ThinFilm XRD

Thin film analysis
Advanced X-ray Workshop, S.N. Bose National Centre
Innovation with Integrity
Thin Films Samples 1

Metal conductor paths (Cu, Al, AlSiCu) Insulators (SiO2, HfO2) in semiconductors Diffusion barriers (Si3N4, Ti/TiN) Semiconductors (SiGe, GaAs, InP) Active zones in lasers and LEDs (InGaN, AlGaAs, GaN) Hard coatings (TiN) Solar cells a.k.a photovoltaics (CuInSe2,CdS, CdTe, organic) Magnetic active layers (CoPtCr) Piezoelectrics(PMN-PT, PZT, PLZT, PbTiO3) Optical coatings Electro-optics (PLZT, PMN-PT) Magnetostrictives (FeGa) Fuel cells (YSZ, Gd-CeO2) Superconductors (MgB2, YBa2Cu3O7)
14-15/12/2011 Advanced X-ray Workshop 2
Thin Films Samples 2

Electrolytes in batteries (LiPO3) Oxide electrodes (SrRuO3) Catalysts (MOFs, CeO2) Coatings (bathroom fixtures, corrosion prevention) Communication/band gap tuning (HEMTs...quantum wells) Thermoelectrics (Pb0.5Sn0.5Te) Energy storage (ultracapacitors using metal carbides) Energy harvesting/ energy conversion
14-15/12/2011
Advanced X-ray Workshop
Thin Film Characteristics

A thin film is a layer of material ranging from fractions of nanometers (monolayer) to several micrometers in thickness. Thin films can have different degree of crystallinity: from amorphous to single crystal.
Degree of order Amorphous Polycrytal. Single crystal Front-end SiGe Organic monolayer Magn. storage Nanoparticles in matrix Back-end (Semi.) Low-k oxides LEDs Oxyde Semi. Coatings
1 nm
10 nm
100 nm
1 m
Layer thickness
14-15/12/2011
Thin Film XRD Methods Parameters of Interest

Grazing incidence Diffraction (GIXRD)
depth dependent information phase identification lattice parameter microstructure (size/strain) residual stress
X-Ray Reflectometry
layer thickness composition roughness density porosity
Stress and Texture

orientation distribution orientation quantification residual stress epitaxial relationship
High-Resolution X-Ray Diffraction

thickness lattice parameter lattice mismatch composition strain & relaxation lateral structure mosaicity (crystallinity) defects
14-15/12/2011
Reciprocal Space Mapping

lattice parameter lattice mismatch composition orientation relaxation lateral structure
In-Plane GIXRD
IP-lattice parameter IP-crystallite size IP-orientation epitaxial relation
Bruker Confidential

X-Ray Reflectometry
Stress and Texture


14-15/12/2011

In-Plane GIXRD
Bruker Confidential
What is X-ray Reflectometry (XRR)?

A surface-sensitive X-ray scattering technique
Non-destructive method Wavelength probes on nanometer scale Works for crystalline and amorphous materials
What does XRR provide?

Layer thickness 0.1 nm 1000 nm Material density < 1-2% Roughness of surfaces and interfaces < 3-5 nm
14-15/12/2011
Analytical tasks
Layer thickness
(electron density)
Chemical Composition
Roughness
Lateral structure
Specular XRR
Diffuse
14-15/12/2011
The specular XRR scattering geometry

z x
q=(0,0,qz)
Wavevector transfer has a non-zero component perpendicular to the sample surface
q z = 2k sin
ki kf
For Cu-K (=1.54)
q z = 2 / 140 [nm 1 ]
XRR probes the laterally averaged electron density
S (q z ) ( z ) exp( iq z z )dz
2
14-15/12/2011
( z ) = ( x, y , z )
9
x, y
The reflectivity from a substrate

(z) exp(iqz) T exp(iQz) R exp(-iqz) 0
Fresnel reflectivity
q Q rF (q ) = RF (q ) = q+Q
2
14-15/12/2011
with
Q = q 2 16 re
10
Density dependency of the reflectivity

