1、BS ISO15472:2010ICS 17.180.30; 71.040.40NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDSurface chemicalanalysis X-rayphotoelectronspectrometers Calibration of energyscalesThis British Standardwas published under theauthority of the StandardsPolicy and StrategyC
2、ommittee on 31 May 2010 BSI 2010ISBN 978 0 580 71539 6Amendments/corrigenda issued since publicationDate CommentsBS ISO 15472:2010National forewordThis British Standard is the UK implementation of ISO 15472:2010. Itsupersedes BS ISO 15472:2001 which is withdrawn.The UK participation in its preparati
3、on was entrusted to TechnicalCommittee CII/60, Surface chemical analysis.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contract. Users are responsible for its correct appl
4、ication.Compliance with a British Standard cannot confer immunityfrom legal obligations.BS ISO 15472:2010Reference numberISO 15472:2010(E)ISO 2010INTERNATIONAL STANDARD ISO15472Second edition2010-05-01Surface chemical analysis X-ray photoelectron spectrometers Calibration of energy scales Analyse ch
5、imique des surfaces Spectromtres de photolectrons X talonnage en nergie BS ISO 15472:2010ISO 15472:2010(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobes licensing policy, this file may be printed or viewed but shall not be edited unless the typefaces which ar
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10、ublished in Switzerland ii ISO 2010 All rights reservedBS ISO 15472:2010ISO 15472:2010(E) ISO 2010 All rights reserved iiiContents Page Foreword iv Introduction.v 1 Scope1 2 Normative references1 3 Symbols and abbreviated terms 1 4 Outline of method2 5 Procedure for calibrating the energy scale 5 5.
11、1 Obtaining the reference samples.5 5.2 Mounting the samples.6 5.3 Cleaning the samples6 5.4 Choosing the spectrometer settings for which energy calibration is required6 5.5 Operating the instrument6 5.6 Options for initial or subsequent calibration measurements.7 5.7 Measurements for the peak bindi
12、ng-energy repeatability standard deviation and the scale linearity.7 5.8 Calculating the peak binding-energy repeatability standard deviation.8 5.9 Checking the binding-energy scale linearity11 5.10 Procedure for the regular determination of the calibration error.12 5.11 Procedures for correction of
13、 the instrument binding-energy scale 13 5.12 Next calibration15 5.13 Establishing the calibration interval15 Annex A (normative) Least-squares determination of the peak binding energy by a simple computational method16 Annex B (informative) Derivation of uncertainties 19 Annex C (informative) Citati
14、on of the uncertainties of measured binding energies21 Annex D (informative) Measurements of modified Auger parameters measured using XPS instruments equipped with a monochromated Al X-ray source.23 Bibliography26 BS ISO 15472:2010ISO 15472:2010(E) iv ISO 2010 All rights reservedForeword ISO (the In
15、ternational Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee h
16、as been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical
17、 standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodi
18、es for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any
19、or all such patent rights. ISO 15472 was prepared by Technical Committee ISO/TC 201, Surface chemical analysis, Subcommittee SC 7, X-ray photoelectron spectroscopy. This second edition cancels and replaces the first edition (ISO 15472:2001), of which it constitutes a minor revision affecting only Su
20、bclause 5.8.1.2. As a result of use of ISO 15472:2001, it became clear that the constraint in 5.8.1.2 limiting users to start and finish at intensities in the range 87 % to 95 % of the peak intensity above zero intensity was over-cautious. For a narrow peak, such as that for gold, it is necessary to
21、 include more of the peak to include the required number of data points. This can be done as indicated in the new text of 5.8.1.2 without compromising the accuracy. BS ISO 15472:2010ISO 15472:2010(E) ISO 2010 All rights reserved vIntroduction X-ray photoelectron spectroscopy (XPS) is used extensivel
22、y for the surface analysis of materials. Elements in the sample (with the exception of hydrogen and helium) are identified from comparisons of the binding energies of their core levels, determined from the measured photoelectron spectra, with tabulations of those energies for the different elements.
