View
35
Download
3
Category
Preview:
Citation preview
Webinar
ALD Basics: ALD on Powders
December 19th, 2019
dhiggs@forgenano.com
smoulton@forgenano.com
Founded in 2013
30 Employees
1,500 m2 facility in Louisville, CO, USA
Expansion in 2020
Mission: To become the world leader of innovative
materials solutions
A LITTLE BIT ABOUT US
We are your global ALD experts!
INVESTORS
MIKE TALARICO, INBOUND MARKETING LEAD
Role: To create the fun and engaging learning tools that help our
partners develop an understanding and appreciation for the possibilities
of ALD on powders and its underlying technology.
Experience:
NOT AN ALD EXPERT
15 years of Marketing experience
10 years International Marketing management
15 years production and event management
Enjoys:
Long walks on the beach, the way the air smells after it rains.
Drawing, sculpting, anything creative, spending time with my wife and
kiddos.
STACI MOULTON, PHD, MBA, APPLICATION ENGINEER
Role: To help you get up to speed on what is possible and what is not
possible with ALD including the likelihood of commercial viability for
your product and the path required to get there.
Experience:
- PI ARPA-E ALD projects for catalysis and commercial opportunities
- I-CORP Program for Lean Launch Process
- 10 years experience in ALD on powders
Education:Ph.D. Chemical Engineering, CU Boulder (Prof. Al Weimer)
MBA, CU Denver
B.S. Chemical Engineering, Oregon State University
Enjoys:
Recreational Aviation, Sailing, Travel, Family Time, Ranching
DANIEL HIGGS, PHD, BUSINESS DEVELOPMENT MGR
Role: To work with you on structuring and implementing a
commercially-focused joint development project to move from
proofs of concept to products.
Experience:
- 10 years in ALD/MLD/ALE field
- Inventor of multiple ALD process and system patents
- Entrepreneurship and technical business development
Education:
Ph.D. Chemistry, Uni. of Colorado Boulder (Prof. Steven George)
MBA, University of Colorado Denver.
Enjoys:
Gardening, cooking, traveling, languages, jazz trumpet, and tea.
AGENDA
• ALD on powders (Staci)
• ALD at scale (Staci)
• Example applications (Daniel)
• How you can work with Forge Nano (Daniel)
• Q & A
STACI MOULTON
ALD ON POWDERS
ALD AT SCALE
ALD is all about the sequential deposition of thin films atomic layer by atomic layer
Purge
Pulse A Pulse B
ATOMIC LAYER DEPOSITION: THE BASICS
Pulse A
Pulse B
Purge
Based on spontaneous, sequential, self-limitingthermal reactions that add material with atomic level control
Vervuurt, R.H.J., Kessels, W.M.M.E., and Bol, A.A. (2017) Adv. Mater. Interfaces, 1700232, 1700232
ATOMIC LAYER DEPOSITION: THE BASICS
1952
Principal of “molecular layering” first proposed in Russia
1970
ALD developed forTFEL displays(Finland)
1983
Pilot production of TFEL displays
1985
Interest in semiconductor ALD
20031990
ALD scale down microelectronic devices
2013 2023
100million $$
600million $$
2.3billion $$
TIMELINE FOR WAFER ALD
3D structures and area-selective ALD$
NANO-COATING TECHNOLOGIES
ALD offers more control than any other coating technology
WHY ARE SURFACE COATINGS IMPORTANT?
-Defect passivation -Barrier to moisture/oxygen -Corrosion resistance -Surface functionalization -Optical enhancement -Porosity control
… for stronger performance and higher efficiency.
Many important chemical processes rely heavily on interfacial interactions.
