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2019 AIMCAL R2R CONFERENCE USA
Mike Simmons, Intellivation, Fort Collins, COFrank Papa, Nano4Energy/GP Plasma, Medina OH
Ivan Fernandez, Nano4Energy, Madrid, SpainMark George, Rex Chang, Jason Bloking, Marty Rosenblum, Vitriflex, San Jose CA
Coating Properties of Transparent Ultra-Barrier Films on PET Web via High Power Impulse Magnetron Sputtering
(HIPIMS) with Positive Voltage Reversal
2019 AIMCAL R2R CONFERENCE USA
AgendaHigh-End Transparent Barrier ApplicationsDeposition Energy & Film MorphologyBipolar Pulsed DC, and HIPIMSEquipment SetupReactive HIPIMS Process, TiO2Barrier Defect Overview ‘A’ Layer Barrier FilmsSi/Al Barrier FilmsConclusions Dual Rotary Magnetrons,
Intellivation 55” web coater
2019 AIMCAL R2R CONFERENCE USA
Flexible, Transparent Ultra-Barrier FilmsFor Printed, Flexible and Roll-to-Roll Electronics
Lightweight Thin Film SolarQuantum Dot LCD
Flexible OLED Display Flexible OLED Lighting
Audi AG
Requirements often include:<5E-3 g/m2/day WVTR>90% light transmissionLow cost / high productivity
2019 AIMCAL R2R CONFERENCE USA
Deposition Energy & Film MorphologyHow can energy be added to growing films in R2R coating to increase
adatom mobility and affect film structure? Thermal & e-beam evaporation Secondary Ion Beam Source; Substrate Temperature
Dual Magnetron Sputtering Pressure; Magnetics; Substrate Temperature; Mid-Frequency Power Delivery Mid-Frequency AC DC Bipolar Pulsing
HIPIMS+VR All the same methods as in Mid-Frequency Bipolar Pulsing Ion bombardment (from pulse and from positive voltage reversal)
2019 AIMCAL R2R CONFERENCE USA
DC, Bipolar Pulsed DC, and HIPIMS
• HIPIMS• High peak power (500-2000 W/cm2)• Reasonable average power (up to 80kW)• Low duty factor (0.5-5%)
THE ADVANTAGE OF HIPIMS IS TO IONIZE AND ENERGIZE THE TARGET MATERIAL. THE POSITIVE VOLTAGE REVERSAL RESULTS IN A SELF ION-ASSIST.
DC – always onBipolar Pulsed DC – mostly onHIPIMS – mostly off
2019 AIMCAL R2R CONFERENCE USA
Equipment Setup Intellivation Application Lab R2R330
4 deposition & 1 pre-treatment zones 330mm [13”] coated width
Web path without any coated surface roller contact Dual Rotary Targets, 100mm Diameter
“A” – High Refractive Index Al:Si (8%Al) – Low Refractive Index
Sputter Power Supplies Evaluated MFAC, Advanced Energy PEII Bipolar Pulsed DC, Advanced Energy DMS Bipolar Pulsed DC, TRUMPF TruPlasma G2.1 nano4Energy HIPIMS
All of the coatings discussed in this presentation were deposited in this coating tool
2019 AIMCAL R2R CONFERENCE USA
TiOx Film Process Details
Utilized two zones in the R2R330TiO1.9 target, Single rotary magnetronPure Ti target, Dual rotary magnetrons
Plasma Emission Monitoring (PEM) process controlEvaluated Pulsed DC, MFAC, Bipolar Pulsed DC,
and HIPIMS+VRPEM Control
Delivers the right amount of reactive gas to the process
Coating Drum
2019 AIMCAL R2R CONFERENCE USA
TiOx Dynamic Deposition Rates
Pure Metallic Ti TargetFully reactive deposition
TiO1.9 TargetSemi-reactive deposition
HIPIMS processes incorporate reactive gas more efficiently than traditional magnetron sputtering does.
HIPIMS DDR via suboxide target was comparable to bipolar pulsed DC sputtering in many cases.
2019 AIMCAL R2R CONFERENCE USA
Reactive TiOx, Metallic Target
200A peak current conditions show similar deposition rate as bipolar pulsed DC.
