XPS系統(tǒng)軟件操作指南

XPS系統(tǒng)軟件操作指南──MANUALOFPERKINELMERPHI5000CESCASYTEM戴維林編EditedbyDaiWei-Lin（復(fù)旦大學(xué)化學(xué)系表面化學(xué)實(shí)驗(yàn)室）(Surf.Chem.Lab.,Dept.ofChem.,FudanUniv.)0

第一部分?jǐn)?shù)據(jù)采集軟件—PHI系統(tǒng)§1.概述：該系統(tǒng)通過(guò)PC137數(shù)據(jù)采集板把XPS數(shù)據(jù)和圖譜存進(jìn)計(jì)算機(jī)，支持軟件為PHI系統(tǒng)。PERKINELMER公司提供了多種版本的軟件，從最初的DOS系統(tǒng)軟件到如今的WINDOWS系統(tǒng)軟件。目前最常用的為VERSION1.2B也能使用。該軟件功能較強(qiáng)，可進(jìn)行寬、窄迭加，并可適應(yīng)不同的能量分析器，還可在VERSION2.0A版本。掃描，多次錄譜譜圖上定出峰位、半峰寬，并且可進(jìn)行平滑化、微分等操作?！?.軟件安裝及初始化將拷有PHI軟件的軟盤插入驅(qū)動(dòng)器，鍵入命令：C:>install_A:_C:\phiSCASCDorCMASCDorSCAMCD?其中，_代表空格；A:指源程序盤；C:\phi為安裝后的子目錄；SCASCD、CMASCD和SCAMCD分別指不同的能量分析器。安裝后，可通過(guò)簡(jiǎn)單的指令使其窗口化，即可直接在WINDOWS下用鼠標(biāo)來(lái)操作。下面主要講一些VERSION2.0A的具體格式化過(guò)程：進(jìn)入PHI后，屏幕上為一排指令，F(xiàn)ILE、CONTROL、PARMS、DATA和WINDOW。首先鍵擊CONTROL進(jìn)入CONFIGURE。選擇所需的指令，如本實(shí)驗(yàn)室的各項(xiàng)指令為：1

SCA/SCD、MODEL80-365A、MODEL137TIMER、EXTENTED（LENSTYPE）。然后儲(chǔ)存這些參數(shù)（用SAVE指令）。再鍵擊FILE，擊OPEN，查看C:\phi下各?PHI文件。1)將MODEL137COUNTER文件中INPUTSELECT置于ECLIN1[PC]，COUNTUP/DOWN置于UP。2)將SCACONTROL、MODEL80-365A內(nèi)各項(xiàng)進(jìn)行更改。WORKFUNCTION（功函數(shù)）置于測(cè)定值（用Ag、Au或Cu定標(biāo)），DRLLPORTTYPE置于MODEL137，MULTIPLIER（VOLTS）置于測(cè)定值（這在EMS條下會(huì)作解釋），LENS3MODE置于XPSMODE，別的條目最好不要?jiǎng)印?)將SCASCD中，各項(xiàng)設(shè)置成：FIXEDANALYZETRANSMISION，WORKFUNCTION修改為所測(cè)值，PASSENERGY置于所需值，一般為23.5eV，對(duì)信號(hào)弱的可置于46.95或93.90eV。MULTIPLIER按（2）修改。LENS3MODE為XPS，WORKINGDISTANCE置于1.5INCHES,SOURCESELECTION置于SOURCE#1，ANODE可選Mg（#1）或Al（#2）。4)將SCAXPSR中各項(xiàng)設(shè)置成所需的條件，如REGIONNAME可為各元素名，SWEEPNUMBER可設(shè)成5～30次，TIMEPERSTEP為100MS,STEPSIZE為0.1～1eV。隨所需2掃描的寬度及精度而定。5)EMS中高壓的確定：這是確定電子倍增器高壓的必須過(guò)程。首先將儀器全部打開，進(jìn)入掃譜狀態(tài)，然后，打開EMS文件，執(zhí)行EXCUTE，觀察屏幕上的圖形，一般為膝形，取剛進(jìn)入平穩(wěn)段的電壓值為MUTIPLIER所需高壓值。新儀器為1600V,以后慢慢會(huì)往高電壓處上升，直到2400V。此時(shí)，就該更換電子倍增器了?？傊?，應(yīng)將有關(guān)的?phi文件中與特定的能量分析器相關(guān)的全部設(shè)置成所需的參數(shù)，方可進(jìn)入下一階段?！?.通用的掃描步驟：1)進(jìn)入PHI系統(tǒng)。2)打開COUNT137.phi，改DOWN為UP。3)進(jìn)入SCASCD.phi，更改所需參數(shù)（主要改功函數(shù)[WORKFUNCTION];掃描模式FATorFRR;通能PASSENERGY;陽(yáng)極靶MgorAl）。注意：更改Mg靶為Al靶時(shí)，只用更改ANODE#1為ANODE#2即可，其能量1253.6eV將會(huì)自動(dòng)變?yōu)?486.6eV.4)進(jìn)入SCAXPSR?phi更改各所需參數(shù)。用鼠標(biāo)加鍵盤即可完成對(duì)各參數(shù)的設(shè)置。主要有REGIONNAME改為所掃描的元素符號(hào)，如C、O、K等；SWEEPNUMBER改為所需值，寬掃描1~5次，窄掃描5~100次不等；TIMEPERSTEP3

