1、BRITISH STANDARDBS ISO 24237:2005Surface chemical analysis X-ray photoelectron spectroscopy Repeatability and constancy of intensity scaleICS 71.040.40g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40
2、g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS ISO 24237:2005This British Standard was published under the authority of the Standards Policy and Strategy Committee on 26 August 2005 BSI 26 August 2005ISBN 0 580 46280 3National forewordThis British Standard reproduces verbatim ISO 24237:2005 a
3、nd implements it as the UK national standard.The UK participation in its preparation was entrusted to Technical Committee CII/60, Surface chemical analysis, which has the responsibility to: A list of organizations represented on this committee can be obtained on request to its secretary.Cross-refere
4、ncesThe British Standards which implement international publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Onl
5、ine.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsib
6、le international/European committee any enquiries on the interpretation, or proposals for change, and keep UK interests informed; monitor related international and European developments and promulgate them in the UK.Summary of pagesThis document comprises a front cover, an inside front cover, the IS
7、O title page, cover.The BSI copyright notice displayed in this document indicates when the document was last issued.Amendments issued since publicationAmd. No. Date Commentspages ii to v, a blank page, pages 1 to 12, an inside back cover and a back Reference numberISO 24237:2005(E)INTERNATIONAL STAN
8、DARD ISO24237First edition2005-06-01Surface chemical analysis X-ray photoelectron spectroscopy Repeatability and constancy of intensity scale Analyse chimique des surfaces Spectroscopie de photolectrons par rayons X Rptabilit et constance de lchelle dintensit BS ISO 24237:2005ii iiiContents Page For
9、eword iv Introduction v 1 Scope . 1 2 Symbols and abbreviations . 1 3 Outline of method . 2 4 Method for evaluating the repeatability and constancy of the intensity scale. 2 4.1 Obtaining the reference sample 2 4.2 Mounting the sample 3 4.3 Cleaning the sample. 3 4.4 Choosing the spectrometer settin
10、gs for which intensity stability is to be determined 4 4.5 Operating the instrument. 5 4.6 Options for initial or subsequent evaluation measurements. 5 4.7 Measurements for the intensity and repeatability. 5 4.8 Calculating the peak area intensities, intensity ratios and uncertainties. 6 4.9 Procedu
11、re for the regular evaluation of the constancy of the intensity scale . 7 4.10 Next evaluation . 7 Annex A (informative) Example of calculations and measurements of the intensity repeatability for a commercial X-ray photoelectron spectrometer using unmonochromated Mg K X-rays. 9 Bibliography . 12 BS
12、 ISO 24237:2005iv Foreword ISO (the International 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 sub
13、ject for which a technical committee has 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 (I
14、EC) on all matters of electrotechnical 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 commit
15、tees are circulated to the member bodies 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
16、 held responsible for identifying any or all such patent rights. ISO 24237 was prepared by Technical Committee ISO/TC 201, Surface chemical analysis, Subcommittee SC 7, X-ray photoelectron spectroscopy. BS ISO 24237:2005vIntroduction X-ray photoelectron spectroscopy (XPS) is used extensively for the
17、 surface analysis of materials. Elements in the sample (with the exception of hydrogen and helium) are identified from comparisons of the measured binding energies of their core levels with tabulations of those energies for the different elements. Information on the quantities of such elements can b
18、e derived from the measured photoelectron intensities. Calculation of the quantities present may then be made using formulae and relative sensitivity factors provided by the spectrometer manufacturer. It is important that the sensitivity factors are appropriate for the instrument and this will gener
19、ally be the case directly after installation of the equipment or calibration of the instrument intensity/energy response function by an appropriate organization. There are two important instrumental contributions to the uncertainty of XPS intensity measurements that are addressed in this Internation
20、al Standard: (i) the repeatability of intensity measurements and (ii) the drift of the intensities with time. Repeatability is important for analysing the trends and differences between samples that are similar. The instrumental issues that limit the measurement repeatability include the stability o
21、f the X-ray source, the settings of the detector, the sensitivity of the instrument to the sample placement, the data acquisition parameters and the data-processing procedure. The drift of the instrument intensity scale will limit the overall accuracy of any quantitative interpretation and arises fr
22、om such effects as the ageing of components of the structure of the spectrometer, of its electronic supplies and of the detector. In XPS instruments, it has been found that, in service, the instrument intensity/energy response function may change as the instrument ages. This International Standard d
23、escribes a simple method for determining the repeatability and constancy of the intensity scale of the instrument so that remedial action, such as improving the operating procedure, resetting of the instrument parameters or recalibration of the intensity/energy response function, may be made. This m
24、ethod should, therefore, be conducted at regular intervals and is most useful if the data include a period in which the instrument has been checked to be working correctly by the manufacturer or other appropriate body. This method uses a sample of pure copper (Cu) and is applicable to X-ray photoele
25、ctron spectrometers with unmonochromated aluminium (Al) or magnesium (Mg) X-rays or monochromated Al X-rays. This method does not address all of the possible defects of instruments since the required tests would be very time-consuming and need both specialist knowledge and equipment. This method is,
26、 however, designed to address the basic common problem of repeatability and of drift of the intensity scales of XPS instruments. This method may be conducted at the same time as the spectrometer energy calibration using ISO 154721. BS ISO 24237:2005blank1Surface chemical analysis X-ray photoelectron
27、 spectroscopy Repeatability and constancy of intensity scale 1 Scope This International Standard specifies a method for evaluating the repeatability and constancy of the intensity scale of X-ray photoelectron spectrometers, for general analytical purposes, using unmonochromated Al or Mg X-rays or mo
