Method to suppress period doubling during manufacture of micro and nano scale wrinkled structures

Abstract

The range of stretch-tunability of sinusoidal wrinkled surfaces that are obtained by compression of supported thin films is limited by the emergence of a period-doubled mode at high compressive strains. This disclosure presents a method to suppress the emergence of the period-doubled mode at high strains. This is achieved by compressing pre-patterned supported thin films, wherein the pre-patterns are substantially similar to the natural pattern of the supported thin film system. As compared to flat thin film systems, pre-patterned thin film systems exhibit period doubling behavior at a higher compressive strain. The onset strain for emergence of period-doubling is tuned by altering the amplitude of the pre-patterns.

Claims

1. A method of suppressing the phenomenon of period doubling at high strains during wrinkling of bilayers, comprising the steps of: providing a topographically patterned surface, wherein the topographic pattern is a sinusoidal periodic pattern and has a period that is substantially similar to the natural period of the bilayer; replicating the patterned surface onto a base substrate, thereby forming a non-flat pre-patterned surface on the base; stretching the pre-patterned base substrate beyond the nominal period doubling onset strain, thereby forming a stretched and pre-patterned base layer; generating a thin film on top of the stretched pre-patterned base layer, wherein the film conforms to the pre-patterned surface, thereby forming a composite pre-patterned material comprising a thin film on top of a stretched and pre-patterned base layer; partially releasing the stretch in the stretched pre-patterned base layer of the composite pre-patterned material, wherein the thin film buckles into the pre-patterned mode upon releasing the stretch, thereby leading to an increase in the amplitude of pre-patterns on the pre-patterned composite material; fully releasing the stretch in the stretched pre-patterned base layer of the composite material, wherein releasing the stretch leads to a further increase in the amplitude of the pre-patterns without emergence of a period that is different from that of the pre-pattern, thereby forming a high aspect ratio wrinkled surface with the same period as that of the pre-pattern.

2. The method of claim 1, wherein the stretch in the base layer is along a single axis.

3. The method of claim 1, wherein the topographical periodic pattern is aligned along the direction of stretch in the base layer.

4. The method of claim 1, wherein the topographical periodic pattern is formed by the process of wrinkling of flat films, comprising the steps of: providing a flat non-patterned base substrate; stretching the base substrate, thereby forming a stretched base layer; generating a thin film on top of the stretched base layer, thereby forming a composite material comprising a thin film on top of a stretched base layer; releasing the stretch in the stretched base layer of the composite material; and wherein releasing the stretch causes the thin film to buckle, thereby forming a periodic wrinkled surface.

5. The method of claim 1, wherein the topographical periodic pattern is formed by the process of wrinkling of non-flat films, comprising the steps of: providing a non-flat pre-patterned base substrate; stretching the base substrate, thereby forming a stretched and pre-patterned base layer; generating a thin film on top of the stretched and pre-patterned base layer, wherein the film conforms to the pre-patterned surface, thereby forming a composite pre-patterned material comprising a thin film on top of a stretched and pre-patterned base layer; releasing the stretch in the stretched and pre-patterned base layer of the composite material; and wherein releasing the stretch causes the thin film to buckle, thereby forming a periodic wrinkled surface.

6. Method of claim 1, wherein the patterned surface is replicated onto the base substrate by the process of delayed and aligned imprinting, comprising the steps of: providing a coupon with the patterned surface, wherein the coupon has alignment features; providing a thermally curing base material, wherein the base material undergoes a liquid-to-solid phase transition during curing; providing a mold for curing the base material, wherein the mold surface has alignment features that correspond to the direction of stretch that will be applied after curing; heating the base material to a temperature below a threshold value to initiate the first thermal curing cycle, wherein the viscosity of the base material increases with time but the base material does not undergo a liquid-to-solid phase transition by the end of the cycle; aligning the coupon with the patterned surface by locating the alignment features on the coupon with respect to the alignment features on the mold, wherein the patterned surface is not yet in contact with the base material; placing the coupon with the patterned surface on top of the base material before the end of the first thermal curing cycle; further heating the base material to a temperature below a threshold value to initiate the second thermal curing cycle, wherein the base material undergoes a liquid-to-solid phase transition; separating the coupon with the patterned surface from the base material after the onset of phase transition, thereby replicating the patterned surface onto the base material and generating a pre-patterned base substrate.

