Reactive magnetron sputtered

ZrCN decorative films for plastic

substrates
Michael Brazil
Vergason Technology, Inc.
Van Etten, NY

4/2017 - page 1
Persistent desire for durable, shiny, dark finishes
Markets
Sanitary fixtures
Automotive
Desired properties
Matte or gloss
Electrochemical stability
Hardness

5/1/2017 page 2
 Great value for coating on plastic
ABS or PC/ABS blends
ABS/PC blend is qualified for many applications
Butadiene etch required for electroplate adhesion
Softening temperature between 95C and 130C
3D, often complex geometries
Automobile trim
Sanitary fixtures: electroplated before decorative coating applied

5/1/2017 page 3
Performance requirements can be challenge
Appearance
D65 (L*,a*,b*) near (40,0,0)
Glossy
No visible defects
Durability - must survive:
Xe exposure: no change
Thermal shock
Immersion in common (harsh) cleaners
Corrosion
Abrasion
5/1/2017 page 4
Abrasion evaluated with steel wool
Ako or Brillo pad: steel wool with soap
Wet
Ridge orientation makes a difference
20 N/cm2 (29 psi)
1000 cycles
No visible change
Rated as % area removed

5/1/2017 page 5
ZrCN offers hardness & a range of colors
Nitrides and Carbonitrides in general
Hard cutting tools
Blue, green, yellow, red, gold, grey
Changing concentrations of free d electrons
Literature reports ZrCN with exceptional
chemical stability
Good for sanitary market

5/1/2017 page 6
Sputtering offers advantages over arc
Past: cathodic arc for ZrCN
Sputter can be lower temperature
Bias may not be needed
Existing installed base of sputter tools
Smoother: avoid macro-particles

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Zr sputtered in reactive gases
50/50 Ar/N2, with enough N2 to poison target
Gold coating
Varied relative amount N2/C2H2
Target insulates rapidly if too much C2H2
Chamber anode: rapidly disappeared
Discrete anode
Water cooled anode
Advanced Energy AMS/DMS with high duty cycle and
moderate frequency (20 - 40 kHz)
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Heat load sets thickness upper limit
Substrate heating mechanisms* for reactive magnetron sputtering:
Electron heating
Kinetic and condensation heat of sputtered atoms
Bombardment of Argon ions reflected from the sputter target
Bombardment of reactive gas ions from the sputter target
Radiation from the sputter target
Radiation from the plasma
Heat of condensation is unavoidable, minimize by:
Magnetron design and vacuum chamber geometry
Specific levels of total pressure
Reactive gas partial pressure
Sputter power during film growth
*Howson. R.P. and JAfer, H.A., Thin Solid Films 193-194 (1990) p. 127-137

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Minimum thickness determined by absorption
and hardness
Thicker coating more heat
Hardness thickness must be enough for durability
Color based on absorption, not interference
Sputtering is directional
Uniform thickness on complex, 3D geometry difficult
Rely on complete absorption to avoid interference rainbows
Given bounding materials, combination of absorption and thickness keeps
reflection from back surface small enough
Need method to optimize process for absorption

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Simple, low cost absorption evaluation
Measure T() and film side R () at same location
Simple spectrometer: Ocean Optics USB2000
No attempt to fit to a dispersion model
No need for expense of specialized software or ellipsometer
Known sources of error can be ignored
Back side reflection
Position error between T and R
Interference
( ) d
A() = 1 T() R() A( ) e
Gives indication of final color
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Higher C2H2 has flatter spectra
Transition
between 15%
and 33% C2H2.
Move on to
opaque
thickness

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 High C2H2 Absorption
Power Gas Alpha (550 Absorption tracks C2H2/N2
Run Ar N2 C2H2 anode
(W cm-2) source nm) m-1
5
A 54% 45% 2% 19 chamber far 1.37

550 nm absorptivity (um-1)