23、 Information on the chemical state of such elements can be derived from the chemical shifts of measured photoelectron and Auger electron features with respect to those for reference states. Identification of chemical states is based on measurements of chemical shifts with accuracies in the range dow
24、n to 0,1 eV; individual measurements should therefore be made and reference sources need to be available with appropriate accuracies. Calibrations of the binding-energy scales of XPS instruments are therefore required, often with an uncertainty of 0,2 eV or less. This method for calibrating instrume
25、ntal binding-energy scales uses metallic samples of pure copper (Cu), silver (Ag) and gold (Au) and is applicable to X-ray photoelectron spectrometers with unmonochromated aluminium (Al) or magnesium (Mg) X-rays or monochromated Al X-rays. It is valid for the binding-energy range 0 eV to 1 040 eV. X
26、PS instruments calibrated for providing analyses within the scope of ISO/IEC 170251and for other purposes may need a statement of the estimated calibration uncertainty. These instruments are in calibration for binding-energy measurements within certain defined tolerance limits, d. The value of d is
27、not defined in this International Standard since it will depend on the application and design of the XPS instrument. The value of d is selected by the user of this International Standard, based on experience in the use of the standard, the calibration stability of the instrument, the uncertainty req
28、uired for binding-energy measurements in the intended applications of the instrument and the effort incurred in conducting the calibration. This International Standard provides information by which a suitable value of d may be chosen. Typically, d is equal to or greater than 0,1 eV and greater than
29、about 4 times the repeatability standard deviation, sR. To be in calibration, the divergence from the reference binding-energy values plus the expanded calibration uncertainty for a 95 % confidence level, when added to the instrumental drift with time, must not exceed the chosen tolerance limits. Be
30、fore the instrument is likely to be out of calibration, it will have to be re-calibrated to remain in calibration. An instrument is re-calibrated when a calibration measurement is made and action is taken to reduce the difference between the measured and reference values. This difference may not nec
31、essarily be reduced to zero but will normally be reduced to a small fraction of the tolerance limits required for the analytical work. This International Standard does not address all of the possible defects of instruments, since the required tests would be very time-consuming and need both speciali
32、st knowledge and equipment. This International Standard is, however, designed to address the basic common problems in the calibration of the binding-energy scales of XPS instruments. BS ISO 15472:2010BS ISO 15472:2010INTERNATIONAL STANDARD ISO 15472:2010(E) ISO 2010 All rights reserved 1Surface chem
33、ical analysis X-ray photoelectron spectrometers Calibration of energy scales 1 Scope This International Standard specifies a method for calibrating the binding-energy scales of X-ray photoelectron spectrometers, for general analytical purposes, using unmonochromated Al or Mg X-rays or monochromated
34、Al X-rays. It is only applicable to instruments which incorporate an ion gun for sputter cleaning. This International Standard further specifies a method to establish a calibration schedule, to test for the binding-energy scale linearity at one intermediate energy, to confirm the uncertainty of the
35、scale calibration at one low and one high binding-energy value, to correct for small drifts of that scale and to define the expanded uncertainty of the calibration of the binding-energy scale for a confidence level of 95 %. This uncertainty includes contributions for behaviours observed in interlabo
36、ratory studies but does not cover all of the defects that could occur. This International Standard is not applicable to instruments with binding-energy scale errors that are significantly non-linear with energy, to instruments operated in the constant retardation ratio mode at retardation ratios les
37、s than 10, to instruments with a spectrometer resolution worse than 1,5 eV, or to instruments requiring tolerance limits of 0,03 eV or less. This International Standard does not provide a full calibration check, which would confirm the energy measured at each addressable point on the energy scale an
38、d which would have to be performed in accordance with the manufacturers recommended procedures. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest e
39、dition of the referenced document (including any amendments) applies. ISO 18115-1, Surface chemical analysis Vocabulary Part 1: General terms and terms used in spectroscopy. 3 Symbols and abbreviated terms a measured energy-scaling error b measured zero-offset error, in eV Ecorrcorrected result for
40、the binding energy corresponding to a given Emeas, in eV Eelembinding energy of a frequently measured element at which the indicated binding-energy scale is set, after calibration, to read correctly, in eV Emeasa measured binding energy, in eV Emeas naverage of the measured binding energies for a pe
41、ak, n, in Table 2, in eV Emeas nione of a set of measurements of binding energy for peak n in Table 2, in eV Eref nreference values for the position on the binding-energy scale of peak n in Table 2, in eV BS ISO 15472:2010ISO 15472:2010(E) 2 ISO 2010 All rights reservedFWHM full width at half maximu
42、m peak intensity above the background, in eV j number of repeat measurements for a new peak k number of repeat measurements for the Au 4f7/2, Cu 2p3/2and Ag 3d5/2or Cu L3VV peaks in the repeatability standard deviation and linearity determinations m number of repeat measurements for the Au 4f7/2and
43、Cu 2p3/2peaks in the regular calibrations n designation of the peak identifier in Table 2 txStudents t-value for x degrees of freedom of a two-sided distribution for a confidence level of 95 % U95total uncertainty of the calibrated energy scale at a confidence level of 95 %, in eV c95U (E) uncertain
44、ty at a confidence level of 95 % arising from the calibration using the Au 4f7/2and Cu 2p3/2peaks at binding energy E, assuming perfect scale linearity, in eV l95U uncertainty of e2or e3at a confidence level of 95 % from Equation (7), in eV cl95U uncertainty of the calibration at a confidence level
45、of 95 % in the absence of a linearity error, from Equations (12) and (13) XPS X-ray photoelectron spectroscopy Dnoffset energy, given by the average measured binding energy for a calibration peak minus the reference energy, in eV, for n = 1, 2, 3, 4 in Table 2, for a given X-ray source DEcorrcorrect
46、ion to be added to Emeas, after calibration, to provide the corrected result for the binding energy Df the average of D1and D4from Equation (16) d value of the tolerance limit of energy calibration at a confidence level of 95 % (set by the analyst), in eV e2measured scale linearity error at the Ag 3
47、d5/2peak from Equation (4), in eV e3measured scale linearity error at the Cu L3VV peak from Equation (5) or (6), in eV sRmaximum of sR1, sR2or sR3, and sR4sRnrepeatability standard deviation for the seven measurements of the binding energy of peak n in Table 2, in eV sRnewrepeatability standard devi
48、ation for a new peak, in eV A list of additional symbols used in Annexes A and D will be found in those annexes. 4 Outline of method Here, the method is outlined so that the detailed procedure, given in Clause 5, may be understood in context. To calibrate an X-ray photoelectron spectrometer using th
49、is International Standard, it will be necessary to obtain and prepare copper and gold reference foils in order to measure the binding energies of the Cu 2p3/2and Au 4f7/2photoelectron peaks with the appropriate instrumental settings. These peaks are chosen as they are near the high and low binding-energy limits used in practical analysis. For binding-energy scale linearity tests with instruments using monochromated Al Ka X-rays, a silver reference sample is also needed and, for BS ISO 15472:2010ISO 15472:2010(E) ISO 2010 All ri
