Application of X-ray reflectivity and X-ray · Application of X-ray reflectivity and X-ray standing wave techniques to ... 5-6/10/2016, XRM Workshop 2016, University of Twente, O

5-6/10/2016, XRM Workshop 2016, University of Twente, O. KonovalovPage 2

Application of X-ray

reflectivity and X-ray

standing wave techniques to

soft matter studies

Oleg Konovalov

ESRF-The European Synchrotron, France

ID10 - Soft Interfaces and Coherent Scattering

Beamline.

[email protected]

OUTLOOK

5-6/10/2016, XRM Workshop 2016, University of Twente, O. Konovalov

3

1. Introduction

2. Surface sensitivity

3. Theory and Applications of

• X-ray reflectivity

• X-ray Standing waves

4. Conclusions

Page 4

A MODEL OF INTERNATIONAL COOPERATION: 21 PARTNER NATIONS

13 Member states:

France 27,5 %

Germany 24 %

Italy 13,2 %

United Kingdom 10,5 %

Russia 6 %

Benesync 5,8 %(Belgium, The Netherlands)

Nordsync 5 %(Denmark, Finland, Norway, Sweden)

Spain 4 %

Switzerland 4 %

8 Associate countries:

Israel 1,5 %

Austria 1,3 %

Centralsync 1,05%(Czech Republic, Hungary, Slovakia)

Poland 1 %

Portugal 1 %

South Africa 0,3 %21 partner nations

Members of staff: 630 of 40 different nationalitiesC

on

tribu

tion

to th

e b

ud

ge

t in %


A UNIQUE SITE FOR RESEARCH AND INNOVATION

Page 5

Institut

Laue-Langevin

European

Molecular Biology

LaboratoryInstitut de Biologie

Structurale

European

Synchrotron

Radiation Facility


AT THE HEART OF THE GLOBAL INNOVATION CAMPUS GIANT

Page 6

Assembling research, innovation

and higher education in one location


The X Ray-Imaging groupID10: THE SOFT INTERFACES AND COHERENT SCATTERING BEAMLINE

Page 7 5-6/10/2016, XRM Workshop 2016, University of Twente, O. Konovalov

263944.55260.461.565.7 056.5 29.9323670m

EH2 (Coherent Scattering) EH1 (Liquid Surfaces and Interfaces Scattering)

Photo by Pierre Jayet

ID10 BEAMLINE


ID10: The Soft Interfaces and Coherent Scattering Beamline

• Flux: ~1013 ph/s @200 mA

• Energy range: 7-30keV

• Focusing (v): ~6 mm

• Sample-Detector distance 4m

• Anomalous option

• Brilliance: B~1020

(photons/s/mm2/mrad2/0.1%BW) l=1 Å

• Coherent flux: Ic= 8.0x1010 coh.ph./s/(10x10mm2 )

• Sample-Detector distance 7m

ID10-SI ID10-CS

X-ray photon correlation spectroscopy (XPCS)

(time window of 10-8 s < t < 10+3 s)Study of dynamics in various condensed matter systems:

Colloidal suspensions, gels, supercooled liquids, polymers,

Atomic/molecular motion in glasses and alloys, critical

fluctuations, aging behavior, dynamics of liquid surfaces.

Coherent X-ray Diffraction imaging (CXDI)High resolution 2D and 3D imaging of non-crystalline

isolated specimens, biological samples with nano-

meters resolution

X-ray Reflectivity (XRR)organic and inorganic films structure,

complex fluids, polymers, “green” chemistry,

surfaces and interfaces

Grazing Incidence Diffraction (GID)Langmuir films, membranes, macromolecules,

organic solar cells

GI Small-Angle X-ray Scattering (GISAXS)2D organization of nano-scaled systems

GI X-ray Fluorescence (GIXF)elements distribution at interfaces

Techniques

Main Parameters

SOFT CONDENSED MATTER - INCREASING LEVEL OF COMPLEXITIES

5-6/10/2016, XRM Workshop 2016, University of Twente, O. Konovalov9

Soft matter - variety of physical states that

are easily deformed by thermal stresses

or thermal fluctuations.

