Advanced X-ray Analytics for Innovative Coating Technologies...HRXRD SAXS XPCI Imaging: 2D, 3D X-ray tool & methods optimisation for materials & system studies Low to high Energies

Advanced X-ray Analytics for Innovative Coating Technologies

Antonia Neels & Alex Dommann

Empa Swiss Federal Laboratories for Materials Science and Technology

[email protected]

www.empa.ch\x-ray

Empa: Swiss Federal Laboratories for Materials Sciences and Technology

Empa

Advanced Materials and

Surfaces

Functional Materials

Civil and Mechanical Engineering

Materials meet Life

Biomimetic Membranes and Textiles

Particles-Biology Interactions Biointerfaces Transport at Nanoscale

Interfaces Nanoscale Materials

Science Center for X-ray

Analytics

Mobility, Energy and Environment

2

Empa’s Center for X-ray Analytics

Imaging Seeing the invisible !

Molecular Structures Where are the atoms ?

Electrospun fibers

X-ray image today

X-ray image: 1896

Syringe needle Blocked by plastic

parts

Crystal structures

watch

Crystal structures

Nano-Assemblies Understanding Interactions !

Nanoparticles

Partially ordered polymers

3

Thin films

Semi-conductors

Phases in calcifications

X-ray Analytics: Methods & Tools

X-RAYS Absorption

XRD HRXRD

SAXS

XPCI

Imaging: 2D, 3D

X-ray tool & methods optimisation for materials & system studies

Low to high Energies

In-situ studies: - Temperature - Humidity - Mechanical stresses - Fluidics

Detector developments

4

X-ray Diffraction and Scattering Labs

SC-XRD & 2D Diffraction

Surface & HRXRD Powder XRD

XPCI

5

PHILIPPS XSW

BRUKER D8

BRUKER Nanostar

MOLMET

X-ray CT Labs

High energy CT with 6 MeV linear accelerator

300 kV -CT

-CT Lab

Nano-CT Lab

6

Talbot-Lau Grating Interferometer

Non-ambient in-situ

analysis

X-ray Analytics

FIB ToF-SIMS

Fluorescence Microscopy

FIB TEM STEM

Comple- mentary

Characterization (mechanical &

electrical)

Analytics @ Empa

7

HRSEM AFM

7

Structural properties addressed by X-ray techniques

Domain ordering

Phases

Mosaicity

Stress / Strain

Crystallite Size

Density

XRD / HRXRD

(Interface) roughness

Layer thickness

Texture

Defects

Nano-particle Size Distribution

SAXS / GISAXD

Reflectivity

3D molecular structures for new materials

Orientation

8

Thin film systems:

Structural Analysis

Epitaxial Layers: HRXRD

In-situ surface reactions: XRD

Multilayers: Reflectivity & XRD

9

Oxides on sapphire PZT texturing

BTO: in- and out-of-plane LTO on STO:

in plane mapping SiGe MQW:RSM

Oxidation barriers at HT Expanded Austenite kinetics

Epitaxial Layers: HRXRD

MOSFET devices: transistor types used for amplifying or switching electronic signals

Layer deposition: MBE

10

The BaTiO3 system: HRXRD

“Low Temperature Epitaxial Barium Titanate Growth in High Vacuum CVD” M. Reinke, Y. Kuzminykh, F. Eltes, S. Abel, T. LaGrange, A. Neels, J. Fompeyrine, P. Hoffmann, Advanced Materials Interfaces, 2017, 1700116, 1-8.

11.04.2018 11 Center for X-ray Analytics: [email protected] 11.04.2018 Center for X-ray Anal 11ytics: [email protected]

• d mismatch • mosaicity • relaxation

• shape

• position 2

2

002

200

103

BaTiO3: reflections (002), (200) and (103)

11

= strain = d/d = - /tan = stress = E

E = Young’s Modulus 1. Strain 2. Curvature 3. Defects from diffused scattering

HRXRD X-ray Rocking Curve (RC): Reciprocal Space Mapping (RSM):

-0.2 -0.1 0.0 0.1 -0.3

-0.2

-0.1

-0.0

0.1

0.2

0.3

X-ray scattering can be separate into distinct features:

34.40 34.45 34.50 34.55 34.60 34.65 34.70Omega (°)

Inte

nsity

(cou

nts)

Wafer surface: polished diced

Strain

Tilt

RC RSM

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In-plane diffraction

Thin film X-ray Diffraction: Geometries

Out-off-plane diffraction

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Thin epitaxial films: Out-off plane BTO(002)

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BaTiO3: reflection (002) on Si Out-off-plane diffraction

d-spacing FWHM FWHM (RC) BTO-Si 1.9975 0.45 1.401

M. Reinke, P. Hoffmann, A. Dommann, A. Neels

13.04.2018 15 Center for X-ray Analytics: [email protected] 13.04.2018 Center for X-ray Anal 15ytics: [email protected]

