A case study in the translation of basic research in nanotechnology

Alex Robinson

IRRESISTIBLE MATERIALS

Etching Metallization Doping

Background – The Need

Develop

Positive Tone Negative Tone

2

Moore’s Law

1965

Gordon Moore proposed in 1965 that the number of components that could be produced at minimum cost on a single chip would double every year for a decade

G.E. Moore, Electronics, 38 114 (1965)

3

Diffraction

Far field (Fraunhoffer) diffraction: L > d2/λ Large source/aperture/ image separation - plane waves

d

L

4

Clearly resolved Rayleigh Not resolved

Minimum resolvable separation is when the first minimum of one aperture's image is at the centre of the other’s image

Rayleigh’s Criterion: (∆l)min= 1.22 = k1 fλ d

λ NA

f = focal length of lens d = feature diameter NA = Numerical Aperture k1 = process constant

(∆l)min

157nm Lithography 2004 - Present

International Technology Roadmap for Semiconductors, 2001

157 nm Abandoned

EUV Delayed

5

More Moore

International Technology Roadmap for Semiconductors, Update 2010

The feature size required for microelectronic devices shrinks every year “Technology Node”

65 nm 45 nm 32 nm 22 nm 16 nm 11 nm

Year of Introduction 2007 2010 2013 2016 2019 2022

Resolution Definitions

DRAM halfpitch

MPU Gate in Resist

pitch

Gate width

pitch

6

Current Generation Lithography

Extending 193 nm Lithography to fill the gap has required every trick in the book

J.H. Bruning, Proc SPIE, vol. 6520, 652004 (2007).

7

Immersion Lithography

U. Takayuki, NEC Technical Journal, vol. 4, (2009)

8

Off Axis Illumination

R.P. Seisyan, Technical Physics, vol. 56, 1061 (2011)

8

Phase Shifting Mask

R.P. Seisyan, Technical Physics, vol. 56, 1061 (2011)

Optical Proximity Correction

Mask Layout Aerial Image Resist Pattern

OPC Serifs

Double Patterning

International Technology Roadmap for Semiconductors, 2011

9

Cost of Ownership for DP

http://www.newelectronics.co.uk/electronics-technology/the-economics-of-chip-manufacture-on-advanced-technologies/35562/

10

The Future – More of the Same?

Self Aligned Quadruple Patterning

K. Nakayama et al, Proc SPIE, vol. 8327, 83270V (2012)

11

Imprint?

http://spie.org/x33843.xml

12

Directed Self Assembly?

B. Rathsack et al, Proc. SPIE, vol. 8323, 83230B, (2012)

Parallel Electron Beam?

http://www.eetimes.com/electronics-news/4370573/ISPD--Semiconductors-aim-for-8-nm-node

MAPPER

13

Extreme Ultraviolet Lithography?

http://www.betasights.net/wordpress/?p=1079

13.5 nm light Multilayer Reflective Optics

High Vacuum Exposure

14

A New NGL Resist - The Original Idea 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

15

The Original Idea 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

The first demonstration of C60 as a resist was by Rao et al, who showed that exposure to 514.5 or 488.0 nm light to a dose of 5 W/cm2 caused a photopolymerisation of the molecules.

A.M. Rao, et al, Science, 259, 955 (1993)

hν

16

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Fullerene Resists

Advantages of this Resist • Very high etch resistance (Etch Rate = 1/7.5 of silicon) • High resolution (<20 nm)

Disadvantages of this Resist: • Very low sensitivity10 mC/cm2 • Requires vacuum sublimation for coating

Tada and Kanayama found that the fullerene C60 demonstrates negative tone behaviour on irradiation with electrons

T. Tada, et al, Jpn. J. Appl. Phys., 35, L63 (1996)

R

R

17

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Fullerene Resists

To improve the solubility and therefore allow spin coating fullerene derivatives were synthesised by the addition of one or more addends to a fullerene cage

Methano Diels Alder

R

R

RR

R

R

18

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

19

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Triphenylene Resists

Several polysubstituted triphenylenes, are liquid crystalline materials, allowing the deposition of smooth films by spin coating.