The higher the electron density (z) of a material the higher the critical angle
c
The higher the electron density, the more intensity is scattered at higher angles
c r 2
This limits the accessible angular range for light materials like softmatter films
14-15/12/2011
11
Influence of Roughness Waviness

small inclinations of the surface normal on a large scale of some 100 nm broadening of the specular reflected beam reflected intensity
The broadening of the specular reflected beam decreases the It does not contains any information about internal sample
structure
Samples should have a flat surface

waviness
14-15/12/2011
12
Influence of Roughness Microscopic Roughness

large inclinations of the surface normal on an atomic scale of a few nanometers leads to diffuse reflection of the incident beam the intensity of the specular reflected beam decreases
microscopic roughness
waviness
14-15/12/2011
13
Influence of Roughness
Roughness decreases the reflected intensity dramatically XRR is highly sensitive to roughness Roughness causes diffuse scattering
The interface roughness should not be larger than 2-3 nm.
14-15/12/2011
14
XRR from single layer on substrate: Thickness fringes

The interference of the waves reflected from the interfaces causes oscillations of period
q z = 2 / d
The minimal observable thickness is limited by the maximal measurable range The maximal observable thickness is limited by the instrumental resolution The sample should have thicknesses observable with the instrumental setup.
14-15/12/2011
15
Thickness fringes Amplitude

Amplitude of the thickness fringes increases with increasing density contrast XRR is quite sensitive to variations of the electron density
The sample should have a good contrast in the electron density.
14-15/12/2011
16
XRR from multilayers
10
10
-1
2 - layer system 10 nm Ag 60 nm Au Si - substrat
Reflectivity
10
-2
10
-3
10
-4
10
-5
10
-6
0,0
0,5
1,0
1,5
2,0
2,5
3,0
Incidence angle []
14-15/12/2011
17
X-ray Reflectometry in Practise Demands on Sample Properties

Golden Rule: You should be able to see your reflection on the surface of the sample! Flat and lateral homogeneous - not structured Sample roughness < 5nm Good contrast in electron density for layered samples Length of at least 3-5 mm in beam direction
14-15/12/2011
18
Simplest Setup for XRR
Reasonable resolution requires slit of 50-100 m Intensity is on the order of 107 cps Full energy spectrum creates high background
14-15/12/2011 Advanced X-ray Workshop
19
Principle of the Gbel Mirror
Goebel mirror Parabola
X-ray source
Sample
Mirror converts 0.35 into a parallel beam of 1.2 mm Integrated intensity >109 cps Mainly K-radiation is reflected
14-15/12/2011
20
The standard XRR setup for thin films
Slits can be easily exchanged to tune resolution A reasonable resolution requires a slit size of 0.1 0.2 mm Integrated intensity 2x108 cps
21
Reflectometry with different slits
1e7
1e6
1e5
Int. [cps]
with 0.6 mm slit with 0.1 mm slit ~ 5 min ~ 6.5 h
1e4
1000
100
2/[]
Use slits to balance flux and resolution

22
XRR setup for very thin layers
Full beam on primary side Soller with resolution down to 0.1 Integrated intensity 8x108 cps
23
Limits of X-Ray Reflectometry Thin layers Example: LaZrO on Si

1*10 1*10 1*10 Intensity [au] 1*10 1*10 1*10 1*10 1*10 1*10
0
-1
-2
-3
-4
6.7 nm LaZrO Si (111)
-5
-6
-7
-8
6 2 []
10
12
14
14-15/12/2011
24
XRR with an analyzer crystal
Analyzer crystal improves the resolution:
1-bounce Ge(220) 3-bounce Ge(220)
Analyzer crystal separates K1, suppresses diffuse scattering and fluorescence Crystal can accept the full incident beam Integrated intensity 3x107 cps (for a 3-bounce analyzer)
25
XRR setup for thick layers
Monochromator crystal:
4-bounce Ge
Analyzer crystal:
1-bounce Ge(220s) 3-bounce Ge(220s)
Monochromator cystals provide highly parallel and monochromatic beam Crystals can accept the full incident beam Integrated intensity 105 - 106 cps
26
Limits of X-ray Reflectometry Thick layers example: SiO2 on Si
1e4
1000
Int. [au]
1014 nm SiO2:H Si
100
10 5 0.11 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
2 []
27
Resolution of differents setups

