The X-Ray SEF Scott Speakman [email protected]

The X-Ray SEFThe X-Ray SEF

Scott SpeakmanScott Speakman13-4009A13-4009Ax3-6887x3-6887

[email protected]@mit.edu

http://prism.mit.edu/xrayhttp://prism.mit.edu/xray

This molecule is essential to life…This molecule is essential to life…

D. June Sutor, D. June Sutor, Acta Cryst. Acta Cryst. 1111 (1958) 453 (1958) 453

10 15 20 25 302 (deg.)

Inte

nsity

(a.

u.)

The crystal structure of caffeine The crystal structure of caffeine was solved using X-ray diffractionwas solved using X-ray diffraction

http://prism.mit.edu/xray

Caffeine is a crystal because its molecule Caffeine is a crystal because its molecule repeats in an orderly manner to fill spacerepeats in an orderly manner to fill space


X-Ray Diffraction is used to study X-Ray Diffraction is used to study crystalline materialscrystalline materials

X-rays scatter off of the X-rays scatter off of the atoms in a sampleatoms in a sample

If those atoms are If those atoms are systematically ordered, the systematically ordered, the scattered X-rays tell us: scattered X-rays tell us: what atoms are presentwhat atoms are present how they are arrangedhow they are arranged


Anhydrous Caffeine

10 15 20 25 302 (deg.)

Caffeine Hydrate

Inte

nsity

(a.

u.)

The XRD pattern of every crystalline The XRD pattern of every crystalline material is as distinct as your material is as distinct as your

fingerprintfingerprintC8H10N4O2

C8H10N4O2H2O

10 15 20 25 30

2 (deg.)

Inte

nsi

ty (

a.u

.)

Basic Diffractometer OperationBasic Diffractometer Operation

A detector rotates around the sample, measuring A detector rotates around the sample, measuring intensity as a function of the diffraction angle 2theta intensity as a function of the diffraction angle 2theta

XRD uses information about the XRD uses information about the positionposition, , intensityintensity, , widthwidth, and , and shapeshape of diffraction peaks in a pattern from a of diffraction peaks in a pattern from a polycrystalline sample.polycrystalline sample.

X-ray tube

Detector

The X-ray SEF hasThe X-ray SEF has Rigaku High-Speed Powder DiffractometerRigaku High-Speed Powder Diffractometer

PANalytical X’Pert Pro Multipurpose PANalytical X’Pert Pro Multipurpose DiffractometerDiffractometer

Bruker D8 Diffractometer with 2D DetectorBruker D8 Diffractometer with 2D Detector

Bruker D8 High-Resolution Thin-Film Bruker D8 High-Resolution Thin-Film DiffractometerDiffractometer

PANalytical Back-Reflection Laue Single PANalytical Back-Reflection Laue Single Crystal DiffractometerCrystal Diffractometer

Bruker Apex Single Crystal DiffractometerBruker Apex Single Crystal Diffractometer

Bruker Small Angle X-ray Scattering Bruker Small Angle X-ray Scattering InstrumentInstrument

Sample RequirementsSample Requirements

Sample SizeSample Size Powder: 90 to 482 mmPowder: 90 to 482 mm33

minimum 1.6 mmminimum 1.6 mm33

Solid: 10mm x 10mmSolid: 10mm x 10mm min: 1mm x 1mmmin: 1mm x 1mm max: 55mm x 25mmmax: 55mm x 25mm

1” to 6” wafer1” to 6” wafer

CharacteristicsCharacteristics flatflat grain size <10 grain size <10 mm smoothsmooth densely packeddensely packed infinitely thick (>0.3mm)infinitely thick (>0.3mm)

Multilayers: Multilayers: Co(10nm)/Fe(15nm)/Co(10nm)/Fe(15nm)/

MgO(2nm)/SiMgO(2nm)/Si 42 alternating layers of 42 alternating layers of

GaAs(104nm) and GaAs(104nm) and AlAl0.9410.941GaGa0.0590.059As(127nm) As(127nm)

PowderPowder 3 specks of blue paint3 specks of blue paint 0.05mm thick coating of 0.05mm thick coating of

air-sensitiveair-sensitive battery battery materialsmaterials

brake rotorbrake rotor particles in suspensionparticles in suspension

The Ideal Sample Real Samples

Analyses Done RoutinelyAnalyses Done Routinely in the X-ray SEF in the X-ray SEF

Phase IdentificationPhase Identification Crystallite Size EstimationCrystallite Size Estimation Lattice Parameter RefinementLattice Parameter Refinement Residual Stress AnalysisResidual Stress Analysis Evaluate Thin Film QualityEvaluate Thin Film Quality Reflectivity for Multilayer Thin Reflectivity for Multilayer Thin

