A.P.G. Robinson Nanoscale Physics Research Laboratory The … · 2014-04-08 · the assistance of Drs H. Solak, V. Auzelyte and P. Sahoo of the Paul Scherrer Institute 50 nm Half

NPRLNanoscale Physics Research Laboratory

Feasibility to Spin-out:Chemically amplified NGL photo-resists

A.P.G. RobinsonNanoscale Physics Research Laboratory

The University of Birmingham

http://nprl.bham.ac.uk


Outline

• The Application

• The Solution

• Meeting Commerical Requirements

• Testing Commercial Feasibility

• Spin-out

• Conclusions and Acknowledgments


The Application - LithographyMicroelectronic devices are created by doping, etching or metalizing asemiconductor wafer to selectively change its electronic properties.

Lithography is used to pattern a chemical film, or resist, which then protectscertain areas of the substrate, whilst other areas are modified.

Resist

Wafer

The Lithographic (exposure and development) step accounts for upto 40% of the manufacturing time.

Mask

Energy


EUV or Innovative Technology

EUV

193i DP

193i

193

Moore’s Law

After International Technology Roadmap for Semiconductors, 2008

The feature size required for microelectronic devices shrinks every year

Intel 32 nm node Intel

22 nm node

Intel 16 nm node

Intel 11 nm node

Ready for HVM Introduction

βeta Testin

g

Proof of Concept

Resist Development Timeline for EUV

“Technology Node”65 nm 45 nm 32 nm 22 nm 16 nm 11 nm

Year of Introduction2007 2010 2013 2016 2019 2022

Resolution Definitions

DRAM halfpitch

MPU Gate in Resist

pitch

Gatewidth

pitch


The RLS TradeoffThe Resolution, Linewidth Roughness and Sensitivity of a resist are

correlated. One or two can be improved at a cost to the third.

R3 ×L2 × S ≈ Material Constant “Z-Factor”

Year of Introduction 2013 2016

Technology Node 32 22

DRAM halfpitch (nm) 32 23

MPU Gate in Resist (nm) 25 18

LWR (nm, 3σ) 2.0 1.4

Sensitivity (mJ/cm2) 10** (5 – 30) 10** (5 – 30)

** Intel Roadmap / IEUVI Resist Working Group Target

Line

wid

th R

ough

ness

Improve RLS by changing material

* International Technology Roadmap for Semiconductors, 2008

Resist Targets*

Film

Thic

knes

s

Higher Dose

Unexposed(Soluble)

Exposed(Insoluble)

Sensitivity

LWR = 3σ Variation of Linewidth from design

pitch

Resolution is usually taken as half of the acheivable pitch


The Solution – Molecular ResistsTraditional resists are polymeric materials with masses of hundreds of

kilodaltons. Molecular resists are much smaller, typical < 2,000 Da.

Polymeric Resist

Unit of PHOST Resist Fullerene

Molecular Resist

* D. Drygiannakis et al, Microelectron. Eng, 84, 1062 (2007)

Simulations indicate that molecular resists may shrink the RLS tradeoff*

L L


*A.M. Rao, et al, Science, 259, 955 (1993)†T. Tada, et al, Jpn. J. Appl. Phys., 35, L63 (1996)

C60 photopolymerisation was first demonstrated by Rao*. hν

Electron beam resist behaviour was first shown by Tada†.

Insoluble Graphitic Material

e-

Fullerene Resists


Advantages of C60 Resist: Very high etch resistanceHigh resolution (< 20 nm)

Very low sensitivity (10 mC/cm2)Coating by vacuum sublimationDisadvantages of C60 Resist:

Improving the C60 Resist:Derivatise to improve solubility

Fullerene Resists


Fullerene Resists

20 nm linewidth

Dose = 30,000 pC/cm at 30 keVPAB = NonePEB = None Develop = 10 s, MCBRinse = 10 s, IPA

30,000 pC/cm


Meeting Commerical RequirementsThe Sensitivity Problem

Solution

LMW Resists typically have poor sensitivity - the bestfullerene resist sensitivity is ~ 370 µC/cm2.

