . Kowalczyk, R.A. Pollak, F, A. McFeely, L Ley, and 0. A. Shirley, Phys. Rev. 88, 2087 (1973) 1M. G. Kaplunov, Yu, M, Shut Phys. Stat, Soli, 73, 396 (1976) K.S. Kim and N. Winograd, J. Catal 35, 66 (1974) K.S. Kim, N, Winograd, and R, E. Davis, J. Am. Chem. Soe. $3, €296 (37 ‘A.W. C. Lin, N.P. Atmstrong, and T. Kuwana, Anal. Chem, cer G4. Leigh and W. Sremser, J, Cher. Soe. (Dalton) 1972 1217 G. Leonhardt, A, Berndisson, J. Hedman, M. Klason, R. Nilsson, & C. NNordiing, Phys. Stat. Sol 60, 241 (1973) . Larsson, B. Folkesson, and G. Schién, Chem, Ser. 3, 88 (1973) B. J. Lindberg, K. Hamrin, G. Johansson, U. Gellus, A. Fahimann, C. Nordiing, ane K. Siegbahn, Phys. Scr. 1,277 (1970), LL Lavielle and H. Kessier, J. Elect. Spectros. 8,95 (1978) LL Ley, 8. P. Kowalczyk, FR. McFeely, A. A. Pollak, and D. A. Stiley, Phys. Rev. 88, 2092 (1979) LL Loy, F. A. McFeoly, S. P. Kowalezyh, J. G, Jenkin, and 0. A. Shirley, Phys. Rev. 811, 60 (1975) |. Lindau, P. Pianeta, K. Y. Yu, and W. E, Spicer, Phys. Rev. B13, 492 (sre) T.-H. Lee and J. W, Rabalals, J, Elect. Spectros, 11, 123 (1977) N.S. Melntyre and M. G, Cook, Anal. Chem, 47, 2210 (1975) ‘JM. Mariot and G. Dufour, Chem. Phys, Lett, 0, 219 (1977) G. Mavel, J. Escard, P. Costa, and J. Castaing, Sur Sei 35, 109 1973) F, R, McFeely, S. P. Kowalczyk, L. Ley, R.A. Pollak, and 0. A. Shirley, Phys. Rev. 87, 8228 (1973) CE. Mixan and J. B. Lambert, J. Org. Chem. 38, 1951 (1973) G, Maccagnani, A. Mangini, and 8, Pignataro, Tetrahedron Lett. 36, 9659 (1972) RR. Mason, D. M. P. Mingos, G. Ruccl, and J. A. Connor, J. Chem. Soc. (alton) 1872 1730 N.S. Mcintyre, T. €. Rumery, M. G. Cook, and 0. Owen, J Electrochem. Sos. 123, 1185 (1978) W. E. Morgan. W. J. Stec, RG. Albridge, and J. A. Van Wazer, Inorg. Chem, 10, 926 (197%) G.E. McGuita, G. K. Schweiz 2481 (1973) W.€. Morgan, W. J. Stee, and J. R. Van Wazer, Inorg. Chem. 12, (873) G.Maimsten, |. Thoren, S. Hogberg, J. €. Bergmark, and S. E, Karlsson, Phys. Scr. 3.98 (1971), i K, | Pokhodnya, and Yu. G. Boredko, 1228 : ‘and T. A. Carlson, Inorg. Chem. 12,Mv vs naw vi wa sow “mye Mz “N NAB. NB NBA *NBK Nom Noo NH NH2 NB NT oNMS nse nso *NSK NSL ons Nem on out ow W. E, Morgan and J. A. Van Wazer, J. Phys. Chem. 77, 96 (1973) W. E. Morgan, J. A. Van Wazer, and W. J. Stec, J. Am. Chem. Soc. 5, 781 (1973) |. Matsuura and M. W. J. Wolfs, J. Catal, 37, 174 (1975) M. Murata, K. Waking, and S. iKeda, J. Elect. Spectros. 6 459 (1975) 1. €. Madey, C. 0. Wacner, and A, Joshi, J. Elect. Spectros. 10, 359 (is77) 4. F. McGilp, P. Weightman, and EJ. McGuire, J. Phys. C: Solid State Phys. 10, 3485 (197) LL.J. Matienzo, L. ©. Yin, $0. Grim, and W. €. Swartz, Inorg. Chem. 12, 2764 (1973) N.S. Mcintyre and’. G. Zetaruk, Anal. Chem. 9, 1621 (1977) V. 1 Nefedoy, J. Elect. Specttos, 12, 459 (1977) R. Nordberg, R, G. Alurdge, T. Bergmark, U. Ericson, J. Hedman, C. Nordling, K. Siegbann, and B. J. Lindberg, Arkiv Kemi 28, 257 (1966) V. 1. Nefedoy & 1, 8. Baranowski, Zh. Neorg. Khim. 17, 468 (1972) R. Nordberg, H, Brecht, R. G. Albridge, A, Fahimann, and J. R. Van Wiazer, Inorg. Chem. 9, 2469 (1970), V. |, Nefedov, Yu. A. Buslaey, A.A. Kuznetsova, and L. F. Yan'kina, Zn, Neorg. Khim’ 19, 1616 (1978) V. 1. Netedov. |. 