Spectroscopic characterization of acid generation and concentration and free volume evolution in chemically amplified resists

We report on the measurement of proton concentration and local viscosity in a polymeric chemically amplified photoresist material. We interrogate these properties using crystal violet, a cationic triphenylmethane dye molecule. To determine the quantity of acid generated by the chemically amplified photoresist material on exposure to UV light, we characterize the pH-dependent linear optical response of crystal violet. To establish a frame of reference for these data, we determine the acid dissociation constants of crystal violet in aqueous solution. The viscosity of the resist material is related to the transient optical response of crystal violet. The data on the photoresist material demonstrate a rapid and persistent pH change in the polymer matrix upon UV irradiation, with the viscosity of the matrix changing by a relatively small amount, going from ∼150 cP prior to processing to ∼190 cP after UV exposure and heating.

[1]  A. Allal,et al.  Free-volume viscosity model for fluids in the dense and gaseous states. , 2001, Physical review. E, Statistical, nonlinear, and soft matter physics.

[2]  H. Satozono,et al.  Ground- and Excited-State Isomerization of Triphenylmethane Dyes in the Femtosecond Regime , 1999 .

[3]  H. Nakatsuka,et al.  Triphenylmethane Dyes Revealing Heterogeneity of Their Nanoenvironment: Femtosecond, Picosecond, and Single-Molecule Studies , 1999 .

[4]  James W. Taylor,et al.  On-wafer photoacid determination and imaging technique for chemically amplified photoresists , 1998 .

[5]  Roger F. Sinta,et al.  A Novel Photometric Method for the Determination of Photoacid Generation Efficiencies Using Benzothiazole and Xanthene Dyes as Acid Sensors , 1997 .

[6]  C. Bowman,et al.  Photopolymerization : fundamentals and applications , 1997 .

[7]  H. Nakatsuka,et al.  Microscopic dynamics of the glass transition investigated by time-resolved fluorescence measurements of doped chromophores , 1997 .

[8]  J. Scaiano,et al.  Aromatic Monoazines as Fluorescent Sensors for Photoacid Generation in Thin Polymer Films , 1996 .

[9]  Ye,et al.  Glass transition of associated solvents studied by fluorescence measurement of doped chromophores. , 1996, Physical review. B, Condensed matter.

[10]  H. Satozono,et al.  Femtosecond Isomerization of Crystal Violet in Alcohols , 1996 .

[11]  Richard P. Haugland,et al.  Handbook of fluorescent probes and research chemicals , 1996 .

[12]  H. Nakatsuka,et al.  DIFFUSIVE TORSIONAL DYNAMICS OF MALACHITE GREEN MOLECULES IN SOLID MATRICES PROBED BY FLUORESCENCE DECAY , 1995 .

[13]  H. Nakatsuka,et al.  Local Dynamics in Solid Matrices Investigated by Malachite Green Optical Microprobes , 1995, Spectral Hole-Burning and Related Spectroscopies: Science and Applications.

[14]  G. Blanchard,et al.  Synchronous pumping of two dye lasers using a single uv excitation source , 1993 .

[15]  D. F. Duxbury.  The photochemistry and photophysics of triphenylmethane dyes in solid and liquid media , 1993 .

[16]  P. Georges,et al.  Time-resolved saturated absorption recovery in malachite green-doped xerogel , 1991 .

[17]  J. Stewart.  Optimization of parameters for semiempirical methods II. Applications , 1989 .

[18]  J. G. Victor,et al.  On measuring the distribution of local free volume in glassy polymers by photochromic and fluorescence techniques , 1987 .

[19]  D. Ben‐Amotz,et al.  Torsional dynamics of molecules on barrierless potentials in liquids. II. Test of theoretical models , 1987 .

[20]  D. Ben‐Amotz,et al.  Torsional dynamics of molecules on barrierless potentials in liquids. I. Temperature and wavelength dependent picosecond studies of triphenyl‐methane dyes , 1987 .

[21]  G. Blanchard,et al.  Measurement of small absorbances by picosecond pump-probe spectrometry , 1986 .

[22]  D. Ben‐Amotz,et al.  Ground- and excited-state torsional dynamics of a triphenylmethane dye in low-viscosity solvents , 1985 .

[23]  R. E. Lowry,et al.  Novel excimer fluorescence method for monitoring polymerization: 1. Polymerization of methyl methacrylate , 1984 .

[24]  Stuart A. Rice,et al.  Shot‐noise‐limited detection scheme for two‐beam laser spectroscopies , 1984 .

[25]  Y. Kawai,et al.  Production of a large diameter hot‐electron plasma by electron cyclotron resonance heating , 1982 .

[26]  P. Bado,et al.  Multiple modulation for optical pump‐probe spectroscopy , 1982 .

[27]  E. Ippen,et al.  Picosecond recovery dynamics of malachite green , 1976 .

[28]  O. W. Kolling,et al.  Photometric and Visual Titration of Certain Alkaloids in Glacial Acetic Acid Using Malachite Green as Indicator , 1960 .

[29]  R. Landel,et al.  The Temperature Dependence of Relaxation Mechanisms in Amorphous Polymers and Other Glass-Forming Liquids , 1955 .

[30]  J. Conant,et al.  THE DETERMINATION OF THE STRENGTH OF WEAK BASES AND PSEUDO BASES IN GLACIAL ACETIC ACID SOLUTIONS1 , 1930 .