Chemical Amplification to enhance sensitivity

Unexposed Resist Exposed Resist

PhotoacidGenerator H⊕ ∆T

hν

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


Meeting Commerical Requirements

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

(c)

(a) (b)

R R

R

R

RR

RR

O

O O O

O OO

O

Tetra, Penta, Hexa Mix

OH

OH

S+ S S+SbF6

- SbF6-

OO

OO

OO

1.8

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)

Nom

alis

ed F

ilm T

hick

ness

(%)

Dose (C/cm2)

550 µC/cm28 µC/cm2


MF07-01 CA Resist System

Name Number AverageMolecular Weight (Mn)

Number of Epoxy Groups

EpoxideEquivalent Weight

CL1-1

CL1-2

CL2-1

CL2-2

CL2-3

CL2-4

2.2

3.6

2.7

4.8

5.0

5.4

345

570

540

1080

870

1270

157

158

200

225

174

235

Poly[phenyl glycidyl ether)-co-formaldehyde]

Poly[(o-cresyl glycidyl ether)-co-formaldehyde]


Sensitivity vs Composition

Exposure = 20 keVDevelop = MCB:IPA [1:1]

PAB = 75 ºC for 600 sPEB = 90 °C for 180 s


Resolution vs CrosslinkerSparse Features


12 nm Linewidth

Dose = 300 pC/cm at 30 keVPAB = 75 ºC for 600sPEB = 90 °C for 180 sDev = 10 s, MCB:IPA [1:1]Rinse = 10 s, IPA

MF07-01 : CL1-1 : PAG

20 nm Half Pitch

Dose = 140 pC/cmPAB = 75 ºC for 600sPEB = 90 °C for 180 sDev = 10 s, MCB:IPA [1:1]Rinse = None

300 pC/cm


MF07-01 : CL1-1 : PAG15 nm Sparse Features


Line Width RoughnessSparse Resolutions of 12 nm and dense resolutions of 20nm have been achieved at < 10 µC/cm2 sensitivities. Linewidth roughness is typically about 4 - 5 nm, but < 2.0 nmhas been seen under certain circumstances.

Have studied line width roughness in relation to:

DosePitchPABPEBCrosslinker

PAG ConcentrationBase ConcentrationFilm ThicknessCasting SolventDeveloper

LWR measured with IMEL Demokritos software


Best LWRs

MF07-01:CL1-1:PAG [1: 2 :1]Cast ChloroformPAB 75 ºC, 5 minPEB 90 ºC, 3 minDev. MCB:IPA(1:1) / IPA rinseFilm thickness 35 nm

LWR = 2.2 nm, LW = 17.2 nm

MF0701:CL1-1:PAG [1: 2 :1] + Base 1wt%Cast ChloroformPAB 75 ºC, 10 minPEB 90 ºC, 3 minDev. MCB:IPA(1:1) / IPA rinseFilm thickness 35 nm

LWR = 2.1 nm, LW = 16.9 nm

MF0701:CL1-1:PAG [1: 2 :1]Cast ChloroformPAB 75 ºC, 10 minPEB 90 ºC, 3 minDev. MCB:IPA(1:1) / IPA rinseFilm thickness 62 nm

LWR = 1.9 nm, LW = 21.7 nm

LWR = 2.3 nm, LW = 13.5 nm MF07-01:CL1-1:PAG [1: 2 :1.25]Cast ChloroformPAB 75 ºC, 10 minPEB 90 ºC, 3 minDev. MCB:IPA(1:1) / IPA rinseFilm thickness 35 nm


Testing Commercial FeasibilityIn addition to showing high resolution and sensitivity and lowlinewidth roughness, it is necessary to quantify many otherparameters for full commercial feasiblity.

These include pattern transfer, stability to processconditions and ageing, exposure on industry standard toolsand so on. Much of the year prior to spin-out has focussedon addressing such issues.


Etch Durability

200 nm pitch Si structures

25 nm half pitch Si structures

Crosslinker CL1-1


Solvents

Chloroform

Anisole

PGM

EA

MCB Anisole:IPAAnisoleIPA:H2OMCB:IPA PGMEAMIBK:IPA Xylene TMAH

Developer

Casting S

olvent


Sensitivity vs PEB Temperature

MF07-01:CL1-1:PAG [1:2:1]

PAB = 75 ºC for 10 mPEB = Variable



Resolution vs PEB

PEB = 90 ºC, 3m No PEB

400 pC/cm 240 pC/cm

480 pC/cm 360 pC/cm

LW = 17 nmLWR = 3.8 nm

LW = 17 nmLWR = 3.4 nm

HP = 25 nmLWR = 4.0 nm

HP = 25 nmLWR = 5.2 nm


Sensitivity vs PED

MF07-01:CL1-1:PAG [1:2:1]

PAB = 75 ºC for 10 mPEB = 90 ºC for 3m



Resolution after 24 hr PED

PEB = 90 ºC, 3m No PEB

400 pC/cm 240 pC/cm

520 pC/cm 440 pC/cm

LW = 17 nm LW = 16 nm

HP = 25 nm HP = 25 nm


Ageing

New Resist Aged 7 days Aged 30 days


Initial EUV Results

Exposure time at PSI was kindly provided by Intel Corp, (Dr M.J. Leeson), and exposures were done with the assistance of Drs H. Solak, V. Auzelyte and P. Sahoo of the Paul Scherrer Institute

50 nm Half Pitch in CL2-4


Spinning OutWhere to Start

1. Identify business opportunity and draft summary overview. Include:a. What technology will business be based around?b. What is the business problem the technology can address ?c. Some basic information on the market the technology/business will enter (size, competition, etc…)

2. Approach University licensing group/departmenta. Ensure IPR is protected on technology. File patents if necessary.b. Liaise re: business opportunity and requirements (the licensing dept should be able to assist with many aspects of

the spin out process).

