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IAEA Regional Training Course , 8-12 November 2010


Nano structured
materials

Multilayer Films,
Polycrystalline,
Nanocomposites,
Patterned structures,
Bulk structures,
Liquid crystals,
Biological samples,
Fractals,
Gels,
and etc.

When scientists have learned how to control the arrangment


of matter at a very small scale, they will see materials take an
enormously richer variety of properties
Richard Feynman (1959)
1013 photon/s/mm2
High flux, more intensed x-rays

108 photon/s/mm2
Widely used flux, conventional x-rays
Different formed aggregats can be investigated Lamellar

Diluted -I Densed -I

The other densed systems


Diluted -II Densed -II
03.01 -20.07 2009
SWAXS (Small and Wide Angle X-Ray Scattering) Analizleri

I (Scattering intensity) I (Scattering intensity)


-k
q k
2
k
q, X-ray scattering vector

q= k-k q (-1) q (-1)

|q|=2 k sin

q= 4 sin /
A(q) Fourier T. (r)
= Ae (r) exp(-iq.r) dr = [A(q)/Ae] exp(iq.r) dq
Scattered wave amplitude Radial electron density

I(q)= |A(q)|2 P(r)


= Ae2 | (r) exp(-iq.r) dr |2 Fourier T. = (u+r) (u) du
= P(r) exp(-iq.r) dr = I(q) exp(iq.r) dq
Scattered wave intensity Distance distribution function

Reciprocal space Real space


The followed process to determine structures is used

Measuring data In addition to SAXS technique


other techniques are:
SANS ( Small angle neutron
Determining of structural
parameters R, M, V etc. scattering)
XAFS (X-ray Absorption

Defining model structure in real Fine structure),


space and for this purpose using XRD (X-ray Diff.) and
other collaborative techniques
Microscopy techniques.
More sensitive and recordable
structural results can be
Construction of the model in q obtained by this combination .
space and fitting of the
experimental and theoretical results
1. region 2. region 3. region
I Experimental curve

I(q) = N [F(q)]2 S(q)

q
P Particle Form Factor P(q)= F(q) 2
F(q)= 3V (1-2) [ sin(qR) qR cos(qR) ] / (qR)3

S Solution Structure Factor

I(q) = N [P(q)] Diluted identical q


I(q) = N1 [P1(q)]+ N2 [P2(q)] Dilute two type particles It defines the relatonship between
the positions of the particles
I(q) = N g(R) [P(q)] dR Dilute polydisperse

q
WAXS
sample: lactose powder
sample-detector distance: 29.5 cm
active length of detector ~ 5 cm
1024 pixels 50 m/pixel

2~18 2~26
4.8 3.2

Calibration of the q-scale (WAXS)


with p-Br-BA powder:
SAXS
Primary beam
center of incident
(attenuated)
Calibration of the q- primary beam FWHM ~ 350 m
scale (SAXS)
with Ag-behenate sample: Lupolen
powder: 2665 sample-detector distance: 28 cm
800 active length of detector ~ 5 cm
Lamellar d-spacing: 1024 pixels 50 m/pixel

d = 58.38 2~8
11
Diluted systems-I
Protein or polymer solutions, etc.

First determined structural information


- Radius of gyration,
- Mass, volume and shape

I Guinier
ln I Guinier line
region
I(q) =I(0) exp(-R2q2/3) tan = -R2/3

1/R . q(nm-1)
q2
Spherical nano crystals embeded SiO2

Nanocrystals glass Noncrystallized


Nanocrystals aggregations Different electron densities

Before cystallization After the cryst.

R<R0 R=R0 R<R0


r 2 (r) d3r
Radius of gyration R2 =
(r) d3r

____________
Elipsoid R= (a2+b2+c2)/5 Guinier law
a,b,c elipsoid axes
(q0)
____
Sphere R= (3/5) r = 0.77 r
r, radius

I(q)q4
Porod law (q)
Porod region
lim I(q) q4 = constant
lim I(q)= 2 (1-2)2 S / q4
S, surface area

q (-1)
Kratky plots Q = V <2>
Fluctuation in the electron
densities
Invariant V Total volume causing the
I.q2 (nm) -2

scattering

Q Sample: Amorph and crystalline


regions in the structure
Two phase polymers
Q = V (k-a)2 ak
k , a electron densities of the phases
q (nm) -1 a , k volume fractions of the phases

Kratky plots with Porod law


Lamellar Structures
I

The positions of
Bragg peaks for
h = 1, 2, 3 give
the lamellar
distance (1/d)
q

If we look through the perpendicular direction of the lamelar structure,


we may define crystallographic order in SAXS range. In this case, by
using scattering intensity ratios and peak positions, some scattering
rules ( for hexagonal, cubic etc.) controlled and compaired to obtain
the real phases.
Some ordered cubic morphologies

80 80 80

60 60 60

40 40 40

I(q)
I(q)
I(q)

20 20 20

0 0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.0 0.1 0.2 0.3 0.4 0.5 0.0 0.1 0.2 0.3 0.4 0.5

q q q

Im3m P-surface Pn3 D-surface Ia3d G-surface


m
Figures, H. Amenitsch,
SR School-ICTP
Lamellar fluid Hegzagonal struct.

?
I.
III.