7. Method of claim 1, wherein the base material is polydimethylsiloxane.

8. Method of claim 1, wherein the thin film is metallic.

9. Method of claim 1, wherein the thin film is polymeric.

10. Method of claim 1, wherein the thin film is generated on top of the pre-patterned base layer by exposing the base layer to plasma.

11. Method of claim 1, wherein the thin film is generated on top of the pre-patterned base layer by depositing the material via vapor deposition process.

12. Method of claim 1, wherein the period of the pre-pattern is identical to the natural period of the composite pre-patterned material.

13. Method of claim 1, wherein the stretch in the pre-patterned base layer lies in the range of 18% to 30%.

14. An article comprising a high aspect ratio wrinkled pattern generated by the method of claim 1.

15. A method of suppressing the phenomenon of period doubling at high strains during wrinkling of bilayers, comprising the steps of: providing a topographically patterned surface, wherein the topographic pattern is a sinusoidal periodic pattern and has a period that is substantially similar to the natural period of the bilayer; replicating the patterned surface onto a base substrate, thereby forming a non-flat pre-patterned surface on the base; stretching the pre-patterned base substrate along two different directions, wherein one stretch direction is aligned along the pre-pattern, and wherein the stretch along this aligned direction is higher than the nominal period doubling onset strain, thereby forming a stretched and pre-patterned base layer; generating a thin film on top of the stretched pre-patterned base layer, wherein the film conforms to the pre-patterned surface, thereby forming a composite pre-patterned material comprising a thin film on top of a stretched and pre-patterned base layer; releasing the stretch along the aligned direction, wherein releasing the stretch leads to an increase in the amplitude of the pre-patterns without emergence of a period that is different from that of the pre-pattern, thereby forming a high aspect ratio wrinkled surface with the same period as that of the pre-pattern; subsequently releasing the stretch along the second direction, wherein releasing the stretch leads to the thin film to buckle along the second direction, thereby forming a high aspect ratio biaxially wrinkled surface.

16. Method of claim 15, wherein the period of the pre-pattern is identical to the natural period of the composite pre-patterned material.

17. Method of claim 15, wherein the stretch in the pre-patterned base layer along the aligned direction lies in the range of 18% to 30%.

18. A method of suppressing the phenomenon of period doubling at high strains during wrinkling of bilayers, comprising the steps of: providing a topographically patterned surface, wherein the topographic pattern is a sinusoidal periodic pattern and has a period that is substantially similar to the natural period of the bilayer; replicating the patterned surface onto a base substrate, thereby forming a non-flat pre-patterned surface on the base; stretching the pre-patterned base substrate along two different directions, wherein one stretch direction is aligned along the pre-pattern, and wherein the stretch along this aligned direction is higher than the nominal period doubling onset strain, thereby forming a stretched and pre-patterned base layer; generating a thin film on top of the stretched pre-patterned base layer, wherein the film conforms to the pre-patterned surface, thereby forming a composite pre-patterned material comprising a thin film on top of a stretched and pre-patterned base layer; simultaneously releasing the stretch along both the directions, wherein releasing the stretch leads to the thin film to buckle along both the directions, and wherein releasing the stretch leads to an increase in the amplitude of the pre-patterns along one direction without emergence of a period that is different from that of the pre-pattern, thereby forming a high aspect ratio biaxially wrinkled surface.

19. Method of claim 18, wherein the period of the pre-pattern is identical to the natural period of the composite pre-patterned material.

20. Method of claim 18, wherein the stretch along the two directions are released simultaneously but at an unequal rate along the two directions.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1 is a schematic illustration of sinusoidal wrinkle formation during uniaxial compression of a flat bilayer system.

[0009] FIG. 2 is a schematic illustration of period doubling at strains during uniaxial. compression of a flat bilayer system.

[0010] FIG. 3 is a schematic illustration of wrinkle formation and suppression of period doubling during compression of a non-flat pre-patterned bilayer system.

[0011] FIG. 4 is a schematic representation of the pre-patterning process based on replication of wrinkled surfaces.

[0012] FIG. 5 illustrates finite element simulation results that demonstrate the effect of pre-pattern amplitude on the onset strain for period doubling. The pre-pattern period is identical to the natural period in these simulations.

