Materials Science

Volume 6, Number 1

TM

Patterning Tomorrows Electronics

/

Methods for Nanopatterning and Lithography

SIGMA_MM6-1_JP_110525.indd a2 11.5.26 4:10:12 PM

Volume 6, Number 1

TM

2011Material Matters

IBM Almaden Research Center193 nmFraunhofer InstituteChemnitz University of TechnologyGlasgowFaiz RahmanSheffieldGraham LeggettUVUV10 nm

45 nm10 nmUV

20116Websigma-aldrich.com/japan

sigma-aldrich.com/japan

Kaushik Patel, Ph.D.Materials ScienceSigma-Aldrich Corporation

Your Materials Matter.

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SIGMA_MM6-1_JP_110525.indd 2 11.5.26 4:10:14 PM

Wisconsin-MadisonPaul Nealey4-vinylbenzocyclobuteneVBCBAldrich733377 1250VBCBTg 2

Your Material Matters

Jeff Thurston, PresidentAldrich Chemical Co., Inc.

HFA-MA

193 nm 8

UV UV 8

PAG 11

12

18

ITOFTO 19

PEDOT

22

27

PMMAPDMS 29

References(1) Ryu, D. Y.; Shin, K.; Drockenmuller, E.; Hawker, C. J.; Russell, T. P. Science 2005,

308, 236-239.(2) So, Y.-H.; Hahn, S. F.; Li, Y.; Reinhard, M. T. J. Polym. Sci., Part A: Polym. Chem. 2008, 46,

2799-2806

sialjpts@sial.com

enetub olcyc ozneb lyniV-4VBCB[99717-87-0] C10H10 FW 130.19

H2C

733377-1G 1g

Tel:03-5796-7340Fax:03-5796-7345 E-mail : safcjp@sial.com

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SIGMA_MM6-1_JP_110525.indd 3 11.5.26 4:10:15 PM

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Moore's Law1 1,2

solubility switch 3-5PAGphotoacid generator 3-5

1

RNAk10.50.25 1,2 1-54-PHSpolyhydroxystyrene248 nm193 nm193 nm 3-51248 nm0.26NTMAH193 nm

Daniel P. Sanders, Ratnam Sooriyakumaran, Richard A. DiPietro*

IBM Almaden Research Center, San Jose, CA

*Email: dipietro@almaden.ibm.com

1 1

Positive tone

Negative tone

DevelopRelief Image

TransferPattern

StripResist Film

ExposePattern

ApplyResist Film

substrate resist

mask

R = k1NA

Tel:03-5796-7330Fax:03-5796-7335 E-mail : sialjpts@sial.comsi

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SIGMA_MM6-1_JP_110525.indd 4 11.5.26 4:10:16 PM

HFA 3,6HFA1,1,1,3,3,3-hexafluoro-2-propanolAldrich325244pKa11 7

HFA248 nm193 nm157 nmHFA2193 nm 3,6,8-10

3QCMquartz crystal microbalanceHFAPoly1

HFA2HFAAIBN110 kDaCTAchain transfer agent1-dodecanethiolAldrich471364CTAHFA 11,1245HFA 6,8-10 1TMAH 12-14

2 193 nmHFA

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4

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CF 3F3 C OH

Polymerizable group

Linking group

Hydrophobic, alkali soluble group

400

350

300

250

200

150

100

50

0

1000

800

600

400

200

0

Time in 0.26 N TMAH (seconds)

Calc

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(nm

)

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tfihS

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Thickness Resistance Shift

130 nm/s

0 2 4 6 8 10

175

150

125

100

75

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0

1000

800

600

400

200

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Time in 0.26 N TMAH (seconds)

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3 QCMpolymethyl methacrylate-co-methacrylic acid 41Aldrich37691421HFA

PolymeraMn

[g/mol] PDI T

Dissolution Rate in TMAH Static water contact angle

Static, advancing contact angleb

Static, receding contact angleb0.26N 0.52N

Poly(1) 4220 1.56 89 C 125 nm/s 1010 nm/s 83 87 66

Poly(2) 6130 1.14 66 C 990 nm/s - 71 77 50

Poly(3) 5920 1.56 55 C 245 nm/s - 75 83 58

Poly(4) 9290 1.32 159 C ~0 nm/s 3.2 nm/s 77 81 65

Poly(5) 11000 1.26 148 C ~0 nm/s ~0 nm/s 86 86 74

aPrepared from Monomers 1-5 in Figure 2, respectively, using AIBN-initiated free radical polymerization. bMeasured using a tilting table contact angle goniometer.