一般為100MS；STEPSIZE寬掃描1eV,窄掃描0.05~0.5eV不等，視具體情況而定。至于掃描區(qū)間，要改為所需區(qū)間，如碳（C）：280~300eV。再更改所需模式，KineticEnergyorBindingEnergy。如果要讓計(jì)算機(jī)掃完一個(gè)元素后，接著掃第二個(gè)、第三個(gè)……，可擊ADDREGION,按上述步驟添加即可。不過(guò)，這種方式建議不要采用。因?yàn)榉恋K以后的數(shù)據(jù)處理。5)全部修改完，進(jìn)入CONTROL,擊EXECUTE,開始掃描。待屏幕上呈現(xiàn)EXECUTIONCOMPLETE!可擊OK，然后擊FILE,進(jìn)行文件存儲(chǔ)工作。一般存為?phi(saveas)、?pcw(saveasMatlab)或?asc(saveasAscII)。6)如需對(duì)曲線進(jìn)行平滑，可按DATA內(nèi)的SMOOTH，或用手按住“S”，并用鼠標(biāo)箭頭連擊DATA，至滿意為止。7)存完一文件后，進(jìn)入下一個(gè)元素的掃描?！?.總結(jié)以上為最常用和最基本的操作方法，掌握后即可進(jìn)行日常的采譜和處理工作。如需進(jìn)行一些高級(jí)動(dòng)作，可請(qǐng)教這方面的專家或自己鉆研PHI程序手冊(cè)。4

第二部分?jǐn)?shù)據(jù)處理軟件──PHIMAT系統(tǒng)§1.概述該軟件主要進(jìn)行?pcw文件的處理，可有多種功能，如：平滑、積分、迭加、差譜、譜峰解迭、峰位確定、半峰寬及峰面積的列表等?；旧峡赏瓿蓪?duì)多種價(jià)態(tài)的分解、擬合，表面元素豐度的定量，等等。一般來(lái)說(shuō)，一臺(tái)增強(qiáng)的386或更好的機(jī)型，內(nèi)存8M的配置即可滿足要求。相對(duì)來(lái)說(shuō)，還算比較方便?！?.安裝和初始化1.安裝該軟件的安裝極其簡(jiǎn)單，只需將“PHIMAT”安裝盤插入驅(qū)動(dòng)器，鍵入C:>INSTALL_B:_C:\PHIMAT?。注意：安裝完畢務(wù)必重新啟動(dòng)計(jì)算機(jī)?。?！接下來(lái)再安裝MATLAB軟件，同樣在驅(qū)動(dòng)器中插入MATLAB安裝盤，鍵入C:>INSTALL_B:_C:\MATLAB?即可。然后按照提示完成接下來(lái)的安裝步驟。5

最后，將其置入WINDOWS窗口，啟動(dòng)MATLAB?，鍵入盤面的登錄序號(hào)（SERIALNUMBER），即告完成。2.初始化必須對(duì)一些文件進(jìn)行更改，方可使打印機(jī)正常工作。（1）在C：根區(qū)下進(jìn)入MATLAB\MATLAB>，更改PRINTzM。C:\MATLAB\MATLAB>EDITPRINTzM?更改其中的打印機(jī)設(shè)置格式即可。將文件中的“！GPP_METATMP_/DEPSD”一行改為：EPSON打印機(jī)：!GPP_METATMP_/DEPSD_/FPRNHPLASERJET:!GPP_METATMP_/DJET_/FPRNHPDESKJET:!GPP_METATMP_/DDESK_/FPRNEPSONLQ,DRAFT:!GPP_METATMP_/DLQD_/FPRNEPSONLQ,FINAL:!GPP_METATMP_/DLQF_/FPRN對(duì)特殊型號(hào)的打印機(jī)可參閱“MATLAB”一書1-31頁(yè)進(jìn)行修改。（2）在C：根區(qū)下進(jìn)入MATLAB\BIN>，更改GPPzBAT。C:\MATLAB\BIN>EDIT_GPP.BAT?更改所有的“PCGPP”為“GPP386”；更改PCGPP_%1_/DESD_/FPRN為GPP386_%1_/D*_/FPRN(注：*為參照（1）所改的對(duì)應(yīng)于各打印機(jī)的參數(shù)。)6

