SANS Experimental Methods

Sung-Min Choi

NCNR Summer School

Neutron Small Angle Scattering and

Reflectometry from Submicron Structures
June 5 - 9 2000
 Outline

• Procedure of SANS Measurements

- From the initial planning
to SANS data in absolute scale
- Sample preparation
- What to measure

• Further consideration
- Effects of Q-resolution
- Multiple Scattering

• Summary
Procedure of SANS measurements

1) Initial planning
2) Sample preparation
3) Setup proper SANS configurations
4) Sample scattering
5) Additional measurements for correction
6) Absolute scaling
 Initial Planning
• What information do I want to measure ?
 dΣ(Q)
 
 dΩ  sample
• Is it accessible with SANS ?
- Length scale of interest (~10 Å - ~5000 Å)
- Sample size
- Neutron scattering contrast
- Sample environment
(Temperature, Pressure, Magnetic field and etc.)
- How long would it take ?

• Use NCNR Web based tools

• Consultation with SANS staff members

 Sample Preparation

• SANS can handle various forms of samples.

Liquid, Gel, and Solid
Typical size

• How much sample do I need ?

1.0 ~ 2.5 cm
- Depends on sample (beam diameter)
- Neutron transmission
0.1 ~ 10 mm
• Prepare proper neutron contrast

• Standard SANS sample cell

• Custom made sample cell

 What Should Sample Thickness Be?

• To decide the sample thickness, we need to understand what is happening

in the sample
d
Incident beam, Io 1) Transmitted beam, I

2) Coherent Scattering

3) Incoherent Scattering

4) Absorption
5) Multiple Coherent
Scattering
I
• Transmission T = = exp(−Σ T d) where Σ T = Σ coh + Σ inc + Σ abs
Io
 dΣcoh 
• Scattered Intensity Is ∝ d T ∝ d exp(−Σ T d )
dΩ 
 Optimal Sample Thickness

• Is is maximum
d exp(−Σ T d ) when d = 1/ Σ T
Is

d = 1/ Σ T T = exp (−Σ T d )
= 1/e = 37%
d

• When Σ T ≈ Σcoh d = 1/ Σ T is too large.

will have multiple scattering problem
want T ≥ 90%

• When Σ coh << Σ T ≈ Σ inc + Σ abs d = 1/ Σ T , T = 37%

 Examples of Sample Thickness
• When λ = 5Å

Σ T ≈ Σcoh Σ coh << Σ T ≈ Σ abs + Σinc

(want T > 90%) (T = 1/e = 37 % is optimal)

Silica 0.5 mm, T = 96 % H2O 1 mm, T = 52 %

1 mm, T = 92 %* 1.5 mm, T = 38 % *

3 mm, T = 78 % 3 mm, T = 14 %

σcoh = 10.62 barns σcoh = 7.75 barns

σinc = 0.005 barns σinc = 164 barns
σabs = 0.17 barns σabs = 0.66 barns
Wavelength Dependence of Transmission
• Neutron cross-section depends on neutron wavelength λ.
• Total cross-section increases as the neutron wavelength increases.

1 1mm Silica
1mm H 2 O
0.8
Transmission

0.6

0.4

0.2

0
4 6 8 10 12 14 16
Wavelength λ (Å)
 Calculation of Scattering Length Density
D2O

SLD (10 10 cm-2)

n
6.65
∑ bi ρ  H2O + D2O
ρSLD = i
V  Mw 
( )
= N A  mass  Σ bi
i molecule
(1:1 volume)
2.88

N A = Avogadro' s number = 6 × 10 23 H2O

M w = molecular weight -0.56
bi = bound coherent scattering length of atom i 0

• H2O • H2O + D2O mixture (1:1 volume)

 1.0 g / cm  3
ρ SLD , H2O = (6 × 10 23 / mol )  (2 × b H + bO ) ρSLD, Mixture = x H2 O × ρ SLD,H 2 O + (1− x H2 O ) × ρ SLD, D2 O
 18 g / mol  −2 −2
−2 = 0.5 × (−0.56 × 1010 cm ) + 0.5 × (6.32 × 1010 cm )
= − 0.56 × 10 cm 10

