1、Designation: F1845 08 (Reapproved 2016)Standard Test Method forTrace Metallic Impurities in Electronic Grade Aluminum-Copper, Aluminum-Silicon, and Aluminum-Copper-SiliconAlloys by High-Mass-Resolution Glow Discharge MassSpectrometer1This standard is issued under the fixed designation F1845; the num
2、ber immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope
3、1.1 This test method determines the concentrations of tracemetallic impurities in high purity (99.99 wt. % pure, or purer,with respect to metallic trace impurities) aluminum-copper,aluminum-silicon and aluminum-copper-silicon alloys withmajor alloy constituents as follows:aluminum Greater than 95.0
4、%copper Less or equal than 5.0 %silicon Less or equal than 5.0 %1.2 This test method pertains to analysis by magnetic-sectorglow discharge mass spectrometer (GDMS).1.3 This test method does not include all the informationneeded to complete GDMS analyses. Sophisticated computer-controlled laboratory
5、equipment, skillfully used by an experi-enced operator, is required to achieve the required sensitivity.This test method does cover the particular factors (for example,specimen preparation, setting of relative sensitivity factors,determination of detection limits, etc.) known by the respon-sible tec
6、hnical committee to effect the reliability of high purityaluminum analyses.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determin
7、e the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2E135 Terminology Relating to Analytical Chemistry forMetals, Ores, and Related MaterialsE1593 Guide forAssessing the Efficacy ofAir Care Productsin Reducing the Perception of Indoor Malodor3. Termi
8、nology3.1 Terminology in this test method is consistent withTerminology E135. Required terminology specific to this testmethod, not covered in Terminology E135, is indicated in 3.2.3.2 Definitions:3.2.1 campaigna test procedure to determine the accuracyof the instrument, which was normally performed
9、 at thebeginning of the day or after the instrument modification, orboth.3.2.2 reference samplematerial accepted as suitable foruse as a calibration/sensitivity reference standard by all partiesconcerned with the analyses.3.2.3 specimena suitably sized piece cut from a referenceor test sample, prepa
10、red for installation in the GDMS ionsource, and analyzed.3.2.4 test samplematerial (aluminum alloy) to be analyzedfor trace metallic impurities by this GDMS method.3.2.4.1 DiscussionGenerally the test sample is extractedfrom a larger batch (lot, casting) of product and is intended tobe representativ
11、e of the batch.4. Summary of Test Method4.1 A specimen is mounted in a plasma discharge cell.Atoms subsequently sputtered from the specimen surface areionized, and then focused as an ion beam through a double-focusing magnetic-sector mass separation apparatus. The massspectrum (the ion current) is c
12、ollected as magnetic field oracceleration voltage, (or both) is scanned.4.2 The ion current of an isotope at mass Miis the totalmeasured current, less contributions from all other interferingsources. Portions of the measured current may originate fromthe ion detector alone (detector noise). Portions
13、 may be due toincompletely mass resolved ions of an isotope or molecule withmass close to, but not identical with, Mi. In all such instances1This test method is under the jurisdiction of ASTM Committee F01 onElectronics and is the direct responsibility of Subcommittee F01.17 on SputterMetallization.
14、Current edition approved May 1, 2016. Published May 2016. Originallyapproved in 1997. Last previous edition approved in 2008 as F1845 08. DOI:10.1520/F1845-08R16.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book
15、of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1the interfering contributions must be estimated and subtractedfrom the measured signa
16、l.4.2.1 If the source of interfering contributions to the mea-sured ion current at Micannot be determined unambiguously,the measured current less the interfering contributions fromidentified sources constitutes an upper bound of the detectionlimit for the current due to the isotope.4.3 The compositi
17、on of the test specimen is calculated fromthe mass spectrum by applying a relative sensitivity factor(RSF(X/M) for each contaminant element, X, compared to thematrix element, M. RSFs are determined in a separate analysisof a reference material performed under the same analyticalconditions, source co
18、nfiguration, and operating protocol as forthe test specimen.4.4 The relative concentrations of elements X and Y arecalculated from the relative isotopic ion currents I(Xi) and I(Yj)in the mass spectrum, adjusted for the appropriate isotopicabundance factors (A(Xi), A(Yj) and RSFs. I(Xi) and I(Yj) re
