merck pattern enhancement material · pdf file22 confidential merck pattern enhancement...

$: MERCK PATTERN ENHANCEMENT MATERIAL · PDF file22 Confidential Merck Pattern Enhancement Material TARC optical theory(simple vertical incidence case) Required refractive index to be$
Merck PM-I, Global R&D Lithography, Global Application Asia26th January, 2017

Product category : TARC

MERCK PATTERN ENHANCEMENT MATERIAL

PIP No. RDATW17004

2 Confidential2

Merck Pattern Enhancement Material

TARC optical theory(simple vertical incidence case)

Required refractive index to be equalized light intensity in A and B

nTARC = (nairnresist)1/2 = nresist

1/2 n : Refractive index

Required thickness to be shifted optical phase at π in A and B

d =λ / 4nTARC d : Film thickness of TARC

λ : Wavelength

wavelengthideal NTARC

MERCK TARCn

OptimalTARC FT

365nm 1.33 1.42 64nm

248nm 1.33 1.45 43nm

193nm 1.30 1.52 30nm

A B

Resist

Substrate

d

Air (n=1)

TARC(k=0)

R% on Si even with ideal TARC: constant(54%)

Merck pattern enhancement material

3 Confidential3


Merck TARC concept

Industry Standard

Almost 100% of market share for i-line

>90% of market share for KrF & ArF-d

Chemicals

Fluorine polymer chemistry with surfactant in water solvent

Acid and foaming material

Reflectivity Control

Lowest refractive index & no absorbance based on optical theory

Human & Environment Friendly

From Surfactant to Polymer chemistry

PBT(Persistency, Bioaccumulation, Toxicity)

Resist Compatibility

Management of acidity for CA resist

No intermixing with resist

Easy Process & Side Benefit

Removal with water, TMAH during resist development

Defect reduction by surfactant function


4 Confidential4


Merck TARC RD Road map

2003199X 2005 2007 2013 Year2009 2011 2015

PFOA base

PFOA base F-Polymer base

High

wettability

PFOS base pH adjustment

PFOA base F-Polymer base

AZ AQUATAR-III

(n=1.44@248nm)

AZ AQUATAR-VIII-A

(n=1.44@248nm)

AZ AQUATAR-8B

(n=1.46@248nm)

AZ AQUATAR

(n=1.44@365nm)

AZ AQUARISTi 55

(n=1.44@365nm)

AZ Exp.

AQUARISTi-III 45

(n=1.44@365nm)


5 Confidential5


Material Properties of Merck i-line TARC

Cauchyparameter

AZ AQUATAR AZ AQUATAR-VIII-A 45 AZ AQUARISTi 55 AZ Exp. AQUARISTi-III 45

A 1.412 1.384 1.420 1.420

B(1/nm2) 5.226E+03 5.035E+03 4.619E+03 4.619E+03

C(1/nm4) 0.000E+00 0.000E+00 0.000E+00 0.000E+00

*N633nm 1.43 1.40 1.43 1.43

Cauchy expression: Nλ = A + B/λ2+C/λ4

*N value@633nm is calculated by Cauchy expression.

365nmwavelength


*N365nm 1.44 1.42 1.44 1.44

*K365nm 0.00 0.00 0.00 0.00

OptimalFT(nm)

63 63 63 63

Optimal FT(nm) = /4Nλ

*N/K values@365nm are measured by Ellipsometer(M2000D).

Recommendations• Process

“CBCB” or “CBC” process(TARC PAB: 90C60s) “Static” or “Stamic” coating DIW pre-removal in resist dev. process

• Utility EBR/BSR by DIW Dedicated cup, tube, connection & pump for “acid material” PE filter with pre-wet treatment

• Treatment Don’t mixed with alkaline base materials(AZ Shrink

Materials etc.) Follow local chemical regulation for waste TARC


6 Confidential6


Technical Summary of Merck i-line TARC

AZ AQUATAR AZ AQUATAR-8A 45 AZ AQUARISTi 55AZ Exp.

AQUARISTi-III 45

Optical parameter N@365nm 1.44 1.42 1.44 1.44

Swing Reduction Ratio 86% 88% 86% 86%

EL margin 500nm L/S +/- 10% 21% 22% 21% 22%

DoF margin@10%EL 500nm L/S +/- 10% 1.2um 1.2um 1.2um 1.2um

Defect density(pcs/cm2)

Coating defect on PR 0.03 0.02 0.02 0.02

Patterned defect 0.03 0.07 0.04 0.04

Resist compatibility500nm L/S

@950nm resist FT


7 Confidential7


Material Properties of Merck KrF TARC

Cauchy parameter AZ AQUATAR-VIII-A 30 AZ AQUATAR-8B 30

A 1.384 1.404

B(1/nm2) 5.035E+03 5.100E+03

C(1/nm4) 0.000E+00 0.000E+00

*N633nm 1.40 1.42

Cauchy expression: Nλ = A + B/λ2+C/λ4

*N value@633nm is calculated by Cauchy expression.