BaTiO3: asymmetric reflection (103) on Si

BTO

BaTiO3: reflection (103) on Si asymmetrical reflection

15 M. Reinke, P. Hoffmann, A. Dommann, A. Neels

BTO

BTO

BaTiO3: reflection (200) on Si in-plane diffraction

Thin epitaxial films: In-plane BTO(200)

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Lattice parameter a (Å)

Lattice parameter c (Å) c/a

BTO-Si 4.009(5) 3.995(5) 0.996 BTO-STO 4.005(5) 4.023(5) 1.004 BTO-MgO 4.018(5) 4.0232(5) 1.001

M. Reinke, P. Hoffmann, A. Dommann, A. Neels

Monolithic X-ray Detectors

NEXRAY

Direct detection of X-rays in a germanium layer Monolithically integrated in ASIC (CMOS) No requirement of bump-bonding

ʺEpitaxial growth and structural characterization of 3D Ge quantum well crystals on patterned Si substratesʺ

F. Isa, M. Meduňa, C. V. Falub, E. Müller, D. Chrastina, G. Isella, P. Niedermann, and H. von Känel.

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New concept in absorber Fabrication

Space-filling arrays of Ge-crystals

Avoidance of crack formation

Problems related to SiGe Epitaxy:

Ge growth on unpatterned Si

Solution

33.0 33.5 34.0 34.5Omega/2Theta (°)

0

200

800

1800

3200

5000

7200

9800

12800

counts/s

Patterned: fully

relaxed

Unpatterned: partially strained Si(004)

Ge(004)

Patterned: Si in pillars

Slightly strained

200

800

1800

3200

5000

7200

9800

12800

PPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaatttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttttteeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeerrrrrrrrrrnnfffu

rerererererereerereeereereereeererrerrererererrrerrererrrrreeeeeeerrreereeerrererrrrrrellaaallllllllllllllllllllllllllllll x

GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((00000000000000

Strained Ge Tetragonal Lattice distortion. Strain: 0.15 %

A. Neels, C. Falub, F. Isa, H. v. Känel, A. Dommann 18

Selective Epitaxy on pre-patterned Si

Si Ge Dislocations

STEM and TEM 8 m Ge pillars on Si (7.4 nm/s, 500 °C)

- small amounts of defects close to the Si substrate- defects move into the nearest surface - patterned Si substrate gives space for Ge relaxation → stress-free and low-defect Germanium layers

- deposition of 1 micron Ge @ 500 C & 2.2 nm/s followed by cycling annealing (600-850 °C) - + 7 microns Ge @ 500 C & 7.4 nm/s

19 A. Neels, C. Falub, F. Isa, H. v. Känel, A. Dommann

Ge-based monolitic X-ray detectors

Collaboration with: Empa Microscopy Center, ETHZ, CERN, G-ray Objective:

Prototyping of a new X-ray Detector Defect and stress free Ge absorber layers

HRXRD HRXRDD

20 A. Neels, C. Falub, F. Isa, H. v. Känel, A. Dommann

From Material Science to New Systems

a)

b)

GeSi

Ge

Si32.8 33.0 33.2 33.4 33.6 33.8 34.0 34.2 34.4 34.6 34.8

Omega (°)

0

2500

10000

22500

40000

Inte

nsity

(cou

nts)

32.92 32.96 33.00 33.04 33.08

Patte

rned

Si

Un-patterned Si

-22 -2 18 38Qx*10000(rlu)

7025

7075

7375

Qy*10000(rlu)c) d)

123

4

Si

Ge

A. Neels, C. Falub, F. Isa, H. v. Känel, A. Dommann 21

Integration in CMOS process

Thin film systems:

Structural Analysis

Epitaxial Layers: HRXRD

In-situ surface reactions: XRD

Multilayers: Reflectivity & XRD

22

Oxides on sapphire PZT texturing

BTO: in- and out-of-plane LTO on STO:

in plane mapping SiGe MQW:RSM

Oxidation barriers at HT Expanded Austenite kinetics

MMMMMMMMMMMMMMultilayers: Reflectiviiiiiiiiiiiiiittttttttttttttyyyyyyyyyyyyyy

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Thin film multilayers: PZT

Piezoelectric materials for switches

Layer deposition: Sol-gel

“High piezoelectric longitudinal coefficients in sol-gel PZT thin film multilayers” D. Balma, A. Mazzalai, N. Chidambaram, C.S. Sandu, A. Neels, A. Dommann, P. Hess, D. Binz, P. Muralt, (2014) Journal of the American Ceramic Society, 97, 2069–2075.

Platinum Lead Zirconium Titanium Oxide

Pt(1

11)

Pt(0

02)

PZT(

011)

PZT(

111)

PZT(

001)

PZT(

112)

Pt(2

20)

PZT(

002)

PZT(

012)

Phase analysis

24

001 011 111

002 012 112

PZT layers trough sol-gel deposition: Pole figures show the PZT fiber texture, the preferred orientation direction is (001):

From Pt(111)

Texture analysis: PZT pole figures

25

PZT layers trough sputtering: Pole figures show the PZT fiber texture, the preferred orientation direction is (001). Much higher texturing compared to the sol-gel deposition process.