19、ferto the measured ion current from isotopes Xiand Yj,respectively, of atomic species X and Y as follows:X!/Y! 5 RSFX/M!/RSFY/M! 3 AYj!/AXi! 3 IXi!/IYj! (1)where (X)/(Y) is the concentration ratio of atomic species Xto species Y. If species Y is taken to be the aluminum matrix(RSF(M/M) = 1.0), (X) i
20、s (with only very small error for puremetal matrices) the absolute impurity concentration of X.5. Significance and Use5.1 This test method is intended for application in thesemiconductor industry for evaluating the purity of materials(for example, sputtering targets, evaporation sources) used inthin
21、 film metallization processes. This test method may beuseful in additional applications, not envisioned by the respon-sible technical committee, as agreed upon between the partiesconcerned.5.2 This test method is intended for use by GDMS analystsin various laboratories for unifying the protocol and
22、parametersfor determining trace impurities in aluminum-copper,aluminum-silicon, and aluminum-copper-silicon alloys. Theobjective is to improve laboratory-to-laboratory agreement ofanalysis data. This test method is also directed to the users ofGDMS analyses as an aid to understanding the determinati
23、onmethod, and the significance and reliability of reported GDMSdata.5.3 For most metallic species the detection limit for routineanalysis is on the order of 0.01 wt. ppm. With specialprecautions, detection limits to sub-ppb levels are possible.5.4 This test method may be used as a referee method for
24、producers and users of electronic-grade aluminum-copper,aluminum-silicon and aluminum-copper-silicon materials.6. Apparatus6.1 Glow Discharge Mass Spectrometer , with mass resolu-tion greater than 3500, and associated equipment and supplies.The GDMS must be fitted with an ion source specimen cell th
25、atis cooled by liquid nitrogen, Peltier cooled, or cooled by anequivalent method.6.2 Machining Apparatus, capable of preparing specimensand reference samples in the desired geometry and with smoothsurfaces.6.3 Electro-Polishing Apparatus , capable of removing thecontaminants from the surfaces of spe
26、cimens.7. Reagents and Materials7.1 ReagentsReagent and high purity grade reagents asrequired (MeOH, HNO3and HCl).7.2 Demineralized Water.7.3 Tantalum Reference Sample.7.4 Aluminum Reference Sample.7.4.1 To the extent available, aluminum reference materialsshall be used to produce the GDMS relative
27、sensitivity factorsfor the various elements being determined (see Table 1).7.4.1.1 As necessary, non-aluminum reference materialsmay be used to produce the GDMS relative sensitivity factorsfor the various elements being determined.7.4.2 Reference materials should be homogeneous (see11.1) and free of
28、 cracks or porosity.7.4.3 At least two reference materials are required to estab-lish the relative sensitivity factors, including a 99.9999 % purealuminum metal to establish the background contribution inanalyses.7.4.4 The concentration of each analyte for relative sensi-tivity factor determination
29、should be at a factor of 100 greaterthan the detection limit determined using a 99.9999 % purealuminum specimen, but less than 100 ppmw.7.4.5 To meet expected analysis precision, it is necessarythat specimens of reference and test material present the samesize and configuration (shape and exposed le
30、ngth) in the glowdischarge ion source, with a tolerance of 0.2 mm in diameterand 0.5 mm in the distance of sample to cell ion exit slit.8. Preparation of Reference Standards and TestSpecimens8.1 The surface of the parent material must not be includedin the specimen.8.2 The machined surface of the sp
31、ecimen must be cleanedby electropolishing or etching immediately prior to mountingthe specimen and inserting it into the glow discharge ionsource.TABLE 1 Suite of Impurity Elements to Be AnalyzedANOTE 1Establish RSFs for the following suite of elements:silver arsenic gold boron beryllium calcium cer
32、ium chromium cesium copper ironpotassium lithium magnesium manganese sodium nickel phosphorus antimony silicon tin thoriumtitanium uranium vanadium zinc zirconiumAAdditional species may be determined and reported, as agreed upon between all parties concerned with the analyses.F1845 08 (2016)28.2.1 I
33、n order to obtain a representative bulk composition ina reasonable analytical time, surface cleaning must remove allcontaminants without altering the composition of the specimensurface.8.2.2 To minimize the possibility of contamination, cleaneach specimen separately immediately prior to mounting in
34、theglow discharge ion source.8.2.3 Prepare and use electropolishing or etching solutionsin a clean container insoluble in the contained solution.8.2.3.1 Electropolishing perform electropolishing in asuitable electropolishing solution (2:1 MeOH:HNO3was foundapplicable). Apply 5 to 15 V (dc) across th
