Guided wrinkling in swollen, pre-patterned photoresist thin films with a crosslinking gradient

A new thin film buckling system was developed from photosensitive SU-8 thin films doped with UV light absorbing dye, resulting in a depth-wise gradient modulus after photocrosslinking. When the film was swollen by an organic solvent, a wide range of wrinkling patterns was obtained, including lamella, peanut and semi-hexagonal patterns. Both the morphology and wavelength were found to be dependent on the original film thickness. By leveraging the thermoplasticity of SU-8, we imprinted one-dimensional (1-D) patterns on the dyed SU-8 with variable pitch and height from 1 μm to 20 μm and 15 nm to 2 μm, respectively. We then swelled the patterned films and investigated the interactions between the intrinsic buckling waves (both size and morphology) and the pre-patterns. As the pre-pattern pitch decreased, the swollen film in the patterned region evolved from isotropic wrinkles to out-of-phase, anisotropic waves, which further became in-phase when the pre-pattern pitch was smaller than the intrinsic wrinkle wavelength. For the latter, the aligned wrinkle morphology varied dramatically when the pre-pattern height decreased: from perpendicular to the pre-pattern wavevector to dual orientation with one set of wrinkles remained perpendicularly ordered and the other set of local buckling patterns aligned in parallel to the pre-pattern, and finally back to isotropic ones. Since the pre-patterns of different size and shape could be readily prepared, the combination of physical confinement together with controlled swelling in a graded thin film offers a new approach to access a wide range of controllable hierarchical patterns.

[1]  J. Burdick,et al.  Swelling‐Induced Surface Patterns in Hydrogels with Gradient Crosslinking Density , 2009 .

[2]  Rui Huang,et al.  Anisotropic, Hierarchical Surface Patterns via Surface Wrinkling of Nanopatterned Polymer Films , 2022 .

[3]  R. Vendamme,et al.  Spatial Forcing of Self‐Organized Microwrinkles by Periodic Nanopatterns , 2007 .

[4]  Toyoichi Tanaka,et al.  Mechanical instability of gels at the phase transition , 1987, Nature.

[5]  Alfred J. Crosby,et al.  Effect of stress state on wrinkle morphology , 2011 .

[6]  Shu Yang,et al.  Strain responsive concave and convex microlens arrays , 2007 .

[7]  Masatsugu Shimomura,et al.  Geometry-dependent stripe rearrangement processes induced by strain on preordered microwrinkle patterns. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[8]  George M. Whitesides,et al.  Spontaneous formation of ordered structures in thin films of metals supported on an elastomeric polymer , 1998, Nature.

[9]  C. Stafford,et al.  Diffusion‐Controlled, Self‐Organized Growth of Symmetric Wrinkling Patterns , 2009 .

[10]  Yonggang Huang,et al.  Stretchable and Foldable Silicon Integrated Circuits , 2008, Science.

[11]  Lionel Buchaillot,et al.  Variation of absorption coefficient and determination of critical dose of SU-8 at 365 nm , 2006 .

[12]  P. Yoo,et al.  Wave interactions in buckling: Self-organization of a metal surface on a structured polymer layer , 2004 .

[13]  Alfred J. Crosby,et al.  Surface Wrinkles for Smart Adhesion , 2008 .

[14]  A. Crosby,et al.  Self‐Wrinkling of UV‐Cured Polymer Films , 2010, Advanced materials.

[15]  K. Suh,et al.  Physical Self-Assembly of Microstructures by Anisotropic Buckling , 2002 .

[16]  Alfred J. Crosby,et al.  Fabricating Microlens Arrays by Surface Wrinkling , 2006 .

[17]  Ying Zhang,et al.  Fabrication of hierarchical pillar arrays from thermoplastic and photosensitive SU-8. , 2010, Small.

[18]  G. Briggs,et al.  Spontaneous Formation of Ordered Lateral Patterns in Polymer Thin‐Film Structures , 2004 .

[19]  P. Damman,et al.  Wrinkling of stimuloresponsive surfaces: mechanical instability coupled to diffusion. , 2008, Physical review letters.