DESCRIPTION OF THE PREFERRED EMBODIMENT

[0013] Fabrication of wrinkled micro and nano scale structures via compression of flat bilayers is a well-developed art. One embodiment for fabrication of wrinkles has been previously disclosed in U.S. patent application Ser. No. 14/590,448 (“Biaxial tensile stage for fabricating and tuning wrinkles”). The process steps are: (i) pre-stretching a compliant base, (ii) generating a thin film on top of the stretched base, and (iii) releasing the pre-stretch in the base. In addition, the technique of pre-patterning the bilayers by using the wrinkled surfaces as molds has been previously disclosed in U.S. patent application Ser. No. 14/669,925 (“Wrinkled surfaces with tunable hierarchy and methods for the preparation thereof”) and Ser. No. 14/922,146 (“Method to fabricate pre-patterned surfaces during manufacture of complex wrinkled structures”). The contents of these three applications (Ser. Nos. 14/590,448; 14/669,925; and 14/922,146) are incorporated herein by reference.

[0014] In one embodiment of the presently disclosed invention, period doubling at high strains is suppressed by performing a series of two wrinkle-patterning operations with an intermediate imprinting pattern transfer process between the two steps. This scheme is illustrated in FIG. 3. In the first wrinkle-patterning step one starts with a flat non-patterned bilayer system, whereas in the second wrinkle-patterning step one starts with a pre-patterned non-flat bilayer surface. The wrinkle pattern 40 obtained after the first step is utilized as a mold to generate the pre-patterned bilayer via replication.

[0015] To enable the fabrication of wrinkle patterns, one must solve these sub-problems: (i) fabrication of flat and pre-patterned bilayer systems with the desired material properties and geometry and (ii) compression of the top stiff film.

[0016] Stretchable bilayers with large stiffness ratio can be fabricated by attaching or growing a thin stiff film 10 on top of a thick elastomeric base 12. For example, exposing a polydimethylsiloxane (PDMS) film to air or oxygen plasma leads to the formation of a thin glassy layer on top of the exposed PDMS surface via oxidation. Alternatively, a metallic or polymeric thin film may be deposited on top of PDMS to obtain the desired bilayer. The top 120 layer thickness can be tuned by controlling the duration of plasma oxidation or the deposition process; whereas the stiffness ratio may be tuned by selecting the appropriate top/bottom materials. In the preferred embodiment, both plasma oxidation and metal/polymer film deposition techniques are used to generate a stiff thin film on top of an elastomeric PDMS layer.

[0017] Compression of the top film can be achieved by either directly compressing the bilayer or by generating a residual compressive strain in the top layer. As direct compression requires sustained loading to maintain the wrinkles, residual compression is often the preferred scheme. During mechanical loading, residual compression is generated by first stretching the PDMS base and then attaching/growing the stiff film on top of this pre-stretched base layer. On releasing the pre-stretch in the PDMS, the top layer undergoes compression that leads to formation of wrinkles. In the preferred embodiment of the pre-patterned bilayer, the pre-stretch is selected to be higher than the nominal period doubling onset strain for the equivalent flat bilayer.

[0018] The pre-patterned bilayers are fabricated by using the wrinkled surfaces as the molds/templates to generate the top surface of the PDMS casts 44. The curing process for fabrication of the pre-patterned base is same as that for the first wrinkling step and presented in U.S. patent application Ser. Nos. 14/669,925 and 14/922,146. Imprinting is performed by “gently” placing the pre-patterned coupon on top of the exposed surface of the curing PDMS 42 by aligning it to the direction of subsequent stretch.sup.4. Additionally, delayed imprinting is performed, i.e., imprinting close to, but before, the gelation point instead of at the beginning of the curing process. This ensures that the uncured PDMS is sufficiently viscous to support the pre-pattern during the curing process. One must be careful not to cross the gelation point as the phase change at this point prevents pattern replication.

[0019] To ensure that no additional modes are generated during the second wrinkling step with the pre-patterned bilayer, the following conditions must be met: (i) the period of the pre-pattern must be ‘substantially similar’ to the ‘natural period’ of the bilayer system and (ii) the pre-pattern must be aligned along the subsequent stretch direction.

[0020] Natural period: The natural period (λ.sub.n) is the period of the pattern that is observed for an un-patterned flat bilayer system that has the same material properties as the pre-patterned bilayer system and is compressed by the same strain. The natural period of a bilayer system can be experimentally determined by eliminating the pre-pattern imprinting step from the sequence of steps shown in FIG. 4. It may also be estimated by the following relationship that is available in literature.sup.3: λ.sub.n=chη.sup.1/3. Here, ‘h’ is the thickness of the thin film, ‘η’ is the ratio of Young's moduli of the film to the base, and ‘c’ is a proportionality constant that depends on the Poisson's ratio of the film and the base.

