FCSEL

Plasma enhanced chemical vapor deposition: From laboratory to large scale production
Ludvik Martinu and Jolanta E. Klemberg-Sapieha
Functional Coating and Surface Engineering Laboratory FCSEL-LaRFIS Engineering Physics Department Thin Film Research Center - GCM Ecole Polytechnique, Montreal, Quebec, Canada

5th Mikkeli International Industrial Coating Seminar MIICS-5, Mikkeli, March 17, 2010

Acknowledgements
PhD students and post-docs this work: A. Amassian M. Azzi E. Bousser S. Guruvenket S. Hassani P. Jedrzejowski S. Larouche R. Vernhes Research associate: O. Zabieda Recent publication: L. Martinu, O. Zabieda, J.E. Klemberg-Sapieha: Plasma-Enhanced Chemical Vapor Deposition of Functional Coatings, in the Handbook on Thin Film Deposition Technologies, P.M. Martin, ed., Elsevier, Amsterdam, 2009, pp. 394-467.

Concept of Functional Coatings

Automobile Industry Photovoltaics

Aerospace /Defense

Telecom

Biotechnology

Functional Coating and Surface Engineering

VLSI

Optical Films Manufacturing

MEMS

Overview

1.

Plasma-surface interactions and plasma systems Film growth in the energetic plasma environment

2.

Hard protective PECVD coatings From tribological coatings for aerospace and automobile to biomedical applications

3.

Optical and multifuntional coatings From optical filters to smart windows, displays and solar cells

4.

Conclusions and perspectives

Plasma-surface interactions
1. Ion bombardment effects: Energy per deposited particle Ep ~ Ei . i / n Ei < 1 keV, IEDF, i ion flux, n flux of condensing particles, SZM Control of Ei and i / n :

- surface biasing mA - unbalanced magnetrons - gas phase ionization (plasma assistance) - ionization / biasing (PA-EBE, ECR, PECVD, MW/RF) - plasma pulsing (PMS, HIPIMS, p-PECVD)

N = rD

N A

2. UV and VUV radiation

- strong radiation below 200 nm - crosslinking, surface volatilization

B.A. Movchan, A.V. Demchishin, 1969 J.A. Thornton, 1974 R. Messier et al, 1984 P.J. Kelly, R.D. Arnell, 1998 J. Musil, 1992 A. Anders, 2009

Ion bombardment in deposition processes

Ion bombardment is essential to the optical and functional coatings industry
PVD techniques Magnetron sputtering (MS), incl. HIPIMS Ion-assisted deposition (IAD) Plasma-assisted deposition (e.g. ion plating)
PVD ({) SiO2 () dielectrics () metals () semiconductors PECVD (A) Si3N4:H (B) SiO2:H (C) a-C:H (D) TiO2

i /n

Plasma-CVD techniques PECVD, pulsed plasma fp, DC PICVD pulse-bias PECVD

Dense films with smooth surfaces

Ion/particle arrival rate ratio

10

F
0

I-1 I-2 P

10

D P

No film
SiO2 Ta2O5 TiO2

10

-1

10

-2

i : ion flux n deposition rate

10

-3

I-1 - IBAD-1 I-2 - IBAD-2 M -MS D -DIBS P -PECVD F -FCAD

100 10
1
eV/particle
2 3 4 5

No effect
10
-4

10

10

10

10

10

10

J.M.E. Harper et al., 1989 Modified after: Martinu and Poitras JVST A18 (2000) 2619

Ion energy Ei [eV]

J.E. Klemberg-Sapieha et al., Appl. Opt., 2004

Plasma deposition processes and systems

Externalparameters Internalparameters Filmproperties

Reactor geometry

Pumping speedand gasflow Excitation powerand frequency Substratecooling orheating intensity

Plasma density, ne Electron temperature, Te Concentration of radicals, nR Plasma potential, Vp Photons Radicals Ions Reactionproducts Secondaryelectrons Sputteredatoms Film composition and microstructure

Mechanical

Optical

Electrical

Surfacetemperature,TS Surfacepotential,VS

Tribological

Reactors

Plasmareactions Diagnostics

PECVDMaterials

Basicfilmproperties Functional characteristicsand applications

Reactor configurations of low-, midand radio-frequency PECVD systems

Gas (O2, Ar, )