[20]  Christopher M. Stafford,et al.  Surface Wrinkling: A Versatile Platform for Measuring Thin‐Film Properties , 2011, Advanced materials.

[21]  M D Thouless,et al.  Surface instability of an elastic half space with material properties varying with depth. , 2008, Journal of the mechanics and physics of solids.

[22]  A. Jagota,et al.  Mechanically tunable dry adhesive from wrinkled elastomers , 2008 .

[23]  Yanping Cao,et al.  Localized ridge wrinkling of stiff films on compliant substrates , 2012 .

[24]  J. Karp,et al.  A "Self-Pinning" Adhesive Based on Responsive Surface Wrinkles. , 2011, Journal of polymer science. Part B, Polymer physics.

[25]  M. Jamal,et al.  Differentially photo-crosslinked polymers enable self-assembling microfluidics. , 2011, Nature communications.

[26]  J. Burdick,et al.  Kinetic study of swelling-induced surface pattern formation and ordering in hydrogel films with depth-wise crosslinking gradient , 2010 .

[27]  A. Crosby,et al.  Surface wrinkling behavior of finite circular plates , 2009 .

[28]  L. Mahadevan,et al.  Nested self-similar wrinkling patterns in skins , 2005, Nature materials.

[29]  Yanchun Han,et al.  Highly oriented tunable wrinkling in polymer bilayer films confined with a soft mold induced by water vapor. , 2007, The Journal of chemical physics.

[30]  P. Patrício,et al.  Wrinkling Labyrinth Patterns on Elastomeric Janus Particles , 2011, Wrinkled Polymer Surfaces.

[31]  Qian Liu,et al.  Path-guided wrinkling of nanoscale metal films. , 2012, Advanced materials.

[32]  Rui Huang,et al.  Dynamics of wrinkle growth and coarsening in stressed thin films. , 2006, Physical review. E, Statistical, nonlinear, and soft matter physics.

[33]  A. Crosby,et al.  Adhesion of nonplanar wrinkled surfaces , 2011 .

[34]  H. H. Lee,et al.  Capillary Force Lithography , 2001 .

[35]  Kevin Kit Parker,et al.  Hierarchical wrinkling patterns , 2010 .

[36]  Soon Moon Jeong,et al.  Light extraction from organic light-emitting diodes enhanced by spontaneously formed buckles , 2010 .

[37]  C. Stafford,et al.  Photoinitator surface segregation induced instabilities from polymerization of a liquid coating on a rigid substrate , 2012 .

[38]  Jian Yin,et al.  Hierarchical surface wrinkles directed by wrinkled templates , 2012 .

[39]  Yonggang Huang,et al.  Biaxially stretchable "wavy" silicon nanomembranes. , 2007, Nano letters.

[40]  Masatsugu Shimomura,et al.  Ordering of microwrinkle patterns by compressive strain , 2004 .

[41]  J. Groenewold Wrinkling of plates coupled with soft elastic media , 2001 .

[42]  A. Crosby,et al.  Spontaneous formation of stable aligned wrinkling patterns. , 2006, Soft matter.

[43]  A. Crosby,et al.  Wrinkling and Strain Localizations in Polymer Thin Films , 2012 .

[44]  Pei-Chun Lin,et al.  Spontaneous formation of one-dimensional ripples in transit to highly ordered two-dimensional herringbone structures through sequential and unequal biaxial mechanical stretching , 2007 .

[45]  H. Stone,et al.  Hierarchical folding of elastic membranes under biaxial compressive stress. , 2011, Nature materials.

[46]  M. Shimomura,et al.  Effect of thermal annealing and compression on the stability of microwrinkle patterns. , 2005, Physical review. E, Statistical, nonlinear, and soft matter physics.

[47]  A. Boisen,et al.  Processing of thin SU-8 films , 2008 .

[48]  P. Yoo,et al.  Complex pattern formation by adhesion-controlled anisotropic wrinkling. , 2008, Langmuir : the ACS journal of surfaces and colloids.