o Liquids

o Colloids

o Polymers

o Surfactants

o Foams

o Gels

o Granular materials

o Biological materials

o …

Pierre-Gilles de Gennes

Nobel Prize in physics in 1991

SOFT CONDENSED MATTER - INCREASING LEVEL OF COMPLEXITIES


Soft matter - variety of physical states that

are easily deformed by thermal stresses

or thermal fluctuations.

o Liquids

o Colloids

o Polymers

o Surfactants

o Foams

o Gels

o Granular materials

o Biological materials

o …

Soft condensed matter science

covers a large range of length

scales from nanometre to several

micron

WHY STUDY SURFACES, INTERFACES AND THIN FILMS


? phase boundary

? crystal growth

? chemical reaction on surfaces

catalysis

? physics of 2D systems

? thin films, membranes

? ….

HOW TO STUDY SURFACES AND INTERFACES ?


2

exp N

k

kk rqifqI

22~ fNNfNI BS

B

S

B

S

B

S

d

d

N

N

I

I

3

4

7

1010

10

100

100

m

nm

I

I

B

S

m

X-rays

Detector

dS

dB

SURFACE SENSITIVITY


13

aT

aan1

n2

kIkR

kT

rk IiII eAE rkR

iRR eAE

rkTiTT eAE

z

x

TRI AAA

T

T

R

R

I

I kAkAkA

Wave and its derivative are continuous at z=0

RI kkk

Tknk

For X-rays:el

er

l

2

2

in 1 610~ 1na 2~c

zkzikTkiT TTT

eeAeA aaa ImRez

TTT i aaa ImRe Intensity falls off with 1/e penetration depth L

Tk aIm2

1L

- component

ml

4

nn

nT

1

2

cos

cos

a

a

Snell's law

mradc ~a

SURFACE SCATTERING TECHNIQUES


XR

X-ray Reflectivity (α=β, γ =0)

In-depth electron density profile – thickness, density and

roughness of films

GISAXS

Grazing Incidence Small-Angle X-ray Scattering (α < αc,

γ 0, β 0)

Particle geometry, size distributions and spatial

correlations on nanometer scale

GID

Grazing Incidence Diffraction (α < αc, γ 0, β 0)

Two dimensional crystals (lattice parameters, molecular

structure, tilt angle of molecules, in-plain correlation lengths

GIXF

Grazing Incidence X-ray Fluorescence

(α < αc, γ = 90°)

In-depth elemental distribution profile

α / αC

Dαi < 0.1αi

αβΛ(ρ, α)

SUBSTRATE

)1(

fdFILM

)2(

fd

bulk

surface

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

102

103

Pen

etr

ati

on

dep

th,

1/A

Grazing angle, a/ac

Water @ λ=1.55 Å

Pen

etra

tion

dept

hΛ

, Å

αi 0.1˚

at 8 keV

a

g

qx

qz

qy

a

g

ag

l

sinsin

sincos

coscoscos2

q

ID10-SI: SIMULTANEOUS MULTIPLE DETECTION SCHEME


Large area detectors(simultaneous GID/GIWAXS and GISAXS)

GISAXS

GID/GIWAXS

XRR

Fluorecence

XRS

X-RAY REFLECTIVITY (XRR)


incidence

beam

scattered

beam

s

β=αα

I0 I

qZ

X-RAY REFLECTIVITY PRINCIPLE

Page 17

0.0 0.2 0.4 0.6 0.8 1.010

-9

10-8

10-7

10-6

10-5

10-4

10-3

10-2

10-1

100

Refl

ecti

vit

y

Qz, A

-1

2

22

222

sinsinsin

sinsinsin

4

4)(

C

C

zF qRaaa

aaa

l

l

qx

hea

d

wat

er

tail

(z)

'(z)

s

Z

4

4

16)(

z

czF

q

qqR

Asymptotic behaviour (qz>3qc)