28、nochromated Al X-rays. It is only applicable to instruments that incorporate an ion gun for sputter cleaning. It is not intended to be a calibration of the intensity/energy response function. That calibration may be made by the instrument manufacturer or other organization. The present procedure pro
29、vides data to evaluate and confirm the accuracy with which the intensity/energy response function remains constant with instrument usage. Guidance is given on some of the instrument settings that may affect this constancy. 2 Symbols and abbreviations A2average peak area for the Cu 2p3/2peak after re
30、moving the Shirley background A2ja value contributing to A2for the jth measurement in a set of measurements A3average peak area for the Cu 3p peak after removing the Shirley background A3ja value contributing to A3for the jth measurement in a set of measurements i identifier for one of the three par
31、ameters Pij index for one of the individual measures of the parameter PijPiparameter representing the mean value of any of A2, A3and A3/A2Pijthe jth measure of parameter with average value PiU95(Pi) uncertainty in the mean value of Pi, at 95 % confidence level XPS X-ray photoelectron spectroscopy va
32、lue of the tolerance limit for A3/A2for compliance at 95 % confidence level (set by the analyst) energy offset for the instrumental binding energy scale, equal to the measured Cu 2p3/2binding energy value for the maximum intensity at the peak minus 932,7 eV (Pi) repeatability standard deviation for
33、the parameter PiBS ISO 24237:20052 3 Outline of method Here, the method is outlined so that the detailed procedure, given in Clause 4, may be understood in context. To evaluate an X-ray photoelectron spectrometer using this procedure, it is necessary to obtain and prepare a copper reference foil in
34、order to measure the intensities of the Cu 2p3/2and Cu 3p X-ray photoelectron 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. These peaks are well established for this purpose and relevant re
35、ference data exist. The initial steps of procuring the sample and setting up the instrument are described from 4.1 to 4.5, as shown in the flowchart of Figure 1 with the relevant subclause headings paraphrased. From 4.6, a user will move to 4.7 unless there has been a previous determination of the i
36、ntensity repeatability. In 4.7, measurements are made of the intensities of the Cu 2p3/2and Cu 3p peaks in a sequence repeated seven times. These data give the repeatability standard deviations of the peak intensities. These repeatabilities have contributions from the stability of the X-ray source,
37、the spectrometer detector and the electronic supplies, from the sensitivity of the measured peak intensity to the sample position and from the statistical noise at the peak. In the method, conditions are defined to ensure that the statistical noise at the measured intensities is relatively small. Th
38、is is discussed in Annex A. The value of the repeatability standard deviation may depend on the sample-positioning procedure. In 4.7.1, the use of a consistent sample-positioning procedure is required and the final calibration is only valid for samples positioned using this positioning procedure. Th
39、e absolute values of the intensities of the two peaks are known for well-defined conditions and so, in principle, these two intensity values could be used to establish part of the spectrometer intensity/energy response function2. However, these response functions may have a complex dependence on ene
40、rgy3and so a determination of the intensities at two energies is insufficient. In this method, therefore, the scope is limited to evaluating the constancy of the intensity/energy response function as indicated by the constancy of the intensities at these two energies and of their ratio of intensitie
41、s, within an uncertainty derived from the measurement repeatability. These determinations are made in 4.7 and the calculation is based on these measurements and performed in 4.8, as shown in the flowchart of Figure 1. Following this, the first of the simpler determinations of intensity constancy is
42、made in 4.9. In practice, the intensity/energy response function of spectrometers may change significantly with instrument use. If this occurs, it may modify quantified results deduced from spectra. In this case, it is important to consider the following actions: (i) improving the sample positioning
43、, (ii) using longer warm-up times, (iii) re-setting the equipment to regain the original response function, (iv) re-determining the relative sensitivity factors used for quantification either experimentally or by calculation, or (v) increasing the stated uncertainty of any quantified results obtaine
44、d. The choice of action will depend on the requirements and on the rate of drift of the intensity ratios recorded in this procedure. For Auger electron spectrometers operated in the “constant E/E mode” (also known as the constant retardation ratio mode or fixed retardation ratio mode), rates of drif
45、t as high as 40 % per year have been measured with major changes occurring after installing a new detector4. For XPS instruments operated in the “constant E mode” (also known as the constant analyser energy mode or fixed analyser energy mode), these effects are thought to be weaker. Thus, three mont
46、hs after the first of the regular assessments in 4.9, or after any substantive changes have been made to the spectrometer, the procedure from 4.2 to 4.5 is repeated, followed by a regular assessment as described in 4.9, at intervals of three months. 4 Method for evaluating the repeatability and cons
47、tancy of the intensity scale 4.1 Obtaining the reference sample A sample of polycrystalline Cu of at least 99,8 % purity shall be used. For convenience, this sample is usually in the form of foil typically measuring 10 mm by 10 mm, and 0,1 mm to 0,2 mm thick. NOTE If the sample appears to need clean
48、ing, a short dip in 1 % nitric acid may be used with subsequent rinsing in distilled water. If the sample has been stored in the air for more than a few days, the dip in nitric acid will make the sample cleaning, required later in 4.3.1, easier. BS ISO 24237:20053Figure 1 Flowchart of the sequence o
49、f operations of the method (subclause numbers are given with items for cross-referencing with the body of the text) 4.2 Mounting the sample Mount the sample on the sample holder using fixing screws, or other metallic means, to ensure electrical contact. Do not use double-sided adhesive tape. NOTE 1 Repeat measurements of the sample are required at intervals of three months. Mounting the sample so that it may be kept in the vacuum system is a useful convenience. NOTE 2 Double-sided adhesive tape may lead to contamination, charging or vacuum degradat