365nm wavelength AZ AQUATAR-VIII-A 30 AZ AQUATAR-8B 30

*N365nm 1.45 1.46

*K365nm 0.00 0.00

Optimal FT(nm) 43 42

Optimal FT(nm) = /4Nλ

*N/K values@365nm are measured by Ellipsometer(M2000D).

Recommendations• Process

“CBCB” or “CBC” process(TARC PAB: 90C60s) “Static” or “Stamic” coating DIW pre-removal in resist dev. process

• Utility EBR/BSR by DIW Dedicated cup, tube, connection & pump for “acid material” PE filter with pre-wet treatment

• Treatment Don’t mixed with alkaline base materials(AZ Shrink Materials etc.) Follow local chemical regulation for waste TARC


8 Confidential8


Technical Summary of Merck KrF TARC

AZ AQUATAR-VIII-A 30 AZ AQUATAR-8B 30

Optical parameter N@248nm 1.45 1.46

Swing Reduction Ratio 86% 84%

EL margin200nm L/S +/- 10% 20% 18%

200nm C/H +/- 10% 27% 26%

DoF margin@10%EL200nm L/S +/- 10% 1.5um 1.5um

200nm C/H +/- 10% 1.6um 1.5um

Defect density(pcs/cm2)

Coating defect on Si 0.00 0.00

Patterned defect 0.03 0.05

Resist compatibility200nm L/S

@370nm resist FT

Resist compatibility200nm C/H

@370nm resist FT without TARC

without TARC


9 Confidential9


Merck TARC Product Line Up

Product Name AZ AQUATAR AZ AQUARISTi AZ Exp. AQUARISTi-III AZ AQUATAR-VIII-A AZ AQUATAR-8B

Grade 65 55 45 25/30/45 30

FT@2500rpm 72nm 54nm 49nm 24/36/49nm 33nm

n@193nm 1.56 1.55 1.55 1.52 1.55

n@248nm 1.48 1.48 1.48 1.45 1.46

n@365nm 1.44 1.44 1.44 1.42 1.43

Chemical PFOAPFOX &

C8 telomer freePFOX &



C8 telomer free

Application i-line i-line i-line All All

i-line TARC

• AQUARISTi series

Next generation i-line TARC(PFOX & Telomer free) to replace AQUATAR(PFOA)

KrF & ArF-d TARC

• AQUATAR-VIII-A

Standard version, the most universal PFOX & Telomer free TARC

• AQUATAR-8B

Tuned for low activation CA resist, or negative CA resistMerck pattern enhancement material

10 Confidential

I-LINE APPLICATION

11 Confidential11


Swing Curve

TARCsSwing reduction ratio[1 – (ATARC / Aw/o TARC)]

AZ AQUATAR 86%

AZ AQUATAR-VIII-A 45 88%

AZ AQUARISTi 55 86%

AZ AQUARISTi-III 45 86%

Process condition

Substrate : Si with HMDS (90C60s)

Resist : AZ MiR-701, FT=various, PB=90C60s, PEB=110C90s

TARC : Merck TARCs, FT=65nm, PB=90C60s

illumination : ASML/250 i-line stepper, NA=0.56, Sigma=0.75, Conventional

Develop : AZ 300MIF (2.38wt% TMAH), puddle 60s

Mask : 500nm L/S, Binary


12 Confidential12


Exposure Latitude

TARCsEL margin

[500nm L/S : +/-10%]

AZ AQUATAR 21%


AZ AQUARISTi 55 21%

AZ AQUARISTi-III 45 22%

Process condition


Resist : AZ MiR-701, FT=950nm, PB=90C60s, PEB=110C90s






13 Confidential13


DoF

TARCsDoF margin@10% EL

[500nm L/S : +/-10%]

AZ AQUATAR 1.2um

AZ AQUATAR-VIII-A 45 1.2um

AZ AQUARISTi 55 1.2um

AZ AQUARISTi-III 45 1.2um

Process condition








14 Confidential14


Coating defectivity on PR

AQUATAR AQUATAR-VIII-A 45 AQUARISTi 55Exp.