2

0

exp)(1

)()( zziqz

zqR

I

IqR z

s

zFz

la /sin4zq elec r la 212sin2

incidence

beam

scattered

beam

s

β=αα

I0 I

qZ

Subphase


XRR: FRESNEL FORMULAS


18

a

a in

n

nT

1cos

cos

1

2

aT

aan1

n2

kIkR

kT

rk IiII eAE rkR

iRR eAE

rkTiTT eAE

z

x

TRI AAA

T

T

R

R

I

I kAkAkA

Wave and its derivative are continuous at z=0

RI kkk

Tknk

aa

aa

aa

aa

aa

aa

2sinsin

2sinsin

cossin

cossin

sinsin

sinsin

2

2

22

22

21

21

n

n

nn

nn

A

Ar

T

T

I

R

T

T

I

R

nn

nn

A

Ar

aa

aa

sinsin

sinsin

12

12

||

||

||

TI

T

nn

n

A

At

aa

a

sinsin

sin2

21

1

TI

T

nn

n

A

At

aa

a

sinsin

sin2

12

1

||

||

||

ca 2sin2

elec r la 212

XRR: REFLECTIVITY CALCULATION (PARRATT VERSION )


19

0: d0, 0, 0, s0

j: dj, j, j, sj-1,j

j+1: dj+1, j+1, j+1, sj,j+1

M-1: dM-1, M-1, M-1, sM-2,M-1

M: dM, M, M, sM-1,M

Rj,j+1

Rj+1,j+2Tj,j+1

Tj-1,j

j

j+1

0

1: d1, 1, 1, s1

R0,1

T0,1

Q

Parratt L.G. Physical Review., 1954, v.95, p.359

Reflectivity is I(q)=R0,1(q)2,

where R0,1(q) is calculated from

recursive formula

R aR F

R Fn n n

n n n n

n n n n

1 14 1 1

1 11,

, ,

, ,

Rn,n+1=an2En

R/En,

Fn-1,n=(n-1-n)/(n-1+n),

n=(Nn2+cos2())1/2,

an=exp(-ikndn/2),

n=0,1,2,...,M; k=2/l,

l- wave length,

En , EnR –amplitudes of transmitted and

reflected fields in the layer n,

dn – thickness of layer n, material index

Nn=1-n-in;

n=M for substrate,

RM,M+1=0.

WHAT IS WHAT IN X-RAY REFLECTIVITY


0.0 0.2 0.4 0.6 0.8 1.0

1E-9

1E-8

1E-7

1E-6

1E-5

1E-4

1E-3

0.01

0.1

1

Re

fle

ctivity

Qz, 1/A

XRR: TYPICAL EXAMPLES OF REFLECTIVITY CURVES

Page 21

0.00 0.05 0.10

1E-4

1E-3

0.01

0.1

1

Re

fle

ctivity

Qz, 1/A

air-H2O

H2O-Si

air-Si Media 1: Qzc1

Media 2: Qzc2

Qzc

2

1

2

2 zczczc QQQ

Electron Density




0.00 0.02 0.04 0.06 0.08 0.10

1E-3

0.01

0.1

1

Re

fle

ctivity

Qz, 1/A

/=100

/=10

/=4

inn

n1

1

2

Media 1: n1

Media 2: n2

Ratio between imaginary and real part of the refraction index decrement


Page 23

0.0 0.2 0.4 0.6 0.8 1.0

1E-9

1E-8

1E-7

1E-6

1E-5

1E-4

1E-3

0.01

0.1

1

DQz=2/d

Re

fle

ctivity

Qz, 1/A

H2O film on Si

d=20 A

d=40 A

d=80 A

Film thickness

d= 2/DQz



0.0 0.2 0.4 0.6 0.8 1.0

1E-9

1E-8

1E-7

1E-6

1E-5

1E-4

1E-3

0.01

0.1

1

Re

fle

ctivity

Qz, 1/A

air/20A/80A/Si

Film thickness: many layers

d1=2 nm

d2=8 nm


Page 25

0.0 0.1 0.2 0.3 0.4 0.5

1E-9

1E-8

1E-7

1E-6

1E-5

1E-4

1E-3

0.01

0.1

1

Re

fle

ctivity

Qz, 1/A

s=0 A

s=3 A

s=5 A

4~

zq

4~

zqg

s

l

sin

4zq

qz

kf

ki

Interfacial roughness

))(exp( 2

zqsg

2

21

212

2,1

g

F

)(2sin2

jjj i




0.0 0.2 0.4 0.6 0.8 1.0

1E-8

1E-7

1E-6

1E-5

1E-4

1E-3

0.01

0.1

1

Re

fle

ctivity

Qz, 1/A

Multilayer (d=32A)

10xD/Si

0.5xD+10xD/Si

10xD+0.5xD/Si

Periodic structure: 1D crystal

Nd

d

½ d

½ d

VAPOUR-LIQUID INTERFACE STRUCTURE ?


