Apresentado pelo professor Thierry Czerwiec (Institut Jean Lamour, Nancy, France) no dia 12 de junho na Universidade de Caxias do Sul, em seminário realizado pelo Instituto Nacional de Engenharia de Superfícies e o PGMAT da UCS para um público de 16 estudantes e professores.

1. Plasma, electron and ion beams surface patterning of metals
T. Czerwiec, G. Marcos
Institut Jean Lamour (IJL), Ecole des Mines de Nancy, Parc de Saurupt, CS 14234, 54 042 Nancy, France.
Jacques Callot (c. 1592 – 1635) was a draftsman that
was working in Nancy and important figure in the
development of the old master print (engraving,
etching…)
Stanislas place in Nancy

2.  Introduction what is patterning and why surface patterning?
 Strategies for creating surface patterns
 Photolithography
 Advanced serial mask-less processes
 Additive parallel processes with masks (templates)
 Removal serial and parallel processes : energy beams
Moving parallel processes : patterning by nitriding
 Last experiments done on combining stainless steel patterning by
photolithography and nitriding
 Conclusion

3. Introduction: what is surface patterning?
Surface patterning, also known as surface texturation or surface structuration is a
part of surface engineering that consists in the production of a "patterned" surface
with some regular array of surface height features on the size scale of several
micrometers to some nanometres
Integrated 3D
gold nanoboxes
Austenitic stainless steel
patterning by plasma assisted
diffusion treatments
Deposition of SiOx by atmospheric pressure CVD with localized remote plasma
NbOx nano-pilar with a mushroom-like shape prepared by using ultra-thin alumina mask
t=3s t =10 s

4. Introduction: Why creating surface pattern?
Bio-inspired structured surfaces
Shark skin effect
Lotus effect Gecko (Tarentola mauritanica)
Corse, France
S.J. Abbott, P.H. Gaskell, Proc. IMechE, Part C, J. Mechanical Engineering Science, 221 (2007) 1181

5. Introduction: Why creating surface pattern?
Wp
Wh
h
s
h : height of the patterned layer, s : period of the patterned layer
Wp: length of the protrusion, Wh: length of the cavity
Aspect ratio h/s
µm
4
3.8
Bio-inspired structured surfaces: 3.6 Drag reduction in air and water :
Shark skin effect…
3.4
Lotus effect, Gecko, Cicada wings… 3.2
3
aeronautics, microfluidics…
Self-cleaning and antireflective surfaces 2.8
2.6
2.4
2.2
2
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
Nanodots Tribology (Lubrication…)
Magnetic data storage Piston ring in automotive…
T. Czerwiec, “Patterning of metals for surface engineering: from top-down towards self assembly”, conference
presented at the 61th workshop of the international union for vacuum science, technique and applications (IUVTA)

6. Application of patterned surfaces to drag reduction
NASA Langley Research Centre (USA)
Shear stress with (t) and
without (t0) riblets
Drag reduction
S+ dimensionless
riblet spacing
ONERA/CERT (France)
Use of riblets
Wind tunnel
experiments Fly tests
with 3M (Mach
riblets on a Drag reduction in number
1:11 scale of
an Airbus
the range 5 -8% 0.77-0.79)
on an
A-320 for bladelike ribs Airbus A-
with h/s ≥ 0.6 320
100 ≤ h ≤ 200 mm
aircraft
D.W. Bechert, M. Bruse, W. Hage, R. Meyer, Naturwissenschaften, 87 (2000) 157
P.R.Viswanath, Progress in Aerospace Sciences, 38 (2002) 571

7. Application of patterned surfaces to magnetic data storage
Overview of granular versus the patterned media for data storage
Hard
disk drive
Co dots
h = 20 nm
s = 350 nm
Superparamagnetic effect limits the size of a bit
A.O. Adeyeye, N. Singh, J. Phys. D, 41 (2008) 153001
R. Luttge, J. Phys. D, 42 (2009) 123001
E.A. Dobisz, Z.Z. Bandic, T.W. Wu, T. Albrecht, Proc. IEEE, 96 (2008) 1836