Pure Metallic Ti TargetFully reactive deposition
2019 AIMCAL R2R CONFERENCE USA
TiOx Film SEM – Ti and TiOx Targets
DMS HIPIMS 200 A - 60 μs – +240 V
HIPIMS 400 A - 40 μs – +288 V
DMS
TiOx coatingvia Ti Target
HIPIMS 400 A - 75 μs – +240 V
TiOx coatingvia TiO1.9 Target
2019 AIMCAL R2R CONFERENCE USA
• No evidence of any crystalline structure in thin film XRD scans for either bipolar Pulsed DC or HIPIMS
TiOx XRD
2019 AIMCAL R2R CONFERENCE USA
Barrier Performance is Highly Dependent on Defects
Extrinsic defects : particles, scratches, gouges, inclusions, surface adhesion Extrinsic defect control measures
Surface Smoothness via Planarization Class 100 Solution Coater Surface Roughness < 2 nm Sa, Surface Kurtosis – Sku < 1000 Surface protect film applied at time of Planarization & Removed in
coater Surface Protect Film Manufactured in Class 100 Environment
Eliminate Coated Surface Roller Contact Eliminates transfer of particles to coated surface Eliminate potential imprint of defect into coated surface
Particle growth defect propagates in a sputtered oxide thin film stack
SVC 2004, M. George
2019 AIMCAL R2R CONFERENCE USA
Intrinsic Defect Control Intrinsic defects : columnar growth, crystalline defects, arc damage Intrinsic defect control measures
Sputtering Plasma Control Dual Magnetron Sputtering
Prevents Lost Anode Advanced Arc Detection/Management
AC Mid-Frequency Bipolar Pulsed DC HIPIMS +VR
Deposition Energy Mid-Frequency Pulsing Known to Increase Adatom Energy
20 to 150 kHz preferred
Columnar growth defect in sputtered oxide thin film
Particle growth defect in sputtered oxide thin film stack
SVC 2004, M. George
SID 2005, M. George
2019 AIMCAL R2R CONFERENCE USA
Barrier Film Process DetailsUtilized one zone in the R2R330Dual rotary magnetrons Plasma Emission Monitoring (PEM) process control Controls reactive gas (oxygen)
Vitriflex-proprietary PET substrate and planarization layer (production qualified)
Two target materials tested Vitriflex-proprietary blend, high index (‘A’ layer) Silicon/Aluminum, low index (8% aluminum)
Evaluated MFAC, Bipolar Pulsed DC, and HIPIMS+VR
PEM ControlDelivers the right amount of reactive gas to the process
Coating Drum
2019 AIMCAL R2R CONFERENCE USA
Barrier Film Characterization Characterization Equipment MOCON W-700 and Aquatran AQ3
Test Procedures Proper handling and mounting of samples is vital
Mocon AQ3WVTR 5e-5 gram/m2/day
Mocon W-700WVTR 5e-3 gram/m2/day
2019 AIMCAL R2R CONFERENCE USA
Barrier Performance ‘A’ Layer
Morphology of Vitriflex ‘A’ Layer is Amorphous and Featureless for all power supplies tested
Amorphous films are desired for barrierapplications
2019 AIMCAL R2R CONFERENCE USA
05 06 07HIPIMS-2
08 MFAC-2TruPlasma0304 DMS
02
HIPIMS Looks to HaveLess Structure ThanBipolar Pulsed and MFAC
WVTR 1 grm/m2/day
WVTR 5 grm/m2/day(SEM Sample Too Thin)
WVTR 5 grm/m2/day
SEM samples are much thicker than the barrier samples, but are deposited under the same process conditions.
HIPIMS-1 HIPIMS-3 HIPIMS-4
Film Morphology of Al:SiO2
2019 AIMCAL R2R CONFERENCE USA
Barrier Performance Al:SiO2
HIPIMS Run 2
08
PEII Run 2
2019 AIMCAL R2R CONFERENCE USA
Production Throughput
Barrier Coating
Power Supply
Max DDR / Zone [nm-
m/min]
Barrier Thk [nm]
Max Line Speed per zone [m/min]
Max Line Speed per 6 Zones [nm-
m/min]
WVTR [gm/m2/day]
A DMS 153 100 1.53 9.2 < 5E-5A HIPIMS-1 111 100 1.11 6.7 < 5E-5A MFAC 158 100 1.58 9.5 < 5E-5A TruPlasma 160 100 1.60 9.6 < 5E-5Al:SiO2 DMS 54 100 0.54 3.2 5Al:SiO2 HIPIMS-3 25 60 0.42 2.5 1Al:SiO2 MFAC-2 84 85 0.98 5.9 5Al:SiO2 TruPlasma 52 100 0.52 3.1 4
2019 AIMCAL R2R CONFERENCE USA
Conclusions Demonstrated dual rotary HIPIMS in fully reactive mode with PEM
control.
Produced ultra-barrier films in the Intellivation Application Lab R2R330 tool.
In the case of the ‘A’ layer barrier film, there was no detectable difference in barrier performance or film morphology in SEM imaging, for films deposited with different power supplies.
In the case of Si/Al, the HIPIMS coating yielded a 5x improvement in barrier performance and a clearly more amorphous film structure.
HIPIMS is a useful tool for tuning film morphology of many materials.