8. Saranowskil A. K. Molodkin, and V. 0. Omuralieva, Zh. Neosg. Khim. 18, 1295 (1973) V. |. Nefedoy, D. Gati. 8. F. Dzhurinskii, N. P. Sergushin, and Ya. V. Salya, Zh. Neorg. Khir. 20, 2907 (1975) KT. Ng, and D. M. Hercules, J, Am, Chem, Soc. 97, 4169 (1974) K.T.Ng, and D. M. Hercules, J. Phys. Chem. 80, 2095 (1976) V. I, Nefedov. Yu. V. Kokunoy, Yu. A. Busiaey, M. A. Poral-Koshits, M, P. Gustyakova, & EG. IV'n, Zh. Neorg. Khim. 18, 991 (1973) Y. Niwa, H. Kobayashi, and T. Tsuchiya, Inorg. Chem. 13, 2891 (1974) V. |, Nefedov, A. K. Molodkin, Ya. V. Salyn, 0. M. Ivanova, M. A. Poral- Koshits, T. A. Balakaeva, and Z. V. Belyakova, Zh. Neorg. Khim. 19, 2628 (1974), V. |. Netedov, Ya, V. Salyn, |. 8, Baranovskil, and A. 8, Nikolski, Zh, Neorg. Khim: 22, 1715 (1977) V. |. Nefedoy, Ya. V. Salyn, A.A. Chertkov, and L. N. Padurets, Zh, Neorg. Khim: 19, 1445 (1978) V. |, Nefedoy, E. F, Schubochkina, . S. Kolomnikoy, |. 8. Barsnovski V.P. Kukolev, M, A. Golubnichaya, LK. Shubochkin, M. A. Poral Koshits, and M. &. Vo'pin, Zh. Neorg. Khim. 18, 845 (1973) V. 1 Nefedov, Ya. V. Salyn, G, Leonhardt, and R. Schelbe, J. Elect, Spectros. 19, 121 (1877) V. 1. Nefedov, Ya, V. Salyn, A. G. Mairova, L.A. Nazarova, and I. B. Baronovski, Zh. Neorg. Khim 19, 1959 (1974) V1, Nefedoy, |. A. Zakharova, |, Moiseev, M. A, Poral-Koshits, N.N. Vargallik, and A. P. Belov, Zh. Neorg. Khim. 18, 3284 (1973) M. Oku, and K. Hirokawa, J. Elect. Spectros. 8 475 (1976) M. Oku, K. Hirokawa, and 8. Ikeda, J. Elect. Spectros. 7, 485 (1975) J. L. Ogilvie and A. Wolberg, Appl. Spec. 28, 402 (1972) ‘Many data not used ovK Pot PFO “PHM Pan Ps Mo PNS n 80 FHT ie aR ws st sz 33 SA sol SF SFS sec sca “sma swe SNF T. Ohta, M. Yamada, and H, Kuroda, Bull. Chem: Soe. Japan, 47, 1158 iar) T. A. Patterson, J. C. Carver, DE. Leyden, and 0, M. Hercules, J Phys. Chem. 80, 1702 (1976) - 8. Pignataro, A. Fotlani, and G., Distefano, Chem. Phys. Lett. 20, 251 (973), M. Palavin, 0. N. Hendrickson, J. M. Hollander, and W. L. Jolly, J. Phys, Cher. 74,1116 (1970) ‘A. Platau, L. 1, Johansson, A. L. Hagstrom, S. E. Karlsson, and 8, 6 IM Hagstrom, Surf Sei. 63, 159(1977) S, Pignataro, L. Lunazzi, C. A. Boiceli,R, DiMarino, A. Rcl, A. Mangini, R. Danial, and . Emilia, Tetrahedron Letters 52, 5344 (1972) J.J. Pireaux, N. Martensson, R. Didrikson, K. Slegbalin, J. Riga, and J Verbist, Chem. Phys. Lett, 48, 215 (1977) (©. M. Petrukhin, VI, Nefedov, Ya. V. Salyn, and V. N. Shevchenko, Zn Neorg. Khim. 19, 1818 (1972) W.M. Riggs, Anal. Chem. #8, 890 (1972) T. Robert, M. Bartel, and G. Offergeld, Sur. Sci. 93, 128 (1972) L Ramavist, K. Hamrin, G. Johansson, A. Fahimann, and C. Nordling, 4 Pays. Chem. Solids 30, 1835 (1969) L Ramavist, K Hamrin, 6. Johansson, U. Gelius, and C. Nordting, J. Phys. Chem. Solids 31, 2863 (1970) M. Romang, and M. Roubin, Analusis 4, 309 (1976) E.D. Roberts, P. Weigntman, and C. E, Johnson, J. Phys, C: Solid State Physics 8, 1201 (1975) G. Schéin, J. Elect. Specteos. 