For Cu-K radiation: 1.54 Values for were obtained by scanning the direct beam Obtained from the rough estimation d / 2
Tube side GM + 1.2mm GM + 0.2mm 2xGe(220a) GM 2xGe(220a) 4xGe(220s) 4xGe(440s) Detector side 0.2 soller 0.2mm slits 0.2mm slits 3xGe(220s) 3xGe(220s) 3xGe(220s) 3xGe(220s) [deg] 0.06 0.029 0.026 0.013 0.01 0.006 < 0.006 dmax [nm] 73 150 170 340 440 735 > 735
28
14-15/12/2011
Geometrical corrections The footprint
d : beam width L : sample length || beam D : illuminated area
L
D = d / sin
Footprint of the beam on surface: Beam matches the sample size at: Below B the intensity is reduced by:
B = arcsin( d / L)
B = sin( ) / sin( B )
29
14-15/12/2011
Geometrical corrections The footprint
Beamsize : 200 m
Sample size reduces the reflected intensity at small angles Sample must be sufficiently large for XRR
30
Controlling the footprint The Knife Edge Collimator
The KEC allows the removal of the footprint effect by making the probed
area smaller than the sample size For higher angles, the KEC needs to be lifted from the surface to gain flux The measurement with KEC will be upscaled to the curve without KEC
31
14-15/12/2011
Controlling the footprint The Knife Edge Collimator

with KEC without KEC
10
8
Measurement with KEC must be performed up to at least 2B The high-angle measurement without KEC must have an overlap with the KEC measurement to rescale the data properly
10
7
Intensity
10
10
10
0,0
0,5
1,0
1,5
2,0
2 [deg]
14-15/12/2011
32
Evaluation of Sample Fitting Procedure
Sample Model parameterized by {p1,pN}
XRR Simulation
Comparison with Experiment, 2 cost function
Minimization of 2 using Genetic Algorithm, Levenberg-Marquardt, Simplex, Simulated Annealing, etc. in view of {p1..pN}
Tolerance
14-15/12/2011
33
Amorphous HfO2 film Ultra thin films
[degees]
14-15/12/2011
34
XRR on MEMS Ru/SiN film
14-15/12/2011
35
GMR Heterostructure 8 Layers
Sample courtesy of Dr. Schug, IBM Mainz
14-15/12/2011
36

X-Ray Reflectometry
Stress and Texture


14-15/12/2011

In-Plane GIXRD
Bruker Confidential
37
Remarks for Coatings

For coatings (few microns down to sub-micron range), the Bragg-Brentano geometry (BB) is still the best configuration. This is basically the classical powder diffraction case and BB will offer the best grain statistic and the easiest instrumental function characterization. Providing that the preferred orientation is weak, quantitative phase analysis or microstructure investigation (size/strain) are quite easy to perform. Limitations of the BB set-up: If the substrate is a single crystal, the huge intensity from the substrate peak will emphasize all minor peaks originating from the energy spectrum of the tube and other aberrations (K, tube tails, Ni absorption edge, W lines,) with the consequence that a significant part of the scan wont be usable.
14-15/12/2011
38
Polycrystalline Thin Films Constrains

Even if a layer is polycrystalline, several characteristics differentiate a polycrystalline thin film with a loosed powder: Due to the limited layer thickness, the grain statistics is limited. The classical BB geometry might fail in providing necessary peak intensity for further analysis. An alternative is then to go for GIXRD. The confinement of the grains into a limited volume very often causes preferred orientation and the quantitative phase analysis might become impossible. The grain interaction during growth can also induce residual stress. A composition gradient through the layer may also appear during the growth.
14-15/12/2011
39
Grazing Incidence X-Ray Diffraction Instrumental Set-up Requirements