Film AnalysisFilm Analysis Small Angle Diffraction of Small Angle Diffraction of

Nano- and Meso- structuresNano- and Meso- structures MicrodiffractionMicrodiffraction Texture AnalysisTexture Analysis In-situ DiffractionIn-situ Diffraction

Index and Solve Crystal Index and Solve Crystal Structures Structures

Percent CrystallinityPercent Crystallinity Thin Film AnalysisThin Film Analysis

Reciprocal Space MappingReciprocal Space Mapping Relaxation & StrainRelaxation & Strain Defect DensityDefect Density

Single Crystal DiffractionSingle Crystal Diffraction Crystal OrientationCrystal Orientation Twinning & Other DefectsTwinning & Other Defects

Small Angle X-ray ScatteringSmall Angle X-ray Scattering order/disorder of polymersorder/disorder of polymers microstructure and porositymicrostructure and porosity amorphous textureamorphous texture

Discussed Today Other Techniques

25 30 35 40

2 (deg.)

Inte

nsi

ty (

a.u

.)

Red Paint Pigment Mixture

Phase Identification and QuantificationPhase Identification and Quantification

28 wt% 28 wt% Hematite, FeHematite, Fe22OO33

21 wt% 21 wt% Anatase, TiOAnatase, TiO22

51 wt% Rutile, TiO51 wt% Rutile, TiO22

What phases, and how much of each, are present in this mixture of pigments?

22 23 24 25 26 27 28 29

2 (deg.)

Inte

nsi

ty (

a.u

.)

Red Paint Pigment Mixture

Crystallite Size AnalysisCrystallite Size Analysis

Hematite: XS> 100 nmHematite: XS> 100 nm

Rutile: XS> 100 nmRutile: XS> 100 nm

Anatase: XS= 25 nmAnatase: XS= 25 nm

Are any of the phases nanocrystalline; if so, what is their average crystallite size?

Lattice Parameter RefinementLattice Parameter Refinement

28.0 28.5 29.0 29.5

2 (deg.)

Inte

nsi

ty (

a.u

.)

La2Zr2O7 undoped

4% Y-doping

8% Y-doping

10.809

10.812

10.815

10.818

10.821

0 5 10

mol% Y

Lattic

e P

ara

mete

r (A

)

5.0E-05

1.0E-04

1.5E-04

2.0E-04

2.5E-04

3.0E-04

3.5E-04

4.0E-04

Conductivity (S

/cm

)

How does doping change the lattice parameter of this fuel cell electrolyte?

in situ in situ XRDXRD

we can perform these analyses, and many more, as a we can perform these analyses, and many more, as a function of:function of: temperaturetemperature

cryostat: 11 K to RTcryostat: 11 K to RT Powder Furnace: RT to 1200 CPowder Furnace: RT to 1200 C Plate Furnace: RT to 900 CPlate Furnace: RT to 900 C

environmentenvironment airair vacuumvacuum inert gasinert gas mildly reactive gasmildly reactive gas

timetime time resolution as fast as 10 sectime resolution as fast as 10 sec more typical is 5+ min time resolutionmore typical is 5+ min time resolution

in situin situ XRD of lattice parameters XRD of lattice parameters

21 22 23 24 25 26 27 282 (deg.)

Inte

nsi

ty (

a.u

.)

-0.5

-0.3

-0.1

0.1

0.3

0.5

0.7

0.9

1.1

1.3

1.5

0 200 400 600 800 1000 1200 1400 1600

Temp (C)

delta

L/L

o (%

)

a axis

b axis

c axis

angle

How does the lattice parameter of LSO change with temperature?

in situ in situ XRD of phase compositionXRD of phase composition

0

20

40

60

80

0 10000 20000 30000 40000 50000 60000 70000 80000

NaHNa3AlH6NaAlH4Al

Ph

as

e Q

ua

nti

ty (

wt

%)

Elapsed Time (sec)

How does the phase composition of this hydrogen storage material change with time at 150°C?

tkNaAlHNaAlH eNN 1

44

0

N Na3AlH 6

1

3N

NaAlH 4

0 k1

k2 k1e k1t e k2t

N

Na3AlH 6

0 e k2t

39.4 39.5 39.6 39.7 39.8 39.9 40.0 40.1 40.2 40.3 40.4 40.5 40.6 40.72 (deg.)

Inte

nsi

ty (

a.u

.)

-60

-40

-20

0

20

40

60

0 100 200 300 400 500 600

Temp (°C)

Str

ess (M

Pa)

Pd in H2

Pd in He

Pd

Residual Stress AnalysisResidual Stress Analysis

H2

XRD at 50°C

How do stresses in a Pd film change with H2 and temperature?

