1. Thin Films Technology 2014 Lecture 3: Physical Vapor Deposition PVD
Jari Koskinen
Aalto University
Page 1

2. Contents Plasma Ion surface interactions Film growth mechanisms
Different PVD methods
Commercial PVD coatings
Scale up 2

3. Contents Plasma Ion surface interactions Film growth mechanisms
Different PVD methods
Commercial PVD coatings
Scale up 3

4. PVD Plasma Plasma Colliding electrons ionise atoms
Ions and electrons accelerate in electric field
collisions excite atoms
de-excitation creates photons – visible light

5. Glow discharge

6. Glow discharge

7. Glow discharge

8. Glow discharge

9. Glow discharge

10. Glow discharge

11. Glow discharge

12. Glow discharge

13. DC Plasma glow discharge and arc

14. RF Plasma glow discharge

15. RF Plasma glow discharge self bias
M. Ohring

16. Self bias at electrodes4
Sivu 16

17. Energetic ion surface interactions

18. PVD coating process (High) vacuum long mean free path of ions
high ion energy
cleaning of surface
desorption of gas
sputtering of surface
removal of
oils
water
oxides

19. Total pressure of residual gasses
Average mean free path (distance between collission) in nitrogen residual gas
<λ>
Ultra
Good High
High
Inter-mediate
Rough
Total pressure of residual gasses

20. Contents Plasma Ion surface interactions Film growth mechanisms
Different PVD methods
Commercial PVD coatings
Scale up 20

21. Source materials Coating material from solid target or gas

22. Energetic ion and surface interactions
collision cascade – s
thermal spike – s
Fast diffusion
fast cooling
relaxation
Kts. simulaatio

23. Sputter yield angle dependence and energy distribution
Sputter yield on different directions of 60° Kr+ ions on W Θ
Energy distribution of target atoms after 900 eV Ar+ bombardment

24. Sputter yield and sublimation energy

25. Sputter yield angle and energy dependence

26. Sputter yield angle and energy dependence for different metals and ions

27. Sputtering yield
Argon

28. Contents Plasma Ion surface interactions Film growth mechanisms
Different PVD methods
Commercial PVD coatings
Scale up 28

29. PVD (Physical Vapour Deposition)
Material from solid or gas
Plasma
Energetic ions hit surface
Ions and neutrals grow the film

30. PVD growth process Ion energy Ei 10 - 1000 eV
Surface temperature -190°C - 500°C (normally < 200°C)
incidence angle
Ion density
Gas pressure
Substrate surface
Chemistry
Impurities
Topography

31. Competition of growing crystals
Handbook of Deposition Technologies for Films and Coatings - Science, Applications and Technology (3rd Edition)
Edited by: Martin, Peter M. © 2010 William Andrew Publishing
Sivu 31

32. Coating structure and plasma parameters
hot
slow
temperature
ions
cold
fast
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33. Modified Thorton diagram
A. Anders, Thin Solid Films 518 (2010) 4087–4090
Sivu 33

34. Subplantation
Sivu 34

35. Subplantation
Schematic diagram of densification by subplantation. A fraction of the incident ions penetrate the film and densify it, the remainder end up on the surface to give thickness growth.
Sivu 35

36. Subplantation and experiments -Carbon
Sivu 36

37. evolution of roughness
Fig. 2. Schematic of roughness variation with film thickness in a general case. At first, the films consist of a series of islands where the new phase has nucleated, and the roughness increases quickly. Then the roughness peaks and decreases as the islands coalesce to form a closed, continuous film. The third stage consists of a constant roughness for epitaxial films. Finally, the roughness increases gradually above a ‘roughening transition’.
The smoothness of tetrahedral amorphous carbon
Diamond and Related Materials, Volume 14, Issues 3-7, March-July 2005, Pages
C. Casiraghi, A.C. Ferrari, J. Robertson

38. Stress Control Gas pressure /temperature
Tensile stress due to collapsing of voids
Higher temperature annealing of structure – low stress
Compressive stress – subplantation
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39. Compressive stress fFD = conc. of Frenkel defects fAr = conc. of argon
ΔΩFD = volume change due to Frenkel defects
ΔΩAr = volume change due to argon entrapped
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40. Tensile stress
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41. Ion beam nano roughening
Enhanced adhesion

42. Contents Plasma Ion surface interactions Film growth mechanisms
Different PVD methods
Commercial PVD coatings
Scale up 42

