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Thermal Characterization of Ultra-Thin Resist Films: Polymer Study and Spin Coating Modeling

This confidential review explores the thermal properties of ultra-thin resist films, analyzing polymer behavior and spin coating processes for advanced research. Key insights address thin film expansion and modeling for improved performance. Recommendations include light filtering for enhanced durability.

alfredramsey
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Thermal Characterization of Ultra-Thin Resist Films: Polymer Study and Spin Coating Modeling

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  1. LTM contribution to SP3-WP6 • Two tasks: • Thermal characterization of ultra thin resist films (D 3.6.1.3.1) • Spin Coating and bake modeling for Ultra thin resist films (M 3.6.1.5) Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  2. Thermal characterization of ultra thin resist films (D 3.6.1.3.1) • Thermal expansion of thin films followed by ellipsometry • Simple homopolymer studied : • Polystyrene (PS) • PMMA • Poly Hydroxystyrene (soluble part of CAR) • Studies of Clariant resist : • MMC2 (copolymer) • MMC3 (CAR) • MMC4 (terpolymer) Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  3. Simple polymer 1 : PS(4000 g/mol, Tg ~ 80°C) • No variation of Tg • Increase of the coefficients of thermal expansion for thickness below 50 nm Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  4. Simple polymer 2 : PMMA(950 000 g/mol, Tg ~ 120°C) 47 nm • No variation of Tg •  Influence of the interface effects? • Si/PMMA interactions : • Tg variations and  are not significative • To be continued for thinnest films… Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  5. Simple polymer 3 : PHS (8000 g/mol, Tg ~ 170°C) Solvent evaporation Diminution of the thickness during successive cycles : Degradation or relaxation of PHS chains? Mechanism? • Kinetic measurements shows compaction even for long time • Degradation or chemical modification of PHS with light Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  6. Clariant Resist 1 : MMC2 copolymer hydroxystyrene – butoxystyrene(no PAG) Tg ~ 155°C • Diminution of Tg for thickness below 50 nm (significative?) • Diminution of the thermal expansion •  Contradictory results ? Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  7. Clariant Resist 2 : MMC3 2-methyl-2-adamantol methacrylate (MAdMA)/Mevalonic lactone methacrylate(contains PAG) Thermal compaction of the film above Tg • Presence of PAG : photo activation of the resist with the spot ligth above Tg Compaction Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  8. Clariant Resist 3 : MMC4Terpolymer hydroxystyrene – styrene-butylmethacrylate(no PAG) Tg ~ 160°C Diminution of the thickness of the films during successive cycles : Photo degradation Cycle 2 for 46 nm and 165 nm films : Tg is not detectable Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  9. Thermal properties of Ultra thin resists films • results: • No obvious Tg changes with thickness • Strong influence of the thickness on thermal expansion of the film • Thin layer properties for material if e<100 nm for all materials • Important recommendation • Ligth filtering to avoid photo degradation Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  10. Spin-Coating modeling • Four steps while Spin-coating: 1: Resist deposition Composition unchanged 2 : Film generation 3 : Matter ejection predominant for film thinning 4 : Solvant evaporation predominant Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  11. Film thinning Evaporation at the free surface  concentration gradient and diffusion Hypothesis: wall slows the intermolecular mobility, hence increases the friction parameter between macromolecules Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  12. Spin-Coating Simulation Exemple of the coating of a wafer with a resist Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  13. No wall influence On film homogeneity Post Applied Bake Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

  14. Accuracy of the model • Without wall effects: the model predicts accurately the spin curves and film compaction while heating • With wall effects: No significant differences after Post Applied Bake on the film structure  Friction parameter accurate? • Conclusion: Further studies are needed to properly simulate wall effects Review Meeting More Moore_SP3-WP CONSORTIUM CONFIDENTIAL

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