MERCK PATTERN ENHANCEMENT MATERIAL Product category : Merck PM-I, Global R&D Lithography, Global Application Asia 26 th January, 2017 PIP No. RDATW17004
optical theory(simple vertical incidence case) Air (n=1) (k=0) d wavelength ideal N MERCK n Optimal FT 365nm 1.33 1.42 64nm 248nm 1.33 1.45 43nm 193nm 1.30 1.52 30nm Resist A B R% on Si even with ideal : constant(54%) Required refractive index to be equalized light intensity in A and B n = (n air n resist ) 1/2 = n 1/2 resist n : Refractive index Required thickness to be shifted optical phase at π in A and B d =λ / 4n d : Film thickness of λ : Wavelength 2
Merck 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 3
Merck RD Road map 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) PFOS base ph adjustment AZ AQUATAR (n=1.44@365nm) PFOA base F-Polymer base AZ AQUARISTi 55 (n=1.44@365nm) AZ Exp. AQUARISTi-III 45 (n=1.44@365nm) PFOA base High wettability 199X 2003 2005 2007 2009 2011 2013 2015 Year 4
Material Properties of Merck i-line Cauchy parameter 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/nm 2 ) 5.226E+03 5.035E+03 4.619E+03 4.619E+03 C(1/nm 4 ) 0.000E+00 0.000E+00 0.000E+00 0.000E+00 *N 633nm 1.43 1.40 1.43 1.43 Cauchy expression: N λ = A + B/λ 2 +C/λ 4 *N value@633nm is calculated by Cauchy expression. 365nm wavelength AZ AQUATAR AZ AQUATAR-VIII-A 45 AZ AQUARISTi 55 AZ Exp. AQUARISTi-III 45 *N365nm 1.44 1.42 1.44 1.44 *K365nm 0.00 0.00 0.00 0.00 Optimal FT(nm) 63 63 63 63 Optimal FT(nm) = /4N λ *N/K values@365nm are measured by Ellipsometer(M2000D). Recommendations Process CBCB or CBC process( 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 5
Technical Summary of Merck i-line AZ AQUATAR AZ AQUATAR-8A 45 AZ AQUARISTi 55 AZ 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/cm 2 ) Coating defect on PR 0.03 0.02 0.02 0.02 Patterned defect 0.03 0.07 0.04 0.04 Resist compatibility 500nm L/S @950nm resist FT 6
Material Properties of Merck KrF Cauchy parameter AZ AQUATAR-VIII-A 30 AZ AQUATAR-8B 30 A 1.384 1.404 B(1/nm 2 ) 5.035E+03 5.100E+03 C(1/nm 4 ) 0.000E+00 0.000E+00 *N 633nm 1.40 1.42 Cauchy expression: N λ = A + B/λ 2 +C/λ 4 *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) = /4N λ *N/K values@365nm are measured by Ellipsometer(M2000D). Recommendations Process CBCB or CBC process( 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 7
Technical Summary of Merck KrF AZ AQUATAR-VIII-A 30 AZ AQUATAR-8B 30 Optical parameter N@248nm 1.45 1.46 Swing Reduction Ratio 86% 84% EL margin DoF margin@10%el Defect density (pcs/cm 2 ) Resist compatibility 200nm L/S @370nm resist FT 200nm L/S +/- 10% 20% 18% 200nm C/H +/- 10% 27% 26% 200nm L/S +/- 10% 1.5um 1.5um 200nm C/H +/- 10% 1.6um 1.5um Coating defect on Si 0.00 0.00 Patterned defect 0.03 0.05 without Resist compatibility 200nm C/H @370nm resist FT without 8