3. University Approvalsa. Head of Department; Faculty Board; Conflicts of Interest

4. Identify ‘start up’ teama. Inventors/researchers to be actively involved (part time or full time)b. Core management team (industry / business specialist)

5. Finalize legal detailsa. Equity split between inventors/researchers, university, management teamb. Company incorporation and articles of association etc…c. License agreements granting company rights to IPR

6. Identify sources of financinga. Start up funds via regional / governmental agencies (e.g. Proof of concept fund in Midlands)b. Private investment from local ‘angel groups’c. Local / regional development agencies for both equity investment and grant support (e.g. Mercia in Midlands for

equity investment, and AWM for matching grant support, IeMRC KTF etc).


Spinning OutNext Steps

• Detailed business planning:• Opportunity (problem and how it is addressed)• Details/dynamics of entry market/industry• Strategic planning (goals of business, business model, and exit opportunities)• Financing requirements and projections/forecasts

• Fund raising• Presentations to investors• Grant applications

• Operational expansion• Team• Facilities (equipment, locations etc…)

• Implementation of business plan• Technology development road map • Strategic alliances• Enhance IPR• Core technology and commercial milestones in line with core business strategy and model (leading to exit)

Once the company has been formed, the core team is in place, all relevant legal matters and approvals are in place the core management team (possibly only one ‘business oriented’ individual supported by the inventors/researchers at this stage) can move to the company forwards the following phases:


Spinning OutFinal Stages

• Acquisition or merger– The most likely scenario for success is a larger industry player acquiring the company– Could be a competitor or a collaborator / alliance partner– To maximize value, it is important to have more than one suitor– If company if merged with another private company, this will typically involve a tie up of stock into the merged

company, slowing down a cash exit.

• Continued operations– Expansion of company through a Series B, C, D etc… (as needed), onto ultimate profitability and ongoing payments of

dividends to stock holders.– Likely to end in an acquisition at a later stage at a higher valuation– Likely to involve a restructuring of management with initial founders often forced out

• Licensing model– Rather than selling the company to one acquirer, the core technology could be licensed to multiple parties

• IPO– The ultimate success story is often taking the company public. This will inevitably involve a number of additional

financing rounds as outlined in ‘Continued Operations’.– In the UK there is the AIM which offers a lower barrier to IPO’s (as low as 20M GBP valuations)

If successful with the technology development and associated road map/milestones, the business will ultimately ‘exit’ via one of the following routes:


AcknowledgmentsMr D. UreIrresistible Materials

Mr J. Manyam, Ms M-Y. Song, Mr J. Lawton, Mr C. Jones, Dr J. Yin, Dr A. Pulisciano, Dr H Zheng, DrF.P. Gibbons, Dr H.M. Zaid, Dr J.C. Barnard, Dr A.J. Parker, Dr M.R.C. Hunt, Prof. R.E. PalmerNanoscale Physics Research Laboratory, University of Birmingham

Dr U. Jonas, Prof. F. DiederichLaboratorium für Organische Chemie, ETH Zentrum, Switzerland

Dr S. Diegoli, Dr M. Manickam, Dr E.J. Shelley, Dr D. Philp, Dr M.T. Allen, Prof. K.D.M. Harris, Prof. J.A.PreeceSchool of Chemistry, The University of Birmingham, UK

Dr E. Tarte, Dr C. Anthony, Dr. J. TengSchool of Engineering, The University of Birmingham, UK

Dr T. Tada, Dr T. KanyamaJoint Research Center for Atom Technology, NAIR, Japan

Dr C. FigguresSowerby Research Centre, BAe Systems, UK

Dr J. Mackevich, Dr R. Brainard, Dr T. Zampini, Dr K. O’ConnellRohm and Haas (Electronic Materials), Marlborough USA

Dr J.H. TortaiCNRS, France

Dr L. RumizSincrotrone Trieste S.C.p.A., Italy

Dr M.J. LeesonIntel Corp

Dr H. Solak, Dr V. Auzelyte, Dr P. SahooPaul Scherrer Institute, Switzerland

more Moore


Thank You

Documents

A.P.G. Robinson Nanoscale Physics Research Laboratory The … · 2014-04-08 · the assistance of Drs H. Solak, V. Auzelyte and P. Sahoo of the Paul Scherrer Institute 50 nm Half