How liquid is terminated ?

What interface brings to the

molecules arraignment ?

XRR: REFLECTIVITY ON AIR-WATER INTERFACE


0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.710

-9

10-8

10-7

10-6

10-5

10-4

10-3

10-2

10-1

100

Reflectivity

Qz, A-1

measurement

theory: s=0 A

theory: s=3.9 A D

gg

s/2 2

||

||||2

gq

dqqTkB

max

0

2

||

2 /ln4

qB gqTk

gg

s D

ggs

/ln

2

max2

g

qTkB

D

110

max

33 102.1,/10

,/72,20

D

mqmkg

mmNCT o

g

m10104 s

Buff, Lovett, Stillinger, Phys.Rev.Lett., 15, 621 (1965)Braslau at al., Phys.Rev.Lett., 54, 114 (1985)


Examples

REFLECTIVITY ON AIR-MERCURY INTERFACE


110

max

33

102.3

,/1066.13

,/5.486

,20

D

mq

mkg

mmN

CT

Hg

Hg

o

g

mHg

10105.1 s

0.0 0.5 1.0 1.510

-9

10-8

10-7

10-6

10-5

10-4

10-3

10-2

10-1

100

Reflectivity

Qz, A-1

T=20oC

theory: H2O s=3.9 A

theory: Hg s=1.5 A

ggs

/ln

2

max2

g

qTkB

D

XRR: BURIED INTERFACES

Page 31

J.F.L. Duval et al., Phys. Rev. Lett. 108, 206102 (2012)

Ionic spatial distribution at polarised mercury surfaces

Reflectivity e-density profile


Electrolytes

LiBr, LiCl and MgSO4



Decay of correlations in inhomogeneous fluids

K. Nygård & O.Konovalov, Soft Matter 8, 5180 (2012)

Ludox SM-30 SiO2 colloids:

Average diameter D0 = 10.3 nm

Polydispersity ΔD/D0 = 0.21

Debye length κ-1 = 3.4 nm

Bulk volume fraction ϕ = 0.18

fits with the stratified fluid model

the number density profile model

silica concentration profiles C(z)

d/D0

wavelength

ξ/D0

decay

z0/D0

position

air 1.32 ± 0.03 0.99 1.19 ± 0.02

wh 1.38 ± 0.07 0.99 1.46 ± 0.02

h 1.39 ± 0.03 1.27 1.11 ± 0.02

bulk 1.34 0.79

z0 d

D0

2

0

22 ss mm

SURFACE SCATTERING ON MEMBRANES MIMICKED WITH LANGMUIR METHOD


Control

area per molecule

(i.e. surface pressure)

temperature

phase transition:

gas – liquid – crystal

subphase

(water)

sample molecules in solvent

Wilhelmy plate

ai=2 mrag

foot print at 100 mm beam is 50 mm

XRR: LIPID MONOLAYERS ON WATER, SOL AND GEL SURFACE


34

Glycerol

backbone

Hydrophilic

headgroup

Hydrophobic carbon

chains

Montmorillonite

Used as additive in many industrial

processes

The Mineral

- Phyllosilicate

- Disc shaped nano particles

- Surface area ~400 m2/g

- Charge deficiency of 0.7 / unit cell

- Charging: surface , edges

- With water: gives clear and colourless

dispersions and gels

The Gel

- Thixotropic, highly viscous

- Ionic bonds, not affected by temperature

- Gel Formation at concentrations < 1% in

water

~ 1 nm

~100 nm

I) Gelation of clays

After some hours:

Gel formation – House of cards

Dispersion

Hydratisation

Dry: Aggregated

ParticlesSol

Water

DSPC

DPPA

II) Phosholipids

Struth B., et.al. Phys. Rev. Let., 88, 25502, (2002)