2,75 (1973) G. Schén, Acta Chem. Scand. 27, 2623 (1973) G. Sohn, Surt Sel. 35, 98 (1973) 'S. Sommer, Amar. Minaralogist 80, 483 (1975) G. A, Sawatzky and E, Antonides, J. de Physique Colloque C4 Suppl at can7 4. Sharma, D, 8. Downs, Z,Iabal, and F. J. Owens, J. Chem. Phys. 67, ‘04s (1977), H. Schultheiss, and E. Fluck, J. Inorg, Nucl. Chem. 37, 2109 (1975) FB, Shalvoy, G. 8. Fisher, and P. J. Stiles, Phys. Rev. 815, 1680 (arn W. E. Swartz. RC. Gray, J. C. Carver, B.C. Taylor, and 0. M. Hercules, Spectrochimica Acta 308, 1561 (1974) 4. Sharma, T. Gora, J.D. Rimstidt, and R. Staley, Chem. Phys. Lett. 15 233 (1972) W. J. Stee, W. €. Morgan, R.G. Albridge, and J. R. Van Wazer, Inorg, Chem. 10,926 (1977) SS. Svensson, N. Martenson, E. Basilier, P. A. Mamavist, U. Gellus,and K, Siegbahn, J. Elect. Spectros. 9, 51 (1976) K. Slegbahn, ©. Nording, A. Fahimann, R. Noraberg, K. Hamrin J Hedman, G. Johansson, T. Bergmark, ES. Karlsson, | Lindgren, and B. Lindberg, "ESCA, Atamic, Molecular, and Solid Siate Structure Studied by Means of Electron Spectroscopy,” Aimqvist and Wiksells, Uppsala, 1967 PERKIN-ELMER 17sP3 SAH sta *sTH TRL vo vae 178 0, Simon, C, Pein, and P, Bali, C.A. Acad. Sc, Paris G24, 203 (976) W. . Swart, J. K. ult, and 0. M, Hercules, J. Am. Chem, Soc, 94 5277 (1972) ‘Yu. M. Shulga, V. N. Troltskii, M. A. Aivazoy, and Yu. G. Borod’ko, Zn Neorg. Khim. 21,2621 (1876) M. Seno, S, Tsuchiya, M. Hidai, and Y, Uchida, Bull, Chem. Soc. Japan 49, 1184 (1976) M.J. Tricker, Inorg, Chem. 13, 743 (1974) .A. Tolman, W.M. Riggs, WJ. Linn, C. M. King, and A. C. Wendt, Inorg. Chem. 12, 2770 (1973) 4J.M Thomas and M. J. Ticker, J. Chem. Soc. Far Il 71, 329 (1975) N.+G. Vannerberg, Chem. Sor. 9, 122 ('976) . W, Veal, . J. Lam, H. Diamond, and H. A. Hoekstra, Phys, Rev. ‘B15, 2929 (1977) 4. Verbist, J. Riga, J. J. Preaux, and R. Caudano, J. Elect. Spectros. 5, ye (197) D. F, Van de Vondel L. F. Wuyts, G.P. Van der Kelen, and L. Bevernage, J. Elect. Spectros. 10, 989 (1977) PHYSICAL ELECTRONICS wi we wa WwHP WM wsP sym ya, zH C. 0. Wagner, Shell Development Company unpublished data. C.D. Wagner, J. Chem. Soc. Far. Disc. 60, 306 (1975) ©. 0. Wagner, Chapter 7, Handbook of X-Ray and Ultra-Violet Photoelectron Spectroscopy, 0. Biggs, editor, Heyden & Sons, London, 1977 A. E, Watson, J. Hudis, and M. Perlman, Phys, Rev. 84, 4139 (1971) ‘A, Westernof and H. J deL. Meijer, J. Organometal. Chem. 148, 61 Garay U, Weser, G. Sokolowski, and W. Pilz, J. Elect. Spectros. 