8. Application of patterned surfaces to tribology (lubrication)
Stribeck curve Comparison between flat surfaces and textured
surface produced by laser surface texturing
Pin-on-disk friction test
Elastohydrodynamic (steel ball, load 0.16 to
or mixed lubrication 1.6 Pa, speed 0.015 to
(moderate wear) 0.75 ms-1)
Boundary lubrication Full-film lubrication
(sever wear) (negligible wear)
m: friction coefficient
Higher lubricant
film thickness
h = 5.5 mm
s =200 mm Dimples
density
h.v/P: viscosity. speed/pressure 12%
A. Kovalchenko, O. Ajayia, A. Erdemir, G. Fenske, I. Etsion, Tribology International, 38 (2005) 219.

9. Application of patterned surfaces to tribology (lubrication)
Better with dimples with low area coverage (10 to 15%) and h/s < 0.02 to 0.03 for s around 100 mm
Application to piston ring in automotive
h = 9-10 mm
s =100-110 mm
Dynamometer tests on a compression engine have shown
4% lower fuel consumption for textured piston rings
Patterned surfaces leads to an improvement in load capacity, wear resistance, friction coefficient etc..
They can act as oil reservoirs and entrap wear particles (in either lubricated or dry sliding)
They aid in the film formation of lubricant oil
They act as micro-reservoir for lubricant in case of starved lubrication conditions.
Surface patterning can be combined Application in sliding guideways of machine tools
with deposition of lubricant layers Sliding contact elements
Magnetic storage disc surfaces
(MoS2, DLC…) Mechanical face seals
http://www.appropedia.org/Laser_surface_texturing#cite_note-nine-8
I. Etsion, E. Sher, Tribology International, 42 (2009) 542

10. Strategies for creating surface patterns:
top-down, bottom-up, self-assembly
With or without mask (template) ? Serial or parallel?

11. Strategies for creating surface patterns
 Adding material: the patterned
surfaces are created by addition of material to
the desired surface, creating small areas of
relief.
 Removing material: the patterned
surfaces are produced by removal of material
of the surface, creating small depressions.
Metal  Moving material: the change in the
surface structure is attributable to elastic or
patterning
plastic deformation and redistribution of
material from some parts of the surface to
others.
 Self-forming: a disordered system of
components, already on the surface or brought
to the surface, forms an organized pattern as a
consequence of specific, local interactions
among the components themselves.
K.P. Rajurkar, G. Levy, A. Malshe, M.M. Sundaram, J. McGeough, X. Hu, R. Resnick, A. DeSilva, Annals of the
CIRP, 55 (2006) 643
Bruzzone A.A.G., Costa H.L., Lonardo P.M., Lucca D.A., CIRP Annals. Manufacturing Technology 57 (2008) 750

12. Elaboration techniques: photolithography as a standard top-down approach
Substrate covered by a photosensitive material resist
Mask with the pattern to be transferred
Mask generation
Writing with a
rigid stylus
(micromachining,
STM, AFM…
Etched Si with a
gold layer as a mask Writing with a
beam (photons,
electrons, ions)
Writing with an electric field,
or a magnetic field
Gold deposition
through a
polymeric mask
Resolution below 500 nm and around 45
S. Roy, J. Phys. D, 40 (2005) R413 to 25 nm for DUV and EUV lithography
M. Geissler, Y. Xia, Adv. Mater., 16 (2004) 1249
R. Luttge, J. Phys. D, 42 (2009) 123001

13. Advanced serial
mask-less processes

14. Advanced serial mask-less processes
Electro-physical and electro-chemical processes
Electro-physical process (dielectric liquid) Electro-chemical process (conductive liquid: electrolyte)
Micro-electro-discharge machining
Chemical reactions with electron transfer across an interface
Mn+ + n e- ↔ M0
Electrochemical printing (EcP) Mn+ + n e- → M0
Electrochemical dissolution or machining M0 →Mn+ + n e-
Classical ECM use masks for localize etching
S.Roy, J. Phys. D, 40 (2005) R413
K.P. Rajurkar, G. Levy, A. Malshe, M.M. Sundaram, J. McGeough, X. Hu, R. Resnick, A. DeSilva, Annals of the CIRP, 55 (2006) 643
Chakravarty Reddy Alla Chaitanya, Kenichi Takahata, J. Micromech. Microeng., 18 (2008) 105009

