X射線衍射儀實(shí)驗(yàn)技術(shù)與應(yīng)用

1、第4章 X射線衍射儀實(shí)驗(yàn)技術(shù)與應(yīng)用 Beijing China , 2010.09 He Chong Zhi 1. D8 X射線衍射儀系列系統(tǒng)與功能簡介 2. 核心部件與功能 3. Bragg-Brentano 衍射幾何 4. 光學(xué)系統(tǒng)及其參數(shù)選擇對采集數(shù)據(jù)質(zhì)量影響 5. 平行光束-Geobel 鏡和掠射入射衍射 6. X射線透鏡 7. 探測器 8. 控測、采集數(shù)據(jù)與測量條件 9. 非常態(tài)結(jié)構(gòu)動(dòng)態(tài)衍射分析 10. 應(yīng)用X射線衍射儀衍射關(guān)心的具體問題 1. D8 X射線衍射儀系列系統(tǒng)與功能簡介 配置光學(xué)編碼器的測角儀 高精度的Dovetail導(dǎo)軌, 模塊化的 光學(xué)器件快速互換 射線防護(hù)好：0.2

2、mSv/h 通過歐 洲安全論證，2 套安全電路 配置各種特 殊功能的附件，即可組 成具有各種功能的衍射儀系統(tǒng)，如高 低溫及不同氣氛與壓力下的結(jié)構(gòu)變化 的動(dòng)態(tài)分析等。 在 D8 Advance 基礎(chǔ)上,組建 D8 X射線 衍射儀系列產(chǎn)品。 D8 Advance D8 DISCOVER 單晶外延膜、薄膜分析 高分辨衍射分析單晶外延膜的結(jié)構(gòu)特征， 用Bond法超精度地測點(diǎn)陣參數(shù)、點(diǎn)陣錯(cuò) 配、化學(xué)組份，用Rocking曲線測定測算 嵌鑲結(jié)構(gòu)、取向,作倒易空間測繪; 用 于分析薄膜的厚度、密度、表面與界面 粗糙度等。 高精度的尤拉環(huán) 高強(qiáng)度的織構(gòu)及應(yīng)力測量 D8 GADDS 系統(tǒng)Fast phase I

3、Dmicrodiffractionpercent crystallinity功能:Powders, Texture, Stress,SAXS.特點(diǎn):Fast speed,Micro-diffraction, Versatility.fast stressfast texture2D SAXS GADDS - all applications with ONE instrument 18Kw 轉(zhuǎn)靶 X射線衍射儀 X射線光源: X射線發(fā)生器最大輸出功率18kW ;額定電壓20-60kV; 最大額定電流450 mA;電流電壓穩(wěn)定度 優(yōu)于±0.01% (外 電壓波動(dòng)10%時(shí)), X光源自旋轉(zhuǎn)

4、陽極; 光源震動(dòng)0.2 微米以下; 焦斑尺寸0.5 x 10 mm 測角儀: 掃描方式 q/2q測角儀，測角儀垂直放置; 測角儀采 用光學(xué)編碼器技術(shù);角度重 現(xiàn)性 0.0001°, 驅(qū)動(dòng)方式：步進(jìn) 馬達(dá)驅(qū)動(dòng); 最高定位速度：1500°/min狹縫系統(tǒng)：包括索拉狹 縫、發(fā)散狹縫、防散射狹縫、接受狹縫等 閃爍計(jì)數(shù)器；線性范圍：2 x 106 cps; 背底噪聲： 0.5 cps,可配備閃爍計(jì)數(shù)器、萬特探測器、固體探測器、面探測器 等。 循環(huán)水冷系統(tǒng):要求連續(xù)工作; 控溫精度±2; 供水流量, 滿足發(fā)生器要求, 進(jìn)水 度可調(diào); 過熱保護(hù) 最新X射線衍射技術(shù)-The Ne

5、w D8 ADVANCE with DAVINCI.DESIGN DAVINCI.DESIGN: A revolutionary 3-level design DAVINCI.MODE Component Recognition DAVINCI.SNAP-LOCK Tool-free Change of Optics DIFFRAC.DAVINCI The Virtual Goniometer DIFFRAC.DAVINCI=The Virtual Goniometer Graphical representation of the actual goniometer showing all