10, 429 1977), XK. 8. Yatsimirskil, V, V. Nemoshkalenko, Yu. P. Nazarenko, V. . Aeshin, V.V. Znilinskaya, and Yu. D. Taiderko, Dokl. Akad. Nauk 217, 1374 (1978) XK. 8, Yatsimirskii,V, V. Nemosnkalenko, Yu. P. Nazarenko, V. G. Aeshin, V.V. Zhilinskaya, and N.A, Tomashevsky, J. Elect, Spectros, 10, 239 (1977) M.V. Zeller and P.G. Hayes, Chom. Phys. Lett. 10, 610 (1971) Many data not usedClit CGC CC CCC CC CCC CC CC CeCe Cte 7 7? III. APPENDIXThe tables presented in this section of the Hand- book greatly facilitate the interpretation of ESCA data. Table 5, a compilation of relative elemental sensitivity factors for the various elements based on peak areas, will assist in data quantification. A brief description is included with the table, Tables, 1 through 4, compilations of photoelectron and Auger line energies, are essential to the inter- pretation of the ESCA spectrum itself. The first two tables are comprehensive listings of line positions on a binding energy scale for all of the lines of the various elements that can be generated by MgKe and AlKe photons. All of the core photoelectron lines with a binding energy greater than 10 eV plus most of the Auger lines with the intensity and sharpness to be observable are included. (Additional small Auger lines, displayed in differentiated form, can be found in the Handbook of Auger Electron Spectroscopy, also published by Physical Electronics. The energies of the strongest photoelectron lines in Tables 1 and 2 indicate the center of the range of energies exhibited by the various chemical states of each element, with certain exceptions: 1) the elemental state was not included in the range for alkali and alkaline earth metals, 2) the oxygenated halogen anions were not included in the range for the halogens, and 8) the data for the rare gases are for implanted rare gas ions in metals. The reason for 1) and 2) is that the values otherwise shown would be between extremes and would be characteristic of no chemical state at all, With these exceptions, the ranges shown en- compass data on all chemical forms. These data are derived from the literature and from the ex- perience of the authors, Alter the appropriate center value for the strong photoelectron line was chosen, the values for the other lines were calculated utilizing averaged line difference data from the literature and from our laboratory. The same was done independently for the Auger line ranges and energies. Almost all of the line energies were calculable from those ex- perimental data. Some interpolations were necessary for $3 and 4s lines. For some of the minor lines of the heavier elements, the line sep- arations in the original table by Siegbaha, et al.” were used. Because of the large number of references used, they are not enumerated here, except for the extremely helpful and extensive ar- ticle by Jorgensen and Berthou” which supplied many of the data on the line separations