[0021] Substantial similarity: A substantially similar pre-pattern is one which leads to no growth 155 of an additional mode (i.e., no mode other than the pre-patterned period) when compressed up to at least the nominal onset strain for period doubling of the equivalent flat bilayer (ε.sub.2,0). Ideally, the pre-patterned period must be identical to the natural period. However, this condition is impossible to achieve in a practical system. When the pre-pattern period is dissimilar from the natural period, hierarchical wrinkles are expected to emerge beyond a transition strain (ε.sub.t). Nevertheless, due to the phenomenon of mode lock-in, the pre-pattern persists up to the transition strain. When the pre-pattern period is ‘substantially similar’ to the natural period, the transition strain for hierarchy (ε.sub.t) is higher than the period doubling onset strain (ε.sub.2,p). Thus, during compression of such a ‘substantially similar’ bilayer one does not observe any additional modes at high strains. This ‘substantial similarity’ range can be easily obtained by experimental verification. A conservative estimate for this range can also be made by comparing the transition strain for hierarchy.sup.4 (ε.sub.t) with the nominal doubling onset strain for the flat bilayer (ε.sub.2,0) as:

(1+2m.sup.3−3m.sup.2).sup.2−12k(1+2m.sup.3)<0   Eq. (1)

Here, m=λ.sub.p/λ.sub.n and λ.sub.p is the period of the pre-pattern. The non-dimensional parameter ‘k’ is given by:

[00001]$\begin{array}{cc}k=\frac{1}{{\mathrm{.Math.}}_{2,0}}.Math.{\left(\frac{\pi .Math..Math.A_p}{{\lambda }_n}\right)}^2& \mathrm{Eq}..Math.\left(2\right)\end{array}$

Here, A.sub.p is the amplitude of the pre-patterns. Pre-patterns that satisfy inequality (1) are guaranteed to be ‘substantially similar’.

[0022] The onset strain for period doubling (ε.sub.2,p) can be tuned by controlling the amplitude of the pre-pattern (A.sub.p). Finite element simulations were performed to verify the effect of pre-patterning on the onset strain. As shown in FIG. 5, the onset strain increases with an increase in the amplitude of the pre-patterns.

[0023] It is recognized that modifications and variations of the present invention will be apparent to those of ordinary skill in the art and it is intended that all such modifications and variations be included within the scope of the appended claims.

[0024] In one variation, the pre-patterns may be fabricated by a process other than wrinkling. In such a scheme, the manufacturing advantages of using a single fabrication process are lost. However, such a scheme may be necessary when pre-patterns are desired outside the feasible range of pre-patterns that can be fabricated via wrinkling. For example, pre-patterns may be fabricated via an alternate process when large amplitudes are desired.

[0025] In another variation, biaxial strains can be applied during the pre-stretch step and the stretch can be released in sequence along the two directions so that high-aspect ratio wrinkles are formed along the pre-patterned direction followed by buckling along the other direction. The subsequent biaxially wrinkled pattern can be stretch-tuned along the pre-patterned direction over a range that is larger than that of an equivalent flat bilayer system.

[0026] In another variation, biaxial strains can be applied during the pre-stretch step and the stretch along the two directions can be simultaneously released (at equal or unequal rate) so that a complex wrinkled pattern is formed that comprises of high-aspect ratio mode along the pre-patterned direction. This complex pattern can be stretch-tuned along the pre-patterned direction over a range that is larger than that of an equivalent flat bilayer system.

REFERENCES

[0027] 1. Auguste, A., Jin, L., Suo, Z., & Hayward, R. C. (2014). The role of substrate pre-stretch in post-wrinkling bifurcations. Soft Matter, 10(34), 6520-6529. doi: 10.1039/C4SM01038H [0028] 2. Chen. Y.-C., & Crosby, A. J. (2014). High Aspect Ratio Wrinkles via Substrate Prestretch. Advanced Materials 26(32), 5626-5631. doi: 10.1002/adma.201401444 [0029] 3. Groenewold, J. (2001). Wrinkling of plates coupled with soft elastic media. Physica A: Statistical Mechanics and its Applications 298(1-2), 32-45. [0030] 4. Saha, S. K., & Culpepper, M. L. (2014). Wrinkled Surfaces With Tunable Hierarchy and Methods for the Preparation Thereof. U.S. patent application Ser. No. 14/669,925.