= 2.88 × 1010 cm −2

• D2O  1.1g / cm 3 
ρSLD , D 2 O = (6 × 10 23
/ mol )
 20 g / mol 
(2 × b D + bO )
- bound coherent scattering length (10-13 cm-1)
= 6.32 × 10 10 cm −2 bH = -3.74 bD = 6.67 bO = 5.80
 Coherent and Incoherent Scattering
• Coherent scattering contains the structural information of sample
• Incoherent scattering is flat background.
• Examples
H2O or Hydrocarbons ~ 1 cm-1 ster-1
D2O or Deuterated sample ~ 0.1 cm-1 ster-1
SiO2 (amorphous) ~ 0.02 cm-1 ster-1
• Large incoherent scattering reduce the dynamic range of measurement.
• Use deuterated solvent whenever it is possible.
Large Σinc Small Σinc
100 100
dΣ(Q)/d Ω ( cm -1 )

dΣ(Q)/d Ω ( cm -1 )
10 10

1 1

0.1 0.1

0.01 0.01
0.01 0.1 0.01 0.1
Q (Å-1 ) Q (Å-1 )
 SANS Sample Holders

Liquid Gel or Polymer Melt Solid

Glue on a Cd mask
Path length (Volume) Path length (Volume)
Size mountable on a standard
1 mm (0.3 ml) 1 mm (0.3 ml)
Sample changer
2 mm (0.6 ml) 2 mm (0.6 ml)
width < 3.5 cm
5 mm (1.5 ml) 4 mm (1.2 ml)
height < 5 cm
Diameter = 2.0 cm Diameter = 2.0 cm thickness < 2cm
 Set up SANS Configuration
• Q-range cover : Qmin to Qmax (1, 2, or 3 configuration)
• Q-resolution needed
4
• Beam intensity available, I ∝ Qmin
- neutron wavelength (5 - 20Å)
- wavelength spread (∆λ/λ=10−30%)
- source to sample distance (L1, #of guide, 4-15m)
Use SASCAL or - sample to detector distance ( L2, 1-15m)
Web Based Tools - detector offset ( 0 - 25 cm)
- sample ( 1- 2.5cm) and source(1.5-5cm) aperture sizes
- position of beam attenuator during transmission measurement (0-8)
Beam
attenutator Neutron Guide 2D detector

Velocity
selector

sample
L1 L2

Source Sample
Aperture, A1 Aperture, A2
 Sample Scattering
• Contribution to detector counts
1) Scattering from sample
2) Scattering from other than sample (neutrons still go through sample)
3) Stray neutrons and electronic noise (neutrons don’t go through sample)
aperture
sample
Incident beam

air

cell Stray neutrons

and Electronic noise
Counting time
• We need MORE measurements ISAM = (Count Rate)sample t
σ I SAM = ISAM σ I SAM / ISAM
 Additional Measurements
• Empty Beam • Blocked Beam • Detector sensitivity

Source Source Why ?

1) Scattering from empty cell
2) Scattering from windows
and collimation slits
3) Air scattering
- Minimize air in beam path
- Carefully choose cell and
window materials
- Measure an empty cell
1) Detector dark current
2) Stray neutrons
3) Cosmic radiation
- Measure a blocked beam
(6Li or Boronated material)
1) Sensitivity of each pixel is
slightly different (~ 1%)
- Use isotropic scattering material
(Plexiglass or water)
- We calibrate each reactor cycle

t background Count Rate background

• Counting time =
t sample Count Rate sample
 Data Correction
Measured Raw Data
  dΣ (Q)  dΣ (Q)  
ISAM = CO Tsample +cell  + + IBlocked Beam
  dΩ  sample  dΩ  EMP 
 dΣ(Q)
IEMP = CO Tcell
 dΩ  EMP + Blocked Beam
I

I BGD = I Blocked Beam

Tsample +cell and Tcell
CO = φ A d∆Ω ε t φ = incident neutron flux ∆Ω = solid angle of each pixel
A = sample area ε = detector efficiency
d = sample thickness t = counting time

Corrected SANS data

 Tsample+ cell 
ICOR = (ISAM − I BGD ) −   (IEMP − I BGD)
 Tcell 

• The corrected SANS data is then calibrated with detector sensitivity.

ICAL = ICOR /(Normalized Detector Sensitivity)
 Absolute Scaling
• This is what we have
 dΣ (Q)
I(Q)CAL = φ A d Tsample+ cell  dΩ  sample ∆Ω ε t

• Direct Beam Flux Method

- Measure a direct beam with nothing in the beam except an attenuator.

 dΣ(Q)  I(Q)CAL   1   Tatten. 