that were difficult to obtain elsewhere. Tables 3 and 4 are designed to facilitate the iden- tification of unknown lines in the spectrum. Lines from elements that do not occur naturally are not included in these tables. Otherwise, Tables 3 and 4 are based upon the data in Tables 1 and 2. How- ever, they include only one Auger line per ele- ment, and two photoelectron lines which are not both members of one spin doublet. The lines are the most intense and sharpest in the spectrum— those most likely to be detected when the ele- ment is present in trace amounts. In the case of a spin doublet, the number following a line designa- tion indicates the energy interval, to higher bin- ding energy, where the less intense member of the spin doublet should be found. (This was not done, however, for 4p doublets because of the variability and low intensity of the 4,9 line nor for the 4d lines of some rare earths where complex processes make the character of the doublet variable with chemical state.) “eter 1 Section 2p, 174 lor eleronces (GNF 8n6 8)Table 1. Line Positions” from Mg X-rays, — ts 22) toy_ 3436) tos Bh Be Ay tos ton_| “Wo 3 S| 2 8 ls Be ow 3 xe OP ot be e)8 3 adi 182 PuysicaL etecTRoNicsCt 444 4 4 4 tt ft A SS Son S65 S44 6560. OyVee) Table 2. Line Positions” from Al X-rays, by Element ment ci Muti Kits Kenta” wengggrozooge hs Mala Mitts of mie ping and liter rosea, 184 puvsicat evectaonicsqeceeee cee Oe t € €€€CCCCCCEOEE toy Tape a an My ty $5 So Boy Boy Sy OG toy PM | Mat MyM MM Mata MEY MAY i] Le | i 2|8 7 2) 2 : z |e BLE PERKINELMER 18517 Htaf, («102 Si2p, 1) 206 Nb3d, (3) » 359 Ludp, (63) | 575 Te3d, (10) 863 Nets 23 02s 105 Ga3p, @) 208 Kr3p, (8) | 359 Hadd, (20) | 577 Cr2p, @) 872 Cd (A) 25 Tat, (2) ~| 108 Cead, (4) 219 Hfad, (11) | 362 Gd (A) 594 Ce (A) 875 N (A) 30 F2s 110 Abad, (1) 229 S25 364 NoSp, (15) | 599 F (A) 882 Ce3d, (18) 31 Gead, (1) | 113 Bets 229 Tadd, (12) | 368 Ag3d, (6) | 618 Cd3p, (34) 897 Ag (A) 34waf, | 113 Ge (A) 230 Mo3d, (3) | 378 K2s 619 13d, (11) 920 Sc (A) 40 V3p 114 Prag 238 Rb3p,. (9) | 380 Uat, (11) | 632 La (A) 928 Pd (A) 41 Ne2s 418 Tat, (4) 241 Ar2p, (2) | 385 Ti4d, (21) | 641 Mn2p, (11) 930 Prd, (20) 43 Ref, (2) | 119 Al2s 245 wad, (12) | 396 Mop, (17) | 657 Ba (A) 934 Cuzp, (20) 44 As3d, (1) | 120 Nada 263 Redd, (14) | 402 Nis 666 In3p, (38) 954 Bh (A) 45 Cr3p, (1) | 124 Gedp, (4) 264 Na (A) 402 Eu (4) 670 Mn (A) 961 Ca (A) 48. Mn3p, (1) | 132 Smad 265 Zn (A) 402 Sc2p, (6) | 672 Xe3d, (13) 970 U (A) 50 14d, (2) | 183 P2p, (1) 269 Sr3p, (11) | 405 Ca3d, (7) | 677 Thad, (37) 980 Nd3d, (21) 51 Mg 2p 183 Sr3d, 270 Ci2s 440 Ni (A) 684 Cs (A) 981 Fu (A) 52 Osat, (3) | 198 Evad 273 Os4d, (15) | 413 Pad, (22) | 686 Fis 993 © (A) 55 Fesp, (1) | 188 Pb4t, (6) 282 Rusd, (4) | 495 Ne (A) 710 Fe2p, (13) | 1003 K (A) 56 Lits 143 As3p, (6) | 284 To4p, (83) | 439 Cazs 711 Xe (A) 4005 Th (A) 57 Se3d, (1) | 150 Thad 287 Cis 440 