§3.圖譜解析1.基本命令（1）OPEN_C:\FILES\****zPCW?對(duì)用PHI軟件采集的數(shù)據(jù)，只要“SAVEASMATLAB”，便可產(chǎn)生一個(gè)后綴為zPCW的文件。此時(shí)可用“OPEN”打開。同時(shí)要注意對(duì)打開的文件名前加上路徑，即待處理之XPS文件所處的目錄等。（2）CLOSE?、CLOSEALL?分別為關(guān)閉當(dāng)前的文件和所有打開的文件。（3）EXP：為選取所需的范圍，即橫坐標(biāo)上指定的能量區(qū)間。如，EXP150:170?等。（4）LINE?：為對(duì)所范圍與零點(diǎn)拉基線，以便求面積。（5）PEAKAREA?：求XPS峰與所拉基線間的選取的面積。（6）TABLE?：列出面積的具體數(shù)值。（7）MERGE?：對(duì)所打開的文件（必須具有相同的區(qū)間，步長(zhǎng)，步進(jìn)）進(jìn)行迭加。（8）DIS?：顯示所打開文件的XPS圖譜。（9）GRTIME_*?：定義圖譜顯示的時(shí)間。*為數(shù)值時(shí)，代表顯示的秒數(shù)；*為“KEY”時(shí)，表示任意鍵。即只要敲擊鍵盤上任何鍵即可停止顯示。（10）SUBMIN?：使MERGE后的圖譜進(jìn)行等基線迭7

加。即將所有的圖譜起點(diǎn)均定義在零點(diǎn)。（11）SUBTRACT_*?：以某一圖譜為本底，作差譜。*代表本底圖譜的序號(hào)。比如，打開的文件共有3個(gè)，計(jì)算機(jī)將它們列為1、2和3號(hào)，如想作2、3號(hào)與1號(hào)的差譜，只要鍵入SUBTRACT_1?即可。（12）*為文件號(hào)。DELETE_*?：刪除某個(gè)文件。（13）DIR_***\***>?：列出所選路徑內(nèi)的所有文件。（14）LOAD_***\***zPCW?:功能同“OPEN”。（15）REOPEN_***\***zPCW?:再次打開已打開之文件。（16）SAVE?：存儲(chǔ)已處理或進(jìn)行過(guò)各種變化的文件。（17）FILES?：選擇所打開文件中的一個(gè)。（18）PC137?：設(shè)置所取文件來(lái)源為PC137板。（19）PCW?：設(shè)置所取文件來(lái)源為*PCW文件。z（20）REGIONS?：選擇所需的區(qū)域（每個(gè)文件可由若干區(qū)域組成）。（21）RENAMEREGION?：重命名所選區(qū)域。（22）DTIME?：顯示時(shí)間和日期。（23）EXIT?：退出MATLAB。（24）CURSOR?：顯示（用鼠標(biāo)左鍵輕擊）各點(diǎn)的能量、峰強(qiáng)度。（25）LEFT?：左半顯示。8

（26）RIGHT?：右半顯示。（27）LOWER?：下半顯示。（28）UPPER?：上半顯示。（29）UL?：上左顯示。（30）LR?：下右顯示。（31）LL?：左下顯示。（32）UR?：左上顯示。2.圖譜解析(1)open_c:\files\***.pcw?(2)cfsetup_**?(**為元素名稱，C、N、Cu等。)在進(jìn)入窗口命令后，可用鼠標(biāo)來(lái)完成對(duì)以下各參數(shù)的確定：當(dāng)確定新峰時(shí)，鍵擊NEW（新峰）進(jìn)入下一窗口：POSITION（峰位）/HEIGHT（峰高）、FWHM（半峰寬）、%GAUSSIAN（高斯函數(shù)在GAUSSIAN-LORENTZIAN函數(shù)中的百分比），其中TAILLENGTH、TAILSCALE、AREALOCK和SEPARATIONLOCK均為特殊處理命令，分別代表不對(duì)稱峰拖尾長(zhǎng)度、拖尾比例、峰面積鎖定和各峰分別鎖定。一般用得不多，如特殊場(chǎng)合需要使用，可再詳細(xì)研究其具體使用辦法。每完成一個(gè)新峰，均用DONE來(lái)結(jié)束。然后繼續(xù)開始另一峰的確定。如果所分的峰被認(rèn)為是不對(duì)稱的，則應(yīng)在SETPARAMETER中的FITTYPE確定其為ASYMMETRICGAUSSIAN-LORENTZIAN，如為純粹的高9

斯函數(shù)，則選擇GAUSSIAN。另外，亦可選擇SETPARAMETER中的BACKGROUNDTYPE、MULTIPLETLOCK和INTERATIONS等命令進(jìn)行一些特殊處理。而SELECT、EDIT和DELETE分別指對(duì)已有之峰（已經(jīng)分好或直接繼承上次的分峰結(jié)果）進(jìn)行選擇、編輯和刪除等操作。ABORT指放棄剛剛所進(jìn)行的各種操作。最后，用DONE來(lái)回到上一命令。再次擊DONE，退回到PHI>下。（2）CURVEFIT_**?。對(duì)手動(dòng)分的峰用計(jì)算機(jī)進(jìn)行迭代，直至誤差小到滿意為止。一般機(jī)器設(shè)置迭代次數(shù)為15次，如已經(jīng)趨平，則一次即可停止。否則，可繼續(xù)運(yùn)行CURVEFIT命令，直至滿意為止。（3）CFSUM?。顯示分峰結(jié)果。（4）PASSPRINT?。打印出所分之峰。注：這里很需要一些技巧和經(jīng)驗(yàn)，而且對(duì)各元素的峰形、半峰寬均要熟悉?？筛鶕?jù)不同的情況進(jìn)行特殊處理，如不需CURVEFIT，亦不必強(qiáng)求。因?yàn)榈蠛芸赡苊婺咳?，但此時(shí)打印出的包絡(luò)線將為小圓圈而不是迭代后的虛線。具體的細(xì)節(jié)可參考外文說(shuō)明書。§4.小結(jié)以上雖只是粗略的介紹了一些基本命令和操作，但用于一般的譜峰解迭和處理亦已足夠。日常使用最多的操作分別10