IDirect = φ A Tatten. ∆Ω ε t   =   
 dΩ  sample  IDirect   d   Tsample+cell 

• Standard Sample Calibration

- Use a sample with known absolute scattering cross-section at Q=0.
- Measure the standard sample with the exactly same configuration
 dΣ(Q = 0)
I(Q = 0)STD = φ A d STD TSTD+cell ∆Ω ε t .
 dΩ  STD

 dΣ(Q)  I(Q)CAL   d STD   TSTD+cell   dΣ(Q = 0)

  =    
 dΩ  sample  I(Q = 0) STD   d   Tsample+cell   dΩ  STD
 Circular 1D Average
• Take average over annulus
• Each annulus corresponds to one data point in
reduced 1D SANS data

1200

1000

dΣ(Q)/d Ω (cm -1 )
800

600

400

200

0 0.02 0.04 0.06 0.08

-1
Q (Å )
 Q-Resolution Function
2 2 2
4π  θ  2π  δQ   δθ   δλ 
Q= sin  ≈ θ = +
λ 2 λ Q θ  λ

collimation wavelength
spread
• Collimation : L1, L2, A1, A2, δD (detector resolution)
Q-Resolution Function
in Gaussian Approximation
δQ/Q
R(Q,Qo) = A exp( -(Q-Qo)2/δQ2)
80 80

30%
70
collimation 70 collimation
60 dominated 60
dominated
∆λ/λ
50 dominated 50
δQ/Q

40 40
∆λ/λ
30 30 dominated
20 20
5%
10 10

0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Q (Å-1) Q (Å-1)
 Smearing Effect
• The magnitude of smearing effect is proportional to
the curvature of scattering function
d 2 I(Q)
Ismeared (Qo ) ≅ I(Qo ) + Aσ
2
Q 2
+ ⋅⋅ ⋅
dQ Q=Q o

Sharp features are smeared the most.

10 3
High resolution No smearing Form factor
Small A1, A2, High resolution
of a monodisperse sphere
Long L1, L2 Medium resolution
10 2 (R=200Å)
Small ∆λ/λ Low resolution
I(Q) (cm -1 ster-1)

Large λ
10 1
Low Resolution
Large A1, A2,
Short L1, L2 10 0
Large ∆λ/λ
Small λ
10 -1
0.01 0.1
Q (Å -1 )
 Multiple Scattering
d
sample
Incident
beam

• When sample has a strong coherent scattering X-section and thick.

• Final scattering angle is added incoherently
• To reduce the multiple scattering, we need to reduce d.
10 5
Im(0) T=0.9
Im(0) T=0.5 When attenuation is only
10 4 Im(0) T=0.1 due to coherent scattering
ster -1 )

I(q)
10 3
-1

10 2
Im (Q) (cm

10 1

10 0

10 -1 (J.G. Barker)
0 0.005 0.01 0.015 0.02
Q (Å -1 )
 Summary

• Now We have a whole picture of SANS

Experiment.

- Sample preparation
- Optimization of configuration.
- What to measure.

• To get good quality of data,

Initial Planning is VERY Important.

• Use Beamtime Efficiently

Appendix
Beam Alignment and Initial Measurements
• Align the center of sample with neutron beam
- laser beam and neutron camera

• Measure a beam center • Align beamstop

- Q = 0 position - 1, 2, 3, 4 inch diameter
- Use a proper beam attenuator - NO attenuator

128 x 128
pixels

Beam center
(65.94, 63.87)

(Beamstop needs to move down and left)

Appendix
Wavelength Dependence of Cross-Section
• Neutron cross-section depends on neutron wavelength λ.

• Absorption Cross-Section • Scattering Cross-Section

- Scattering lengths, b, listed in table are
Σ abs ∝ 1/ vn ∝ λ bound scattering length.
where vn = neutron velocity

At T=0K
(B10, ΣΤ ~ Σabs) 2
 A + 1
σ bound =  σ A=atomic number
A  free

σ free

Neutron Energy/Chemical Binding Energy

For light element σ bound > σ free

( Hydrogen, σ bound = 4 σ free )

For heavy element σ bound ≈ σ free

Appendix
Q-Resolution Function
• The measured scattering intensity is I(Q) of sample convoluted
with a resolution function R(Q,Qo).

Ismeared (Qo ) = ∫ R(Q,Qo )I(Q)dQ

• Q-resolution Function R(Q,Qo) is determined by :

1) Beam collimation 2) Detector resolution
3) Wavelength 4) Wavelength spread

Qy

 2π  2 2  2
2 ∆λ
σ =   σθ + Q  
2
collimation ∆λ/λ+ collimation
Q
 λ  λ
1) 2) 3) 4)
2 2
1  A1  A22  1 1  σ d  2
σ θ2 =   +  +  + 
16  L1  16  L1 L2  L
 2
Qx