15. Advanced serial mask-less processes
Elaboration techniques: other processes
Electrochemical micro-patterning with nano-second voltage pulses Other add-on processes
 Laser induced chemical vapor deposition (LCVD)
 Focused beam (ions or electrons) CVD
 Inkjet printing
 Dip-pen nanolithography
 Electro-hydrodynamic atomization
3M HCl/6M HF electrolyte with a 143 ns pulse
Electrochemical nano-patterning by scanning tunneling microscope (STM)
Ni sheets patterned by W STM tips 0.2M electrolyte with 2 ns pulses
S.Roy, J. Phys. D, 40 (2005) R413
R. Schuster, ChemPhysChem, 8(2007) 34.
K.P. Rajurkar, G. Levy, A. Malshe, M.M. Sundaram, J. McGeough, X. Hu, R. Resnick, A. DeSilva, Annals of the CIRP, 55 (2006) 643
L. Cagnon, V. Kirchner , M. Kock, R. Schuster1, G. Ertl1, W. T. Gmelin, H. Kück, Z. Phys. Chem., 217 (2003) 299
M. Geissler, Y. Xia, Adv. Mater., 16 (2004) 1249

16. Advanced serial mask-less processes (self-assembly?)
Serial mask-less processes : localized PACVD
Gases
Metal
tube
HV DC 
Cu wire
450MHz ~ ~
Capillary
( 100 µm)
~3 mm
‟Tower‟ of hydrocarbon deposited by microjet CVD
„Tower‟ of tungsten oxide deposited by wire spraying (10 s, 8 sccm acetylene, 0.25 mm capillary, 8.4 mm
away from the substrate, 12 W rf) The peak is 2.4 mm
high.
Y. Shimizu et al., Surf. Coat. Technol. 200 (2006) 4251
A. Holländer and L. Abhinandan, Surf. Coat. Technol. 174-175 (2003) 1175

17. Advanced serial mask-less processes (self-assembly?)
Serial mask-less processes : localized PACVD
Using self-assembly
The formation of these self-organized
structures may be explained by the presence of
strong electromagnetic EM fields at the
processing surface.
A. Holländer and L. Abhinandan, Surf. Coat. Technol. 174-175 (2003) 1175
D. Mariotti, V. Svrcek, D.G. Kim, Appl. Phys. Lett., 91 (2007) 18311.

18. Advanced serial mask-less processes (self-assembly?)
Serial mask-less processes : localized PACVD
Atmospheric pressure CVD by localized remote plasma
Ar-10%O2 (275 sccm)
Plasma Power: ~120 W
Hole diameter: 400 µm
Ar-0.17% HMDSO (200+30 sccm)
HMDSO
inner wall
plasma of the cavity
Ar-10%O2

19. Advanced serial mask-less processes (self-assembly?)
Serial mask-less processes : localized PACVD
Atmospheric pressure CVD by localized remote plasma
« nest-like » structure From hexagonal walls
SiOx 200 nm
to 6 µm
Between 0.5 et 5mm
nano-dots
pleated film
19

20. Additive parallel processes
With masks (templates)

21. Advanced parallel processes with mask (directed self-assembly)
Additive processes : nano-patterning using ultra-thin alumina masks (UTAM)
Electrochemical method combined with nano-
patterning techniques
 Highly ordered porous aluminum
oxide layers can be formed in
optimized acid electrolytes
 Pore diameter (10-200 nm) and cell
size (25-420 nm) with an hexagonal
arrangement
 Membranes formed in these nano-
porous anodic aluminum oxide can be
used as templates
Fabrication process of attached UTAMs Fabrication process of connected UTAMs
H. Masuda, K. Fukuda, Science, 268 (1995) 1466 and H. Masuda, M. Satoh, Jpn J. Appl. Phys., 35 (1996), L126
Yong Lei, Weiping Cai, Gerhard Wilde, Progress in Materials Science, 52 (2007) 465