為：（1）表面元素濃度的確定。依據(jù)所測(cè)各元素特征峰的面積，采用元素靈敏度因子進(jìn)行校正后，將所有的元素峰面積歸一化，便可算出各元素所占的比例，亦即表面各元素的濃度。這里要特別小心的是，不同元素不同能級(jí)的靈敏度因子是絕對(duì)不會(huì)相同的，千萬(wàn)不要搞錯(cuò)。而且所測(cè)的值也只是相對(duì)比較精確，絕對(duì)誤差可能較大（10~20%），所以，如需精確定量，最好采用已知濃度的標(biāo)樣進(jìn)行標(biāo)定。（2）由于軟件功能所限，很難將許多圖譜等間隔排列并進(jìn)行比較。不過(guò)，可以通過(guò)“SAVEASASCII”將XPS數(shù)據(jù)輸入到SIGMAPLOT或ORINGIN等處理軟件中處理來(lái)解決這一困難。（3）平常只要對(duì)一些對(duì)稱峰（如C1s、O1s、Ag3d5/2等）進(jìn)行分峰處理即可。如本身不對(duì)稱的峰（如Fe2p、Co2p、Ni2p等），則分峰即非易事。需要足夠的耐心和經(jīng)驗(yàn)，否則謬之千里也！總之，該手冊(cè)不可能包羅一切，如有問(wèn)題，請(qǐng)立即向這方面的專家請(qǐng)教或自己鉆研原版的手冊(cè)。11

UsingXPSPEAKVersion4.1November2000

ContentsPageNumberXPSPeakFittingProgramforWIN95/98XPSPEAKVersion4.11ProgramInstallation1Introduction1FirstVersion1Version2.01Version3.01Version3.12Version4.02Version4.12FutureVersions2GeneralInformation(fromR.Kwok)3UsingXPSPeak3OverviewofProcessing3Appearance4OpeningFiles4OpeningaKratos(*.des)textfile4OpeningMultipleKratos(*.des)textfiles5SavingFiles6RegionParameters6LoadingRegionParameters6SavingParameters6AvailableBackgrounds6Averaging7Shirley+LinearBackground7Tougaard8Adding/AdjustingtheBackground8Adding/AdjustingPeaks9PeakTypes:p,dandf10PeakConstraints11PeakParameters11PeakFunction12RegionShift13Optimisation14Print/Export15Export15ProgramOptions15Compatibility16FileI/O16Limitations17CautionsforPeakFitting17