Hastelloy

Texture Pole FiguresTexture Pole FiguresHow are the grains oriented in this refractory alloy for a satellite power system?

Distribution of <100> and <111> directions in rolled Nb-1Zr

Rolled to 20% Reduction in Thickness(less deformed)

Rolled 95% Reduction in Thickness(more deformed)

Thin Film Rocking CurveThin Film Rocking Curve

30.6 30.7 30.8 30.9 31.0 31.1 31.2 31.3 31.4

2 (deg.)

Inte

nsity

(a.

u.)

What is the quality of epitaxial semiconductor thin films compared to the perfect single crystal substrate?

Perfect Single Crystal Substrate

Good Epitaxial Thin Film

Poor Epitaxial Thin Film

Horrible Quality, Not Epitaxial At All, Thin Film

Thin Film ReflectivityThin Film Reflectivity

1 2 3 4 5

2 (deg.)

Log

Inte

nsity

(a.

u.)

What is the arrangement and surface characteristics of a thin film of GaAs on a Si substrate?

Thickness Thickness (nm)(nm)

Roughness Roughness (nm)(nm)

Density Density (g/cm(g/cm33))

CC 9.29.2 1.091.09 0.980.98

GaGa22OO33 1.021.02 0.200.20 2.892.89

GaAsGaAs 19.419.4 0.350.35 5.325.32

SiOSiO22 2.12.1 0.710.71 2.762.76

SiSi ∞∞ 0.310.31 2.332.33

10.056nm10.056nm

5.901nm5.150nm

3.924nm

88.27 58.85 44.14 35.31 29.43 25.22

d-spacing (Å)

Inte

nsity

(a.

u.)

Glancing Incident Angle Small Angle Glancing Incident Angle Small Angle X-ray DiffractionX-ray Diffraction

Do quantum dots arrange themselves in a systematic manner with long range order?What is the average distance between the quantum dots?

MicrodiffractionMicrodiffractionHow does the diffraction pattern change at different positions on a sample?

Group classes are held regularly to Group classes are held regularly to train you to use the X-ray lab train you to use the X-ray lab

independentlyindependently Training for Self-Use RequiresTraining for Self-Use Requires

1 hour X-ray Safety Course from EHS1 hour X-ray Safety Course from EHS 1 hour Lab Specific Safety Training1 hour Lab Specific Safety Training 2 hr Instrument Specific Training2 hr Instrument Specific Training 2 hr Practical XRD Lecture2 hr Practical XRD Lecture 3 hr Data Analysis Workshop3 hr Data Analysis Workshop

next session: late January or early Februarynext session: late January or early February see see prism.mit.edu/xrayprism.mit.edu/xray for schedule updates for schedule updates


Assisted Use Assisted Use

I will gladly work with you to collect and I will gladly work with you to collect and analyze dataanalyze data usually needs to be scheduled ~2 weeks in usually needs to be scheduled ~2 weeks in

advanceadvance


Contact InformationContact Information

Scott SpeakmanScott Speakman office: 13-4009Aoffice: 13-4009A x3-6887x3-6887 [email protected]@mit.edu generally available 10 am to 4 pmgenerally available 10 am to 4 pm

XRD Lab: 13-4027XRD Lab: 13-4027 XRD Computer Room: 13-4041XRD Computer Room: 13-4041 http://prism.mit.edu/xrayhttp://prism.mit.edu/xray

Upcoming IAP LecturesUpcoming IAP Lectures

Introduction to X-Ray DiffractionIntroduction to X-Ray Diffraction Jan 17, 2-5 pm, room 13-2137Jan 17, 2-5 pm, room 13-2137

Nanocrystallite Size Analysis using XRDNanocrystallite Size Analysis using XRD Jan 24, 2-5 pm, room 13-2137Jan 24, 2-5 pm, room 13-2137

Thin Film Analysis using X-raysThin Film Analysis using X-rays Jan 31, 2-5 pm, room 13-2137Jan 31, 2-5 pm, room 13-2137


Workshops for Existing X-Ray Workshops for Existing X-Ray UsersUsers

Basic Data Analysis with JadeBasic Data Analysis with Jade scheduled on requestscheduled on request

Rietveld Refinement using HighScore PlusRietveld Refinement using HighScore Plus Jan 29 and Jan 30, 1 to 5 pmJan 29 and Jan 30, 1 to 5 pm room 13-4041room 13-4041 RSVP by Jan 25RSVP by Jan 25

Documents

The X-Ray SEF Scott Speakman [email protected]