RF

RF coil

Precursor

gas

A: Parallel plate plasma reactor

B: Downstream (remote) RF inductively coupled plasma reactor

Reactor configurations of microwave frequency PECVD systems - different modes of excitation

MW power Gas (O2, Ar, ) MW power Precursor gas MW applicator MW power Quartz window Quartz jar Gas shower head

Quartz window

C: Linear applicator

D: Remote MW excitation

E: Horn antenna

F: Plasma impulse CVD (PICVD)

MW linear antenna array

Antenna Quartz window

RF

M M MW applicator

G: Electron cyclotron resonance (ECR)

H: Dual-mode MW/RF

I: Distributed antenna array combined with ECR (DECR)

Reactor configurations using different modes of operation

HV DC Ar Precursor gas

RF

HV AC

Dielectric
M

J: Atomic layer deposition (ALD) or CVD

K: Cascade arc

L: Hybrid PECVD/PVD system combining parallel plate RF electrode and magnetron sputtering

M: Atmospheric pressure plasma

Ion energy distributions in nitrogen plasmas

IEDFs of N2+ and N+ ions in HF plasmas in N2 (40 mTorr) in different configurations:
10
7

Grounded electrode

RF-powered electrode

(a)

(d) N2
+

cw-RF in A (VB = 150V)

Relative Intensity [counts / s]

10 10 10 10 10 10 10 10 10 10 10

N2

cw-RF in A (VB = -150 V)

(b)
6

cw-MW in C PMW = 300W

N2
5

N2

(e)

N
4

cw-RF/cw-MW in H (VB = -150 V, PMW = 300 W)

(c)
6

(f) N2
+

Pulsed MW in C (PMW = 300 W fP = 1 kHz D = 0.5)

N2

cw-RF/p-MW in H (VB = -150 V PMW = 300 W fP = 1 kHz, D = 0.5)

300 O.

10

15

50

100

150

200

250

Ion Energy [eV]

Ion Energy [eV]

Zabeida et al., JAP 2000 A. Hallil et al., JVST A 2000

Case study: Deposition of TiN on c-Si - TRIDYN

1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0

2 nm TiN
Ti Ar Si N O

VB = -600 V, i/n 0.4

R = 0.5 nm/s

Emax 690 eV Em 270 eV Bare substrate

1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0

Molar fraction

MC simulation of ballistic transport: - Ions: N2+, N+, and Ar+ - Neutrals: Ti and N

-8

-6

-4

-2

Si O

-8

-6

-4

-2

Depth (nm)

1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0

Molar fraction

Molar fraction

5 nm TiN

Ti Ar Si N O

-8

-6

-4

Depth (nm)

-2

A. Amassian et al., JVST A, 2006, JAP 2007

And HRTEM experimental evidence

Substrate: c-Si(001) Native oxide < 2 nm

TiSiN

TiN

c-Si

RF Pretreatment: Ar VB = -600V P = 50 mtorr 15 minutes Deposit TiSiN/TiN: TiCl4 +N2 + Ar (+ SiH4) VB = -600 V P = 200 mtorr Ts = 500oC

10 n

Overview

1.

Plasma-surface interactions and plasma systems Film growth in the energetic plasma environment

2.

Hard protective PECVD coatings From tribological coatings for aerospace and automobile to biomedical applications

3.

Optical and multifuntional coatings From optical filters to smart windows, displays and solar cells

4.

Conclusions and perspectives

Material
pc-D NCD c-BN/NCD c-BN CN nc-TiCN/SiCN nc-TiN/SiN TiN a -C:H SiCN SiC SiN 1.3 SiO xN y TiO 2 Ta 2O 5 Nb 2O 5 SiO 2 c-BN nc-TiN/SiN TiN Al2O 3 Ta 2O 5 Si3N 4 TiO 2 ITO SiO 2 c -Si SiO 2 quartz SiO 2 glass TiAl6V4 High speed steel PC

Soft

Hard

Superhard

Microhardness of PECVD coatings

PECVD

PVD

Substrate

20

40

60

80

100

Microhardness [GPa]

TiN-based of nanocomposite films

50

(a)

nc-TiN/SiN 1.3

Hardness, H, [GPa]

H Er

400

Young's modulus, Er, [GPa]

40 300 30 200

20

10
1200

100

Resistivity, , [cm]

(b)
800

ellipsometry 4 point

400

Concentration of Si, C Si [at. %]