Merck 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 PFOA PFOX & C8 telomer free PFOX & C8 telomer free PFOX & C8 telomer free PFOX & C8 telomer free Application i-line i-line i-line All All i-line AQUARISTi series Next generation i-line (PFOX & Telomer free) to replace AQUATAR(PFOA) KrF & ArF-d AQUATAR-VIII-A Standard version, the most universal PFOX & Telomer free AQUATAR-8B Tuned for low activation CA resist, or negative CA resist 9
I-LINE APPLICATION 10
Swing Curve Process condition Resist illumination Develop Mask : Si with HMDS (90C60s) : AZ MiR-701, FT=various, PB=90C60s, PEB=110C90s : Merck s, FT=65nm, PB=90C60s : ASML/250 i-line stepper, NA=0.56, Sigma=0.75, Conventional : AZ 300MIF (2.38wt% TMAH), puddle 60s : 500nm L/S, Binary s Swing reduction ratio [1 (A / A w/o )] AZ AQUATAR 86% AZ AQUATAR-VIII-A 45 88% AZ AQUARISTi 55 86% AZ AQUARISTi-III 45 86% 11
Exposure Latitude Process condition Resist illumination Develop Mask : Si with HMDS (90C60s) : AZ MiR-701, FT=950nm, PB=90C60s, PEB=110C90s : Merck s, FT=65nm, PB=90C60s : ASML/250 i-line stepper, NA=0.56, Sigma=0.75, Conventional : AZ 300MIF (2.38wt% TMAH), puddle 60s : 500nm L/S, Binary s EL margin [500nm L/S : +/-10%] AZ AQUATAR 21% AZ AQUATAR-VIII-A 45 22% AZ AQUARISTi 55 21% AZ AQUARISTi-III 45 22% 12
DoF Process condition Resist illumination Develop Mask : Si with HMDS (90C60s) : AZ MiR-701, FT=950nm, PB=90C60s, PEB=110C90s : Merck s, FT=65nm, PB=90C60s : ASML/250 i-line stepper, NA=0.56, Sigma=0.75, Conventional : AZ 300MIF (2.38wt% TMAH), puddle 60s : 500nm L/S, Binary s AZ AQUATAR AZ AQUATAR-VIII-A 45 AZ AQUARISTi 55 AZ AQUARISTi-III 45 DoF margin@10% EL [500nm L/S : +/-10%] 1.2um 1.2um 1.2um 1.2um 13
Coating defectivity on PR Process condition Resist Inspection Review : Si with HMDS (90C60s) : AZ MiR-701, FT=950nm, PB=90C60s, PEB=110C90s : Merck s, FT=65nm, PB=90C60s : KLA KLA-2360, Pix. size = 0.39um, TH=20, visible : Hitachi RS-5500 AQUATAR AQUATAR-VIII-A 45 AQUARISTi 55 Exp. AQUARISTi-III 45 Particle Embedded Defect map Defect density (pcs/cm 2 ) 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 14
Patterned defectivity Process condition Resist illumination Develop Mask Inspection Review : Si with HMDS (90C60s) : AZ MiR-701, FT=950nm, PB=90C60s, PEB=110C90s : Merck s, FT=65nm, PB=90C60s : ASML/250 i-line stepper, NA=0.56, Sigma=0.75, Conventional : AZ 300MIF (2.38wt% TMAH), puddle 60s : 500nm L/S, Binary : KLA KLA-2360, Pix. size = 0.39um, TH=20, visible : Hitachi RS-5500 AQUATAR AQUATAR-VIII-A 45 AQUARISTi 55 Exp. AQUARISTi-III 45 Particle Embedded Defect map Pinching Defect density (pcs/cm 2 ) 0.03 0.07 0.05 0.04 Defect classification Particle 0.02 0.05 0.03 0.03 Pinching 0.01 0.01 0.01 0.01 Embedded - 0.01 0.01-15
KRF APPLICATION 16
