1. IEAE CRP F1.20.16. Ion Beam Modification of Insulators
3rd RCM, Chiang Mai, Thailand, Dec 2007
Ion Beam Modification of Sputtered Metal-Nitride Thin Films -
a Study of the Induced Microstructural Changes
VINČA Institute of Nuclear Sciences, Belgrade, Serbia
- project started in May
researchers:
Momir Milosavljević (Dr)
Davor Peruško (PhD student)
Maja Popović (MSc student)
Mirjana Novaković (MSc student)
other co-workers in the group:
Velimir Milinović (Dr – Goett)
Bane Timotijević (Dr-Surrey)

2. Investigations on this Project - started in May 2006 -
Ion beam modification of Cr-N and TiN thin films on Si reactively sputtered, ~ 250 nm, implanted with 120 keV Ar
Deposition of TiN coatings on pre-implanted stainless steel, 40 KeV nitrogen, 1.3 mm TiN coatings subsequently deposited
Ion beam modification of Al/Ti and AlN/TiN multilayers on Si, with 200 keV Ar or N2 ions

3. VINČA Institute of
Nuclear Sciences

4. Lab for Atomic Physics - research facilities used for this Project -

5. Balzers SPUTTRON II thin film deposition system d. c. and r. f
Balzers SPUTTRON II thin film deposition system d.c. and r.f. sputtering, four target, rective deposition

6. Ion implanter – HV terminal 500 kV, Nielsen or RF ion sources for gases and solids, beam current mA, scanned target area up to 5 cm diameter

7. 2MV Van de Graaff ion accelerator RBS – beam line in preparation

9. TEM – Philips EM400T 120 keV

10. Multimode NanoScope 3D, STM, AFM, MFM…
VEECO NANOINDENTER

11. Results to be presented - from the start of this project -
Ion beam modification of Cr-N and TiN thin films on Si reactively sputtered, ~ 250 nm, RT or 150oC, different N2 pressure, implanted with argon at 120 keV, to 1x1015 and 1x1016 ions/cm2
Deposition of TiN coatings on pre-implanted stainless steel – AISI C1045 steel substrates implanted with 40 KeV nitrogen, to 5x1016 – 5x1017 ions/cm2, 1.3 mm TiN coatings subsequently deposited
Ion beam modification of Al/Ti and AlN/TiN multilayers on Si, with 200 keV Ar or N2 ions, to 5x1016 – 2x1017 /cm2

12. Ion beam modification of Cr-N films on Si
RBS spectra of as-deposited films as a function of N2 pressure (Goettingen)

13. RBS analysis of as-deposited and implanted Cr-N/SiAr

14. XRD analysis => for PN2 = 2 and 3.5x10-4 mbar, Cr2N is formed
for PN2 = 5x10-4 mbar, CrN phase forms
as-deposited
1x1015 Ar/cm2
1x1016 Ar/cm2
analysis of samples deposited at 150oC, PN2 = 5x10-4 mbar,
implanted to 1x1015 and 1x1016 Ar/cm2

15. X-TEM analysis of Cr-N deposited at 150oC, PN2 = 5x10-4 mbar
as-deposited
1x1015 Ar/cm2
1x1016 Ar/cm2

16. Sheet resistance measurements of Cr-N films
Samples deposited at 150oC RT
1500C

17. Ion beam modification of TiN films on Si
RBS analysis of as-deposited films (Goettingen)

18. TEM analysis of TiN deposited at RT
implanted
1x1016Ar/cm2
as-deposited

19. XRD analysis of TiN
deposited at 150o C
Sheet resistance measurements

20. Conclusions for Cr-N and TiN films
Ion irradiation induces local rearrangements in the layer structure, the polycrystalline structure being retained
Original columns become disconnected, nano-particles of the same phase are formed
The resulting structures contain more crystalline defects (point defects in larger grains, nano-particles) which induce higher electrical resistivity
No measurable changes in surface roughness were found
Sheet resistance measurements can be useful to interpret the results of structural analysis

21. Nitrogen pre-implantation of steel substrates
shallow implants at 40 keV
unimplanted
standard XRD of TiN coating
2x1017
5x1017
GXRD of implanted substrate

22. Microhardness measurements

23. Conclusions for substrate pre-implantation
Low energy, high fluence nitrogen implants induce formation of Fe-nitrides in the near surface region of the substrates
Substrate pre-implantation influences preferred orientation of the grown TiN crystal grains
The layers deposited on pre-implanted substrate exhibit a higher microhardness
Total increase of the substrate microhardness after nitrogen pre-implantation and TiN deposition is up to more than eight times

24. Ion beam modification of multilayered thin film structures
nano-scaled multilayered structures TiN/Ti, TiN/AlN, etc, offer numerous advantages over single layer components
higher performance at much lower thickness, higher strength and hardness due to multiple interfaces, can form super lattices, graded structures, etc
ion beams can be useful for preparation and modification in the processes such as IBAD, plasma immersion, or ion implantation – homogenization, more dense and less porous structures

25. High fluence nitrogen implantation in Al/Ti multilayers on Si
10 alternative Al and Ti layers, deposited by ion sputtering in a single vacuum run, total thickness ~ 270 nm
200 keV N2+ ions, to 1x1017 and 2x1017 at/cm2, Rp ~ mid depth
aim – to study interface mixing and formation of metal-nitrides
N2+ ions
Al/Ti
multilayers Si