By tuning the surface we can tune the material behavior…
ALD COATING CHEMISTRY TOOLKIT
Many coating types available – applicable to nearly any substrate
Growth in available precursors spurred by semiconductor industry
ALD Materials
Inorganic Materials
• Metals
• Oxides
• Nitrides
• Sulfides
• Selenides
• Tellurides
• Phosphates
Organic Polymers (MLD)
Hybrid Inorganic/Organic
Mixtures
FORGE NANO’S COATING TYPE EXPERIENCE
Both precursor and process design are expanding available coating space
Forge Nano Direct Experience
Coatings Substrates
AlOx, TiOx, SnOx, LiOx,
ZnOx, NbOx, TiNbxOy,
AlPxOy, MgOx, LiPxOyNz,
LiNbxOy, CoOx, TiPxOy,
LiPxOy, BOx, CeOx, LiAlxOy,
Sn(PO4)x, ZrOx, MgAlxOy,
SiOx, NiOx, Pt, Pd, CeZrxOy,
BiOx, DyOx, TiNx, Alucone,
titanicon, tincone
• Catalysts
• (powders, pellets)
• Metals
• Cathode
• Anodes
• Solid electrolytes
(powders and plates)
• Thermal fillers
• Base metals
Forge Nano Applicable Experience
Coatings Substrates
Metals
Oxides
Nitrides
Phosphates
MLD
Multilayer
Geldar class powders (A-D)
(aeratable, sand-like,
cohesive, and spoutable)
Nano-materials
Objects (flats/foils,
membranes, sponge-like,
and porous)
*Proprietary coatings and substrates not listed
**Coating experience by organizations outside Forge Nano not
listed
translation
Deposits conformal, uniform, pin-hole free films on surfaces of all shapes and sizes
ATOMIC LAYER DEPOSITION: THE BASICS
=1000 ALD Layers
Disperse Nano-Islands
within layers
MultilayersCritical Thickness Nano-Islands
Deposits on all shapes and sizes
ATOMIC LAYER DEPOSITION: THE REAL DEAL
ALD is a highly controllable very thin film process for engineering surfaces
NOT ALL “NANO” COATINGS ARE EQUAL
Only ALD can deposit one atomic layer at a time
Sol Gel ALD
• Sub-nanometer control• Uniform• Conformal• Multi-layer interfaces
1964
Particle ALD Invented in Russia
1992
Fluidized Bed ALDimplemented in Europe
2000 2011
Forge Nanodemonstrates high-throughput particle ALD
Revival of Particle ALDResearch
TIMELINE FOR PARTICLE ALD
Particle ALD is 15 years behind wafer ALD – a Billion–dollar industry
Precursor A
Purge
Precursor B
Purge
Temporal ALD (Batch):
Precursors are separated in time rather than in space
Powder stays in one fixed reactor, precursors are alternately exchanged
Advantages: Versatility
Disadvantages: Difficult to scale, low production rate, low yield and inefficient operation mode
Gas In
Gas Out
REIMAGINING PARTICLE ALD
FLUIDIZATION
Precursor B
Purge
Precursor A
Purge
Spatial Particle ALD (Semi-continuous):
Precursors are separated in space rather than in time
Powder moves between reaction zones, precursors are fixed in space
Advantages: High production rate, high yield and high manufacturing efficiency
Disadvantages: Loss of versatility
REIMAGINING PARTICLE ALD
Substrate materials move and the gases are fixed in space
Advantages: Precursor utilization, speed, high production rate and efficiency
Disadvantages: Versatility, cost scales with ALD cycles
Synchronized controls and powder movement increases
manufacturing efficiency --> continuous processing
SEMI-CONTINUOUS SINGLE VS CONCURRENT BATCH
Semi-continuous is the only demonstrated high-throughput particle ALD system
Prototype
Q3 2013 Q3 2015 Q1 2017
<$1/kg$1,000/kg
Broomfield, CO Louisville, CO New Facility (TBD)
Cost of Production 1
Q1-2020
CommercialPilot
200 kg / day 2.5 tons / day >25 tons / day 272 kg / dayScale of Production
Fluidized Bed
STATE OF DEVELOPMENT
Throughput is directly linked to cost
1. Typical cathode material with alumina coating, 2. 10k MT systems for customer site installation
Lab-scale: ~1 mg to 1 kg
Pilot-scale: 10 - 100 kg Commercial-scale: 100 kg – 3 tons
INNOVATION ROADMAP FOR PARTICLE ALD
Process innovation & materials innovation
1964
Particle ALD Invented in Russia
1992
Fluidized Bed ALDimplemented in Europe
2000 2011
Forge Nanodemonstrates high-throughput particle ALD
2013 2018
1 ton/yr
10 ton/yr
30 ton/yr
1000 ton/yr
2012 2014
Revival of Particle ALDResearch
2020
10000 ton/yr▪ ALD has been around for decades, not adopted because to expensive
▪ No previous innovation around scale-up until 2011
TIMELINE FOR PARTICLE ALD
New spatial ALD process enables high-throughput in recent years
Development
Research
CatalystsEnergy Storage
PARTICLE ALD NEEDS HIGH THROUGHPUT TECHNOLOGY
Particle ALD
DANIEL HIGGS, PHD, BUSINESS DEVELOPMENT MGR
EXAMPLE APPLICATIONS
HOW YOU CAN WORK WITH FORGE
EXAMPLE
APPLICATIONS
ALD ON POWDERS APPLICATION SPACE
ALD is a platform technology that can service a diverse set of applications
CosmeticsProcessing,
Performance
FillersThermal, Optical,
Electrical, Mechanical
PigmentsPaint, Dispersion, Optical Properties
StructuralComposites,
Building, Glass
CatalystsEmissions,
Chemicals, Fuel Cells
Powder Forming3D Printing, Powder Metallurgy, Ceramics
Energy StorageLIB, Beyond Li,
Capacitors, Materials
PharmaControlled Release,
Processing
DisplaysLCD, OLED, QLED
Medical DevicesBiocompatibility, Energy Storage
SeparationsAdsorbents, Membranes
LubricantsTribology, Rheology,Dry & Wet Lubricants
Power GenSolar
Barrier CoatingsCorrosion, Anti-
fouling, Wettability
TextilesAnti-microbial,
Special Properties
SpaceMulti-faceted, Cross-cutting
#1 #2 #3 #5#4
ALD FOR
BATTERIES
DEGRADATION MECHANISMS IN LI-ION CELLS
C.R. Birkl, et. al. Degradation diagnostics for lithium ion cells. J. Power Sources, 341 (2017), pp. 373-386
Degradation occurs at the surface!