6、mountedcomponents plus their statusSoftware validated instrument configuration with real-time conflict detectionDynamic list displayingall currently mountedcomponentsComponentComponentstatusUnique icon ofoptical componentCurrent setting 1.) Component parameterisation 3.) Conflict 2.) Componentdetect

7、ionselection 1) Component parameterisation, e.g. TWIN Optic Component status: OKPush-button switch betweenBragg-Brentano and parallel beam geometry Slit aperture 2) Component selection, e.g. slitsComponentstatus: HINTPush-button selection of anyof the slits configured for thepresent instrument, e.g.

8、- Absorber- Filter- Divergence slit- No slit- .HINT: No slit inserted!- By intention?- By mistake? The new D8 ADVANCETWIST TUBELinefocusLoosenscrewsPointfocustightenscrewsTurn tubehead Secondary TWINPrimaryTWINLYNXEYE TWIN optic for primary beam:TWIN optic for secondary beam: Variable slit Variable

9、slit Göbel mirror Equatorial soller 0.2°Switching modes: motorized software-controlled alignment-free The new D8 ADVANCE TWIN - TWIN for Bragg-Brentano LYNXEYE 1DVariable slitVariable slit The new D8 ADVANCE TWIN - TWIN for GID LYNXEYE 0D Göbel mirror Equatorial soller The new D8 ADVA

10、NCE TWIN - TWIN for XRR LYNXEYE 0DGöbelmirrorKECturned 90°Variable slit The new D8 ADVANCE TWIN - TWIN for Microdiffraction GöbelLYNXEYE 1Dmirror Variable slit Micro slit 150001400013000120001100010000900080007000600050004000300020001000015CompareGreem: D8 ADVANCE+LYNXEYEBlue: D2 PHAS

11、ER+ LYNXEYERed D8 ADVANCE+SC20304050607082-Theta - ScaleFile: LFP-02(SUZHOU)_SC.raw - Type: 2Th/Th locked - Start: 15.000 ? - End: 79.993 ? - Step: 0.020 ? - Step time: 0.5 s - Temp.: 25 ? (Room) - Time Started: 3 s - 2-Theta: 15.000 ? - Theta: 7.500 ? -Operations: ImportCommander Sample ID - File:

12、BJLTP010.6s.raw - Type: Locked Coupled - Start: 14.999 ? - End: 79.991 ? - Step: 0.020 ? - Step time: 0.6 s - Temp.: 25 ? (Room) - Time Started: 0 s - 2-Theta: 14.999Operations: ImportCommander Sample ID - File: BJLTP022.4s.raw - Type: Locked Coupled - Start: 14.999 ? - End: 79.991 ? - Step: 0.020 ?

13、 - Step time: 2.4 s - Temp.: 25 ? (Room) - Time Started: 0 s - 2-Theta: 14.999Operations: Import The D2 PHASER The Whole World of XRD on a Desktop World's fastest desktop X-ray diffractometer Compact all-in-one instrument Mobile for on-location operation New DIFFRAC.SUITE software The D2 PHASERP

14、lug'n Analyze No installation No alignment No instrument configuration 點(diǎn)、線、面探測器比較scintillationdetectorsmall spot measuredscan necessarylong measuring timePSDlarge 2q range measured simultaneouslymedium measuring timeGADDSlarge 2q and chi range measured simultaneouslymeasurement of oriented sampl

15、esvery short measuring timesintensity versus 2q byintegration of the data 2. 核 核心部件核心部件與功能 1)高壓發(fā)生器與X 光管 2)精度測角儀與B-B衍射幾何 3)光學(xué)系統(tǒng)及其參數(shù)選擇對 采集數(shù)據(jù)質(zhì)量影響 4)探測器 5)控測、采集數(shù)據(jù)與數(shù)據(jù)處 理。 高壓發(fā)生器與X光管 4 kW 發(fā)生器穩(wěn)定性： ±0.005% ;3KW 陶瓷X光管，質(zhì)保期4000小時(shí)壽命長，焦斑位置穩(wěn)定;細(xì)焦斑 0.4×12mm，具有比功率高和分辨率好的優(yōu)點(diǎn);管焦斑大小和比功率的重要指標(biāo);冷卻水耗：3.5升/分 流量，如內(nèi)部冷

