Suppression of hydrogen blistering

in Mo/Si layered structures

VICTOR VOLLEMA
ADVA N CED R ES EARCH CE N TER FOR N AN OLITHOGRAPHY
 Why?
Hydrogen storage / welding Nuclear fusion materials

Taken from Allen et al., Scripta Materiala, 2020

Taken from Xu et al., Journal of

Nuclear Materials, 2016

Extreme ultraviolet
Taken from Van den Bos et al., Journal lithography (EUVL)
of Physics D: Applied Physics, 2017
Blistering in EUVL

Taken from Van den Bos et al., Journal of Applied Physics, 2016

Delamination of the multilayer Mirror failure

Hydrogen blistering: the process
Hydrogen blistering: the process
Hydrogen blistering: the process
Hydrogen blistering: the process
Hydrogen blistering: the process
 Simulating multilayer blistering
H2+ H2+ H2+
H2+ H2 + H2+
• Simplified layer structure by DC sputter deposition H2+
H2+
H2+
H2+
using Ar as sputter gas H2+

• Exposure to excessive hydrogen ion

bombardment:
• H2+ , E = 800 eV
• >1017 ions cm-2

• Pre- and post-examination:

• Morphology, structure, hydrogen content
 Si sputter deposition:low Ar pressure
effect of Ar pressure
high Ar pressure

low Ar pressure
So why the difference?

• Both sample types deposited under same conditions, with same thicknesses
• Only difference was the Argon sputter gas pressure during Si deposition: 1∙10-3 – 3∙10-2 mbar
high Ar pressure
 Hydrogen exposure: Structure Changes
Method: X-ray reflectivity High-P – As Dep Low-P – As Dep
High-P – H Exposed Low-P – H Exposed
Mo Mo
θ θ
High-P Low-P

Si, upper
Exposed Si, upper
Si, lower

Si, lower As Dep

• High-P scattering length density (SLD) profile barely changes upon hydrogen exposure compared to the
Low-P case
𝑞𝑧 = 2𝑘 𝑠𝑖𝑛(𝜃) • Low-P shows two interesting trends due to exposure:
1. The total layer expands considerably (‘swelling’), most notably the silicon.
2. The SLD profile has a drop towards zero density between the silicon and molybdenum, which is the blister
interface
 Hydrogen exposure: Hydrogen Content
Method: Elastic Recoil Detection Sample H (1015 at/cm2)
Low-P – As Dep
Low-P As Dep 3±2 High-P – As Dep
Low-P – H Exposed
High-P As Dep 4±2 High-P – H Exposed

Low-P H Exp 14.5 ± 3

E = 2 MeV
High-P H Exp 6.5 ± 2
400%

60%
• Both samples show increased H content upon exposure, even though
time after exposure is significant (>1 month)
• H increase is remarkably less for the High-P case (60%) than the Low-P
case (400%)
Possible hypotheses
• Leaky Si layer: High Ar pressure lowers a-Si density, making the Si permeable for H and H2

• Lower stress: Reduced build-up of in-plane stress during exposure increases the energy
required for blister formation
Testing “Leaky Layers” hypothesis
• If high-P Si is ‘leaky’ for hydrogen, then any low-P
Si layer should be enough to block hydrogen from
escaping

• Fabricate structure with “alternating layers”:

• Low-P top layer to block hydrogen
• High-P lower layer should not matter

• Upon exposure, structure should blister to similar

extent as full low-P structure
Most likely hypothesis

Lower stress:
Reduced build-up of in-plane stress during exposure increases the energy
required for blister formation
Stress hypothesis: outline
1. Depositing at higher Argon pressures
lowers the material density
2. Incorporation of hydrogen atoms
leads to high compressive stress, at
least for low-P deposited films
3. The high compressive stress makes it
energetically favourable for blister
formation to occur (relaxation)

Goal: Direct proof through measurement of stress

during deposition and exposure
Taken from Marquez et al., Journal of Non-Crystalline Solids, 2020
Future work: blistering dynamics
• Suspended single period of multilayer (in this case W/Si)
H2+
H2+
H2+ H2+ H2+
• Transferred through air into Scanning Tunnelling
Microscope, resulting in slight oxidation:
➢ Deposit thin (~ 2nm) layer of metal for stable tunneling
1 period

• Expose H2+ ions to in doses, with imaging in between:

➢ Allows study of the same blister over time
Future work: blistering dynamics

Image Size:
1 x 1 µm2
 Acknowledgments

Prof. Dr. Joost Frenken Dr. ir Jan Verhoeven Arend-Jan van Calcar Dr. Georgios Dr. Cristiane Vilas Dr. Roland Bliem Alessandro Troglia Stefan van Vliet
Kanoutas Boas

Prof dr. Fred Bijkerk Dr. Ir. Robert van der Kruijs Dr. Beata Tyburska-Pueschel Dr. Wim Arnold Bik Dr. Giuseppe Portale