Common Coating ChemistriesConventional oxides (e.g. Al2O3, TiO2, ZrO2, SiO2, ZnO, V2O5)
Borates / Phosphates (e.g. B2O3, AlPO4, TiPO4, LixAlPO4)
Lithium-containing (e.g. LixTiyOz, LixByOz, LixAlyOz)
Nitrides and Other (e.g. TiN, LiPON, CuO, AlF3, AlWF3, Ta2O5)
Observed Enhancements of ALD
• Protection from side reactions• Increased ionic/electronic conductivity• Increased Cycle Life• Higher Voltage Capabilities• Higher Temperature Operation• Decreased Resistance Growth • Increase Thermal Runaway Temperature• Improved Thermal Properties • Lower Gas Formation
Common Raw Materials
Lithium Cobalt Oxide (LCO)Lithium Manganese (Nickel) Oxide (LMO/LMNO) Lithium Nickel Manganese Cobalt Oxide (NMC)Lithium Nickel Cobalt Aluminum Oxide (NCA)
Natural GraphiteSynthetic GraphiteSi-C compositesSiOx
ALD FOR BATTERY MATERIALS
NMC 811 vs ALD-coated NMC 811
0.75
0.8
0.85
0.9
0.95
1
1.05
0 50 100 150 200 250 300
Re
lativ
e C
ap
acity
(%)
Cycle Number
0.75
0.8
0.85
0.9
0.95
1
1.05
0 50 100 150 200 250 300
Re
lativ
e C
ap
acity
(%)
Cycle Number
4.2V
4.4V4.6V
100
110
120
130
140
150
160
170
180
0 200 400 600 800 1000
Ca
pa
city
(mA
h/g
)
Cycle Number
Graphite vs ALD-coated Graphite
ALD-coated NMC811ALD-coated graphite
Uncoated NMC811 Uncoated graphite
ALD FOR BATTERY MATERIALS
ALD FOR 3D
PRINTING
ALD CAN IMPROVE AM POWDERS AND PARTS
ALD coatings provide new ways to address issues with additive materials
Flowability
- Less part defects
- Use of more alloys
- Enabling use of lower cost powders
ALD coatings protect the powder grains from environmental
degradation to extend the powder shelf life and to modify the
powder flowability, compressibility, aeration and shear stressNon-uniform
powder bed
Uniform
powder bed
FLOWABILITY OF AM POWDERS MATTERS
Powder rheology determines the bed density, homogeneity and reproducibility
ALD CAN IMPROVE AM POWDERS AND PARTS
ALD coatings provide new wats to address issues with additive materials
Flowability
- Less part defects
- Use of more alloys
- Enabling use of lower cost powders
Oxygen/Moisture barriers
- Safer transportation
- Longer shelf life
- Increased builds per powder batch
- Smaller powders → finer features
TI64 OXIDATION RESISTANCE
ALD coating can protect against oxidation 3
ALD
Al 2
O3
1 A
LD A
l 2O
3
3 A
LD A
l 2O
3
3 A
LD A
l 2O
3
ALD CAN IMPROVE AM POWDERS AND PARTS
ALD coatings provide new ways to address issues with additive materials
Flowability
- Less part defects
- Use of more alloys
- Enabling use of lower cost powders
Oxygen/Moisture barriers
- Safer transportation
- Longer shelf life
- Increased builds per powder batch
- Smaller powders → finer features
Surface Dopants
- Stronger parts
- Custom alloy generation
- Alloy spec control for incoming materials
- Melt pool surface tension control
Grain structure determines mechanical properties of AM parts
AM Powders can be modified with ALD to affect final grain structure in AM parts
Large grains Small grains
STRENGTH OF PARTS DEPENDS ON MICROSTRUCTURE
Introducing nucleants alters grain growth during 3D printing
Yield strength: too low to measure
Elastic modulus: too low to measure
Ultimate tensile strength: 25.5 MPa
Yield strength: >323 MPa (comparable to wrought)
Elastic modulus: >63 GPa (comparable to wrought)
Ultimate tensile strength: >383 MPa (comparable to wrought)
Pure Al7075 AM Zr-doped Al7075 AM
ALD CAN IMPROVE AM POWDERS AND PARTS
ALD coatings provide new ways to address issues with additive materials
Flowability
- Less part defects
- Use of more alloys
- Enabling use of lower cost powders
Oxygen/Moisture barriers
- Safer transportation
- Longer shelf life
- Increased builds per powder batch
- Smaller powders → finer features
Surface Dopants
- Stronger parts
- Custom alloy generation
- Alloy spec control for incoming materials
- Melt pool surface tension control
Other:
- Coatings on parts for added functionality, e.g.
