Skip to main content
Log in

Influence of material and process parameters in the dry-development of positive-tone, polyaldehyde photoresist

  • Published:
Journal of Materials Research Aims and scope Submit manuscript

Abstract

Poly(phthalaldehyde) (pPHA) and copolymers with aliphatic aldehydes were investigated as dry-develop, positive-tone photoresist. Exposure of the films loaded with a photoacid generator to 248 nm radiation creates an acid that depolymerizes the polymer into volatile monomers, allowing the development of features by vaporization rather than solution-based processes. By controlling the acid content, the vaporization rate of the reaction products, and the degree of liquid formation of the decomposed polymer, control of spatial resolution and the quality of polyaldehyde dry-develop photoresist was achieved. Heat, vacuum, and forced convection were evaluated as development techniques in determining the resist sensitivity, contrast, and resolution. Forced convection of heated nitrogen was the most controllable development method for pPHA films. Five-micron lines and spaces were printed. Poly(aldehyde) copolymer resins had slightly lower spatial resolution but were able to be developed faster due to higher vapor pressure of the depolymerized monomers. Cold photo-exposures and development were used to prevent detrimental liquid formation of the decomposed copolymers. In addition to exploring new dry-development methods that have not been tested before, these findings offer insights into designing better material systems and optimizing processes for dry-develop photoresists.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1.
TABLE 1:
Figure 1:
TABLE 2:
Figure 2:
Figure 3:
TABLE 3:
Figure 4:
TABLE 4:
Figure 5:

Similar content being viewed by others

References

  1. S. Campbell: Engineering at the Micro and Nanoscale, 4th ed. (Oxford University Press, New York, 2013).

    Google Scholar 

  2. A.R. Dick, W.K. Bell, B. Luke, E. Maines, B. Mueller, B. Rawlings, P.A. Kohl, and C. Grant Willson: High aspect ratio patterning of photosensitive polyimide with low thermal expansion coefficient and low dielectric constant. J. Micro/Nanolith. MEM. 15, 033503 (2016).

    Article  Google Scholar 

  3. B.K. Mueller, J.M. Schwartz, A.E. Sutlief, W.K. Bell, C.O. Hayes, E. Elce, C.G. Willson, and P.A. Kohl: Chemically amplified, positive tone, polynorbornene dielectric for microelectronics packaging. ECS J. Solid State Sci. Technol. 4, N3001 (2015).

    Article  CAS  Google Scholar 

  4. H. Ito and C.G. Willson: Chemical amplification in the design of dry developing resist materials. Polym. Eng. Sci. 23, 1012 (1983).

    Article  CAS  Google Scholar 

  5. C.G. Willson, R.R. Dammel, and A. Reiser: Photoresist materials: a historical perspective. In Proceedings of SPIE 3050, Metrology, Inspection, and Process Control for Microlithography XI, Vol. 3050 (1997).

  6. J.M.J. Fréchet, T.G. Tessier, and F.M. Houlihan: Approaches to the design of radiation-sensitive polymeric imaging systems with improved sensitivity and resolution. J. Electrochem. Soc. 133, 181 (1986).

    Article  Google Scholar 

  7. H. Ito and R. Schwalm: Thermally developable, positive resist systems with high sensitivity. J. Electrochem. Soc. 136, 241 (1989).

    Article  CAS  Google Scholar 

  8. J.M.J. Frechet, J. Fahey, C.G. Willson, T. Iizawa, K. Igarashi, and T. Nishikubo: Synthesis of polyformals and their use as dry-developing imgaing systems. Proc. ACS Div. Polym. Mater. Sci. Eng. 60, 174 (1989).

    CAS  Google Scholar 

  9. F.M. Houlihan, F. Bouchard, J.M.J. Fréchet, and C.G. Willson: Thermally depolymerizable polycarbonates. 2. Synthesis of novel linear tertiary copolycarbonates by phase-transfer catalysis. Macromolecules 19, 13 (1986).

    Article  CAS  Google Scholar 

  10. E. Uzunlar, J. Schwartz, O. Phillips, and P.A. Kohl: Decomposable and template polymers: Fundamentals and applications. J. Electron. Packag. Trans. ASME 138, 1 (2016).