43. PVD methods PVD Sputtering Diode Magnetron Ion beam Triode Resistive
Evaporation
Diode
Magnetron
Ion beam
Triode
Resistive
Arc
Inductive
e-beam
Radio freq.
Pulsed cathode
DC sputtering
Pulsed DC
Balanced
Unbalanced
Balanced
Unbalanced
Filtered
Non-filtered
Steered
Random

44. Ion beam sputtering Kaufman

45. Surface coating methods – more details

46. PVD methods

47. Electron beam evaporation
Tyhjiöhöyrystys

48. Ionipinnoitus

49. Sputtering

50. Magnetron-sputtering
Lähde: Angstrom Sciences, Inc.

51. Principles of Sputtering animation Sputtering process in large area
Sputtering process in large area
Sputtering on Si wafers

52. Magnetron-laitteisto
Unballaced magnetron sputtering
Magnetron-laitteisto

53. Magnetron-laitteisto
Closed field magnetron sputtering
Magnetron-laitteisto

54. PVD-pinnoitin

55. “Pulsed Plasma Diffusion”

60. HIPIMS denser films

61. Reactive sputtering

62. Reactive sputtering

63. Reactive sputtering

64. Reactive sputtering

65. Reactive sputtering

66. Reactive sputtering

67. Arc discharge deposition
Arc discharge video

68. Arc disharge – cathode spot

69. Arc discharge process arc current concentrated into filaments – arcs
intense electron emission
intense ion emission due to electron current ( atoms/electrons – 1/100)
ionization of atoms – formation of plasma
flow of ions to cathode – intense sputtering of atoms
A/m2
overlapping thermal spikes
materials is melted and sublimated in cathode spots
cathode spots move randomly or could be steered by using magnets
electons ionize vapor and create more electrons – increase of current
ions accelerate
due to potential difference in plasma
due to multiple collisions with fast electrons
macro particles (up to 10 µm diam.I are formed
Timko, Nordlund simulations

70. Filtered arc

71. Three types of bonding of carbon atoms
sp3
Four string σ bonds in tetraedric directions
sp2
Two σ bonds in plane
One weekπ bond ( non localised electron- conductivity)
sp1
Two σ linear bonds
Two week π bonds (non localised electrons- conductivity)

72. Carbon structures- allotropies
a diamond
b graphite
c lonsdalite (hex diam.)
d fullerene 60C
e fullerene 540C
f fullerene 70C
g amorphous carbon
h carbon nano tube

73. Carbon Carbon has 3 hybridised bondings sp3, sp2, sp1
sp3 bondings form four equal carbon-carbon bonds producing tetrahedral structure of diamond
Graphite has three sp2 hybrid orbitals in plane

74. Diamond-like carbon (DLC)
Various forms of C-H alloys presented in a ternary phase diagram
DLC is a metastable form of amorphous carbon
DLC films have a mixed sp3/ sp2 structure with different sp3 and sp2 proportions depending on deposition technique and parameters 74

76. Properties of ta-C as function of Ei
Sivu 76

77. Composition, effect to properties
Composition as a function of deposition parameters, nitrogen composition (partial pressure of N2)
Sivu 77

78. Pulsed laser deposition PLD
high ionization
evaporation of any material also in reactive gas
stoichimetry of target to the surbstrate
good control of depostion rate
expensive lasers
slow depostion rate
not yet in industrial level

79. Ei as a function of laser pulse energy
Sivu 79

80. Multilayer coatings
TiAlN-multilayer

81. Ultrahard nanocomposte coatings - single layer
At least two immiscible materials
nano-crystalline and amorphous
Crystal growth limited by segregation of other phase in grain boundary
Smaller crystal size -> higher hardness
Typical:
nc-MeN/ nitride
nc-MeN/metal

82. Contents Plasma Ion surface interactions Film growth mechanisms
Different PVD methods
Commercial PVD coatings
Scale up 82

83. PVD coatings - commercial
TiAlN-multilayer
Platit coatings
Coating guide
Barlzers coatings
Hauzer Techno Coating

84. DUPLEX- coating plasmanitrading + PVD-coating

85. Contents Plasma Ion surface interactions Film growth mechanisms
Different PVD methods
Commercial PVD coatings
Scale up 85

86. Large volumes, up scaling Hear reflecting, self cleaning, photo voltaic
/www.

87. New emerging PVD methods
vacuum polymer deposition (VPD)
high-power pulsed magnetron sputtering (HPPMS or HIPIMS)
filtered cathodic arc deposition
glancing angle deposition (GLAD).