22. Advanced parallel processes with mask (self-assembly)
Additive processes : building blocks
Block copolymers Different types of building blocks Colloidal or nanosphere particles
Honeycomb and
isolated-island Cu
Nanolithography for Co
patterns.
dots array fabrication
Cu patterns with 500
nm interval (electroless
plating in CuSO4/HF)
J.Y. Cheng, C.A. Ross, H. I. Smith, E.L. Thomas, Adv. Mater. 18 (2005) 2505
T.W. Haley, Nanotechnology, 14 (2003) R39
Hidetaka Asoh, Seiji Sakamoto, Sachiko Ono, J. Colloid Interface Science, 316 (2007) 547

23. Removal serial
and parallel processes :
energy beams

24. Removal serial mask-less processes
Energy beam processes : laser direct imaging
Metal drilling process Metal writing process
Multi-scaled zirconia
Piston ring (steel) texturation by direct laser imaging
(ZrO2) coating on a
Ti-6Al-4V alloy
substrate. ZrO2
powder was mixed
with a water-based
organic solvent and
was sprayed onto Ti-
6Al-4V substrates and
fused with a pulsed
Nd:YAG laser
operated at 10 kHz
and at a constant
power of 25 W.
S. Roy, J. Phys. D, 40 (2005) R413
P. G. Engleman, A. Kurella, A. Samant, C. A. Blue, N. B. Dahotre, JOM (2005) 46
I. Etsion, E. Sher, Tribology International, 42 (2009) 542

25. Removal serial mask-less processes
Energy beam processes : laser shock peening
Creation of micro dent
(dimples) arrays on a
titanium alloy by laser
shock peening
0,5 mm
Y.B. Guo, R. Caslaru, Fabrication and characterization of micro dent arrays produced by laser shock peening on titanium Ti–6Al–4V
surfaces , Journal of Materials Processing Technology 211 (2011) 729–736

26. Removal and moving serial mask-less processes
Energy beam processes : laser sub-surface patterning (3D)
Nd:YAG laser pulse, peak power density of 1 MW/cm2
Stainless
steel
substrate
Potential applications : security marking, micro-
devices based on porous materials : micro-heater,
micro-insulator and micro-sensor.
Z. L. Li, T. Liu, C. C. Khin, A. C. Tan, L. E. Khoong, H. Y. Zheng, W. Zhou, Direct patterning in sub-surface of stainless steel using laser
pulses, OPTICS EXPRESS 18 (2010) 15990.

27. Removal and moving parallel mask-less processes
Energy beam processes : laser interference metallurgy
 Laser interferences are obtained from the interaction of two or
three laser beams
 The interference pattern covers the size corresponding to the
beam diameter
 The obtained textured surfaces are the negative of the
interference pattern (molten of metal at the interference maxima)
 No mask and no etching
M. D‟Alessandria, A. Lassagni, F. Mücklich, Applied Surface Science, 255 (2008) 3210
M. Duarte, A. Lassagni, R. Giovanelli, J.Narciso, E. Louis, F. Mücklich,, Advanced Engineering Materials, 10 (2008) 554

28. Removal and moving parallel mask-less processes
Energy beam processes : laser interference metallurgy
Line-like periodic pattern
Two laser beams
Cross-like structures, two laser beams → line-like structures
Dot-like periodic pattern
Sample rotation 90°, two laser beams → cross-like structures
Three laser beams
M. D‟Alessandria, A. Lassagni, F. Mücklich, Applied Surface Science, 255 (2008) 3210
M. Duarte, A. Lassagni, R. Giovanelli, J.Narciso, E. Louis, F. Mücklich,, Advanced Engineering Materials, 10 (2008) 554