10

20

30

40

50

e = 12 nm < particle size = 510 nm

P. Jedrzejowski et al, APL 2006

Ralation between erosion rate and the H3/E2 ratio

Spherical solid particle

Substrate Coating

FE modeling: Eroded volume per particle

W V 2.3 r 3.13 p E / (K c1.47 H 2.5t )

Erosion rate= Volume removed Mass of impacting particle

H/E ratio (elastic strain to failure) H3/E2 ratio (resistance to plastic deformation) TiN-based films:and 50m Al2O3 particles at 84 m/s: enhanced erosion resistance is obtained for Coating thickness: > 8 m Kc = 5-6 MPa.m1/2 H3/E2 = 0.5-0.6 GPa H/E 0.15-0.2

Volume removed, W [10-10x cm3]

16 12 8 4 0 0.0 0.2 0.4 0.6 3 2 H /Er [GPa] 0.8 1.0

S. Hassani et al., Wear 2008

Erosion rate vs. H3/E2 : experiment

Erosion conditions (ASTM G-76):
0.08 Erosion rate [mg/g]

Wear conditions (pin on disk): Alumina ball Al2O3 particles, 50 m dia., speed 84 m/s (6 mm dia), sliding speed 1.8 m/min, load 2 N
Wear coefficient, K [10-6mm3/Nm]

12

Cf : 0.45 0.45 0.42

673 K 773 K

0.06

0.04

0.02

4
0.32 0.21 0.18

0.00
0.08

SS410

TiN

nc-TiN/SiN
Wear coefficient, K x [10-6mm3/Nm]

0
12 10 8 6 4 2 0 0.3

TiN

nc-TiN/a-SiN nc-TiCN/a-SiCN

Mass loss (mg/g)

0.06

0.04

0.02

0.00 0.0 0.2 0.4 0.6 0.8

0.4

H3/E2 (GPa)

0.5 0.6 0.7 H3/Er2 [GPa]

0.8

0.9

S. Guruvenket et al., SCT 2009

Tribo-corrosion of DLC-coated stainless steel in the Ringers solution

Open circuit potential measurements during and after the reciprocal sliding test of SS, SS/N3h/DLC, SS/a-SiNx:H, and SS/a-SiNx:H/DLC (Alumina ball, load: 9N, freq.: 1 Hz) Cathodic polarization curves of bare SS and SS/N3h/DLC and SS/SiN/DLC coating systems

M. Azzi et al., Wear 2009

Multi-zone PECVD system

Industrial deposition system for the fabrication of DLC coatings for automotive parts and other applications. Each chamber contains six 1.6 m long electrodes. (Courtesy of Hauzer Techno Coatings)

PECVD system for hard protective coatings

Example of a commercial system for the deposition of hard protective coatings: 1.6 m3 volume chambers, metal carbides, nitrides and borides from halide precursors, 1,600 kg of parts coated in one run in high power medium frequency pulsed plasmas (Rubig power supplies) (Courtesy of PATT Technologies Inc., Canada)

Lubricious coatingsfor hearing devices

Custom-fitted and calibrated protective devices Multiple insertion into the ear

1.0

Friction coefficient,

0.8 0.6 0.4 0.2 0.0

100 mTorr 50 mTorr

0.0

0.5

1.0

1.5

2.0

2.5

Precursor

MW

Ar

Deposition time [hours] Outcome: Quantitative tribological testing methodology Friction reduced by a factor of 10 Production system transferred to Sonomax

Overview

1.

Plasma-surface interactions and plasma systems Film growth in the energetic plasma environment

2.

Hard protective PECVD coatings From tribological coatings for aerospace and automobile to biomedical applications

3.

Optical and multifuntional coatings From optical filters to smart windows, displays and solar cells

4.