XRR: LIPID MONOLAYERS ON WATER, SOL AND GEL SURFACE

Page 35

0.0 0.1 0.2 0.3 0.4 0.5 0.6

1E-8

1E-6

1E-4

0.01

1

Re

fle

ctivity

Qz (Å

-1)

Pure water sol and gel

DSPC layer at the water surface

DSPC layer at the sol surface

DSPC layer at the gel surface

•Identical roughness of free water, sol and gel surfaces

•Lipids form stable monolayers on water, sol and gel

•Attractive electrostatic interactions between the anionic mineral

particles and the zwitterionic lipid headgroup

•These interactions influence the lateral lattice of the monolayer Struth B., et.al. Phys. Rev. Let., 88, 25502, (2002)

~ 1 nm

~100 nm

Montmorillonite


XRR: C-CADHERIN INTERACTION WITH A MEMBRANE MODEL


• Cadherins extend over 230Å. That is shorter than

cadherin length : cadherin may be curved

• High density at large distance : parallel interactions ?

0,0 0,1 0,2 0,3 0,4 0,5

1E-9

1E-8

1E-7

Data

Fit

Ni-NTA-DLGA monolayer

X-R

ay R

efl

ecti

vit

y *

q4

Momentum transfer Qz (Å

-1)

0,0 0,1 0,2 0,3 0,4

1E-10

1E-9

1E-8

1E-7

Data

Fit

Momentum transfer Qz (Å

-1)

X-R

ay R

efl

ecti

vit

y *

q4

C-Cadherin bound to Ni-NTA-DLGA monolayer

0.35 0.40 0.45 0.50250

200

150

100

50

0

water

lipids + C-cadherin 1-5

lipids

Dis

ta

nc

e t

o t

he

ia

r-w

ate

r i

nte

rfa

ce

(Å

)

Electronic density (e-.A

-3)

L. Martel, et. al., J. Phys. IV France, v.12, 365 (2002)

Ca influence

Initial state After EGTA After Ca2+

1) After injecting proteins in the

subphase, a homogenous layer

is obtained in 4 hours

2) The decrease of bound

proteins after adding chelates

divalent ions EGTA is

interpreted as a partial

dissociation of adhesive dimers

3) Subsequent addition of

calcium restores the dimers

MEMBRANE DISCRIMINATION BY ANTIMICROBIAL PEPTIDES : MOLECULAR BASIS


erythrocyte membrane bacterial cell membrane

A.M. peptide

hydrophobic

interaction

electrostatic interaction

hydrophobic interaction

Zwitterionic phospholipids CholesterolAcidic phospholipids

A bacterial cytoplasmic cell membrane was

mimicked with the negatively charged lipids

DiPalmitoyl-PhosphatidylGlycerol (DPPG)

C38H75O10PNH3, MW=740 g/mol.

A mammalian cell membrane was

mimicked with the zwitterionic lipid

DiPalmitoyl-PhosphatidylCholine (DPPC)

C40H80NO8P, MW=734,1 g/mol.

Antimicrobial frog skin peptide –Peptidyl-GlycylLeucine-carboxyamide (PGLa)

21 amino acid residues : H2N-GMASKAGAIAGKIAKVALKAL–COOH

4 résidus chargés positivement (Lysine), MW=1969 g/mol

BENDING RIGIDITY (k) FROM GI DIFFUSE SCATTERING


4

||

2

||

||||

1

qqg

Tk

Aqzqz B

kg D

S. Mora et al., Europhys. Lett., v. 66, p. 694 (2004)

k

gCOQ

0.1 1 10 10010

-3

10-2

10-1

100

g=30 mN/m

g=10 mN/m

g=1 mN/m

g=0.1 mN/m

T=300K

QC

O ,

A-1

k, in kBT

Capillary waves -> height fluctuation spectrum

determided by

the surface energy (g)

associated with the deformation modes (k)[Helfrich, Z. Naturforsch., 28c , 693, (1973)]

qZ

βα

I0 I

qX

||||||2

22

rq)(r(0)

||

2

1,0

2

1,0

1r

)(~

izzq

zq

z

scin

eed

eqttd

d

z

zs

MEMBRANE DISCRIMINATION BY ANTIMICROBIAL PEPTIDES


0.1 110

-10

10-9

10-8

10-7

10-6

10-5

10-4

I/I 0

, deg

Rigidity k kbT)