GIXRD requires a parallel-beam set-up A parallel beam Goebel mirror (mostly Cu radiation is used) A small slit would also work, at the cost of intensity A stage able to precisely adjust the sample height (z-alignment) A parallel beam attachement on secondary side (Soller plate collimator, defining the instrumental resolution) A 0-D detector (e.g. scintillation counter or LYNXEYE in 0-D mode)
14-15/12/2011
40
Grazing incidence diffraction Ag2Te thin film on glass
13000 12000 11000 10000
Bragg-Brentano geometry
13000
Grazing incidence geometry
12000
11000
10000
9000
Lin (Counts)
Lin (Counts)
8000
7000
GIXRD emphasizes the signal of the Ag2Te nanocrystallites, and the glass substrate signal is reduced
9000 8000 7000 6000 5000 4000
6000
5000
4000
3000
3000
2000
2000
1000
1000
0
0 5 10 20 30 40 50 60 70 80 90
10
20
30
40
50
60
70
80
90
2-Theta - Scale
2-Theta - Scale
14-15/12/2011
41
GIXRD The Footprint

Footprint of the beam on surface: The all idea of GIXRD is to increase the number of diffracting crystallites (low incident angle) and increase the flux density (Goebel mirror). Depending on the sample length, the layer density and the expected penetration depth, an incident angle is chosen and remains fixed during the data collection. d : beam width L : sample length || beam D : illuminated area
L
42
14-15/12/2011
42
GIXRD Data collection

A detector scan (or 2 scan) is performed. The use of a Soller plates collimator maintains a good resolution in 2 (given by the acceptance of the Soller plates) while getting diffraction signal from the whole footprint on the sample.
Soller plates collimator defines the instrumental resolution! Available: 0,1, 0,2, 0,3, 0,4
43
14-15/12/2011
43
Grazing Incidence Diffraction Phase ID depth profile

LYNXEYE 0D Gbel mirror
Equatorial soller
XYZ stage
Incident angle Theta=0.2 to few degrees
14-15/12/2011
44
Grazing Incidence Diffraction Phase ID depth profile
At 0,2 deg incident angle, only Mo layer is detected. At higher incident angle, the YH2 layer is reached and starts to diffract.
14-15/12/2011
45
Combination of GIXRD with IP-GIXRD
Standard GIXRD or socalled coplanar geometry
In-plane GIXRD or so-called non-coplanar geometry
The idea remains the same: optimizing the grain statistic when looking at different grain orientations
ULTRA-GID Coplanar vs. Non-Coplanar Diffraction

Coplanar diffraction
(hkl) // sample surface ULTRA-GID @ 0
D 2IP-GID f
Non-coplanar diffraction
In-Plane GID (hkl) sample surface ULTRA-GID @ 90
i i
14-15/12/2011
47
XRR on Si/SiO2/Si
LEPTOS results 100,3 nm SiO2 14,7 nm Si
14-15/12/2011
48
Coplanar GIXRD on Si/SiO2/Si
TOPAS results Cubic Si a=5.41285 A 9 nm normal crystallite size
14-15/12/2011
49
Non-coplanar GIXRD on Si/SiO2/Si
TOPAS results Cubic Si a=5.41285 A 14 nm lateral crystallite size
14-15/12/2011
50
XRR on ZrO2/Si
LEPTOS results 3,2 nm ZrO2
14-15/12/2011
51
Coplanar GIXRD on ZrO2
TOPAS results Tetragonal ZrO2 a=3,5658 A c=5,1614 A 3,4 nm normal crystallite size
14-15/12/2011
52
Non-coplanar GIXRD on ZrO2
TOPAS results Tetragonal ZrO2 a=3,5994 A c=5,18424 A 30,4 nm lateral crystallite size
14-15/12/2011
53