Sm (A) 745 Sn3p, (42) | 1022 Zn2p, (23) 61 Co3p, (2) | 153 Si2s 283 Dy4p, (96) | 443 Bid, (24) | 724 Cs3d, (14) | 1035 Ar (A) 62 raf, (3) | 154 Dy ad 293 K2p, (3) | 445 Ingd, —(@)_-| 729 Cr (A) 4071 CI (A) 63 Xedd, (2) | 158 Y3d, (2) | 297 trad, © (16) | 458 Ti2p, (6) | 7371 A) 1072 Nais 64 Na2s 159 Bi4f, (6) | 301 Yap, (12) | 463 Ruap, (22) | 739 Udd, (42) | 1082 B (A) 67 Ni3p, 2) | 161 Ho4d 308 Ho4p, (38) | 483 Co (A) 743 0 (A) 1083 Sm3d, (27) 69 Brad, (1) | 163 Se3p, (6) | 309 An3d, (5) | 486 Sn3d, (8) | 765 Te (A) 1088 Nb (A) 73 Ptaf, @) | 165 S2p, (1) | 316 Ptdd, (17) | 498 AM3p, (24) | 768 Sb3p, (46) | 1103 S (A) 74 Al2p 169 Er 4d 319 Ar2s 501 Sc2s 780 Badd, (15) | 1117 Gazp, (27) 75 Cs4d, (2) | 180 Tmad 320 Er4p, (42) | 515 V2p, (8) | 781 Co2p, (15) | 1136 Eusd, (30) 77 Cu3p, (2) | 181 2r3d, (2) | 331 ZrSp, (14) | 519 Nd (A) 784 V (A) 1155 Bi (A) 85 Audt, (4) | 182 Br3p, (7)_-| 333 Tm4p, (45) | 530 Sb3d, (9) | 794 Sb (A) 1162 Pb (A) 87 Zn3p, (3) | 185 Yb4d, (9) | 335 Thaf, (9) | 531 O1s 819 Sn (A) 1169 TI (A) 88 Krad, (1) | 189 Ga (A) 336 Audd, (18) | 534 Pd3p, (27) | 822 Te3p, (61) | 1176 Hg (A) 90 Badd, (2) | 191 Bis 337 Pd3d, (5) | 553 Fe (A) 834 Ladd, (17) | 1184 Au (A) 90 Mg 2s, 491 P2s 337 Cu (A) 585 Pr (A) 839 Ti (A) 1186 Gd3d, (33) 100 Hg4t, (4) | 197 Ludd, (10) | 342 Yo4p, (60) | 565 Ti2s 846 In (A) 1192 Pt (A) tor Ladd, (3) | 199 Clap, (a) 347 Cazp, (3) | 573 Ag3p, (1) | 855 Nigp, (18) ‘An Ain parentheses denotes Auger line. Numbers in parentheses are spin doublet separations in electron volts. The sharpest Auger line and the two most intense photoelectron ines per element are included inthe table, For brevity, 295 equals 2bya, ds equals Sdga ee. 186 prvsicat evectnonics( Table 4. Line Positions from Al X-rays, in Numerical Order 17 Hf4f, (2) 110 Rb3d, (1) » 229 Tadd, (12) ) 385 Tid, (21), 877 Thid, (7) | 1072 Nats 23 O2s 113 Beis 230 Mo3d, (3) 396 Mo2n, {iF} 686 Fis 1072 Ti (A) 25 Tadt, (2) 114 Préd 2g Rete, Gh 402 N1s 710 Fe2p, (13) 1079 In (A) 30 F2s 118 That, (4) 241 Ar2p, (2) 402 Sc2p, (5) 715 Sn3p, (42) 1083 Sm3d_ (27) 34 Wat, (2) 119 Al2s 245 Wad, (12) 405 Cd3d, (7) 716 Co (A) 1105 Cd (A) 40 V 3p 120 Nd 4d 263 Redd, (14) 413 Podd, (22) 724 Cs3d, (14) 1108 N (A) 41 Ne 2s 124 Ge3p, (4) 265 Tb (A) 422 Ga (A) 739 Ud4d, (42) 4117 Ga2p, (27) 43 Ret, (2) 132 Sm 4d 266 As (A) 439 Ca2s 752 Nd (A) 1130 Ag (A) 44 Asad, q) 133 P2p, qa) 269 Sr3p, (11). 443 Bidd, (24) 768 Sb3p, (46) 1136 Eu3d, (30) 45 Cr3p, (a) 133 Sr3d, (2) 270 Clas 445 In3d, (8) 780 Ba3d, (15) 1153 Sc (A) 48 Mn3p, (1) 136 Eu dd 279 Os4d, (15) 458 Ti2p, (6) 781 Oo2p, (15) 1461 Pd (A) 50 [4d, (2) 138 Po4t, — (5) 282 RuSd, (4) 463 Ru3p, (22) 786 Fe (A) 1188 Gd3d, (33) 52 Os4f, (3) 141 Gd4d 287 Cis 486 Sn3d, (8) 788 Pr (A) 1187 Rh (A) 55 Fe3p, (1) 142 Ho (A) 293 K2p, (3) 497 Na (A) 822 Te3p, (51) 1194 Ca (A) 66 Liis 150 Tb 4d 297 Ir4d, (16) 498 Zn (A) 827 Ce (A) 1205 U (A) 87 