35、e cell, with thespecimen as anode. Electropolish to expose smooth, cleanmetal over the entire polished surface.8.2.3.2 Etchingperform etching by immersing the speci-men in suitable acid mixture solution (4:1:1 H2O:HF:HNO3was found applicable). Etch the specimen until smooth, cleanmetal is exposed ov
36、er the entire surface.8.3 Immediately after cleaning, wash the specimen withseveral rinses of high purity methanol, or other high purityreagent able to remove water from the specimen surface, anddry the specimen in the laboratory environment.8.4 Immediately mount and insert the specimen into theglow
37、 discharge ion source, minimizing exposure of thecleaned, rinsed and dried specimen surface to the laboratoryenvironment.8.4.1 As necessary, use a noncontacting gage when mount-ing specimens in the analysis cell specimen holder to ensurethe proper sample configuration in the glow discharge cell (see
38、7.4.5).8.5 Sputter etch the specimen surface in the glow dischargeplasma for a period of time before data acquisition to ensurethe cleanness of the surface (see 12.3). Pre-analysis sputteringconditions are limited by the need to maintain sample integrity.Pre-analysis sputtering at twice the power us
39、ed for analysisshould be adequate for sputter etch cleaning.9. Preparation of the GDMS Apparatus9.1 Reference to Test Method E1593, Section 9.10. Instrument Quality Control10.1 Reference to Test Method E1593, Section 10.11. Standardization11.1 The GDMS instrument should be standardized usingNIST tra
40、ceable reference materials, preferably aluminum to theextent such reference samples are available.11.1.1 RSF values should, in the best case, be determinedfrom the ion beam ratio measurements of four randomlyselected specimens from each standard required, with fourindependent measurements of each pi
41、n.11.1.2 RSF values must be determined for the suite ofimpurity elements for which specimens are to be analyzed (seeTable 1) using selected isotopes for measurement and RSFcalculation (see Table 2).12. Analysis Procedure12.1 Establish a suitable data acquisition protocol (DAP)appropriate for the GDM
42、S instrument used for the analysis.12.1.1 The protocol must include, but is not limited to, themeasurement of elements tabulated in Table 1 and isotopestabulated in Table 2 for respective matrix. Annex A1 listssignificant spectral interferences in this testing.12.1.2 Instrumental parameters selected
43、 for isotope mea-surements must be appropriate for the analysis requirements:(a) ion current integration times to achieve desired precisionand detection limits; (b) mass ranges about the analyte masspeak over which measurements are acquired to clarify massinterferences.12.2 Insert the prepared speci
44、men into the GDMS ionsource, allow the specimen to cool to source temperature, andinitiate the glow discharge at pre-analysis sputtering condi-tions.12.3 After at least 5 min of pre-analysis sputtering, adjustthe glow discharge ion source sputtering conditions to theconditions required for analysis,
45、 ensuring that the gas pressurerequired to do so is within normal range.12.4 Analyze the specimen using the DAP protocol andaccept as final the concentration values determined only asdetection limits.12.5 Generate a MDAP protocol including only the ele-ments determined to be present in the sample (f
46、rom results of12.4).TABLE 2 Isotope SelectionANOTE 1Use the following isotopes for establishing RSF values andfor performing analyses on test specimens.Aluminum-Copper Aluminum-SiliconAluminum-Copper-SiliconSilver 109 109 109Arsenic 75 75 75Gold 197 197 197Boron 11 11 11Beryllium 9 9 9Calcium 44 44
47、44Cerium 140 140 140Chromium 52 52 52Cesium 133 133 133Copper 65 65 65Iron 56 56 56Potassium 39 39 39Lithium 7 7 7Magnesium 24 24 24Manganese 55 55 55Sodium 23 23 23Nickel 58 60 60Phosphorus 31 31 31Antimony 121 121 121Silicon 28 28 28Tin 124 119 124Thorium 232 232 232Titanium 48 48 48Uranium 238 23
48、8 238Vanadium 51 51 51Zinc 66 66 66Zirconium 94 90 94AThis selection of isotopes minimizes significant interferences.Additional speciesmay be determined and reported, as agreed upon between all parties concernedwith the analyses.F1845 08 (2016)312.6 Measure the sample at least two additional times (
49、withat least 10-min intervals between the measurements) using theMDAP protocol until the criteria of 12.6.1 is met.12.6.1 If the concentration differences between the last twomeasurements are less than 5, 10 or 20 %, depending onconcentration (Table 3), the measurements are confirmed andthe last two measurements are averaged.12.7 The confirmed values from 12.6 and the detectionlimits determined from 12.4 are reported together as the resultof the analysis.13. Detection Limit Determination13.1 Reference to Test Method E1593, Section 13.14. GDMS Analysis for Thor