Conclusions and perspectives

Material
TiO 2 pc-D Nb 2O 5 TiO 2:C:H BaTiO 3 SrTiO 3 Ta 2O 5 SnO 2 SiN 1.3 SiO xN y PPOS PPHC Al2O 3 SiO 2 SiO 2:F PPFC TiO 2 Nb 2O 5 Ta 2O 5 SiN 1.3 ZrO 2 ITO Y 2O 3 Al2O 3 SiO 2 MgF 2 PET PC SiO 2 glass PMMA SiO 2 quartz

Low

Medium

High

Refractive index of PECVD coatings

PECVD

PVD

Substrate

1.4

1.6

1.8

2.0

2.2

2.4

2.6

Refractive index n @ 550 nm

Optical coating systems: From design to manufacture

Optical filters:
1. Targeted performance 2. Materials and process 3. Design strategy (discrete, inhomogeneous graded, quasi-homogeneous) 4. Fabrication + monitoring 5. Quality control
1.0

RF PLASMA REACTOR
n

Three-band rugate filter TiO2/SiO2

2.2 2 1.8 1.6
T

0.8 0.6 0.4 0.2 0.0 400

Design Experimental 600 800 1000 Wavelength (nm) 1200 1400

5000 10000 Depth (nm)

OpenFilters: S. Larouche et al, Appl. Opt., 2008 S. Larouche et al., Appl. Opt. 2004

Single-material porous/dense optical filters

Relative Intensity ( Counts / s )
10
6

N2 MW plasma

N2, 40 mTorr Rf-powered electrode Vb= -150 V

SiN-based filters, SiH4 + N2 mixtures, reactor H Control strategy: a) substrate bias, b) duty cycle n d n550 ~ 2.0 (RF) n550 ~ 1.6 (MW)

10

N2

10

10

100

Substrate
Multilayers

Ion Energy ( eV )

Graded layers

R. Vernhes et al., Appl. Opt. 2004, 2008

Active thin film devices

Grid p3 i3 aSialloy n3 p1 i1 aSiGe alloy n1 StainlessSteel Transparent Electrode(ITO) p2 i2 aSiGe alloy n2 ZincOxide Silver Barrier encapsulation layer Cathode() (Al/Ag/ITO) Electroninjection layer(Ba/LiF) Electron transferlayer (Alq3) Glasssubstrate Lightemitting organiclayers (dopedAlq3) H2OandO2 sensitive Hole transfer layer(NPB) Holeinjection layer(CuPc) Anode(+)(ITO)

Triple-junction solar cell

S. Guha, J. Yang, J. Non-Cryst. Sol. 2006
FrontGlass Plate IonStorage Layer Electrochromic Layer RearGlass Plate

Thin film display

M. Zeuner, Private comm.
Transparent Conductor(+) IonConductor (Electrolyte) Transparent conductor()

Electrochromic device - smart window

C.G. Granqvist, Sol. En. Mat. and Solar Cells 2008

Commercial systems for PECVD optical coatings

MW PICVD commercial reactor for coating individual lamps - F

J. Segner, in Thin Films for Optical Systems, F.R. Flory (ed.), Marcel Dekker, NY 1995, p.209 Schott Glasswerke

Large area (55 cm x 55 cm) MW PECVD coating system I barriers, AR coatings (Courtesy of Roth & Rau, Germany)

Roll-to-roll PECVD deposition system

Large area roll-to-roll deposition system for the fabrication of triple-junction photovoltaic cells: 2,500m long, 36 cm wide and 125 m thick SS foils; 4 compartments: a) washing, b) back reflector sputtering (Al, ZnO), c) PECVD of 9-layer triple junction nc-Si and SiGe, d) AR coating ITO. System: 90m long, 3m tall, web speed 30 cm/min, 14,5 km of solar cells in 72 hrs. (Courtesy of United Solar Ovonic, USA)

Conclusions and perspectives

PECVD offers a possibility to fabricate films and coatings with a large range of functional properties (n, H, E, ) which are comparable (or better) with respect to their PVD counterparts (H/E, H3/E2, elastic rebound) Pulsed high density PECVD processes with pulse-control biasing open new opportunities to tailor the materials and device characteristics PECVD is suitable to coat 3D object and achieve high deposition rates (this includes coating internal surfaces) Large scale deposition of optical and protective tribological coatings has been demonstrated and is now in production PECVD offers new attractive design strategies and coating architectures (graded inhomogeneous coatings, dense/porous systems, nanocomposites, ) Work in progress: a) Range of materials b) Refinement of the film architectures c) Enhancement of new optical and tribo-corrosion protective systems d) Design of optical coatings with improved tribo-mechanical properties and of protective coatings with tailored optical properties e) Systematic comparison of coatings prepared by p-PECVD, HIPIMS, mod. bias, ... For more information about our work: www.polymtl.ca/larfis, lmartinu@polytml.ca