16、卻<1.8 升/分。 高精度測角儀 步進(jìn)馬達(dá)加光學(xué)編碼器確保測角儀快 速準(zhǔn)確定 位,精度高，角度重現(xiàn)性達(dá) ±0.0001° 直徑在f380760mm之間位置，以利高 分辨率和高強(qiáng)度選擇; 2q角掃描范圍是-110169°，最小步 長.0001° 測角儀步進(jìn)掃描采集數(shù)據(jù)并保存數(shù)據(jù) ; 多種功能應(yīng)用於測定試樣多種信息。 3.Bragg-Brentano 衍射幾何 設(shè)計(jì)原理：R1=R2=R ,試樣轉(zhuǎn)角，探測器轉(zhuǎn)2角（2/偶合） 或試樣不動(dòng)，光管轉(zhuǎn)，探測器轉(zhuǎn)（ / 偶合） 2 聚焦圓隨衍射角大小而變化，衍射角越大、聚焦圓半徑越小，當(dāng) 2=0，聚焦圓半徑r=

17、；當(dāng)2=1800時(shí)，r=R/2,且r = R/2sin。 2010-9-11He Chong Zhi27常規(guī)的X射線衍射 BB 幾何 2010-9-11He Chong Zhi282010-9-11He Chong Zhi29q/2q scan NsNsq 2q Sample Diffracting planes 2010-9-11He Chong Zhi30D8 一維陣列探測器聚焦圓FSample2010-9-11He Chong Zhi一維探測器閃爍或固體探測器31 4.光學(xué)系統(tǒng)及其參數(shù)選擇對采集數(shù)據(jù)質(zhì)量影響 Equatorial Axial 2010-9-11He Chong Zhi33

18、Irradiated specimen length vs detector angle for fixed DS 50454035302520151050010202010-9-11L304050602q (deg.)DS = 2mmDS = 1mm708090100110He Chong ZhiL = Ra / sin qL is irradiated length R is diffractometer radius (250mm)a is divergence angle34 Effect of Divergence slit 19000 18000 17000160001500014

19、00013000120001100010000900080007000600050004000300020001000042.812.0° Div slit0.1° Div slit42.943.043.143.243.343.443.543.643.743.843.92-Theta - ScaleLarger divergence slit results in much more intensity, but the peak position is shifted to lower angle due to flat specimen error. 2010-9-11

20、He Chong Zhi35光學(xué)系統(tǒng) 狹縫大小的選擇決定光束的強(qiáng)度和分辨率 DetectorDivergence slitTubeAntiscatter-slitslitSampleMono-chromator Soller 狹縫限制軸向發(fā)散度 如不用 Soller狹縫，將導(dǎo)致衍射峰的位移與不對稱性 Effect of Soller slits 2100 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 0 24.125262-Theta - Scale 2010

21、-9-11He Chong Zhi38Effect of Detector slit 60005000400030002000100002010-9-1152.252.352.452.552.652.752.852.9He Chong Zhi 0.6 mm,0.2 mm,0.1 mm Inverse relationship between Intensity and Resolution The smaller the slit the better the resolution The larger the slit thebetter the intensity39 狹縫設(shè)置 消除平面試

22、樣導(dǎo)致的半焣焦效應(yīng) 試樣表面的曲率與聚焦圓的半徑隨衍射角的變化而改變。采用平面試 樣“半聚焦”方法衍射線不完全聚焦，出現(xiàn)寬化，入射光束水平發(fā)散增 大時(shí)，更為明顯 。 入射和衍射光路程中，設(shè)置各種狹縫，減少因輻射寬化和發(fā)散造成的測 試誤差。DS和SS稱為發(fā)散和防發(fā)散狹縫，用以防止線束的寬化；RS稱為 接收狹縫用以減少寄生輻射。 入射線和衍射線還存在著垂直發(fā)散。 S1和S2稱為索拉狹縫，用以防止 線束的垂直發(fā)散。 DS,SS,RS,S1,S2,狹縫大小的選擇將影衍射線的強(qiáng)度和分辨率，應(yīng)根據(jù) 實(shí)驗(yàn)?zāi)康奈鏊ミx取。 光學(xué)系統(tǒng)參數(shù)選擇對采集數(shù)據(jù)質(zhì)量影響 考慮原則:在保證強(qiáng)度情況下提高分辨率 根據(jù)實(shí)驗(yàn)要求具