29. Removal parallel mask-less processes
Energy beam processes : Ion beam
µm
Rapid neutrals 1.5

1.4
1.3
Ar+ 1.2
or 2
 1.1
1
0.9
High ion energy (1 keV)
N 0.8
0.7
0.6
 Sputtering
0.5
0.4
Negative transfer to the
0.3
0.2
substrate
0.1
0
« Patterning of magnetic structures on austenitic stainless steel by local ion beam nitriding »
SEM
MFM
Magneto-optic Kerr
E. Menendez, A. Martinavicius, M.O. Liedke, G. Abrasonis, J. Fassbender, J. effect (MOKE)
Sommerlatte, K. Nielsch, S. Surinach, M.D. Baro, J. Nogue´s, J. Sort, Acta magnetometry
Materialia 56 (2008) 4570.

30. Moving parallel processes :
Patterning by nitriding
Toward
stress patterning
engineering

31. Moving parallel processes with mask
Surface Patterning by plasma assisted nitriding at low ion energy
Dilatational or compositional strain (ec) Nitrided layer
Nitrided layer (with nitrogen)
virtually removed from the substrate
(without stress and nitrogen)
Fcc lattice
Substrate Substrate
Nitrogen
introduction
Nitrided layer (with nitrogen)
virtually removed from the substrate
Dx
s e
Internal stress necessary
Substrate action on the layer to return film
to substrate dimension
Stress and anisotropic strain
Dilatational or Elastic strain (ee) Internal stress (s)
compositional strain (ec)
Without mask
With a mask
N N
Initial interface
Elastic and/or plastic deformation induced by nitrogen incorporation
T. Czerwiec, G. Marcos, T. Thiriet, Y. Guo, T. Belmonte, to be published in IOP Conference Series: Materials Science and Engineering

32. Moving parallel processes with mask
Surface Patterning by plasma assisted nitriding at low ion energy
µm
0.75
0.7
0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
50 mm 0.05
0
50 mm

33. Principle of surface patterning by plasma assisted nitriding
Remote plasma assisted nitriding
microwave power supply
Gauge Gas
Copper TEM Grids
inlet
N N
N N
N
N
Antenna N N
N
360 mm
Grid: mesh side
Substrate of 200 * 200 µm2
holder
450 mm
Initial interface
(AISI 316L)
Micropatterning!
With a mask
Primary and turbomolecular pump
Elastic and or plastic deformation induced by nitrogen incorporation

34. Exemple of surface patterning by plasma assisted nitriding
 Plasma: 60% N2 + 40% H2  Pressure: 5.75 Pa
 Substrate temperature: ~ 400 C  Process duration: 1h
10 µm
Cross section of a step
Extraction of profiles :
Surface profilometry µm
µm
1
0.8
0.6
0.6
0.4
20000 0.55 0.2
0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 µm
0.5
12000 Grids 0.45
Profondeur maximale
Valeurs moyennes sur 11 créneaux.
High step mean : ~240 nm 0.333 µm
Profondeur moyenne 0.23 µm
No grids 16000 Largeur 49 µm
0.4
Intensity [A.U.]
µm
10000 0.35
1
0.8
12000 0.3 0.6
8000 0.25
0.4
0.2
0.2 0
8000 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 µm
6000 0.15 1 2 3 4 5 6 7
Profondeur maximale 0.314 µm 0.257 µm 0.274 µm 0.209 µm 0.303 µm 0.266 µm 0.361 µm
0.1
Profondeur moyenne
Largeur
High step mean : ~275 nm
0.266 µm
250 µm
0.255 µm
27.8 µm
0.273 µm
27.8 µm
0.207 µm
27.8 µm
0.289 µm
27.8 µm
0.259 µm
27.8 µm
0.313 µm
250 µm
4000 4000 0.05
46 48 50 52 54 56 58 60 62 64 0
2
X-ray diffraction patterns
2 µm
30 µm
Cross section of one dot

35. Silicon oxide layer patterned: procedure (coll LPN)
UV photolithography
AISI 316L PECVD Spin coating
Polished like-mirror N2O/SiH4 AZ5214 photoresist
CCP RIE CCP RIE
SF6 /CHF3 O2