X-Ray Reflectometry
Stress and Texture


14-15/12/2011

In-Plane GIXRD
Bruker Confidential
54
Residual stress analysis on thin TiN layer The multiple (hkl) approach
The conventional sin2 method using (i) a unique (hkl) Bragg condition and (ii) different sample orientations with respect to the incident beam (iso- or side-inclination mode) has not been successful due to the weak diffracted intensity. For layer thicknesses around 20 nm, the only geometry were intensity is significant enough for further analysis is GIXRD. Using small angle of incidence the effective sampling volume is confined in the surface region resulting higher diffracted intensities than conventional diffraction methods. By measuring lattice strain using different hkl reflections (the incidence angle is kept constant while the detector is moved along the 2 circle) the direction of the diffraction vector can be varied without tilting the specimen physically: under such conditions the inclination angle is equal to hkl = hkl -
14-15/12/2011
55
Experiments with D8 ADVANCE Configuration of the diffractometer

Goniometer Measurement circle Tube Tube power Primary optics Sample stage Secondary optics Detector D8 ADVANCE Theta/Theta 560 mm 2.2 kW Cu long fine focus 40 kV / 40 mA Focusing Goebel mirror (*) 0,4 mm exit slit XYZ stage with vacuum chuck 0,4 deg equatorial Soller slit Scintillation counter or LYNXEYE in 0D mode
(*) A focusing Goebel mirror gives a lower penetration depth resolution, but a higher flux on the sample surface. If the customer has a focusing mirror for capillary measurements, he can definitely use it for GIXRD.
Residual stress analysis on thin films GIXRD scan on a 25 nm TiN layer

GIXRD on Sample 1A : phase ID
[2,0,0] [2,2,2] [4,0,0] [3,3,1] [4,2,0] [ 1, 1, 1] [ 2, 2, 0] [ 3, 1, 1]
370 360 350 340 330 320 310 300 290 280 270 260 250 240 230
TiN osbornite
Lin (Cps)
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
30
40
50
60
70
80
90
100
110
120
[4,2,2]
130
140
[5,1,1]
150
2-Theta - Scale
Commander Sample ID - File: GID@0,3245.raw - Type: Detec tor Scan - Start: 30.000000 - End: 146.00000 0 - Step: 0.100000 - Step time: 40. s - Temp.: 25 C (Room) - Time Started: 0 s - 2-Theta: Operations: Import 03-065-4085 (I) - Osbornite, syn - TiN0.98 - Y: 99.90 % - d x by: 1. - WL: 1.5406 - Cubic - a 4.24190 - b 4.24190 - c 4.24190 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-centered - Fm-3m (225)
14-15/12/2011
57
Residual stress analysis on thin films The refraction effect

The refraction of the incident beam and diffracted beam i at the surface of the specimen causes a positive shift between the measured peak position 2 and the true Bragg angle 2 Brhkl: 2 hkl = 2 2 Brhkl, where 2Brhkl = t- i
Qhkl hkl
Surf. normal
Measuring geometry in GIXRD experiment: the angle of incidence, t the refraction angle, i the incidence angle of the diffracted beam 14-15/12/2011 Advanced X-ray Workshop 58
Residual stress analysis on thin films XRR scan for critical angle determination
C= 0.311
From Leptos fit: 25 nm TiN layer
14-15/12/2011
59
Residual Stress Analysis on Thin Films Data Treatment LEPTOS
Evaluation of the peak K1position
14-15/12/2011
60
Peak shift due to the refraction effect
n=1--i, where sin2c=2 and =(/4)
14-15/12/2011
61
-4,7 0.5 GPa
14-15/12/2011
62
Stress Gradient Multiple (hkl) Approach
1600 1500 1400 1300 1200 1100 1000 900 800 700 600
Incident angle from 0,5 to 3,5
Q(hkl)
(hkl)
Detector scan
Sqrt (Cps)
500 400 300
1,2m TiCrN on Fe
200
100
10
0 31 40 50 60 70 80 90 100 110 120 130 140 150
2-Theta - Scale
File: TiCrN_0.50deg.raw - Type: 2Th alone - Start: 30.000 - End: 150.000 - Step: 0.0 50 - Step ti me: 60. s - Theta: 0.500 Y + 5.0 mm - File: TiCrN_1.25deg.ra w - Type: Detector Scan - Start: 30.000 - End: 150.000 - Step: 0.050 - Step time: 60. s - Theta: 1.250 Y + 10.0 mm - File: TiCrN_2.00deg.raw - Type: Detector Scan - Start: 30.000 - End: 150.000 - Step: 0.050 - Step time: 60. s - Theta: 2. 000 Y + 15.0 mm - File: TiCrN_2.75deg.raw - Type: Detector Scan - Start: 30.000 - End: 150.000 - Step: 0.050 - Step time: 60. s - Theta: 2. 750 Y + 20.0 mm - File: TiCrN_3.50deg.raw - Type: Detector Scan - Start: 30.000 - End: 150.000 - Step: 0.050 - Step time: 60. s - Theta: 3. 500
14-15/12/2011
63
Stress Gradient Multiple (hkl) Approach

