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

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1 Thin Films Technology 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 4

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 13

14 RF Plasma glow discharge 14

15 RF Plasma glow discharge self bias 15 M. Ohring

16 Self bias at electrodes 4 Sivu 16

17 Energetic ion surface interactions 17

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 18

19 Average mean free path (distance between collission) in nitrogen residual gas <λ> Ultra Good High High Intermediate 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 21

22 Energetic ion and surface interactions collision cascade s thermal spike s Fast diffusion fast cooling relaxation 22 Jari Koskinen, Kts. Aalto simulaatio University 2016

23 Sputtering yield 23

24 Sputter yield and sublimation energy 24

25 Sputter yield angle dependence and energy distribution 25

26 Sputter yield angle dependence and energy distribution 26

27 Sputter yield angle dependence and energy distribution 27

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

neutrals grow the film https:// www.youtube.co m/watch?

29 PVD (Physical Vapour Deposition) Material from solid or gas Plasma Energetic ions hit surface Ions and neutrals grow the film m/watch? v=lre5eqx9ofo

30 PVD growth process Ion energy E i ev Surface temperature -190 C C (normally < 200 C) incidence angle Ion density Gas pressure Substrate surface 30 - 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 William Andrew Publishing Sivu 31

32 Coating structure and plasma parameters slow hot fast cold 3/8/16 32

33 Modified Thorton diagram A. Anders, Thin Solid Films 518 (2010) Sivu 33

34 Subplantation Sivu 34

35 Subplantation Sivu 35 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.

36 Subplantation and experiments -Carbon Sivu 36

37 Subplantation Sivu 37

38 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

39 Stress Control Gas pressure /temperature Tensile stress due to collapsing of voids Higher temperature annealing of structure low stress Compressive stress subplantation 3/8/16 39

40 Compressive stress f FD = conc. of Frenkel defects f Ar = conc. of argon ΔΩ FD = volume change due to Frenkel defects ΔΩ Ar = volume change due to argon entrapped 3/8/16 40

41 Tensile stress 3/8/16 41

42 Ion beam nano roughening Enhanced adhesion 42

43 Contents Plasma Ion surface interactions Film growth mechanisms Different PVD methods Commercial PVD coatings Scale up 43

44 PVD methods PVD Sputtering 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

45 Ion beam sputtering Kaufman watch?v=ibcr- B258J8&NR=1

46 Surface coating methods more details

47 PVD methods

48 Electron beam evaporation Tyhjiöhöyrystys

49 Ion plating

50 Sputtering 50

51 Magnetron-sputtering Jari Koskinen, Lähde: Aalto Angstrom University Sciences, 2016 Inc.

52 Sputtering Principles of Sputtering animation Sputtering process, commercial Sputtering on Si wafers 52

53 Unballaced magnetron sputtering Magnetron-laitteisto

54 Closed field magnetron sputtering Magnetron-laitteisto

55 PVD-pinnoitin

56 Pulsed Plasma Diffusion

61 HIPIMS denser films

62 Reactive sputtering

63 Reactive sputtering

64 Reactive sputtering

65 Reactive sputtering

66 Reactive sputtering

67 Reactive sputtering

68 Arc discharge deposition Arc discharge video

69 Arc disharge cathode spot

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

70 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/m 2 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 supplemental/prb/v81/ i18/e184109

71 Filtered arc

72 Three types of bonding of carbon atoms sp 3 - Four string σ bonds in tetraedric directions sp 2 - Two σ bonds in plane - One weekπ bond ( non localised electron- conductivity) sp 1 - Two σ linear bonds - Two week π bonds (non localised electrons- conductivity)

73 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

74 Carbon Carbon has 3 hybridised bondings sp 3, sp 2, sp 1 sp 3 bondings form four equal carbon-carbon bonds producing tetrahedral structure of diamond Graphite has three sp 2 hybrid orbitals in plane 74

75 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 sp 3 / sp 2 structure with different sp 3 and sp 2 proportions depending on deposition technique and parameters 75

76 76

77 Properties of ta-c as function of E i Sivu 77

78 Composition, effect to properties Composition as a function of deposition parameters, nitrogen composition (partial pressure of N2) Sivu 78

Pulsed laser deposition PLD high ionization evaporation of any material also in reactive gas stoichimetry of target to the surbstrate good control

79 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

80 E i as a function of laser pulse energy Sivu 80

81 Multilayer coatings TiAlN-multilayer

82 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

83 Contents Plasma Ion surface interactions Film growth mechanisms Different PVD methods Commercial PVD coatings Scale up 83

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

85 DUPLEX- coating plasmanitrading + PVD-coating

86 Contents Plasma Ion surface interactions Film growth mechanisms Different PVD methods Commercial PVD coatings Scale up 86

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

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

Samankaltaiset tiedostot

Lecture 4: Physical Vapor Deposition PVD

Thin Films Technology Lecture 4: Physical Vapor Deposition PVD Jari Koskinen Aalto University Page 1 Contents Plasma Ion surface interactions Film growth mechanisms Different PVD methods Commercial PVD