lubricity, hydro-/oleo- philicity/phobicity, catalysis
- Enhanced dispersion of powders for binder AM →denser green parts → finer features
- Sintering control
- Anti-segregation coatings for binary systems
- Electrical insultation of metal powders
ALD FOR
CATALYSTS
OPPORTUNITIES FOR ALD CATALYSTS
Atomic level control of catalyst design and synthesis
UndercoatAcid/base sites,
electronic structure, metal support interaction
Active MaterialFilms, nanoparticles,
single sites, mixed composition
OvercoatSite blocking,
sinter resistant, oxidation/reduction
ActivityProduction rate,
process scale
SelectivityProduct stream value,
process efficiency
DurabilityLifetime, sinter resistant,
coke resistant
ALD TOOLBOX
CATALYST BENEFITS
OPPORTUNITIES FOR ALD CATALYSTS
UndercoatAcid/base sites,
electronic structure, metal support interaction
Active MaterialFilms, nanoparticles,
single sites, mixed composition
OvercoatSite blocking,
sinter resistant, oxidation/reduction
ActivityProduction rate,
process scale
SelectivityProduct stream value,
process efficiency
DurabilityLifetime, sinter resistant,
coke resistant
ALD TOOLBOX
CATALYST BENEFITS
Atomic level control of catalyst design and synthesis
OPPORTUNITIES FOR ALD CATALYSTS
UndercoatAcid/base sites,
electronic structure, metal support interaction
Active MaterialFilms, nanoparticles,
single sites, mixed composition
OvercoatSite blocking,
sinter resistant, oxidation/reduction
ActivityProduction rate,
process scale
SelectivityProduct stream value,
process efficiency
DurabilityLifetime, sinter resistant,
coke resistant
ALD TOOLBOX
CATALYST BENEFITS
Atomic level control of catalyst design and synthesis
Pd:Al2O3 catalysts with 0-20 Al2O3 ALD overcoating cycles. [Lu et
al., Surf Sci Reports 71 (2016) 410-472]
Al2O3 ALD overcoating on ALD-derived Pt nanoparticles, showing
effective elimination of sintering/ripening at high temperatures. [Liang
et al. ACS Catalysis, 1, (2011) 1162-1165]
Surface Coatings, Catalyst Deposition, Overcoatings
ALD can significantly reduce the amount of PGM needed for equivalent activity of materials
and ensure that exposure to high temperature does not cause agglomeration of ‘nano-islands’.
OVERCOAT FOR CATALYST IMMOBILITY
ALD to enable lower PGM loadings for lower cost
HOW YOU CAN WORK WITH US
Research Services
• We consult (under NDA) on your materials challenge, suggest a research plan,
then provide you with ALD-coated materials for testing
• May include certain analytical such as ICP, Moisture, BET
R&D Tool Sales
• ATHENA, 3D and porous objects ALD system
• PROMETHEUS, powder ALD system, 5g – 1kg
Commercialization
• Joint development agreements
• Toll coating
• Commercial equipment Sales
PROMETHEUS
ANTHENA
CONTACT THE TEAM
http://www.forgenano.com
Reuben Sarkar Chief Product Officer
rsarkar@forgenano.com
Staci Moulton Applications Engineering
Business Development
smoulton@forgenano.com
Daniel HiggsBusiness Development
Manager
dhiggs@forgenano.com
John Mahoney Business Development
Manager
jmahoney@forgenano.com
Mac BurnsBusiness Development
Manager
mburns@forgenano.com
THANK YOU!
Recommended