ALD Basics: ALD on Powders December 19 th , 2019 - - PowerPoint PPT Presentation
Webinar ALD Basics: ALD on Powders December 19 th , 2019 dhiggs@forgenano.com smoulton@forgenano.com A LITTLE BIT ABOUT US Founded in 2013 30 Employees 1,500 m 2 facility in Louisville, CO, USA Expansion in 2020 Mission: To become the world
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
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:
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:
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
STACI MOULTON
ALD is all about the sequential deposition of thin films atom
ic layer er by atom
ic layer er
Purge Pulse A Pulse B
ATOMIC LAYER DEPOSITION: THE BASICS
Pulse A Pulse B Purge
Based on sponta
neous, sequential, sel elf-li limi miti ting ng thermal 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 for TFEL displays (Finland)
1983
Pilot production of TFEL displays
1985
Interest in semiconductor ALD
2003 1990
ALD scale down microelectronic devices
2013 2023
100 million $$ 600 million $$ 2.3 billion $$
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?
… 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
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
(powders and plates)
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 co conform
al, 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
Multilayers Critical Thickness Nano-Islands
Deposits on all shape apes 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 Sol Gel ALD ALD
1964
Particle ALD Invented in Russia
1992
Fluidized Bed ALD implemented in Europe
2000 2011
Forge Nano demonstrates high- throughput particle ALD Revival of Particle ALD Research
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 Advanta antages ges: : Versatility Disadv advantage antages: : 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 Advanta antages ges: : High production rate, high yield and high manufacturing efficiency Disadv advantage antages: : Loss of versatility
REIMAGINING PARTICLE ALD
Substrate materials move and the gases are fixed in space Advanta antages ges: : Precursor utilization, speed, high production rate and efficiency Disadv advantage antages: : 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
Commercial Pilot
200 kg / day 2.5 tons / day >25 tons / day 2 72 kg / day Scale of Production
Fluidized Bed
STATE OF DEVELOPMENT
Throughput is directly linked to cost
Lab-scale ale: : ~1 mg to to 1 kg Pilot-scale ale: : 10 - 100 kg Com
ercial cial-sc scal ale: : 100 kg – 3 ton tons
INNOVATION ROADMAP FOR PARTICLE ALD
Process innovation & materials innovation
1964
Particle ALD Invented in Russia
1992
Fluidized Bed ALD implemented in Europe
2000 2011
Forge Nano demonstrates high- throughput particle ALD
2013 2018
1 ton/yr 10 ton/yr 30 ton/yr 1000 ton/yr
2012 2014
Revival of Particle ALD Research
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
Develo lopment ment Resear arch ch
Catalysts
En Energy y Stor Storage ge
PARTICLE ALD NEEDS HIGH THROUGHPUT TECHNOLOGY
Particle ALD
DANIEL HIGGS, PHD, BUSINESS DEVELOPMENT MGR
ALD ON POWDERS APPLICATION SPACE
ALD is a platform technology that can service a diverse set of applications
Cosmetics
Processing, Performance
Fillers
Thermal, Optical, Electrical, Mechanical
Pigments
Paint, Dispersion, Optical Properties
Structural
Composites, Building, Glass
Catalysts
Emissions, Chemicals, Fuel Cells
Powder Forming
3D Printing, Powder Metallurgy, Ceramics
Energy Storage
LIB, Beyond Li, Capacitors, Materials
Pharma
Controlled Release, Processing
Displays
LCD, OLED, QLED
Medical Devices
Biocompatibility, Energy Storage
Separations
Adsorbents, Membranes
Lubricants
Tribology, Rheology, Dry & Wet Lubricants
Power Gen
Solar
Barrier Coatings
Corrosion, Anti- fouling, Wettability
Textiles
Anti-microbial, Special Properties
Space
Multi-faceted, Cross-cutting
#1 #2 #3 #5 #4
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!
Com
ing g Che Chemistri mistries es
Convent entional ional oxides es (e.g.
Borates s / Phospha hates es (e.g.
LixAlP lPO4) )
Lithium hium-conta
ining g (e.
e.g.
TiyOz, LixByOz, LixAl AlyOz) )
Nitride rides s and Other (e.
e.g.