1 HFAUV

Tel:03-5796-7340Fax:03-5796-7345 E-mail : safcjp@sial.com

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SIGMA_MM6-1_JP_110525.indd 5 11.5.26 4:10:17 PM

/HFA193 nm

4248 nm193 nm254 nm Hg/Xe248 nm193 nmTMAHLERline edge roughnessLWRline width roughness 44HFA248 nm 8,9

193 nm

157 nm193 nm 151hyper-NA 15193 nm o/n o193 nm

16,175 16-18 16film pulling 19 16-17,19

HFATMAH 12-14,16,20HFA

4 248 nm193 nmpolyt-butyl methacrylate-co-4HFA193 nm

@254 nm exposure: 0 mJ/cm2

1.5 mJ/cm2

2 mJ/cm2

5 mJ/cm2

5 mJ/cm2

7 mJ/cm2

8 mJ/cm2

10 mJ/cm2

20 mJ/cm2

Time in 0.26N TMAH (seconds)

Time in 0.26N TMAH (seconds)

Time in Developer (seconds)

@254 nm exposure: 3 mJ/cm2

4 mJ/cm2

5 mJ/cm2

6 mJ/cm2

Thic

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m)

Thic

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s (n

m)

Thic

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0 10 20 30 40 50 60 70 80 90

0 10 20 30 40 50 60 70 80 90

0 10 20 30 40 50 60 70 80 90

500

400

300

200

100

0

500

400

300

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100

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500

400

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bottom element

Water

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resist componentextraction

particlesbubbles

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amine contamination

intermixing

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SIGMA_MM6-1_JP_110525.indd 6 11.5.26 4:10:18 PM

66 12,161,1,1,3,3,3-hexafluoroprop-2-yl methacrylate6 7 -6 82-acrylamido-2-methyl-1-propanesulfonic acidT-top 14

193 nm

- 16

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References(1) Wallraff , G. M.; Hinsberg, W. D. Chem. Rev. 1999, 99, 1801.(2) Mack, C. Fundamental Principles of Optical Lithography: The Science of Microfabrication.

Wiley: West Sussex, England, 2008.(3) Ito, H. Adv. Polym. Sci. 2005, 172, 37.(4) MacDonald, S. A.; Willson, C. G.; Frchet, J. M. J. Acc. Chem. Res. 1994, 27, 153.(5) Reichmanis, E.; Houlihan, F. M.; Nalamasu, O.; Neenan, T. X. Chem. Mater. 1991, 3, 394.(6) Ito, H.; Truong, H. D.; Allen, R. D.; Li, W.; Varanasi, P. R.; Chen, K.-J.; Khojasteh, M.;

Huang, W.-S.; Burns, S. D.; Pfeiff er, D. Polym. Adv. Technol. 2006, 17, 104.(7) Gandler, J. R.; Jencks, W. P. J. Am. Chem. Soc. 1982, 104, 1937.(8) Varanasi, P. R.; Kwong, R. W.; Khojastech, M.; Patel, K.; Chen, K-J.; Li, W.; Lawson, M. C.;

Allen, R. D.; Sooriyakumaran, R.; Brock, P.; Sundberg, L. K.; Slezak, M.; Dabbagh, G.;Liu, Z.; Nishimura, Y.; Chiba, T.; Shimokawa, T. J. Photopolym. Sci. Technol.2005, 18, 381.

(9) Varanasi, P. R.; Kwong, R. W.; Khojastech, M.; Patel, K.; Chen, K-J.; Li, W.; Lawson, M. C.;Allen, R. D.; Sooriyakumaran, R.; Brock, P.; Sundberg, L. K.; Slezak, M.; Dabbagh, G.;Liu, Z.; Nishimura, Y.; Chiba, T.; Shimokawa, T. Proc. SPIE 2005, 5753, 131.

(10) Patel, K.; Lawson, M.; Varanasi, P.; Medeiros, D.; Wallraff , G.; Brock, P.; DiPietro, R.;Nishimura, Y.; Chiba, T.; Slezak, M. Proc. SPIE 2004, 5376, 94.

(11) Allen, R. D.; Breyta, G.; Brock, P.; DiPietro, R.; Sanders, D.; Sooriyakumaran, R.;Sundberg, L. K. J. Photopolym. Sci. Technol. 2006, 19, 569.

(12) Sanders, D. P.; Sundberg, L. K.; Sooriyakumaran, R.; Brock, P. J.; DiPietro, R. A.;Truong, H. D.; Miller, D. C.; Lawson, M. C.; Allen, R. D. Proc. SPIE 2007, 6519, 651904.

(13) Allen, R. D.; Brock, P. J.; Sundberg, L.; Larson, C. E.; Wallraff , G. M.; Hinsberg, W. D.;Meute, J.; Shimokawa, T.; Chiba, T.; Slezak, M. J. Photopolym. Sci. Technol.2005, 18, 615.

(14) Khojasteh, M.; Popova, I.; Varanasi, P. R.; Sundberg, L.; Robinson, C.; Corliss, D.;Lawson, M.; Dabbagh, G.; Slezak, M.; Colburn, M.; Petrillo, K. Proc. SPIE2007, 6519, 651907.

(15) Lin, B. J. J. Microlith., Microfab., Microsyst. 2004, 3, 377.(16) Sanders, D. P. Chem. Rev. 2010, 110, 321.(17) Wei, Y.; Brainard, R. L. Advanced Processes for 193-nm Immersion Lithography SPIE

Press, Bellingham, WA, 2009.(18) Wallraff , G. M.; Lars