webinar ald basics: ald on powders - forgenano · webinar ald basics: ald on powders december 19th,...

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!