B 53% 44% 3% 19 chamber far 0.91 4
C 51% 43% 6% 19 chamber far 1.09 3
D 47% 39% 14% 19 chamber far 1.19
2
E 40% 59% 2% 19 chamber far 0.37
F 42% 22% 36% 12 discrete far 2.6 1
G 42% 22% 36% 12 discrete close 3.11 0
H 49% 17% 34% 12 discrete close 2.74 0% 20% 40% 60% 80%
K 49% 17% 34% 14 discrete close 3.88 Relative gas flow

Ar N2 C2H2

Linear (N2) Linear (C2H2)

400 < Total gas flow < 600
5/1/2017 page 13
 Thermal expansion a large contributor to stress
Measured stress by curvature of total thermal intrinsic extrinsic
Si wafer
Compressive, -200 MPa to -800
MPa thermal
Ef
s Tdep Tambient
(1 f )
f
Substrate temperature near
100C
total
wafer
thermal
wafer
intrinsic
film

Parameter Nominal value

total
plastic
thermal
plastic
intrinsic
film

Ef 400 GPa
f 0.25 total
wafer
total
plastic
( thermal
wafer
thermal
plastic
)
T65XF
wafer Tdep Tamb
80 x 10-6/K Ef
Si (100) 2.6x10-6/K wafer
plastic

(1 f )
thermal thermal plastic
Tdep 100C
Tamb 25C
-3.1 GPa! Remember: upper bound only
5/1/2017 page 14
Avoid high compressive stress
Extremes had Stress vs C2H2, N2%
high 0.200 StressAvg
MPa
compressive < -800
0.175
stress -800 - -700
0.150
Add for thermal -700 - -600

C2H2%
0.125 -600 - -500
stress: up to -3 0.100 -500 - -400
Gpa -400 - -300
0.075
High stress 0.050
-300 - -200
> -200
spontaneous
delaminations 0.25 0.30 0.35 0.40
N2%
5/1/2017 page 15
Abrasion has a sweet spot
Good Abrasion vs C2H2, N2%
0.200 Abr<2
0.175 < 0
0 - 1
0.150
1 - 2
C2H2%

0.125 2 - 3
0.100 3 - 4
0.075 4 - 5
> 5
0.050

0.25 0.30 0.35 0.40

N2%

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Material color track
0.08 < C2H2/N2 < 1
Desire (L*, a*, b*)
near (40,0,0)
Define chroma, C*

C * a * b*

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Minimum C2H2, N2 for low chroma
L* vs C2H2, N2% Chroma vs C2H2, N2%
0.200 L* 0.200 Chroma
< < 5
0.175 0.175
50.0 - 5 - 10
0.150 52.5 - 0.150
10 - 15
C2H2%

C2H2%
0.125 55.0 - 0.125 15 - 20
57.5 - > 20
0.100 0.100
60.0 -
0.075 62.5 - 0.075
0.050 65.0 - 0.050
>
0.25 0.30 0.35 0.40 0.25 0.30 0.35 0.40
N2% N2%

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Conclusion:
Narrow process window by exclusion
Good Abrasion vs C2H2, N2% Stress vs C2H2, N2%
0.200
0.200
0.175
0.175
0.150

C2H2%
0.150 0.125
C2H2%

0.125 0.100
0.100 0.075

0.075 0.050

0.050 0.25 0.30 0.35 0.40

N2%
0.25 0.30 0.35 0.40
N2%

Chroma vs C2H2, N2%

0.200
0.175
0.150
C2H2%

0.125
0.100
0.075
0.050

0.25 0.30 0.35 0.40

5/1/2017 page 19 N2%
Conclusion
Narrow process window in gas flows
Future possibilities
Active electrodes to dissociate C2H2
Plasma emission monitor

5/1/2017 page 20
VTI Acknowledgments
Rick Smith
Mark Fitch
Toni Jochum
Gary Vergason

5/1/2017 page 21