SampleFiles:17gaas.xps17Cu2p_bg.xps18Kratos.des18ASCII.prn18OtherFiles18

1XPSPeakFittingProgramforWIN95/98XPSPEAKVersion4.1ProgramInstallationXPSPeakisfreeware.PleaseaskRCSMSlabstaffforacopyofthezipped3.3MBfile,ifyouwouldlikeyourowncopyUnziptheXPSPEA4.ZIPfileandrunSetup.exeinWin95orWin98.Note:Ihaven’tsuccessfullyinstalledXPSPEAKonWin95machinesunlesstheyhavebeenrunningWindows95c–CMH.IntroductionRaymondKwok,theauthorofXPSPEAKhadspent>1000hoursonXPSpeakfittingwhenhewasagraduatestudent.Duringthattime,hedreamedofmanyfeaturesintheXPSpeakfittingsoftwarethatcouldhelpobtainmoreinformationfromtheXPSpeaksandreduceprocessingtime.Mostoftheinformationinthisusersguidehascomedirectlyfromthereadme.docfile,automaticallyinstalledwithXPSPEAK4.1FirstVersionIn1994,DrKwokwroteaprogramthatconvertedtheKratosXPSspectralfilestoASCIIdata.Oncethisprogramwasfinished,hefoundthattheprogramcouldbeeasilyconvertedtoapeakfittingprogram.Thenheaddedthedreamedfeaturesintotheprogram,e.g.?AbetterwaytolocateapointatanoisebaselinefortheShirleybackgroundcalculations?Combinethetwopeaksof2p3/2and2p1/2?FitdifferentXPSregionsatthesametimeVersion2.0AfterthefirstversionandVersion2.0,manypeopleemailedDrKwokandgaveadditionalsuggestions.Healsofoundotherfeaturesthatcouldbeputintotheprogram.Version3.0ThemajorchangeinVersion3.0istheadditionofNewton’sMethodforoptimisation?Newton’smethodcangreatlyreducetheoptimisationtimeformultipleregionpeakfitting.2Version3.11.Removedalltherun-timeerrorsthatwerereported2.AShirley+Linearbackgroundwasadded3.TheExporttoClipboardfunctionwasaddedasrequestedbyauser?SomeotherminorgraphicalfeatureswereaddedVersion4.0Added:1.Theasymmetricalpeakfunction.Seenotebelow2.Threeadditionalfileformatsforimportingdata?AfewminoradjustmentsTheadditionoftheAsymmetricalPeakFunctionrequiredthepeakfunctiontobechangedfromtheGaussian-LorentzianproductfunctiontotheGaussian-Lorentziansumfunction.CalculationoftheasymmetricalfunctionusingtheGaussian-Lorentzianproductfunctionwastoodifficulttoimplement.Thesoftwareofsomeinstrumentsusesthesumfunction,whileothersusetheproductfunction,sobothfunctionsareavailableinXPSPEAK.SeePeakFunction,(Page12)fordetailsofhowtosetthisup.Note:Iftheselectionisthefunction,whentheuseropensafilethatwasoptimisedusingtheGaussian-Lorentzianfunction,youhavetore-optimisethespectrausingtheGaussian-Lorentzianfunctionwithadifferent%Gaussian-Lorentzianvalue.Version4.1Version4.1hasonlytwochanges.1.Inversion4.0,theprintedcharacterswereinverted,aproblemthatwasduetoVisualBasic.Afterabouthalfyear,apatchwasreceivedfromMicrosoft,andtheproblemwassolvedbysimplyrecompilingtheprogram2.TheimportofmultipleregionVAMASfileformatwasaddedFutureVersionsTheauthorbelievestheprogramhassomeweaknessinthebackgroundsubtractionroutines.Extensiveliteratureexaminationwillberequiredinordertorevisethem.DrKwokintendstodothatforthenextversion.3GeneralInformation(fromR.Kwok)ThisversionoftheprogramwaswritteninVisualBasic6.0anduses32bitprocesses.Thisisfreeware.Youmayaskforthesourceprogramifyoureallywantto.IhopethisprogramwillbeusefulforpeoplewithoutmodernXPSsoftware.IalsohopethatthenewfeaturesinthisprogramcanbeadoptedbytheXPSmanufacturersinthelaterversionsoftheirsoftware.Ifyouhaveanyquestions/suggestions,pleasesendanemailtome.RaymundW.M.KwokDepartmentofChemistryTheChineseUniversityofHongKongShatin,HongKong(852)-2609-6261Tel:Fax:(852)-2603-5057email:rmkwok@.hkIwouldliketothankthecommentsandsuggestionsfrommanypeople.ForthecompletionofVersion4.0,IwouldliketothinkDr.BernardJ.FlinnfortheroutineofreadingLeyboldasciiformat,Prof.IgorBelloandKelvinDickinsonforprovidingmetheVAMASfilesVGsystems,andmygraduatestudentsfortestingtheprogram.IhopeIwilladdotherfeaturesintotheprograminthenearfuture.RKwok.UsingXPSPeakOverviewofProcessing1.OpenRequiredFiles?SeeOpeningFiles(Page4)2.Makesurebackgroundisthere/suitable?SeeAdding/AdjustingtheBackground,(Page8)3.Add/adjustpeaksasnecessary?SeeAdding/AdjustingPeaks,(Page9),andPeakParameters,(Page11)4.Savefile?SeeSavingFiles,(Page6)5.Exportifnecessary?SeePrint/Export,(Page15)