Swing Curve Process condition Resist illumination Develop Mask : AZ KrF-17B, FT=80nm, PB=180C60s : AZ DX7260P, FT=various, PB=120C90s, PEB=130C90s : Merck s, FT=45nm, PB=No : Canon EX-5 stepper, NA=0.63, 1/2 Annular(0.8/0.4) : AZ 300MIF (2.38wt% TMAH), puddle 60s : 200nm L/S, Binary s Swing reduction ratio [1 (A / A w/o )] AZ AQUATAR-VIII-A 30 88% AZ AQUATAR-8B 30 88% 17
Swing Curve Process condition Resist illumination Develop Mask : AZ KrF-17B, FT=80nm, PB=180C60s : AZ DX7260P, FT=various, PB=120C90s, PEB=130C90s : Merck s, FT=45nm, PB=No : Canon EX-5 stepper, NA=0.63, 1/2 Annular(0.8/0.4) : AZ 300MIF (2.38wt% TMAH), puddle 60s : 200nm L/S, Binary s EL margin [200nm L/S : +/-10%] AZ AQUATAR-VIII-A 30 20% AZ AQUATAR-8B 30 18% 18
DoF Process condition Resist illumination Develop Mask : AZ KrF-17B, FT=80nm, PB=180C60s : AZ DX7260P, FT=various, PB=120C90s, PEB=130C90s : Merck s, FT=45nm, PB=No : Canon EX-5 stepper, NA=0.63, 1/2 Annular(0.8/0.4) : AZ 300MIF (2.38wt% TMAH), puddle 60s : 200nm L/S, Binary s AZ AQUATAR-VIII-A 30 AZ AQUATAR-8B 30 DoF margin [Target CD 200nm+/- 10%] 1.5 um 1.5 um 19
Coating defectivity on PR Process condition Resist Inspection Review : AZ KrF-17B, FT=80nm, PB=180C60s : AZ DX7260P, FT=370nm, PB=120C90s, PEB=130C90s : Merck s, FT=45nm, PB=NO : KLA KLA-2360, Pix. size = 0.25um, TH=20, visible : Hitachi RS-5500 without AQUATAR-VIII-A AQUATAR-8B Particle Defect map Defect density (pcs/cm 2 ) 0.00 0.00 0.00 Defect classification Particle 0.00 0.00 0.00 20
Patterned defectivity Process condition Resist illumination Develop Mask Inspection Review : AZ KrF-17B, FT=80nm, PB=180C60s : AZ DX7260P, FT=370nm, PB=120C90s, PEB=130C90s : Merck s, FT=45nm, PB=NO : Canon EX-5 stepper, NA=0.63, 1/2 Annular(0.8/0.4) : AZ 300MIF (2.38wt% TMAH), puddle 60s : 200nm L/S, Binary : KLA KLA-2360, Pix. size = 0.25um, TH=20, visible : Hitachi RS-5500 AQUATAR AQUATAR-VIII-A 45 AQUARISTi 55 Particle Defect map Defect density (pcs/cm 2 ) 0.04 0.03 0.05 Bridge Defect classification Particle 0.03 0.03 0.04 Bridge 0.01-0.01 21
APPENDIX 22
Chemical & Filter Compatibility DIW Alcohol (IPA, MeOH) Developer (TMAH) Hydrophilic Solvent (PGME etc) Hydrophobic Solvent (PGMEA etc) Acid () 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 VS(Very Soluble): >10%, S(Soluble): 10-1.0%, SS(Slightly Soluble): 1.0-0.1%, IS(Insoluble): <0.1% Nylon PE PTFE hydrophilic hydrophobic hydrophilic hydrophobic PP AZ AQUATAR AZ AQUATAR-VIII-A AZ Exp. AQUARSITi-III 45 X O O with pre-wet treatment O O with pre-wet treatment X Filter suppliers Entegris : Nylon, PE, PTFE Pall : Nylon, PE 3M : Nylon, PE, PTFE, PP Recommend the smallest pore size with proper pump condition 23