Sead, q) 153 Si 2s 301 Y3p, (12) 498 Rh3p, (24) 832 F (A) 1214 Ru (A) 61 Co3p, (2) 154 Dy 4c 305 Mg (A) (501 Sc 2s 834 La3d, (17) 1219 Ge2p, (31) 62 Ir4t, (3) 158 Y3d, (2) 306 Ho4p; (39) 515 V2p, (8) 855 Ni2p, (18) 1226 C (A) 63 Xedd, (2) 158 Bi4t, (5) 309 Rn3d, (5) 530 Sb3d, (9) 863 Ne 1s 4230 Th (A) 64 Na2s 161 Ho 4d 316 Ptdd, = (17) 531 O1s 865 La (A) 1236 K (A) 67 Ni3p, (2) 163 Se3p, (6) 319 Ar2s. 534 Pd3p, (27) 882 Ce3d, (18) 1244 Tb3d, (35) 69 Br3d, (a) 165 S2p, (1) 320 Er4p, (42) 565 Ti2s 890 Ba (A) 1268 Ar (A) 73 Ptaf, — (3) 169 Er 4d 331 Zr3p, (14) 570 Gu (A) 903 Mn (A) 1295 Dy3d, (39) 74 Al2p 180 Tm 4d 333 Tm 4p, (45) 573 Ag3p, (31) 917 Cs (A) 1301 Mo (A) 75 Cs4d, (2) 181 Zr3d, (2) 335 Th4f, (9) 575 Te3d, (10) 930 Pr3d, (20) 1304 Cl (A) 77 Cu3p, (2) 182 Br3p, (7) 336 Audd, (18) 577 Cr2p, (9) 934 Cu2p, (20) 1305 Mg 1s 85 Au4t, (4) 184 Se (A) 337 Pd3d, (5) 595 Gd (A) 944 Xe (A) 1315 B (A) 87 Zn3p, (3) 185 Yb4d, (9) 342 Yb 4p, (50) 618 Cd3p, (34) 962 Cr (A) 1321 Nb (A) 88 Kr3d, (1) 191 Bts 348 Ge (A) 619 13d, (11) 970 1 (A) 1326 As 2p, 90 Badd, (2) 191 P2s 347 Ca2p, (3) 635 Eu (A) 976 O (A) 1336 S (A) 90 Mg 2s 195 Dy (A) 359 Lu4p, (53) 641 Mn2p, (11) 980 Nd3d, (21) 1388 Bi (A) 99 Er (A) 197 Lu4d, (10) 359 Hg4d, (20) 643 Ni (A) 998 Te (A) 1395 Pb (A) 100 Ho4t, (4) 199 Cl2p, (2) 364 Nb3p, (15) 666 In3p, (38) 1017 V (A) 1402 TI (A) 101 Ladd, (3) 206 Nb3d, (3) 368 Ag3d, (6) 668 Ne (A) 1022 Zn2p, (23) 1409 Hg (A) 102 Si2p, (1) 208 Kr3p. (8) 378 K2s 672 Xe3d, (13) 1027 Sb (A) 1417 Au (A) 105 Ga3p, (3) 213 Hi4d, (9) 380 Uf, (11) 673 Sm (A) 1052 Sn (A) 1425 Pt (A) 108 Cedd, (4) 229 S2s PERKIN-ELMER 187Table 5. Atomic Sensitivity Factors (ASF) Spy, = 1.00. This table is based upon caivulated cross-sections cor- rected for the kinetic energy dependence of the spectrometer detection efficiency and an average value for the dependence of 1 on kinetic energy (cf section 1.5.0). The values are only valid for, and should only be applied, when the electron energy analyzer us- ed has the transmission characteristics of the double-pass” cylindrical-mirror type analyzer supplied by Physical Electronics. Data are for Mg x-rays except for those in parentheses that are calculated for Al xrays. Otherwise, the atomic sensitivity factors for Mg and Al agree within ten percent. ASF ASF ASF Ase Z_Element Line (Area) Z_Element Line (Area) Z Element Line (Area) Z_Element Line _ (area) 3 ou ts 01 7 Co ae 45 49 In dy 285 6 TY 3d (26.7) 4 Be ts 039 2 Ni 2p 84 50 Sn Baye 92 4d 1193 Bats ces toes ste Cue opted) BI Sb Bdyg 9.55 68 Dy” 3d @.0) 6 So ts 68 30 Zn Pye 53 52 Te Sy 40 44" 203 eer) 31 Ga ae 88 531 Bdge 4 67 Ho 4d 22 8 One is a 65) 2e 68) 54 Xe Steg 49 6 EM td 219 8 F ts 1.00 82 Ge by 82 $5 C8 dy 85 69 Tm! 44 = 228 10 Ne ts 1.84 Ppa (7.2) 58 Ba 3deq 6.1 7 Yo 4d 238, Na ts 251 ad 30 57 la 3dq 67 7 Wu 4d 45 Na is 227) 33 As pap (Ot) 4a? 1.22 mR He af 155 2 Mg 1s G85) ad 38 88 