20

R1 R2

R1

R2R1

R2

R1 R2

R1

R2R1

R2

C5H11O O

OC5H11

OC5H11C5H11O

C5H11O

X CH2

N C5H11O O

OC5H11

OC5H11O

C5H11O

X CH2

N

XCH2

N

C5H11O O

OC5H11

C5H11O

X CH2

N

O X CH2

N

OXCH2

N

O X CH2

N

C5H11O O

OC5H11O

C5H11O

X CH2

N

XCH2

N

O

O O

OO

O

X CH2

N

R

R

R

R

R

R

CO

CH2

N O

RO

OR

OR

OR

OR

H3C

H3C

O

O

T98.0R1 = C5H11OR2 = C5H11O

T98.6R1 = C5H11OR2 = C7H15O

T98.7R1 = C5H11OR2 = C9H19O

T98.1R1 = C5H11OR2 = C2H5O

T98.4R1 = C5H11OR2 = C4H9O

T98.2R1 = C5H11OR2 = C3H7O

T98.5R1 = C5H11OR2 = C6H13O

T98.8R1 = C6H13OR2 = C6H13O

T98.12R1 = C5H11OR2 = C1H3O T98.15

R1 = C5H11OR2 = OHT98.13

R1 = C7H15OR2 = C3H7O T98.14

R1 = C8H17OR2 = C2H5O

T98.10R1 = C8H17OR2 = C2H15O T98.11

R1 = C5H11OR2 = C5H10COOHT98.9

R1 = C7H15OR2 = C3H7O

SYMMETRIC

ASYMMETRIC

n n

n

n

n

n

n

n

n

n

R=

n1

n

n

LC02-01 - X=CH2, n = 5

LC02-04 - X=CO, n = 5

LC02-03 - X=CO, n = 3

LC02-02 - X=CH2, n = 7

LC02-05 - X=CH2, n = 5

LC02-07 - X=CO, n = 5 LC02-08 -

X=CO, n = 5

LC02-09 - X=CH2, n = 5

LC02-10 - R=C5H11, n = 4, n1 = 5

LC02-13 - R=C7H15, n = 4, n1 = 5

LC02-12 - R=C6H13, n = 4, n1 = 5

LC02-11 - R=C5H11, n = 4, n1 = 10

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

21

C5H11O OC5H11

OC5H11

OC5H11C5H11O

C5H11O

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 Jez Arnold on Flickr, CC BY-SA 2.0

22

Unexposed Resist Exposed Resist

Photoacid Generator H+ ∆T

hν

CA Schematic after: H. Ito, Adv. Polym. Sci., 172, 37 (2005),

Chemical Amplification

23

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

24

O O OH

O

H+

+ R N

O

O

CH2CH

OH

CH2CH

O

CH2CH

O

R N+H+

-CH3OH

Positive Tone Negative Tone

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Chemical Amplification

25

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Chemical Amplification MF03-04MF03-04[CA]

0

20

40

60

80

100

120

1 10 100 1000

650 µC/cm2

Th

ickn

ess (

nm

)

Dose (µC/cm2)

MF03-04MF03-04[CA]

650 µC/cm2

7.5 µC/cm2

MF03-04:PAG:HMMM 1 mg :0.23 mg:1.5 mg 20 keV Exposure PEB = 100 °C / 60 s 10 s MCB Development

26

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Chemical Amplification

MF03-04: PAG2* :HMMM 1 mg : 1.4 mg : 1.1 mg

Dose = 5 nC/cm

PEB = 100ºC/1 m Dev = MIBK:IPA [1:3]/10 s

* PAG2 = Tris(4-tert-butylphenyl)sulfonium perfluoro-1 butane

27

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

(Better) Chemical Amplification

MF03-04:CL05-03:PAG [1:2:1] Exposure = 20 keV PAB = None PEB = 100 °C for 60 s Develop = 5 s, Anisole Rinse = None

0

20

40

60

80

100

10-7

10-6

10-5

0.0001 0.001 0.01

MF03-04MF03-04:CL:PI (1:2:1)

No

ma

lis

ed

Fil

m T

hic

kn

es

s (

%)

Dose (C/cm2)

550 µC/cm28 µC/cm2

28

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

(Better) Chemical Amplification

25 nm linewidth, swelling

Dose = 200 pC/cm at 30 keV PAB = None PEB = 90 °C for 180 s Develop = 5 s, MCB:IPA [1:1] Rinse = None

29

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Triphenylene Chemical Amplification Triphenylene Derivatives -  C5/C0 and C5epoxide -  Sensitivity is sub 10 µC/cm2 -  PAB at 60°C for 10mins

C5H11O

HO

C5H11O OH

C5H11O

OH

C5H11O

O

C5H11O O

C5H11O

O

O

O

O

S+

S S+

SbF6-

SbF6-

30

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

01/10/06 31/03/08 Chemically Amplified Molecular Resists for Electron Beam Lithography

01/03/08 29/01/10 Fullerene Chemical Amplified Resists for Next Generation Lithography

01/09/09 30/11/09 Fullerene Chemical Amplified Resists for Next Generation Lithography: Proof of Concept and Knowledge Transfer Project

01/01/12 31/12/14 Conductive Resists for Nanofabrication on Insulating Substrates

31

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

(Even Better) C60 Chemical Amplification

12 nm Linewidth Dose = 300 pC/cm at 30 keV PAB = 75 ºC for 600s PEB = 90 °C for 180 s Dev = 10 s, MCB:IPA [1:1] Rinse = 10 s, IPA

20 nm Half Pitch Dose = 140 pC/cm PAB = 75 ºC for 600s PEB = 90 °C for 180 s Dev = 10 s, MCB:IPA [1:1] Rinse = None

32

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

First EUV Results

50 nm Half Pitch in CL2-4

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

The Irresistible Era

Irresistible Materials is a spin-out company formed to commercialise UoB research in materials for semiconductor fabrication.