    Article  Google Scholar 

  11. L. Chen, Y.-K. Goh, K. Lawrie, B. Smith, W. Montgomery, P.A. Zimmerman, I. Blakey, and A.K. Whittaker: Non-chemically amplified resists for 193-nm immersion lithography: influence of absorbance on performance. Adv. Resist Mater. Process. Technol. XXVII 7639, 76390V (2010)

    Article  Google Scholar 

  12. K.J. Lawrie, I. Blakey, J.P. Blinco, H.H. Cheng, R. Gronheid, K.S. Jack, I. Pollentier, M.J. Leeson, T.R. Younkin, and A.K. Whittaker: Chain scission resists for extreme ultraviolet lithography based on high performance polysulfone-containing polymers. J. Mater. Chem. 21, 5629 (2011).

    Article  CAS  Google Scholar 

  13. M.J. Bowden and L.F. Thompson: Electron irradiation of poly(olefin sulfones). Application to electron beam resists. J. Appl. Polym. Sci. 17, 3211 (1973).

    Article  Google Scholar 

  14. E. Reichmanis and A.E. Novembre: Lithographic resist materials chemistry. Annu. Rev. Mater. Sci. 23, 11 (1993).

    Article  CAS  Google Scholar 

  15. F. Wang and C.E. Diesendruck: Polyphthalaldehyde: Synthesis, derivatives, and applications. Macromol. Rapid Commun. 39, 1 (2018).

    Article  Google Scholar 

  16. K. Hatada, T. Kitayama, S. Danjo, H. Yuki, H. Aritome, S. Namba, K. Nate, and H. Yokono: Highly sensitive self developing electron-beam resist of aldehyde copolymer. Polym. Bull. 8, 469 (1982).

    Article  CAS  Google Scholar 

  17. K. Nate, T. Inoue, H. Yokono, and K. Hatada: Highly sensitive self-developing soft X-ray resists of silicon-containing aldehyde copolymers and sensitive novolac-based composite resists containing aldehyde copolymer. J. Appl. Polym. Sci. 35, 913 (1988).

    Article  CAS  Google Scholar 

  18. P.C. Paul, A.W. Knoll, F. Holzner, M. Despont, and U. Duerig: Rapid turnaround scanning probe nanolithography. Nanotechnology 22, 275306 (2011).

    Article  Google Scholar 

  19. J.-F. de Marneffe, B.T. Chan, M. Spieser, G. Vereecke, S. Naumov, D. Vanhaeren, H. Wolf, and A.W. Knoll: Conversion of a patterned organic resist into a high performance inorganic hard mask for high resolution pattern transfer. ACS Nano 12, 11152 (2018).

    Article  CAS  Google Scholar 

  20. F. Holzner, P. Paul, M. Despont, L.L. Cheong, J. Hedrick, U. Dürig, and A. Knoll: Thermal probe nanolithography: in-situ inspection, high-speed, high-resolution, 3D. In 29th Eur. Mask Lithogr. Conf., Vol. 888605 (2013).

  21. J.M. Schwartz, O. Phillips, A. Engler, A. Sutlief, J. Lee, and P.A. Kohl: Stable, high-molecular-weight Poly(phthalaldehyde). J. Polym. Sci. Polym. Chem. 55, 1166 (2017).

    Article  CAS  Google Scholar 

  22. J.M.J. Frechet, F. Bouchard, E. Eichler, F.M. Houlihan, T. Iizawa, B. Kryczka, and C.G. Willson: Thermally depolymerizable polycarbonates V. acid catalyzed thermolysis of allylic and benzylic polycarbonates: A new route to resist imaging. Polym. J. 19, 31 (1987).

    Article  CAS  Google Scholar 

  23. A. Engler, O. Phillips, R.C. Miller, C. Tobin, and P.A. Kohl: Cationic copolymerization of o-Phthalaldehyde and functional aliphatic aldehydes. Macromolecules 52, 4020 (2019).

    Article  CAS  Google Scholar 

Download references

Acknowledgement

The authors gratefully acknowledge the financial support of the U.S. Department of Education Graduate Assistance in Areas of National Need (GAANN) program at the Georgia Institute of Technology (Award #P200A180075), and Georgia Tech President’s Undergraduate Research Award.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Paul A. Kohl.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kohl, P.A., Engler, A., Tobin, C. et al. Influence of material and process parameters in the dry-development of positive-tone, polyaldehyde photoresist. Journal of Materials Research 35, 2917–2924 (2020). https://doi.org/10.1557/jmr.2020.243

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1557/jmr.2020.243

Navigation