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Viscoelastic properties of polyamic acid solutions—precursors of polyimides

Samson A. Jenekhe

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Abstract

Abstract The rheology of polyamic acid (PAA) solutions, precursors of polyimides used in microelectronic device applications, has been investigated by dynamic (oscillatory) shear flow measurements. Frequency dependent storage and loss moduli and dynamic viscosity were measured in the frequency range 10 −1 to 10 3 rad/s at 23°C. The storage modulus G ′ (ω) and loss modulus G ″ (ω) exhibited quadratic and linear dependence in frequency at low frequencies respectively, the viscoelastic fluid behavior commonly predicted for polymer solutions from many molecular theories. At high frequencies both dynamic moduli become proportional to ω 2/3 . The results show that PAA solutions are very high loss viscoelastic fluids, judging from the loss tangent values which far exceed unity. It is suggested that dynamic viscoelastic properties could be used to monitor the degree of imidization since there is a gradual change from viscoelastic fluids to soft viscoelastic solids to hard viscoelastic solids as PAA is converted to polyimides. Onset of non‐Newtonian flow as shown on the frequency dependent dynamic viscosity was in the range 30 to 200 rad/s. The viscoelastic constants, zero‐shear rate viscosity η o and steady‐state compliance J e 0 , where also determined from the dynamic data and compared to previous steady shear flow results.

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Abstract The rheology of polyamic acid (PAA) solutions, precursors of polyimides used in microelectronic device applications, has been investigated by dynamic (oscillatory) shear flow measurements. Frequency dependent storage and loss moduli and dynamic viscosity were measured in the frequency range 10 −1 to 10 3 rad/s at 23°C. The storage modulus G ′ (ω) and loss modulus G ″ (ω) exhibited quadratic and linear dependence in frequency at low frequencies respectively, the viscoelastic fluid behavior commonly predicted for polymer solutions from many molecular theories. At high frequencies both dynamic moduli become proportional to ω 2/3 . The results show that PAA solutions are very high loss viscoelastic fluids, judging from the loss tangent values which far exceed unity. It is suggested that dynamic viscoelastic properties could be used to monitor the degree of imidization since there is a gradual change from viscoelastic fluids to soft viscoelastic solids to hard viscoelastic solids as PAA is converted to polyimides. Onset of non‐Newtonian flow as shown on the frequency dependent dynamic viscosity was in the range 30 to 200 rad/s. The viscoelastic constants, zero‐shear rate viscosity η o and steady‐state compliance J e 0 , where also determined from the dynamic data and compared to previous steady shear flow results.

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Available abstract

Abstract The rheology of polyamic acid (PAA) solutions, precursors of polyimides used in microelectronic device applications, has been investigated by dynamic (oscillatory) shear flow measurements. Frequency dependent storage and loss moduli and dynamic viscosity were measured in the frequency range 10 −1 to 10 3 rad/s at 23°C. The storage modulus G ′ (ω) and loss modulus G ″ (ω) exhibited quadratic and linear dependence in frequency at low frequencies respectively, the viscoelastic fluid behavior commonly predicted for polymer solutions from many molecular theories. At high frequencies both dynamic moduli become proportional to ω 2/3 . The results show that PAA solutions are very high loss viscoelastic fluids, judging from the loss tangent values which far exceed unity. It is suggested that dynamic viscoelastic properties could be used to monitor the degree of imidization since there is a gradual change from viscoelastic fluids to soft viscoelastic solids to hard viscoelastic solids as PAA is converted to polyimides. Onset of non‐Newtonian flow as shown on the frequency dependent dynamic viscosity was in the range 30 to 200 rad/s. The viscoelastic constants, zero‐shear rate viscosity η o and steady‐state compliance J e 0 , where also determined from the dynamic data and compared to previous steady shear flow results.

Key concepts: Viscoelasticity, Dynamic modulus, Dynamic mechanical analysis, Materials science, Rheology, Dissipation factor, Rheometry, Shear modulus

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