The company was initially conceived in 2009/2010, formally established in 2011, and continues to operate and grow.

33

August 2011 – December 2012 Formally setup as a University spinout

Commercial Lead: David Ure

Alexandra McClelland, Researcher (0.6 FTE)

Leveraged EPSRC follow on fund, with small investment from Mercia Seed Fund, and strategic alliance with Nano-C.

During year managed to secure additional TSB grant, and develop nearer-term hardmask opportunity.

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

The Irresistible Era

34

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

35

£‐

£200,000

£400,000

£600,000

£800,000

£1,000,000

£1,200,000

£1,400,000

2008 2009 2010 2011 2012

Cumula&veValueofSupportReceivedbyIrresis&bleMaterials

Investments

SourceAccess

AlliancePartner

AlliancePartner

AcademicGrants

Patentsupport

Jan 2013 – April 2014

Experienced Chairman brought in: Stuart McIntosh

Obtained further cash investment from both Mercia, and UK / US angels, and EPSRC FoF support from UoB.

IM Team expanded: Alan Brown joined, Q1 2013, 0.6 FTE Tim O’Connell: P/T Finance Manager

Continued to develop technology and gain customer traction

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

The Irresistible Era

36

May 2014 – December 2014 Customer interest turning into evaluations

CEO hired – Mark Shepherd

Increase Technical Manpower – AB to 1.0 FTE

Investors have continued to support the business whilst customer traction turns into customer/partner commitment

Matching Innovate UK and ABIA grants

Now planning new investment round for 2015 – to see EUV resists through to point of “adoption” by major resist companies

37

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

The Irresistible Era

38

£‐

£500,000

£1,000,000

£1,500,000

£2,000,000

£2,500,000

£3,000,000

2008 2009 2010 2011 2012 2013 2014

Cumula&veValueofSupportReceivedbyIrresis&bleMaterials

Investments

CompanyGrants

SourceAccess

AlliancePartner

AcademicGrants

Patentsupport

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Inflection Points Attracting Investor Support

Seed Funding (2011)

• Inflection: • Proof of

principle; • Evidence of

commercial need

• Commercial lead – DU

• Strong set of advisors and alliance partner

• Ability to lever grant support

Follow on Seed (2013)

• Inflection: • De-risked by

development of nearer-term opportunity

• Initial commercial interest

• Positive technical validation

• Experienced Chairman - SM

• Broader investor base

Bridge Financing (2014)

• Inflection: • Significant

commercial interest / evaluations

• Experienced CEO - MS

• Technological breakthroughs

39

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Summary

When formed, little seed investment existed: needed to lever as much grant funding as possible.

Relationship with Nano-C was key

More money only becomes available as the company develops Function of both commercial and technical evolution

For academics – the Enterprise Training is extremely useful

40

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Customer/End User Driven Technical Progress

41

IRRESISTIBLE MATERIALS

•  Commercial Inertia •  ‘Not Invented Here’ •  Standard Processes •  The little details that trip you up

42

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014

The Path to Date

Electron Beam Resist

EUV Resist

Electron Beam Mask EUV is Back too!

Resist SoC 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014

Spin on Carbon

Gap Fill Solvent Strip/High Temp

Conductive Electron Multibeam/ Conductive Resist

Low Temp Cure

C5Ep on Glass 100 nm pitch 4.6 mC/cm2

PMMA on Glass 200 nm pitch

139 µC/cm2

PMMA on Glass 200 nm pitch

345 µC/cm2

C5Ep on Glass 150 nm pitch

50 µC/cm2

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

43

Conductive Resists for Nanofabrication on Insulating Substrates

Started a new project to develop a resist to enable electron beam lithography on insulating substrates.

44

Dr A. Frommhold, F. Hasan, K. Virzbickas

School of Chemical Engineering, University of Birmingham

G. O'Callaghan, D. Zhao, O. Jones, J.A. Preece School of Chemistry, University of Birmingham, B15 2TT, UK

Mr D.X. Yang, Prof R.E. Palmer Nanoscale Physics Research Laboratory, University of Birmingham

Mr V. Veijins, Mr T. Lada, Mr J. Roth, Dr X. Xue Nano-C

Mr M. Shepherd, Mr D. Ure, Ms A. McClelland, Mr A. Brown, Irresistiblematerials

Dr Y. Ekinci, Ms. M. Vockenhuber Paul Scherrer Institute, Switzerland

Dr J. Bowen School of Chemical Engineering, UoB

Dr C. Szmanda, Dr J. Shelnut The Patent Practice of Szmanda & Shelnut, LLC

Dr R. Brainard CNSE Albany

Mr Jun Sung Chun, Mr Brian Sapp SEMATECH

Acknowledgements

www.irresistiblematerials.com