AQUARISTi-III 45

Defectmap

Defect density (pcs/cm2) 0.03 0.02 0.02 0.02

Defect classification

Particle 0.02 0.01 0.02 0.01

Embedded 0.01 0.01 - 0.01

Process condition




Inspection : KLA KLA-2360, Pix. size = 0.39um, TH=20, visible

Review : Hitachi RS-5500

EmbeddedParticle


15 Confidential15 Merck pattern enhancement material


Patterned defectivity

AQUATAR AQUATAR-VIII-A 45 AQUARISTi 55Exp.

AQUARISTi-III 45

Defectmap

Defect density (pcs/cm2) 0.03 0.07 0.05 0.04


Particle 0.02 0.05 0.03 0.03

Pinching 0.01 0.01 0.01 0.01

Embedded - 0.01 0.01 -

Process condition









EmbeddedParticle

Pinching

16 Confidential

KRF APPLICATION

17 Confidential17


Swing Curve

TARCsSwing reduction ratio[1 – (ATARC / Aw/o TARC)]


AZ AQUATAR-8B 30 88%

Process condition

Substrate : AZ KrF-17B, FT=80nm, PB=180C60s

Resist : AZ DX7260P, FT=various, PB=120C90s, PEB=130C90s

TARC : Merck TARCs, FT=45nm, PB=No

illumination : Canon EX-5 stepper, NA=0.63, 1/2 Annular(0.8/0.4)




18 Confidential18


Swing Curve

TARCsEL margin

[200nm L/S : +/-10%]


AZ AQUATAR-8B 30 18%

Process condition








19 Confidential19


DoF

TARCsDoF margin

[Target CD 200nm+/- 10%]

AZ AQUATAR-VIII-A 30 1.5 um

AZ AQUATAR-8B 30 1.5 um

Process condition








20 Confidential20

without TARC AQUATAR-VIII-A AQUATAR-8B

Defectmap

Defect density (pcs/cm2) 0.00 0.00 0.00


Particle 0.00 0.00 0.00


Coating defectivity on PR

Process condition


Resist : AZ DX7260P, FT=370nm, PB=120C90s, PEB=130C90s

TARC : Merck TARCs, FT=45nm, PB=NO



Particle


21 Confidential21

AQUATAR AQUATAR-VIII-A 45 AQUARISTi 55

Defectmap

Defect density (pcs/cm2) 0.04 0.03 0.05


Particle 0.03 0.03 0.04

Bridge 0.01 - 0.01


Patterned defectivity

Process condition


Resist : AZ DX7260P, FT=370nm, PB=120C90s, PEB=130C90s

TARC : Merck TARCs, FT=45nm, PB=NO






Bridge

Particle


22 Confidential

APPENDIX

23 Confidential23


Chemical & Filter Compatibility

TARC DIWAlcohol

(IPA, MeOH)Developer(TMAH)

HydrophilicSolvent

(PGME etc)

HydrophobicSolvent

(PGMEA etc)

Acid(TARC)

Base(SHM)

AZ AQUATAR VS VS VS VS IS VS IS

AZ AQUATAR-VIII-A VS VS VS VS IS VS IS

AZ Exp. AQUARSITi-III 45 VS VS VS VS IS VS IS

TARC NylonPE PTFE

PPhydrophilic hydrophobic hydrophilic hydrophobic

AZ AQUATAR

X OO

with pre-wet treatment

O Owith pre-wet treatment

XAZ AQUATAR-VIII-A

AZ Exp. AQUARSITi-III 45

VS(Very Soluble): >10%, S(Soluble): 10-1.0%, SS(Slightly Soluble): 1.0-0.1%, IS(Insoluble): <0.1%

Filter suppliersEntegris : Nylon, PE, PTFEPall : Nylon, PE 3M : Nylon, PE, PTFE, PP

• Recommend the smallest pore size with proper pump condition


24 Confidential24


Install Guide (Use the virgin line)

Step Process Solvent Usage Condition Check

1 Flash the line IPA 2 GAL DR=2.0ml/s －

2 Fill in the line IPA － Fill IPA in the line for 1 day －

3 Flush the line IPA 1/2 GAL DR=2.0ml/sParticle check

NG: go to step-1

4 Set up the Filter －－ IPA pre-wet treatment －

5 Flush the line IPA 1 GAL DR=2.15ml/s, DV=8ml/shot －

6 Replace from IPA to DIW DIW 2 GAL DR=2.15ml/s, DV=8ml/shot －

7 Flush the line DIW 1 GAL DR=0.5-1.0ml/s, DV=8ml/shotParticle check

NG: go to step-6

8 Replace from DIW to TARC TARC 2 GAL DR=2.15ml/s, DV=8ml/shot －

9 Flush the line TARC 1 GAL DR=0.5-1.0ml/s, DV=8ml/shotParticle check

NG: go to step-8

10 Set the parameters －－ DR=0.5-1.0ml/sParticle check

NG: go to step-9

Particle check method

• Preparation of a clean Si wafer(pre-particle check)• Material dispense on the Si wafer• Spin dry@2500rpm• Baking@100C for 60s• Particle check by defect inspection tool