4AppearanceXPSPEAKopenswithtwowindows,oneabovetheother,whichlooklikethis:?Thetopwindowopensanddisplaystheactivescan,addsoradjustsabackground,addspeaks,andloadsandsavesparameters.?Thelowerwindowallowspeakprocessingandre-openingandsavingdataOpeningFilesOpeningaKratos(*.des)textfile1.Makesureyourdatafileshavebeenconvertedtotextfiles.SeethebackoftheVisionSoftwaremanualfordetailsofhowtodothis.Remember,fromtheoriginalexperimentfiles,eachregionofeachfilewillnowbeaseparatefile.2.FromtheDatamenuoftheupperwindow,chooseImport(Kratos)?Choosedirectory?Doubleclickonthefileofinterest5?ThespectraopenwithallpreviousprocessingINCLUDEDOpeningMultipleKratos(*.des)textfiles?Youcanopenupamaximumof10filestogether.1.Openthefirstfileasabove?Opensinthefirstregion(1)2.IntheXPSPeakProcessing(lower)window,leftclickonregion),whichmakesthisregionactive2(second3.OpenthesecondfileasinStep2,OpeningaKratos(*.des)textfile,(Page4)?Opensinthesecondregion(2)?Youcanonlyhaveonedescriptionforallthefilesthatareopen.EditwithaclickintheDescriptionbox4.Openfurtherfilesbyclickingonthenextavailableregionnumberthenfollowingtheabovestep.?Youcanonlyhaveonedescriptionforallthefilesthatareopen.EditwithaclickintheDescriptionbox?ToopenafilethathasalreadybeenprocessedandsavedusingXPSPEAK,clickontheOpenXPSbuttoninthelowerwindow.Choosedirectoryandfileasnormal?Theprogramcanstoreallthepeakinformationintoa*.XPSfileforlateruse.Seebelow.6SavingFiles1.TosaveafileclickontheSaveXPSbuttoninthelowerwindow2.ChooseDirectory3.Typeinasuitablefilename4.ClickOK?Everythingthatisopenwillbesavedinthisfile?Theprogramcanalsostore/readthepeakparameterfiles(*.RPA)sothatyoudonotneedtore-typealltheparametersagainforasimilarspectrum.RegionParametersRegionParametersaretheboundariesorlimitsyouhaveusedtosetupthebackgroundandpeaksforyourfiles.Thesevaluescanbesavedasafileofthetype*.rpa.NotethattheseRegionParametersarecompletelydifferentfromthemathematicalparametersdescribedinPeakParameters,(Page11)LoadingRegionParameters1.FromtheParametersmenuintheupperwindow,clickonLoadRegionParameters2.Choosedirectoryandfilename3.ClickonOpenbuttonSavingParameters1.FromtheParametersmenuintheXPSPeakFit(Upper)window,clickonSaveRegionParameters2.Choosedirectoryandfilename3.ClickontheSavebuttonAvailableBackgroundsThisprogramprovidesthebackgroundchoicesof?Shirley?Linear?Tougaard7Averaging?Averagingattheendpointsofthebackgroundcanreducethetimetofindapointatthemiddleofanoisybaseline?TheprogramincludesthechoicesofNone(1point),3,5,7,and9pointaverage?Thiswillaveragetheintensitiesaroundthebindingenergyyouselect.Shirley+LinearBackground1.TheShirley+Linearbackgroundhasbeenaddedforslopingbackgrounds?The"Shirley+Linear"backgroundistheShirleybackgroundplusastraightlinewithstartingpointatthelowBEend-pointandwithaslopevalue?Iftheslopevalueiszero,theoriginalShirleycalculationisused?Iftheslopevalueispositive,thestraightlinehashighervaluesatthehighBEside,whichcanbeusedforspectrawithhigherbackgroundintensitiesatthehighBEside?Similarly,anegativeslopevaluecanbeusedforaspectrumwithlowerbackgroundintensitiesatthehighBEside2.TheOptimizationbuttonmaybeusedwhentheShirleybackgroundishigheratsomepointthanthesignalintensities?TheprogramwillincreasetheslopevalueuntiltheShirleybackgroundisbelowthesignalintensities?Pleaseseetheexamplebelow-Cu2p_bg.xps-whichshowsbackgroundsubtractionusingtheShirleymethod(ThisspectrumwassenttoDrKwokbyDr.RolandSchlesinger).?AshowstheproblematicbackgroundwhentheShirleybackgroundishigherthanthesignalintensities.IntheShirleycalculationroutine,somenegativevaluesweregeneratedandresultedinanon-monotonicincreasebackground?Bshowsa"Shirley+Linear"background.Theslopevaluewasinputbytrial-and-erroruntilthebackgroundwaslowerthanthesignalintensities?CwasobtainedusingtheoptimisationroutineAslope=0Bslope=11Cslope=15.178Note:Thebackgroundsubtractioncalculationcannotcompletelyremovethebackgroundsignals.Forquantitativestudies,thebestprocedureis"consistency".SeeFutureVersions,(Page2).TougaardForaTougaardbackground,theprogramcanoptimisetheB1parameterbyminimisingthe"squareofthedifference"oftheintensitiesoftendatapointsinthehighbindingenergysideoftherangewiththeintensitiesofthecalculatedbackground.Adding/AdjustingtheBackgroundNote:TheMUSTbecorrectbeforecanbeadded.Aswithallbackgrounds,therangeneedstoincludeasmuchofyourpeakaspossibleandaslittleofanythingelseaspossible.1.Makesurethefileofinterestisopenandtheappropriateregionisactive2.ClickonBackgroundintheupperwindow?TheRegion0boxcomesup,whichcontainstheinformationaboutthebackground3.Adjustthefollowingasnecessary.SeeNote.?HighBE(Thisvalueneedstobewithintherangeofyourdata)?LowBE(Thisvalueneedstobewithintherangeofyourdata)NOTE:HighandLowBEarenotautomaticallywithintherangeofyourdata.CHECKCAREFULLYTHATBOTHENDSOFTHEBACKGROUNDAREINSIDETHEEDGEOFYOURDATA.Nothingwillhappenotherwise.?No.ofAve.Ptsatend-points.SeeAveraging,(Page7)?BackgroundType9?NoteforShirley+Linear:ToperformtheShirley+LinearOptimisationroutine:a)Havethefileofinterestopenb)Fromtheupperwindow,clickonBackgroundc)Intheresultingbox,changeoroptimisetheShirley+LinearSlopeasdesired?UsingOptimizeintheShirley+Linearwindowcancauseproblems.Adjustmanuallyifnecessary3.ClickonAcceptwhensatisfiedAdding/AdjustingPeaksNote:TheMUSTbecorrectbeforepeakscanbeadded.Nothingwillhappenotherwise.Seeprevioussection.?Toaddapeak,fromtheRegionWindow,clickonAddPeak?Thepeakwindowappears?ThismaybeadjustedasbelowusingthePeakWindowwhichwillhaveopenedautomaticallyIntheXPSPeakProcessing(lower)window,therewillbealistofRegions,whicharealltheopenfiles,andbesideeachofthesewillbenumbersrepresentingthesyntheticpeaksincludedinthatregion.Regions(files)SyntheticPeaks1.Clickonaregionnumbertoactivatethatregion?Theactiveregionwillbedisplayedintheupperwindow2.Clickonapeaknumbertostartadjustingtheparametersforthatpeak.10?TheProcessingwindowforthatpeakwillopen3.ClickoffFixtoadjustthefollowingusingthemaximum/minimumarrowkeysprovided:?PeakType.(i.e.orbital–s,p,d,f)?S.O.S(?eVbetweenthetwohalvesofthepeak)?Position?FWHM?Area?%Lorenzian-Gaussian?SeethenotesforexplanationsofhowAsymmetryworks.4.ClickonAcceptwhensatisfiedPeakTypes:p,dandf.1.Eachofthesepeakscombinesthetwosplittingpeaks2.TheFWHMisthesameforboththesplittingpeaks,e.g.ap-typepeakwithFWHM=0.7eVisthecombinationofapwithFWHMat0.7eVand3/2ap1/2withFWHMat0.7eV,andwithanarearatioof2to13.Ifthetheoreticalarearatioisnottrueforthesplitpeaks,theoldwayofsettingtwos-typepeaksandaddingtheconstraintsshouldbeused.?TheS.O.S.standsforspinorbitalsplitting.Note:TheFWHMofthep,dorfpeaksaretheFWHMofthep,d3/25/2orf,respectively.TheFWHMofthecombinedpeaks(e.g.combination7/2ofpandp1/2)isshownintheinthePeakParameter3/2Window.11PeakConstraints1.Eachparametercanbereferencedtothesametypeofparameterinotherpeaks.Forexample,forfourpeaks(Peak#0,1,2and3)withknownrelativepeakpositions(0.5eVbetweenadjacentpeaks),thefollowingcanbeused?Position:Peak1=Peak0+0.5eV?Position:Peak2=Peak1+0.5eV?Position:Peak3=Peak2+0.5eV2.Youmayreferencetoanypeakexceptwithloopedreferences.3.Theoptimisationofthe%GLvalueisallowedinthisprogram.?Asuggestiontousethisfeatureistofindanicepeakforacertainsettingofyourinstrumentandoptimisethe%GLforthispeak.?Fixthe%GLinthelaterpeakfittingprocesswhenthesameinstrumentsettingswereused.4.Thisversionalsoincludesthesettingoftheupperandlowerboundsforeachparameter.PeakParametersThisprogramusesthefollowingasymmetricGaussian-Lorentziansumfunction[]????m1+Q+TS1?e?ln(2)?Q?e?6TL.9?QAGL(x,p,w,h,m,TS,TL)=h(1?m)?e?ln(2)?Q+??????Where:??2(?x?p)2?Q=????w?m=0for100%Gaussian?m=1for100%Lorentzian?TSandTLaretheparametersfortheasymmetrictail?TS=0forsymmetricGaussian-Lorentzianfunction12TheprogramalsousesthefollowingsymmetricalGaussian-Lorentzianproductfunction???GL(x,p,w,h,m)=h?e?(1?m)?ln(2)?Q?1+m?Q?Where:x?p??2?Q=????w?m=0for100%Gaussian?m=1for100%LorentzianPeakFunctionNote:Iftheselectionisthesumfunction,whentheuseropensathatwasoptimisedusingtheGaussian-Lorentzianfilefunction,youhavetore-optimisethespectrausingtheGaussian-Lorentzianfunctionwithadifferent%Gaussian-Lorentzianvalue.?Youcanchoosethefunctiontypeyouwant1.Fromthelowerwindow,clickontheOptionsbutton?Thepeakparametersboxcomesup?SelectGLsumfortheGaussian-Lorentziansumfunction?SelectGLproductfortheGaussian-Lorentzianproductfunction.2.FortheGaussian-Lorentziansumfunction,eachpeakcanhavesixparameters?PeakPosition?Area?FWHM?