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/s Particle 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/shot Particle check NG: go to step-6 8 Replace from DIW to 2 GAL DR=2.15ml/s, DV=8ml/shot - 9 Flush the line 1 GAL DR=0.5-1.0ml/s, DV=8ml/shot 10 Set the parameters - - DR=0.5-1.0ml/s Particle check NG: go to step-8 Particle 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 24 DR: Dispense Rate DV: Dispense Volume
Standard Coating Recipe - SOKUDO RF-3(12inch) - Step Time (sec) Spin (rpm) Stamic Coating Acceleration (rpm/s) Dispense Arm-1 Arm-2 1 0.5 0 10000 center home 2 4 0 10000 center home 3 0.5 1000 2500 center home 4 0.5 400 4000 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 Rinse BR: Back Rinse AD: Auto Damper Dispense rate = 1cc/s 25
Film Coverage on PR Process condition Resist : Si with HMDS (90C60s) : AZ MiR-701, FT=950nm, PB=90C60s, PEB=110C90s : Merck s, FT=65nm, PB=90C60s AZ AQUATAR AZ AQUATAR-VIII-A 45 AZ AQUARISTi 55 AZ Exp. AQUARISTi-III 45 Max. Resist Si Min. Coverage image Type Conformal Planar Planar Conformal Max. 66nm 78nm 80nm 68nm FT Min. 63nm 40nm 35nm 63nm Range 3nm 38nm 45nm 5nm 26
Minimal dispense volume on Si WF (8inch) Process condition FT measurement : 8inch Si : Merck s, FT=65nm, PB=90C60s : DNS VM-2110, Mea. points = 19 points Dispense volume ( ml / 8inch WF ) AZ AQUATAR (Ref.) AZ AQUATAR-VIII-A 45 AZ Exp. AQUARISTi-III 45 Film Thickness (A) 0.5 1.0 1.5 2.0 2.5 3.0 Ave. - 653 651 650 - - σ - 4.9 4.9 3.2 - - Minimal disp. volume X X O O OO OO Film Thickness (A) Ave. - - 654 650 649 649 σ - - 4.8 3.7 3.4 2.7 Minimal disp. volume X X X O O OO Film Thickness (A) Ave. 390 661 655 653 650 651 σ 341.4 8.5 3.9 3.5 2.7 2.7 Minimal disp. volume X X O O OO OO Minimal dispense volume on 8inch Si WF AZ AQUATAR : > 2.0 ml AZ AQUATAR-VIII-A 45 : > 2.5 ml 27 AZ Exp.AQUARISTi-III 45 : > 2.0 ml
Minimal dispense volume on PR WF (8inch) Process condition Resist FT measurement : 8inch Si : AZ MiR703, FT=950nm, PB=90C90s : Merck s, FT=65nm, PB=90C60s : DNS VM-2110, Mea. points = 19 points Dispense volume ( ml / 8inch WF ) AZ AQUATAR (Ref.) AZ AQUATAR-VIII-A 45 AZ Exp. AQUARISTi-III 45 Film Thickness (A) 0.5 1.0 1.5 2.0 2.5 3.0 Ave. 651 650 650 - - - σ 4.9 3.2 3.0 - - - Minimal disp. volume O O OO OO OO OO Film Thickness (A) Dispense volume ( ml / 8inch WF ) 2.5 3.0 3.5 4.0 4.5 5.0 Ave. - - 660 650 650 - σ - - 4.6 4.2 3.3 - Minimal disp. volume X X X O O OO Film Thickness (A) Ave. - 663 652 650 - - σ - 8.3 3.9 3.5 - - Minimal disp. volume X X O O OO OO Minimal dispense volume on 8inch PR WF AZ AQUATAR : > 1.0 ml 28 AZ AQUATAR-VIII-A 45 : > 4.5 ml AZ Exp.AQUARISTi-III 45 : > 4.0 ml
Contact angle data on several kinds of substrate Process condition Equipment : Drop Master 700 Measurement method : Liquid dropping method Dropping volume : 1.5uL of s Needle : Teflon coating Contact 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 29