26. Experimental work
Thin film deposition, ion implantation and TEM analysis – Vinča Inst
RBS analysis, 1.5 MeV He+ beam, two detectors, 148.2o scatt in ibm and172.8o in cornel geometry, Data Furnace – University of Surrey
AES primary electron energy 3 keV, two Ar ion guns for sputtering off 5x5 mm2 of the sample area
– Jožef Stefan Inst, Ljubljana

27. RBS experimental spectra (Surrey)

28. as-deposited sample

29. sample implanted to 2x1017 N/cm2

30. 1x1017 N/cm2
RBS depth profiles
as deposited
2x1017 N/cm2

31. 1x1017 N/cm2
AES depth profiles
JS Institute
as deposited
2x1017 N/cm2

32. x-TEM analysis
as-deposited samples
implanted to 2x1017 N/cm2

33. Conclusions for high fluence N implantation in Al/Ti multilayers
Nitrogen implantation can be used to form (Al,Ti)N multilayered structures from Al/Ti layers
The layers are intermixed => tightly bound at the interfaces, have graded composition, but the multilayered structure is preserved
Ion irradiation induces larger grains and formation of lamellar grains stretching over a number of layers
XPS studies are in progress to analyze chemical composition
Microhardness results – shown below

34. Comparative analysis of ion irradiation stability of Al/Ti versus AlN/TiN multilayers
Similar structures as described before, total thickness ~ 270 nm irradiated with 200 keV Ar+, from 5x1015 to 4x1016 ions/cm2
deposition of AlN/TiN done by reactive sputtering

35. RBS spectra of Al/Ti structures on Si (Surrey) as a function of Ar+ fluence

36. RBS analysis of Al/Ti sample irradiated with 200 keV Ar+, to 1x1016 ions/cm2

37. RBS analysis of AlN/TiN structures on Si (Surrey)

38. as-deposited sample

39. Titanium point by point depth profiles
AlN/TiN structure
Al/Ti structure

40. Interface mixing in Al/Ti system

41. TEM analysis of Al/Ti multilayers
implanted to 2x1016 ions/cm2
as-deposited

42. TEM analysis of AlN/TiN multilayers
as-deposited
implanted to 4x1016 ions/cm2
implanted to 2x1016 ions/cm2

43. Other TEM images of AlN/TiN multilayers
as-deposited
implanted to 4x1016 ions/cm2
implanted to 2x1016 ions/cm2

44. Ion Beam Mixing models fo diffusio profiles:
k = Δσ2 /Φ
ξ = [4mM/(mM)2]1/2 – kinematic factor
m, M – masses of the ion and target atom
Γo = – dimensionless constant
N – atomic density of the target
Rd  1nm – minimum separation distance for the production of a stable Frenkel pair
FD – deposited energy per ion per unit length
- Ballistic mixing:
- Global spike mixing:
k1=0.35 nm; k2=27.4 – constants
ΔHr – reaction enthalpy
ΔHcoh – cohesive energy of
the reaction products
- Local spike mixing:
k1’ and k2’ – constants
Zt – atomic number of the target

45. Microhardness measurements indentation depth ~ 200 nm
AlN/TiN and Al/Ti implanted
with Ar
Al/Ti Implanted with N

46. A. Misra, M. J. Demkowicz, X. Zhang, and R. G
A.Misra, M.J.Demkowicz, X.Zhang, and R.G.Hoagland, JOM, Sep 2007, 62-65
T. Höchbauer, A. Misra,a K. Hattar, and R. G. Hoagland, JAP, 98, (2005)
Los Alamos National Laboratory
Cu/Nb irradiated
with high fluence He+,
( keV helium, 1 × 10^17/cm^2)

47. Effects of swift heavy ion irradiation and thermal annealing on nearly
immiscible W/Ni multilayer structure
Sharmistha Bagchi , Satish Potdar, F. Singh, N. P. Lallaa (India)
JAP, 102, (2007)
W/Ni with 120 MeV Au9+,
as-deposited
and 5x1013 ions/cm 2

48. Conclusions for ion irradiation stability of Al/Ti versus AlN/TiN multilayers
Both systems preserve multilayered structure
Al and Ti are chemically reactive => the layers become progressively intermixed with increasing the ion fluence, formation of Al-Ti phases is detected; ion irradiation induces larger grains and formation of lamellar columns stretching over a number of layers
In AlN/TiN system the components are immiscible => no detectable intermixing is observed, it is lower compared even to ballistic mixing, only a small increase of the mean grain size in individual layers can be seen
Non-mixing, or de-mixing published so far only for immiscible metal layers Cu/Nb with He+, W/Ni with Au9+,

49. Presentations and publications:
two at IBMM-2006, five at YUKOMAT 2006 and 2007, two at ECAART , one at IBA 2007
three journal papers and three accepted for NIM B
two papers submitted
2 Msci and 1 PhD thesis
Joint UniS – Vinča Workshop on Ion Beam Applications for Materials
Modification and Analysis – held in Vinča, Belgrade, 2nd September 2006, with 6 lecturers from Surrey, 2 from Germany, 1 from Hungary and 3 from Serbia, and a wide audience of local potential users
Further work will be on investigations of multilayered structures
prepared AlN/Al, TiN/Ti and Ta/Ti for further studies