@ =30mN/m

< c

Rigidity k kbT)

@ >40mN/m

c

DPPG 55 5 145 5

DPPG+PGLa 27 5 20 5

Bending rigidity of the DPPG

membrane decreses upon

insertion of the antimicrobial

peptide PGLa

ai=0,022°, ac=0,0245° @ 22.5 keV

beam size 15 mm

Phospholipid monolayer at hexadecane-water interface

Bending Rigidity (k)

DPPG , =30mN/m

DPPG+PGLa , =30mN/m

DPPG , =40mN/m

DPPG+PGLa , =50mN/m

g = 55mN/m – , c=10:1

E. Saint Martin et al., Thin Solid Films, v.515, p.5678, (2007)

qZ

βα

I0 I

qX

Beam travel path 70 mm

transmission ~20% (22keV)

oil

water


Surface structure of sterically-stabilised ferrofluids

Rosensweig instability

FERROFLUID SAMPLES


0 50 100 150 200 250

D (Å)

CORE SIZE

DISTRIBUTION

(SEM, TEM, XRD)

24 Å100 ÅFe3O4

magnetiteFe3O4 core

stabilizing agent:Na oleateoleic acid

=

water

Concentration C= 2 and 7 % vol.

Surfactant – sodium oleate

(C18H33NaO2) double layer

WATER-BASED FERROFLUID

200 Å

tetradecane

Tetradecane CH3(CH2)12CH3

Surfactant – oleic acid (C18H33OOH)

single layer

Concentration C= 13 % vol.

OIL-BASED FERROFLUID

150 Å

XRR, GISAXS, GID, FLUORECENCE


Oil-based Ferrofluid

3-5 nm

30-40 nm

bulk

10 nm

2-2.5 nm

10-25 nm

bulk

3-6 nm

A. Vorobiev, et al., Phys. Rev. E 79, 031403 (2009)

inte

rfac

e

Aqueous Ferrofluid

0.00 0.02 0.04 0.06 0.08

10-1

100

101

102

103

flu

ore

sce

nce

yie

ld

Qz (Å

-1)

WATER FF

OIL FF

LBL=5nm

Fe

0 100 200 300 4000

2

4

6

8

10

12

ρ(1

0-6

Å-2

)

SLD [10−6 Å−2]

magn. core Fe3O4 40.5

surfactant C18H34O2 8.5

water H2O 9.5

FF bulk 10.0

Depth [Å]

0 100 200 300 400 500 600

0

2

4

6

8

10

12

rho,

10

-6

z, Å

ρOIL

ρBULK

Depth [Å]

SLD [10−6 Å−2]

magn. core Fe3O4 40.5

surfactant C18H34O2 8.5

liq. carrier C14H30 7.5

ρ(1

0-6

Å-2

)

Obtained model of the ferrofluid interface

GISAXS Fluorescence

Surface structure of sterically-stabilised ferrofluids

LANGMUIR TROUGH FOR LIQUID-LIQUID INTERFACE


Air/oil interfaceOil/water interface

Movable barrier

X-ray beam

Barrier

air

water

hexadecane



22222 |]cos|1[|]/)(|1[ hrrE owowowsosw ggggg D

)cos1( rhParticle immersion:

Solid-water contact area: hrA 21

Missing oil-water area: 22

2 sinrA

Young’s equation: ggg cosowswso

Binding energy: owswso AAE ggg 21 )( D

water

oil

gow

gsw

gso

rh

solid

Nanoparticles as surfactants: contact angle & binding energy

BURIED INTERFACES


Formation and Ordering of Au-NPs at the Toluene-Water Interface(chemical reactivity at the liquid-liquid interface)

M.K. Sanyal et al., J. Phys. Chem. C, v. 112, 1739 (2008)

cluster-cluster separation

d1=180 Å

particle-particle separation

d2 = 34 Å

Each cluster consists of

13NPs with Ø 12 Å &

11 Å thick organic layer

3.2 h

4.7 h

6.1 h

4.2 h3.7 h

5.2 h

XRRGISAXS

Tim

e af

ter

reac

tion

initi

atio

n Triphenylphosphine gold chloride

in the toluene

&

Tetrakishydroxymethylphosphonium

chloride in the water


X-Ray Standing Waves (XSW)

Standing-Wave X-Ray Fluorescence

Grazing incidence X-Ray Fluorescence (TRXF)

STANDING WAVE FORMATION


A standing wave field formation

by the superposition of two plane

waves of wavelength λ and

intersection (=scattering) angle 2θ.

The standing wave period D is

QD

l

2sin2

0KKQ R

l

20 RKK

The larger 2θ angle the smaller period D

where

X-ray Standing Wave Techniques” M.J. Bedzyk, in Encyclopedia of

Condensed Matter Physics, edited by F. Bassani, G.L. Liedl, P. Wyder

(Elsevier, Oxford, 2005), Vol. 6, p. 330-341

XSW GENERATION BY CRYSTAL & TOTAL REFLECTION FROM MIRROR


nmSiDc 20)(

mirror

2

0

2

0)(

E

EEI

HSW

r

l

ccD

sin2

-5 0 5 100.00

0.25

0.50

0.75

1.00

Re

lative

Ph

ase

Re

fle

ctivity R

B (arc.sec.)

SW Nodal plane

SW Antinodal plane

Diffraction plane

Hrr 2cos21)(0

2

0

2

0

2

0

E

EC

E

E

E

EEI HHHSW

Incoming

wave

Bragg-reflected

wave

Interference of

incoming and

reflected wave

X-RAY STANDING WAVE FORMATION IN DIFFRACTION CONDITIONS


-5 0 5 100

1

Refle

ctivity

B (arc.sec.)

0

1

2

3

4-5 0 5 10

Ph=0.8

Ph=0.2

Ph=0.5

Norm

aliz

ed

Yie

ld

Ph=1

It describes the

position relative to the

diffraction planes

10 hP

Coherent position

dhkl

h’

Ph=h’/dhkl

)2cos(21 hh PfRRY Secondary radiation yield

COHERENT FRACTION AND COHERENT POSITION


-5 0 5 100

1

Refle

ctivity

B (arc.sec.)

0

1

2

3

4-5 0 5 10

fh=0

fh=0.3

fh=0.7

fh=1

Norm

aliz

ed

Yie

ld

It describes the

degree of ordering

in the system

10 hf

Coherent fraction

dhkl

Δh’

fh=cos(πΔh’/dhkl)

)2cos(21 hh PfRRY Secondary radiation yield

COHERENT FRACTION AND COHERENT POSITION


GIXF : GRAZING INCIDENCE X-RAY FLUORESCENCE (TRXF)


SUBSTRATE

a

)1(

fdFILM)2(

fd

detector

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

102

103

Pen

etr

ati

on

dep

th,

1/A

Grazing angle, a/ac αi / αC

Pen

etra

tion

dept

h,[Å

]

nf > ns

grazing angle

refle

ctivity

flu

ore

sce

nce

MONOLAYERS OF PHTHALOCYANINES AT AIR/WATER INTERFACE


0.5 1.0 1.5 2.00.0

0.5

1.0

Flu

ore

sce

nce y

ield

, a.u

.

, mrad

Refle

ctivity

Sn Pc

Cu/Fe Pc

0.0

0.5

1.0

1.5

One fitting parameter

Me - A/W interface distance

Best fit at D=7 A

S. I. Zheludeva et al., Material Science and Engineering C 23 (2003) 567

E, keV

GIXF: SPECIFIC ION ADSORPTION AND SHORT-RANGE INTERACTIONS

AT THE AIR AQUEOUS SOLUTION INTERFACE

Page 54

V. Padmanabhan et al., Phys. Rev. Lett. 99, 086105 (2007)

ai nm-1

ai-1

(If/I e

)/(I

f/I e

) bulk

KCl 0.1M + KI 0.1M

CsCl 0.1M + CsI 0.1M

KCl 0.1M

depleted layer 3.77 A

elec > solv

dConcentration profiles


So far: heavy elements (metal ions)