23、體考慮 D8 Advance (閃爍計(jì)數(shù)器、固體探測器)DS-SS-RS光學(xué) 參數(shù)常用設(shè)置： 1-1-0.1高分辨率1-1-0.2強(qiáng)度與分辨率2-1-0.2強(qiáng)度與分辨率2-2-0.2高強(qiáng)度2-2-0.6高強(qiáng)度sollor slit=2.3 & 4.0 LynxEye 陣列探測器光學(xué)系統(tǒng)參數(shù)設(shè)置: DS 0.2-1; SS 3 or 8; RS-free 過濾片單色化幾種方法MonochromatorFilterDiffracted Beammonochromator晶體單色器波高分析器 PHA固體探測器能量分辨CommentsRemoves 99% of Kb, suppresses

24、high energyradiation (50% Ka)Removes all of Kb, all of high energy, and samplefluorescence (30% Ka) Energy DispersiveRemoves all of Kb, all of high energy, and sampleDetectorfluorescence (100% Ka)Incident BeamRemoves all of Ka2, all of Kb, all of high energymonochromator(10%)5.平行光束-Geobel 鏡和掠射入射衍射 S

25、cintillation Measurement circlecounterGöbel Mirror Soller slit Sample X-ray Source Geobel 鏡 膜厚度是變化的 襯底：Si片、玻璃、石英。 膜組成：W/B4C, W/Si, Ni/C B-B 衍射中， Quartz試樣位移0.21.2 mm 對峰位的影響 No Sample Displacement 0.2mm Downward Displacement 0.4mm Downward Displacement 1.0 mm Downward Displacement 1.2mm Downward

26、Displacement 0.5mm Upward Displacement 平行光束下試樣位移對峰位的影響 No Sample Displacement 0.2mm Downward Displacement 0.4mm Downward Displacement 1.0 mm Downward Displacement 1.2mm Downward Displacement 0.5mm Upward Displacement 薄膜掠射研究 測量多層膜及薄膜 物相分析 晶粒大小測定 薄膜次序 擇優(yōu)取向測定 Göbel 鏡:高強(qiáng)度的平行光束 掠射角: 0.5,1.0,1.5-5.0

27、度 薄膜反射光路 薄膜反射研究實(shí)際配置 測量多層膜及薄膜 ( 500nm 以下)： 膜的厚度 膜及襯底的密度 表面及界面粗糙度 膜的次序 刀邊準(zhǔn)直器平臺 (KEC)可保證樣品定 位及入射光束的準(zhǔn)直。 Göbel 鏡可提供高強(qiáng)度的平行光束 6.X射線透鏡 利用入射角小于臨界角的全反射原理以毛細(xì)管作為X射線波導(dǎo)管，改 變光束傳播方向，將X射線調(diào)整為平行的或束聚的具有一定形狀和大 小的高強(qiáng)度光束作為X射線源，有效地提高X射線源的利用率。 單管X光透鏡，光束直徑大小可在=50m-1mm調(diào)節(jié)，適用Cr輻射至 Mo輻射之間的波長；與GADDS準(zhǔn)直器可兼容使用;可成倍提高強(qiáng)度。 整體X光透鏡，管長

28、45mm，截獲角4°，出射光束直徑4.5mm；距離焦 點(diǎn)的長度70mm，發(fā)散角.21°FWHM；在1.5kw時(shí)光子流量約1011cps； 用于織構(gòu)測量則強(qiáng)度提高100倍或測量時(shí)間縮短100倍。非常適用于 快速物相鑒定、快速的織構(gòu)研究、快速和高質(zhì)量殘余應(yīng)力研究及快 速薄膜衍射研究等。 多管X射線聚焦透鏡 Intensity Gain with PolyCap Rolled Aluminum sample Settings: Cu Tube with Pointfocus 12mm Ni Filter 40 kV, 40 mA 5 mm Aperture at PolyCap