Incident angle from 0,5 to 3,5
1,2m TiCrN on Fe
14-15/12/2011
Higher stress at the surface

64
Texture analysis on thin films

Pt layer on Si Point focus, Polycap and scintillation counter (311) texture of platinum recorded at 81.6 using a 7 grid 30 min measurement time The fiber texture is apparent
min
max min
max min
max
Simulation using MULTEX software

Texture analysis on thin films

TiN pole figure simulation using MULTEX Point focus, POLYCAP and scintillation counter
(422)
(220)
(111)
As measured
Simulated Residual
14-15/12/2011
66
Innovation with Integrity
reserved. 15. Copyright Dezember Bruker 2011 Corporation. All rights reserved 14-15/12/2011
6767

ThinFilm XRD

Hochgeladen von

Dokumentinformationen

Originalbeschreibung:

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

ThinFilm XRD

Hochgeladen von

Copyright:

Verfügbare Formate

Thin film analysis

Advanced X-ray Workshop, S.N. Bose National Centre

Innovation with Integrity

Thin Films Samples 1

Thin Films Samples 2

Advanced X-ray Workshop

Thin Film Characteristics

Advanced X-ray Workshop

Thin Film XRD Methods Parameters of Interest

Stress and Texture

High-Resolution X-Ray Diffraction

Reciprocal Space Mapping

Advanced X-ray Workshop

Thin Film XRD Methods Parameters of Interest

Stress and Texture

High-Resolution X-Ray Diffraction

Reciprocal Space Mapping

Advanced X-ray Workshop

What is X-ray Reflectometry (XRR)?

What does XRR provide?

Advanced X-ray Workshop

Advanced X-ray Workshop

The specular XRR scattering geometry

Wavevector transfer has a non-zero component perpendicular to the sample surface

XRR probes the laterally averaged electron density

Advanced X-ray Workshop

The reflectivity from a substrate

Advanced X-ray Workshop

Density dependency of the reflectivity

Advanced X-ray Workshop

Influence of Roughness Waviness

Samples should have a flat surface

Advanced X-ray Workshop

Influence of Roughness Microscopic Roughness

Advanced X-ray Workshop

The interface roughness should not be larger than 2-3 nm.

Advanced X-ray Workshop

XRR from single layer on substrate: Thickness fringes

Advanced X-ray Workshop

Thickness fringes Amplitude

The sample should have a good contrast in the electron density.

Advanced X-ray Workshop

XRR from multilayers

2 - layer system 10 nm Ag 60 nm Au Si - substrat

Advanced X-ray Workshop

X-ray Reflectometry in Practise Demands on Sample Properties

Advanced X-ray Workshop

Simplest Setup for XRR

Principle of the Gbel Mirror

Goebel mirror Parabola

Advanced X-ray Workshop

The standard XRR setup for thin films

Reflectometry with different slits

with 0.6 mm slit with 0.1 mm slit ~ 5 min ~ 6.5 h

Use slits to balance flux and resolution

XRR setup for very thin layers

Limits of X-Ray Reflectometry Thin layers Example: LaZrO on Si

6.7 nm LaZrO Si (111)

Advanced X-ray Workshop

XRR with an analyzer crystal

Analyzer crystal improves the resolution:

1-bounce Ge(220) 3-bounce Ge(220)