Ce 3d 125 3 Te 175 Mg 2p 07 ist ootttsd 48 4d 128 mW a 20 1 AL ptt 33° Br ad 59 59 Pd 140 oes ee anges ioe fase eueopeseaiag, 38 Kr Sd a7 4d 138 7 O08 Mtg «| 14 Nose aaa 25) 37° RD ad 88 6 Nd oad 187 7 ot ate 155 16 op a SG re ode 05 46148 a Pe Ata re 7 Gf a8 Sa ccrevieeectaecaetios 61 Pm ad 176 Toe Tage eaige 9) 18 At 2b 42 400 Zr Bdyyp 87 44157 BOG ate ot 19K 2p 55 41 Nb 3dag 1.00 62 Sm” 3d 203 81 Tl alg 23 2 Ca 2p 7 42 Mo dy, 1.2 441.86 8 Pb dig 2.55 2 Sc 2a, 90 eee siege tse Seu od aa 8 Bl lm «= 28 2 Ti 211 440 Fu Ben 1.58 3d (20.2) 90 Th dim 48 2 NS ope A 450 RR Bdag 1.75 4176 eg Ure ste os: 2 Cr Bye 7 ag spdiet adage 20) 64 Gd” ad 94 2 Mn Py 2.1 ata agi sda es 3d (226) 2% Fe 2 38 48 Cd Bd 285 44184 188 PHYSICAL ELECTRONICSCUT ee ee eee ee Table 6. Periodic Table of the Elements feces 4 He 3] 4 sle«6f[7]a 10 Li | Be B}c|n Ne nu [2 3 fu [iw [we [7 | Na | Mg aj osi | ep [os | cf ar atl canes coe [eos oe ee (eee ar) ele ee elie xk | ca] se] ti] v | cr] mn] Fe} co} mi | cu} 2m | Ga} Ge| As | Se | Br | Kr 37 | 3a | 39 | ao | a1 | a2 | 43 | 4a | 45 | a6 | 47 | aa | 49 | so | 81 | 52 | 53 | se ab | se | v | ze] np | mo} te | Ru | ah} Pa | Ag} ca] mn | sn} sh | Te} Xe os | se | 67 | 72 | 73 | 74 | 75 | 7 | 77 | 78 | 79 | ao | 81 | ez | as | ea | a5 | @6 ts | pe] ta] ue} ta| w] pe] os] i | pe | av} Ho | TH] Pb} Bi | Po} At | Rn e7 | as | a9 Fr | Ra | Ac T se | 59 | 60 | 6: | 62 | es | 6¢ | es | os | 67 | 68 | 69 | 70 | 71 ce | pr | nd | Pm} sm| ev] Ga] to} by | Ho} er | Tm] Yb] to v0 | a1 | a2 | 93 | oa | 95 | 96 | 97 | 98 | 99 | 100 Jaor | 102 | 103 th] ea | u | Np | Pu] am] cm] Bk} ct | es | Fm] md} No | bwAtomic Atomic Name Symbol Number Page Name Symbol__Number Page Aluminum Al 13 = + 60 Molybdenum Mo a 104 Antimony Sb 51 120 Nickel Ni 28 80 ‘Argon Ar 18 60 Niobium Nb 41 102 Arsenic As 33 30 Nitrogen N 7 40 Barium Ba 58 130 Oxygen ° 8 42 Beryllium Be 4 34 Palladium Pd 6 110 Bismuth Bi 83 162 Phosphorus P 18 54 Boron B 5 36 Platinum Pt 78 152 Bromine Br 35 94 Potassium = K 19 62 Cadmium == Cd 48 "8 Rhenium Re 75 148 Calcium ca 20 64 Rhodium Rh 45 108 Carbon c 6 38 Ruthenium Ru 44 4106 Cerium Ce 58 134 Samarium Sm 62 136 Cesium Cs 55 128 Scandium So 21 66 Chiorine ci 7 58 Selenium Se 34 92 Chromium Gr 24 72 Silicon Si 14 52 Cobalt Co 2 78 Silver Ag 47 112 Copper cu 29 82 Sodium Na cn 46 Erbium Er 68 440 Strontium Sr 38 96 Fluorine F 9 44 Sulfur s 16 56 Gallium Ga 31 86 Tantalum = Ta B 144 Germanium Ge 32 88 Tellurium Te 52 122 Gold Au 79 184 Terbium Toe 198 Hainium Hf 72 142 Thallium T 81 158 indium In 49 116 Thorium Th 90 164 todine \ 53 124 Tin Sn 50 18 iridium te 7 150 Titanium Ti 22 68 tron Fe 26 78 Tungsten = W 74 146 Lanthanum La 57 132 Uranium uU 2 166 . Lead Pb 82 160 Vanadium =v 23 70 Lithium ui 3 32 Xenon Xe 5a 126 Magnesium Mg 2 48 Yttrium Y 39 98 Manganese Mn 5 4 Zine Zn 30 84 Mercury Hg 80 156 Zirconium = Zr 40 100 190 PrysicaL evectRonics