29、Exit 強(qiáng)度提高100倍！ 單管(MonoCap) X光透鏡原理 Residual Stress Investigations with Cr-Radiation250Aluminium Sample40kV, 45mA, Pinhole versus MonoCap 20mm sample distance2mm anti-scatter slit, no soller, no filter 1mm receiving slit, NaJ Detector0.3mm MonoCapTM 0.3mm Pinhole 0 135.02Q deg160.07. 探測器 NaI晶體閃爍計(jì)數(shù)器：具有

30、低背底（0.4cps）、高 線性范圍2x10 6 cps；新型YAP晶體閃爍計(jì)數(shù)器的線 性范圍高達(dá)1x10 7 cps Si（Li）固體探測器：具有極佳的能量分辨率?？?選擇特定能量的光子進(jìn)行響應(yīng)。背景小于0.01cps。 VANTEC-1一維探測器：根據(jù)其專利Mikrogap技術(shù)， 對收集的數(shù)據(jù)進(jìn)行累計(jì)積分，極大提高數(shù)據(jù)采集速 度和檢測靈敏度。適用快速數(shù)據(jù)采集場合，如高低 溫和化學(xué)反應(yīng)測量微觀結(jié)構(gòu)的動(dòng)態(tài)變化等。 LynxEye 陣列探測器。 常規(guī)探測器 閃爍計(jì)數(shù)器 正比計(jì)數(shù)器 NaI 閃爍計(jì)數(shù)器 YAP 閃爍計(jì)數(shù)器 固體探測器Sol-X Si（Li）固體探測器 適合Cr K、Co K，Mo

31、K 和 Cu K等光源; 無需濾波片或單色器，提高強(qiáng)度 2-4倍; 可去除Cu K輻射、樣品的熒光及 白光等信號,能量分辨率高; 背景低于0.01cps,信噪比極佳; 線性范圍 50,000 cps，電制冷無需液氮冷卻。 Sol-X固體探測器150014001300120011001000900800Measurement on Hematite/Muscovite withcukaNi-Filter1000900700600500400閃爍探測器+Ni濾片30020010007102030402-Theta - ScaleHematite/Muscovite, 2?Soller, 0,5?s

32、lits, 0,2 mm DS, Ni-Filter - Step: 0.020 ? - Step time: 1. sHematiteMuscovite500Sol-X Detector80070060050050400300200100Sec. Monochromator04007300閃爍探測器+單色器2001000710203040502-Theta - ScaleHematite/Muscovite, 2?Soller, 0,5?slits, 0,2 mm DS, sec. Mono - Step: 0.020 ? - Step time: 1. sHematiteMuscovite

33、10203040502-Theta - ScaleHematite/Muscovite, 2?Soller, 0,5?slits, 0,2 mm DS, Solid state Detektor - Step: 0.020 ?- Step time: 1. s HematiteMuscovite去熒光最佳信噪比提高強(qiáng)度2-4倍 VATEC-1 萬特探測器Cu-radiation, 40 kV, 40 mAStep size: 0.013°, 0.02 sec/ step Scan speed: 39°/minuteTotal measurement time: 3:05 m

34、inutesVÅNTEC-1萬特探測器 The New VANTAGE-1 Large active area of 50x16 mm Up to 12° 2q coverage at 435mm measurement circle Fixed-2q-mode capability for 100 msec x-ray snap shots Super speed continuous scan mode No operating gas purge required Patented Mikrogap technology providing >90% quant

35、um efficiency Dynamic range 109 Global count rate >106 cps Very good energy resolution of <25% Can be operated with Cu-, Cr-, Co-, or Mo-radiation Radiation hard LynxEye 陣列探測器特點(diǎn)(2005年推出) 快速原位分析 如高低溫和化學(xué)反應(yīng)微觀結(jié) 構(gòu)的動(dòng)態(tài)變化等 芯片面積: 14.4 x 16 mm , 192 個(gè)探測通道 4° 2theta 覆蓋范圍( 測量圓 401 mm) 適用波長: C r- Cu 靶