36. Patterned mask: features and characteristics
AFM picture (height mode)
µm
1.5
1.4
1.3
1.2
1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
µm
1
SEM picture 0.8 500 nm
Cylindrical dots with diameters from 3 to 15 µm 0.6
0.4
0.2
0
0 2.5 5 7.5 10 12.5 15 17.5 20 22.5 25 27.5 30 32.5 35 37.5 40 42.5 45 47.5 µm

37. Patterned mask and expanded austenite
Dots after nitriding in MDECR: 4 h. at 400 °C (80% N2 – 20 H2), bias 0 V
µm Longueur = 50.0 µm Pt = 0.983 µm Echelle = 1.00 µm
µm
0 10 20 30 40 µm 1
0
1.4 0.8
500 nm
5 1.3
500 nm
0.6
10 1.2
1.1 0.4
15
1 0.2
20 0.9
0
0.8 0 2.5 5 7.5 10 12.5 15 17.5 20 22.5 25 27.5 30 32.5 35 37.5 40 42.5 45 47.5 µm
25
0.7 µm
30 0.6
0.5 1.4
35
0.4 1.3
40
0.3 1.2
45 0.2
1.1
0.1
1
0
µm 0.9
0.8
0.7
µm Longueur = 50.0 µm Pt = 0.843 µm Echelle = 1.00 µm 0.6
1
0.5
0.8 500 nm 550 nm 0.4
0.6 0.3
0.4 0.2
0.1
0.2
AFM picture 0
0
0 2.5 5 7.5 10 12.5 15 17.5 20 22.5 25 27.5 30 32.5 35 37.5 40 42.5 45 47.5 µm
In such conditions, the nitrided layer is 5.6 to 6 µm thick and we are
waiting for a 500 nm to 600 nm expansion (same height for SiO2 dots What happens?
and substrate)

38. Patterned mask and expanded austenite
Dots after nitriding in MDECR: 4 h. at 400 °C (80% N2 – 20 H2), bias 0 V
Dot with a diameter of 7 µm Dot with a diameter of 15 µm
No strongly distortion A toroidal-shell shape!

39. Patterned mask and expanded austenite
Dots after nitriding in MDECR: 4 h. at 400 °C (80% N2 – 20 H2), bias 0 V
Dots
1000 Nitrided parts Nitrided parts
900
800
700
600
500
400
300 200 nm
to
200 750 nm
100
0
-100 500 nm
-200
300 nm
-300 to
-400 900 nm
-500
0 10 20 30 40 50 60 70 80 90 100 110
 Expansion of the nitrided layer (as expected)
 Vertical movement of the SiO2 dots (totally for the smaller ones; at edges for the bigger)
 What is the role of expanded austenite ?

40. Patterned mask and expanded austenite
SEM cross-sections after 2 nitriding processes in MDECR: 4 h. at 400 °C (80% N2 – 20 H2),
bias 0 V
Dot
Expanded austenite
Austenite
 For the small dots: nitrogen completely diffuses under the mask
 For the big dots: only a diffusion under mask edges

41. Progressive mask distortion
Dots with 800 nm of thick. Same shapes.

42. Progressive mask distortion
Different nitriding steps at 400 °C (80% N2 – 20 H2)
1400
4h
1200 6h
1000
8h
10h
800
600
400
nm
200
0
-200
-400
-600
-800
4 4 4 4 5
0,0 2,0x10 4,0x10 6,0x10 8,0x10 1,0x10
nm

43. After 10h nitriding
4h
6h
10h

44. CONCLUSION
Surface patterning was introduced
Some applications of surface patterning (drag reduction, lubrication, self-cleaning and
magnetic data storage) were presented to show the importance of shape and aspect ratio
in surface patterning
Based on an tentative classification of strategies for surface patterning, different
elaboration techniques were presented (photolithography, advanced serial mask-less
processes, advanced parallel processes with masks, advanced parallel mask-less
processes
Finally, a strain driven patterning method developed by us was presented: austenitic
stainless steel patterning by plasma assisted diffusion treatments:

45. ACKNOWLEDGMENTS
IJL “ESPRIT” team