%Gaussian-Lorentzian13?TS?TLIfanyoneknowswhatTSorTLmightbe,pleaseletmeknow.Thanks,CMH3.EachpeakintheGaussian-Lorentzianproductfunctioncanhavefourparameters?PeakPosition?Area?FWHM?%Gaussian-LorentzianSincepeakarearelatestotheatomicconcentrationdirectly,weuseitasapeakparameterandthepeakheightwillnotbeshowntotheuser.Note:Forasymmetricpeaks,theFWHMonlyreferstothehalfofthepeakthatissymmetrical.TheactualFWHMofthepeakiscalculatednumericallyandisshownaftertheactualFWHMinthePeakParameterWindow.Iftheasymmetricpeakisadoublet(p,dorftypepeak),theactualFWHMistheFWHMofthedoublet.RegionShiftARegionShiftparameterwasaddedundertheParametersmenu?Usethisparametertocompensateforthechargingeffect,thefermilevelshiftoranychangeinthesystemworkfunction?Thisvaluewillbeaddedtoallthepeakpositionsintheregionforfittingpurposes.Anexample:?Apolymersurfaceispositivelychargedandallthepeaksareshiftedtothehighbindingenergyby+0.5eV,e.g.aliphaticcarbonat285.0eVshiftsto285.5eV?WhentheRegionShiftparameterissetto+0.5eV,0.5eVwillbeaddedtoallthepeakpositionsintheregionduringpeakfitting,butthelistedpeakpositionsarenotchanged,e.g.285.0eVforaliphaticcarbon.Note:Ihavetriedthiswithoutanyactualshifttakingplace.Ifsomeonefindsouthowtoperformthisoperation,pleaseletmeknow.Thanks,CMH.Inthemeantime,IsuggestyoudotheshiftbeforeconvertingyourfilesfromtheVisionSoftwareformat.14OptimisationYoucanoptimise:1.Asinglepeakparameter?UsetheOptimizebuttonbesidetheparameterinthePeakFittingwindow2.Thepeak(thepeakposition,area,FWHM,andthe%GLifthe"fix"boxisnotticked)?UsetheOptimizePeakbuttonatthebaseofthePeakFittingwindow3.Asingleregion(alltheparametersofallthepeaksinthatregionifthe"fix"boxisnotticked)?UsetheOptimizeRegionmenu(button)intheupperwindow4.Alltheregions?UsetheOptimizeAllbuttoninthelowerwindow15?Duringanytypeofoptimisation,youcanpressthe"StopFitting"buttonandtheprogramwillstoptheprocessinthenextcycle.Print/ExportIntheXPSPeakFitorRegionwindow,FromtheDatamenu,chooseExportorPrintoptionsasdesiredExport?TheprogramcanexporttheASCIIfileofspectrum(*.DAT)formakinghighqualityfiguresusingothersoftware(e.g.SigmaPlot)?Itcanexporttheparameters(*.PAR)forfurthercalculations(e.g.useExcelforatomicratiocalculations)?Itcanalsocopythespectralimagetothesystemclipboardsothatthespectralimagecanbepastedintoadocument(e.g.MSWORD).ProgramOptions1.The%toleranceallowstheoptimisationroutinetostopifthechangeinthedifferenceafteroneloopislessthatthe%tolerance2.ThedefaultsettingoftheoptimisationisNewton'smethod?Thismethodrequiresadeltavaluefortheoptimisationcalculations?Youmayneedtochangethevalueinsomecases,buttheexistingsettingisenoughformostdata.3.Forthebinarysearchmethod,itsearchesthebestfitforeachparameterinuptofourlevelsofvalueranges?Forexample,forapeakposition,infirstlevel,itcalculatesthechi^2whenthepeakpositionischangedby+2eV,+1.5eV,+1eV,+0.5eV,-0.5eV,-1eV,-1.5eV,and-2eV(range2eV,step0.5eV)?Then,itselectsthepositionvaluethatgivesthelowestchi^2?Inthesecondlevel,itsearchesthebestvaluesintherange+0.4eV,+0.3eV,+0.2eV,+0.1eV,-0.1eV,-0.2eV,-0.3eV,and-0.4eV(range0.4eV,step0.1eV)?Inthethirdlevel,itselectsthebestvaluein+0.09eV,+0.08eV,...+0.01eV,-0.01eV,...-0.09eV?Thiswillgivethebestvaluewithtwodigitsafterdecimal?Level4isnotusedinthedefaultsetting16?Therangesettingandthenumberoflevelsintheoptionwindowcanbechangedifneeded.4.TheNewton'sMethodorBinarySearchMethodcanbeselectedbyclickingthe"use"selectionboxofthatmethod.5.TheselectionofthepeakfunctionisalsointheOptionswindow.6.Theusercansave/readtheoptionparameterswiththefileextension*.opa?Theprogramreadsthedefault.opafileatstartup.Therefore,theusercancustomizetheprogramoptionsbysavingtheselectionsintothedefault.opafile.CompatibilityTheprogramcanread:?Kratostext(*.des)filestogetherwiththepeakfittingparametersinthefile?TheASCIIfilesexportedfromPhi'sMultiplexsoftware?TheASCIIfi