36、 (Mo-靶) 效率: >98% for Cu-radiation 最大計(jì)數(shù): >100,000,000 cps 單個(gè)單元通道最大計(jì)數(shù): 700,000 cps 優(yōu)于25%的能量分辨率 角度分辨率基本上等同于點(diǎn)探測器+0.1mm接受狹縫的分辨率 光學(xué)系統(tǒng)參數(shù): SS 3 - 8; RS-free 角度分辨率LynxEyeTMand Scintillation CounterIrel100.00高強(qiáng)度LynxEyeTMand Scintillation Counter150000140000SRM 660a80.0060.0040.0020.000.00115.50116.00201

37、0-9-11ScintiLynxEye116.50117.00117.502q degFolie.8© 2001 Bruker AXS All Rights ReservedNIST 1976150000140000 130000120000 11000010000090000 80000700006000050000 400003000020000 100000253040He Chong Zhi130000120000110000100000900008000070000600005000040000300002000010000034.7134.834.935.035.135.

38、235.32-Theta deg5060702-Theta degLynxEye:138,000 countsScinti:1100 counts35.435.535.635.7Folie.5© 2001 Bruker AXS All Rights Reserved60 8. 控測、采集數(shù)據(jù)與測量條件 標(biāo)準(zhǔn)圖形用戶界面（Windows xp） 通用的視屏，快速點(diǎn)擊，易用，真正多任務(wù)，Windows 應(yīng)用的數(shù)據(jù)和圖象輸出面向題目，上下文菜單儀器調(diào)整， 測量策略 標(biāo)準(zhǔn)測量: 定性,定量測量，織構(gòu)，宏觀應(yīng)力，高低測 量，PSD， HRXRD，LEPTOS, GADDS。 測量條件考慮 a)

39、測量范圍 b)步長 c)每步時(shí)間 根據(jù)實(shí)驗(yàn)要求考慮在保證數(shù)據(jù)質(zhì)量情況下提高效率。 選合適的步長定峰 Defining Peaks with proper step size 步長> FWHM 的1/5步長大小顯著的影響峰的強(qiáng)度與分辨率2010-9-11He Chong Zhi63XRD向?qū)?shù)文件 XRD-Wizard (Parameter File) 1 6 2-4 5 7 2010-9-11He Chong Zhi6464© 2009 Bruker AXSXRD-Wizard Parameter file Detector (1)- LynxEYE (or the righ

40、t detector) Angles (2-5)- Start (10o)- Stop (70o - 80o)- Step size (0.015 or 0.03) Time/step Type of Scan (Default)- Locked Coupled Scan Time- In hh: mm : ss Used with Job Measurement for save*dql2010-9-11 He Chong Zhi12-45765 Lynx-IRIS opening (in mm) if present Start above 10o - default Below 6o -

41、 reduce the sizeSave in the Directory of Interest File save*.DQL (DiffractionQualitative)-5_70_015_0_1s_Iris10_8min.dql(easy to reuse the .dql file)Other Possibilities Multiple segments Variable counting timeGenerator Settings For D2 Phaser Voltage: 35 kVCurrent:10 mA For other instruments- Refer Ap

42、propriate Manuals2010-9-11He Chong Zhi666 Commander for D2 PhaserImmediateMeasurement- FileSave as*.RAWafter the run2010-9-1167© 2009 Bruker AXS2163He Chong Zhi5467 Commander - Immediate Measurement 1 Make sure there are green check marks for Two Theta and Phi - If they are not as shown, Initia

43、lize the respective drives (using INIT icon) 2 Turn on the X-ray - Ramps up to the required voltage and current (For D2: 30 kV and 10 mA) 3-4 Input the Start-, and Stop 2-theta angles - For unknown samples start from 7o to 80o 5 Fill in the Step Size - For crystalline compounds use 0.01 to 0.02 - For semicrystalline or amorphous compounds use 0.03 to 0.05 6 Time (Seconds/step) - For quick run use 0.1 to 0.2 - For longer (better quality) runs use 0.5 to 1 2010-9-11He Chong