Texture analysis: PZT pole figures

001 011 111

002 012 112

26

Only small loss in texture. Quantification trough texture index.

Texture développement in multilayers:

J. Am. Ceram. Soc., 97, 2069–2075 (2014)

27

Thin film systems:

Structural Analysis

Epitaxial Layers: HRXRD

In-situ surface reactions: XRD

Multilayers: Reflectivity & XRD

28

Oxides on sapphire PZT texturing

BTO: in- and out-of-plane LTO on STO:

in plane mapping SiGe MQW:RSM

Oxidation barriers at HT Expanded Austenite kinetics

In-situ surface reactions: XRD

Hard Coatings:

29

Coatings: (Al,Cr)2O3, (Al,Hf)2O3

“Phase formation in cathodic arc synthesized Al-Hf and Al-Hf-O coatings during high temperature annealing in ambient air” X. Maeder, M. Döbeli, A. Dommann, A. Neels, H. Rudigier, B. Widrig, J. Ramm, Surface and Coatings Technology, 2014; 260:56-62. “Thermal stability of thin film corundum-type solid solutions of (Al1-xCrx)2O3 synthesized under low temperature non equilibrium conditions” J. Ramm, M. Ante, H. Brändle, A. Neels, A. Dommann, M. Döbeli, Advanced Engineering Materials, 2007, 9, 604-608.

Support in process development: Hard coatings

Dedicated Design of High Temperature Corrosion Resistant PVD Oxide Coatings for Automotive Applications

Simulations Characterization: XRD, ex- and in-situ RBS Mechanics

Testing

Understanding

Reactive cathodic arc evaporation (PVD)

30

Virgin cathode surface: Binary elements

Used cathode surface: Intermetallics Oxides islands

1μm

Coating: Intermetallics Oxides

Arc process

Deposition

XRD

XRD phase analyses: cathode surface vs layer composition

• Phase transformation at the cathode surface and correlation with the composition of the layer

• Parameter sensitivity analyses by changing the target composition and deposition atmosphere for each system (AlCr; AlHf)

31

Al-Cr system: XRD High temperature experiment

XRD Chamber at 1300°C

• Phase transformation at high temperature

• Progressive oxidation study • Stability of the coating

A. Neels, X. Maeder, A. Dommann, J. Ramm 32

Al-Hf system: XRD High temperature experiment

A. Neels, X. Maeder, A. Dommann, J. Ramm 33

XRD Chamber at 1300°C

• Phase transformation at high temperature

• Progressive oxidation study • Stability of the coating

34

Surface reactions: AISI316L stainless steel

Growth kinetics and structure of expanded austenite by in-situ XRD

Reaction: Low temperature N/C treatment

In-situ kinetics study on the growth of expanded austenite in AISI 316L stainless steels by XRD” Z. Balogh, A. Faeht, S. Kleiner, A. von Känel, J.-M. Rufer, A. Dommann, P. Margraf, G. Tschopp, A. Neels, Journal of Applied Physics, 122,025111.

The in-situ reaction chamber

4 gases (N2, H2, NH3, C2H4) and their mixtures In situ depassivation with HCl Up to 600°C processing temperature Attached to a Bruker D8 Advance

AISI 316L specimens Ex-situ depassivated With protective Ni layer

Nitrocarburizing (both NH3 and C2H4)

35

Measurement and results: kinetics

γ-Fe 111 position constant Expanded austenite layer

Linear parabolic kinetics

Arrhenius dependence for the parabolic part

The activation energy is realistic for interstitials

A. Fäht, S. Kleiner, Z. Balogh 36

Results: expanded austenite, peak shape

The expanded austenite peak is broad

Composition variation Stress

Fitting through sectioning Lattice parameter constant per section Attenuation is composition independent Gaussian function

Plotting the lattice parameter As a function of depth

The thickness is determined by diffusion within the layer, while the exact composition is determined by the uptake at the surface.

37

Antonia Neels 38

X-ray methods

Diffraction

SAXS

WAXS / PDF

GI- SAXS

HR-XRD

XPCI

XCT

2D XRD

System understanding through X-ray analytical methods:

Shoulder

Thin films

Molecules

Nano-particles

Crystal structures

Whatch

Semi-conductors

THANK YOU !

The X-ray team: Zoltan Balogh, Alex Flisch, Jürgen Hofmann, Rolf Kaufmann, Selina Kolokytha, Thomas Lüthi, Mathieu Plamondon, Felix Reifler, Kim von Allmen, Kai Zweiacker, Mahdieh Shakoorioskooie, Amin Sadeghpour, Anjani Maurya, Neda Iranpour, Bekmurza Beisenov, Simone Dolabella.

Xavier Maeder, Paul Muralt, Jürgen Ramm, Michael Reinke, Patrick Hoffmann, Claudiu Falub, Hans von Känel, Simon Kleiner, Alex Dommann