Technique:

metal multilayer support strong Bragg reflection

beam interference x-ray standing wave (XSW)

XSW induces element-characteristic x-ray fluorescence

angle-dependent XSW shape

elemental distributions

at near-Å resolution

New: biologically important „light“ elements S and P

Defined chemical position in biomolecules Parameterization:

z,

zj

jI fluo intensity

XSW

distribution element j

jz

js

center position (± 2 Å)

width (not below 10 Å)

SS

S

P

SP

Molecules:

- lipids

- saccharides

- proteins

STANDING-WAVE X-RAY FLUORESCENCE


Lipid Single Monolayers on Al oxide

Sulfoglycolipids (SGS)

abundant in nerve system and

thylakoids

SGS: S at tip of saccharide

headgroup (hg)

fit: sharp S distribution (s < 10 Å)

center set as zS= 0 (solid surface)

jISymbols: experiment. Solid lines: model

Multilayers: 20x(Ni/Al ), 20 nm period, surface: single crystal sapphire Al oxide terminated

Phospholipids

dominant lipid class in animals

DSPC: P in inner hg region

fit: zP = 4 ± 2 Å

different hg structure

Phospholipids + PEG lipids

5% PEG lipid, N = 114

fit: zP = 3 ± 2 Å

no PEG layer below

monolayer

DEPTH LOCALIZATION WITH NEAR-ANGSTROM PRECISION OF BIOLOGICALLY

IMPORTANT CHEMICAL ELEMENTS IN MOLECULAR LAYERS

5-6/10/2016, XRM Workshop 2016, University of Twente, O. Konovalov56 E. Schneck et al., PNAS (2016)

CONCLUSION


gas-liquid

liquid-liquid

liquid-solid

Langmuir films

Complex fluids

Buried interfaces

- Surface structure of simple and complex fluids- Morphology and crystalline structure

of thin organic and inorganic films- 2D organization of molecules,

macromolecules and nano particles- Bio-mimetic systems & Bio-mineralization- Chemistry & Electrochemistry - Surfactants & ions ordering

Elements distribution

P, A, T

X-ray surface sensitive technique is a powerful tool to study broad spectrum of scienceat surfaces and interfaces

ACKNOWLEDGEMENTS


ID10 staff

Numerous collaborators and users

Thank you !

Yuriy Chushkin, Federico Zontone, Beatrice Ruta, Giovanni Li Destri, Karim Lhoste

Contact: Oleg Konovalov, [email protected]

J. Daillant & A. Gibaud, “X-Ray and Neutron Reflectivity: Principles and Applications”, Springer, 1999

M. Tolan, “X-Ray Scattering from Soft-Matter Thin Films” Springer, 1999

J. Als-Nielsen & D. McMorrow, “Element of Modern X-ray Physics”, John Wiley, 2001

J. Zegenhagen, A. Kazimirov, “The X-Ray Standing Wave Technique Principles and Applications”, World Scientific, 2013

I. K. Robinson and D. J. Tweet, Rept. Prog. Phys. 55, p.599 (1992)

J.Daillant, M.Alba, Rep. Prog. Phys. 63 1725–1777 (2000)

Further reading

If you are interested in this position, please apply on http://www.esrf.fr/Jobs

For further information please contact Diego Pontoni

([email protected]; +33(0)476 88 2817; +33 676 38 96 80)

ID10-SI END STATION: SCIENTIFIC APPLICATIONS


• Surface structure of simple and complex fluids (colloid, gel, sol,…)

• Langmuir films, amphiphilic polymers and nano- particle at the air-water

interface

• Capillary wave and surface roughness

• Structure and growth of two dimensional crystals of molecules,

macromolecules and proteins

• Morphology and crystalline structure of thin organic and non-organic films

on solid substrates

• Phenomena at liquid/liquid and solid/liquid interfaces

• Cell membranes

• Shape, strain, ordering and correlation of crystalline nanostructures,

quantum dots and wires on substrates

Documents

Application of X-ray reflectivity and X-ray · Application of X-ray reflectivity and X-ray standing wave techniques to ... 5-6/10/2016, XRM Workshop 2016, University of Twente, O