DR: Dispense RateDV: Dispense Volume


25 Confidential25


Standard Coating Recipe - SOKUDO RF-3(12inch) -

Stamic Coating

StepTime(sec)

Spin(rpm)

Acceleration(rpm/s)

Dispense Arm-1 Arm-2

1 0.5 0 10000 center home

2 4 0 10000 TARC center home

3 0.5 1000 2500 TARC center home

4 0.5 400 4000 TARC center home

5 5.5 400 4000 home home

6 25 X 10000 home home

7 3 500 1000 home home

8 0.5 1500 1600 SR/BR home home

9 5.5 1500 10000 SR/BR/AD home home

10 1 1500 10000 SR/BR home home

11 5 1500 3000 home home

12 0.5 0 10000 home home

SR: Side RinseBR: Back Rinse

AD: Auto DamperDispense rate = 1cc/s


26 Confidential26


TARC Film Coverage on PR


Coverageimage

Type Conformal Planar Planar Conformal

TARC FT

Max. 66nm 78nm 80nm 68nm

Min. 63nm 40nm 35nm 63nm

Range 3nm 38nm 45nm 5nm

Process condition




Resist

TARC

Si

Max. Min.


27 Confidential27


Minimal dispense volume on Si WF (8inch)

Minimal dispense volume on 8inch Si WFAZ AQUATAR : > 2.0 mlAZ AQUATAR-VIII-A 45 : > 2.5 mlAZ Exp.AQUARISTi-III 45 : > 2.0 ml

Process condition

Substrate : 8inch Si


FT measurement : DNS VM-2110, Mea. points = 19 points

Dispense volume ( ml / 8inch WF )

0.5 1.0 1.5 2.0 2.5 3.0

AZ AQUATAR(Ref.)

FilmThickness

(A)

Ave. - 653 651 650 - -

σ - 4.9 4.9 3.2 - -

Minimal disp. volume X X O O OO OO

AZ AQUATAR-VIII-A 45

FilmThickness

(A)

Ave. - - 654 650 649 649

σ - - 4.8 3.7 3.4 2.7

Minimal disp. volume X X X O O OO

AZ Exp.AQUARISTi-III 45

FilmThickness

(A)

Ave. 390 661 655 653 650 651

σ 341.4 8.5 3.9 3.5 2.7 2.7



28 Confidential28


Minimal dispense volume on PR WF (8inch)

Minimal dispense volume on 8inch PR WFAZ AQUATAR : > 1.0 mlAZ AQUATAR-VIII-A 45 : > 4.5 mlAZ Exp.AQUARISTi-III 45 : > 4.0 ml

Process condition

Substrate : 8inch Si

Resist : AZ MiR703, FT=950nm, PB=90C90s


FT measurement : DNS VM-2110, Mea. points = 19 points


0.5 1.0 1.5 2.0 2.5 3.0

AZ AQUATAR(Ref.)

FilmThickness

(A)

Ave. 651 650 650 - - -

σ 4.9 3.2 3.0 - - -

Minimal disp. volume O O OO OO OO OO


2.5 3.0 3.5 4.0 4.5 5.0

AZ AQUATAR-VIII-A 45

FilmThickness

(A)

Ave. - - 660 650 650 -

σ - - 4.6 4.2 3.3 -

Minimal disp. volume X X X O O OO

AZ Exp.AQUARISTi-III 45

FilmThickness

(A)

Ave. - 663 652 650 - -

σ - 8.3 3.9 3.5 - -



29 Confidential29


Contact angle data on several kinds of substrate

Process condition

Equipment : Drop Master 700

Measurement method : Liquid dropping method

Dropping volume : 1.5uL of TARCs

Needle : Teflon coating

SubstrateContact angle (deg.)

AZ AQUATAR AZ AQUARISTi AZ Exp. AQUARISTi-III AZ AQUATAR-VIII-A AZ AQUATAR-8B

Si < 10 < 10 < 10 < 10 < 10

AZ MiR703 20 35 28 30 29

AZ DX6270P < 10 - - 24 25

AZ AX2110P < 10 - - 10 12


merck pattern enhancement material · pdf file22 confidential merck pattern enhancement...

Documents