II.

lam
hex
According to the observed q ratios PS-b-PEO Co-polymer phase transition

(1) Periodic structure


1 : 2 : 3 : 4;
(2) Cubic
1: 2 : 3 : 4 : 5 . ;
(3) Hegzagonal
1: 3 : 4 : 7 : 9 : 12
Photonic crystals
Interplanar distance is increasing with
increasing temperature

Blue Heating
Light blue
Spin-cap (rotating capillary)

300 s / Frame Sample rotation enhances


SAXS signal-noise ratio

300 s / Frame

45
WAXS

SWAXS scanning of phase transitions

20

www.hecus.at 23
ln I(q) ln I(q)

0.05 0.10 0.15 0.05 0.10 0.15


q (-1) q (-1)

ln I(q) ln I(q) Guinier

Slope

Porod

0.05 0.10 0.15


q (-1) -2.50 -2.00 -1.50 -1.00 ln q
Shape reconstruction
A serial research on pH and temperature dependent-water soluble diblock copolymers
[2-(dietilamino) etil metakrilat]-b-[2-(dimetilamino) etil metakrilat] (DEAn-b-DMAm)

Hydrophillic(repulsion)
Volume hight and base area
DEAn-b-DMAm diblock copoylmers are Hydrophobic (attraction) of the cone were determined
stable (n/m=1/2) in misellar forms at 23C beside of packing parameter
shell
ve pH=7,7. size distributions are narrow
and forms are spherical.
For T=22,0-25,5C, pH=7,6-8,0 and
n/m=0,25-0,73 values, misel numbers per
unit volume, misel sizes, shell thickness,
core radius and densities have been
determined by SAXS analysis.
core

t = thicknes of the shell


t
Rc = core radius
Rc Rs = t + Rc
c
c = core electron density
s
s = shell electtron density
Rs
= solution electron density
pH controls charge level and if the misel size
increase s, electrostatic repulsion becomes
effective.
Cubic structures occured by DNA and peptid connected spherical gold
nanoparticles

13 nm

Y9,Y10

Y11, , Y20

Y9,Y10
liquid paraffin, non-ionic
surfactants (Brij 72 and Brij 721P)
and/or pure water

H3
Formulation Liquid Parafin Brij 721 P/ Brij 72 H2O (%)
(%w/w) (3/1) (%w/w)
A3 70 30 -
H3 - 30 70
L2 6 31 63
F1 40 10 50
AFM View

TEM View
[D.I. Svergun, Biophysics J.
1999, 76, 2879-2886]
Ferroelectric thin films, P.C. Photovoltaics, H. Kurz, Inst. of Multilayered Al-Si Porous
Mclntyre Res. Group, Semiconductor Elect. thin films, C. Orilall ,
Stanford Germany Cornel Univ.

Nonhomogen dielect. SrGa2S4:Ce thin-film, K. Ultra-thin solid oxide fuel cell,


(sculptured) thinfilm, STF, Tanaka, NHK Lab. Japan F.B. Prinz ,RPL Stanford
A. Lakhtakia, Penn State Engineering
n+ Ga As

Sample I (7) Sample II (8)

400 20 mol% 21 mol%

65 55
400 24 24
55 45
27 30
400
n Ga As 45 40
400 i Al Ga As 33 35

n+ Ga As
GaAs , a= 5.65 , = 5.32 g/cm3
AlGaAs, a= 5.66 , = 3,76 g/cm3
k is decay constant (interfacial area) for a
two phase system.
It depends on the total inner surface (S) and
the mean-square electron density fluctuations
dc
dac da

Q
invariant

Volume fractions
It has the
dimention of a
resprocal volume
Total irradiated
volume
d()Sample I (7) d() Sample II (8)

330.00 202.70
184.73 116.40
136.59 80.24
104.70 61.00
82.67 49.87
70.59 42.16
60.41 37.40
52.79 30.35

Mean sizes of the planar aggregations in the content of the sample I and
II are 198.09 and 121.67 , respectively.
R( ) R( )
Sample I Sample II
5.32 6.44
30.77 35.42
56.41 62.79
79.48 83.72
100.02 122.36
125.64 161.10
184.63 194.81
217.94 223.79
258.97 262.43
317.95 281.75
371.80
425.64
453.85
Summary

Analysis of total scattering gives


valuable insight in the structure-
properties relationship

High resolution instruments open the


door to medium-range order
investigations

Usage of collaborative techniques


always preferable to reach more
detailed knowledge.
GISAXS
0.2- 0.6

2. BP

LS
Dzgn 1. BP
ynelmi
tabakalar SB zotropik
+ PB lipozom

W- tarama

www.hecus.at 42
SAXS ile alglanan nano-oluumlar (1-100 nm)
WAXS ile alglanan nano-oluum i yaplar ( 1-10 )

Lc : correlation
Lc SAXS ile elde edilen bilgiler:
distances
*Kesikli izgilerle gsterilen elektron younluk
farklarnn yksek olduu nano oluumlarn
ekli/ekilleri
* Nano-oluumlarn ortalama byklkleri
*Nano-oluumlar aras ortalama uzaklk ve uzaklk
dalmlar
*Birim hacimdeki nano-oluum saylar v.b. bilgiler.

Plaka formu iin yapsal


bilgiler
Polimer iine
kili uzaklk dalmlar dalarak
bulunduklar
genel malzeme
ortamnn
elektron
younluunu
artran
molekler
saaklanmalar
Btn verinin GNOM program ile artlmas
Folie:SAXS6.doc

FourierTransformation of Particle Scattering Curve


I h 4 p r sin ( h r )
hr
dr
0

I(h)

p(r)

p(r)...Pair-Distance Distribution Function within the Particle