N, LiPON, N, CuO, AlF3, AlWF lWF3, Ta2O5)
Observed ed En Enhanc ancem ements ents of
ALD
tection from
ctions
eased ed ionic/e ic/electr lectron
ic conductiv uctivit ity
eased ed Cycle le Life
er Volta tage ge Capabil ilitie ities
er Temper erature Operat atio ion
eased ed Resis ista tance nce Growth th
ease e Thermal mal Runaway y Temperat erature
ed Therma rmal l Propertie ties s
r Gas as Forma rmation tion
Com
Raw Mat Material rials
Lithium hium Cobalt lt Oxide (LCO) CO) Lithium hium Manganes anese e (Nic ickel) l) Oxide (LM LMO/L O/LMNO) NO) Lithium hium Nickel el Manganese anese Cobalt alt Oxide (NMC) NMC) Lithium hium Nickel el Cobalt lt Alumin minum um Oxide (NCA CA) Nat atura ral l Graphite hite Sy Synthe hetic tic Graphi hite Si Si-C C com
posites es SiOx
ALD FOR BATTERY MATERIALS
NMC C 811 1 vs ALD LD-co coat ated ed NMC C 811
0.75 0.8 0.85 0.9 0.95 1 1.05 50 100 150 200 250 300 Relati tive Capacit acity y (%) Cycle le Number er 0.75 0.8 0.85 0.9 0.95 1 1.05 50 100 150 200 250 300 Relati tive Capacit acity y (%) Cycle le Number er 4.2V 4.4V 4.6V 100 110 120 130 140 150 160 170 180 200 400 600 800 1000 Capacit acity y (mAh/g h/g) Cycle le Number er
Graphit ite e vs ALD-coa
ite ALD-coa
d NMC811 C811 ALD-coa
d graphit ite Uncoa coated NMC81 C811 Uncoa coated graphit ite
ALD FOR BATTERY MATERIALS
ALD CAN IMPROVE AM POWDERS AND PARTS
ALD coatings provide new ways to address issues with additive materials
Flowability
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 stress Non-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
Oxygen/Moisture barriers
TI64 OXIDATION RESISTANCE
ALD coating can protect against oxidation 3 ALD Al2O3 1 ALD Al2O3 3 ALD Al2O3 3 ALD Al2O3
ALD CAN IMPROVE AM POWDERS AND PARTS
ALD coatings provide new ways to address issues with additive materials
Flowability
Oxygen/Moisture barriers
Surface Dopants
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
Oxygen/Moisture barriers
Surface Dopants
Other:
lubricity, hydro-/oleo- philicity/phobicity, catalysis
denser green parts → finer features
OPPORTUNITIES FOR ALD CATALYSTS
Atomic level control of catalyst design and synthesis
Undercoat
Acid/base sites, electronic structure, metal support interaction
Active Material
Films, nanoparticles, single sites, mixed composition
Overcoat
Site blocking, sinter resistant,
Activity
Production rate, process scale
Selectivity
Product stream value, process efficiency
Durability
Lifetime, sinter resistant, coke resistant
ALD TOOLBOX CATALYST BENEFITS
OPPORTUNITIES FOR ALD CATALYSTS
Undercoat
Acid/base sites, electronic structure, metal support interaction
Active Material
Films, nanoparticles, single sites, mixed composition
Overcoat
Site blocking, sinter resistant,
Activity
Production rate, process scale
Selectivity
Product stream value, process efficiency
Durability
Lifetime, sinter resistant, coke resistant
ALD TOOLBOX CATALYST BENEFITS
Atomic level control of catalyst design and synthesis
OPPORTUNITIES FOR ALD CATALYSTS
Undercoat
Acid/base sites, electronic structure, metal support interaction
Active Material
Films, nanoparticles, single sites, mixed composition
Overcoat
Site blocking, sinter resistant,
Activity
Production rate, process scale
Selectivity
Product stream value, process efficiency
Durability
Lifetime, 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
then provide you with ALD-coated materials for testing
R&D Tool Sales
Commercialization
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 Higgs
Business Development Manager
dhiggs@forgenano.com
John Mahoney
Business Development Manager
jmahoney@forgenano.com
Mac Burns
Business Development Manager
mburns@forgenano.com