GRADED PORE STRUCTURE WITHOUT PHASE MASK
20230044343 · 2023-02-09
Assignee
- Toyota Motor Engineering & Manufacturing North America, Inc. (Plano, TX, US)
- The Board Of Trustees Of The University Of Illinois (Urbana, IL)
Inventors
- Shailesh N. Joshi (Ann Arbor, MI, US)
- Gaurav Singhal (Champaign, IL, US)
- Paul Vannest Braun (Champaign, IL, US)
- Danny J. Lohan (Ann Arbor, MI, US)
- Kai-Wei Lan (Champaign, IL, US)
Cpc classification
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
G03F7/70408
PHYSICS
G03H2001/0094
PHYSICS
G02B6/1225
PHYSICS
International classification
G02B1/00
PHYSICS
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A method to form a three-dimensional photonic crystal template with a gradient structure involves irradiating a photoresist composition of a thickness of at least 15 μm from at least four laser beams to yield a periodic patterned with a percolating matrix of mass in constructive volumes of a cured photoresist composition and destructive volumes of voids free of condensed matter where the proportion of constructive volume displays a gradient from the irradiated surface to the substrate after development. For a given light intensity, photoinitiator concentration in the photoresist composition, and a given thickness, by irradiating for a relatively short period, a three-dimensional photonic crystal template displaying a gradient having greater constructive volume proximal the air interface forms and a relatively long irradiation period results in a gradient having greater constructive volume proximal the substrate.
Claims
1-12. (canceled)
13. A three-dimensional photonic crystal template comprising: a periodic patterned cured photoresist composition on a conductive reflective substrate, wherein a gradient of a constructive volume of the periodic patterned cured photoresist composition varies from an air interface to the reflective substrate such the three-dimensional photonic crystal template has a porosity gradient.
14. The three-dimensional photonic crystal template according to claim 13, wherein the conductive reflective substrate is a silicon wafer.
15. The three-dimensional photonic crystal template according to claim 13, wherein the periodic patterned cured photoresist composition comprises a polymerized photoresist with a residual photoinitiator.
16. The three-dimensional photonic crystal template according to claim according to claim 15, wherein the polymerized photoresist is polymerized SU-8 and the residual photoinitiator is cyclopentadienyl(fluorene) iron (III) hexafluorophosphate.
17. The three-dimensional photonic crystal template according to claim according to claim 13, wherein a thickness of the three-dimensional photonic crystal template is at least 15 μm.
18. The three-dimensional photonic crystal template according to claim according to claim 13, wherein the gradient of the constructive volume has a greater constructive volume proximal the air interface.
19. The three-dimensional photonic crystal template according to claim according to claim 13, wherein the gradient of the constructive volume has a greater constructive volume distal the air interface.
20. A three-dimensional photonic crystal template comprising: a conductive reflective substrate; and a periodic patterned cured photoresist composition on the conductive reflective substrate, the periodic patterned cured photoresist composition comprising a polymerized photoresist with a residual photoinitiator and a constructive volume with a gradient that varies from an air interface to the reflective substrate such the three-dimensional photonic crystal template has a porosity gradient.
21. The three-dimensional photonic crystal template according to claim 20, wherein the conductive reflective substrate is a silicon wafer.
22. The three-dimensional photonic crystal template according to claim 20, wherein the polymerized photoresist is polymerized SU-8 and the residual photoinitiator is cyclopentadienyl(fluorene) iron (III) hexafluorophosphate.
23. The three-dimensional photonic crystal template according to claim 20, wherein a thickness of the three-dimensional photonic crystal template is at least 15 μm.
24. The three-dimensional photonic crystal template according to claim 20, wherein the gradient of the constructive volume has a greater constructive volume distal the air interface.
25. The three-dimensional photonic crystal template according to claim 20, wherein the gradient of the constructive volume has a greater constructive volume proximal the air interface.
26. A three-dimensional photonic crystal template comprising: a conductive reflective substrate comprising a silicon wafer; and a periodic patterned cured photoresist composition on the conductive reflective substrate, the periodic patterned cured photoresist composition comprising a polymerized SU-8 photoresist with a cyclopentadienyl(fluorene) iron (III) hexafluorophosphate residual photoinitiator and a constructive volume with a gradient that varies from an air interface to the reflective substrate such the three-dimensional photonic crystal template has a porosity gradient.
27. The three-dimensional photonic crystal template according to claim 26, wherein a thickness of the three-dimensional photonic crystal template is at least 15 μm.
28. The three-dimensional photonic crystal template according to claim 26, wherein the gradient of the constructive volume has a greater constructive volume distal the air interface.
29. The three-dimensional photonic crystal template according to claim 26, wherein the gradient of the constructive volume has a greater constructive volume proximal the air interface.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The present teachings will become more fully understood from the detailed description and the accompanying drawings, wherein:
[0012]
[0013]
[0014]
[0015]
[0016]
[0017]
[0018]
[0019]
[0020]
[0021]
[0022]
[0023] It should be noted that the figures set forth herein are intended to exemplify the general characteristics of the methods, algorithms, and devices among those of the present technology, for the purpose of the description of certain aspects. These figures may not precisely reflect the characteristics of any given aspect and are not necessarily intended to define or limit specific embodiments within the scope of this technology. Further, certain aspects may incorporate features from a combination of figures.
DETAILED DESCRIPTION
[0024] The present teachings provide a method for preparing a three-dimensional photonic crystal template on a substrate. For purposes of embodiments, the substrate may be any material, and may be a reflective or a non-reflective substrate. A reflective substrate may be conductive, and, for purposes of some embodiments, the substrate is conductive when the substrate material displays a conductivity greater than deionized water. In various embodiments, the three-dimensional photonic crystal template has a periodic structure without features due to an unintended degree of cross-linking initiated by reflected light rays in destructive volumes, which are regions with destructive interference during lithography and intended to be removed from constructive volumes upon dissolving a photoresist composition from the destructive volumes during a development step of the template. A reflective substrate is employed with no insulating antireflective coating situated between the substrate and the patterned cured photoresist to minimize reflectance. For many applications, a sufficient conductivity of the substrate is desired of the three-dimensional photonic crystal template. The three-dimensional photonic crystal template is suitable for preparing periodic porous structures for use in supported catalysts, metallic heat transfer devices, other metallic devices, or other non-metallic devices, where metallic devices can be formed by electroplating. The remaining mass of the cured photoresist features in the constructive volume varies in a gradient along the depth of the template formed and this gradient is controlled by the light dose that is employed relative to a photoinitiator content for generation of an initiating species in any given development recipe and the thickness of the photoresist deposited.
[0025] The presently disclosed three-dimensional photonic crystal templates are generated by an interference lithographic method using four or more laser beams where the beams are of unequal intensity. The periodicity of the three-dimensional photonic crystal template is controlled by the orientation of the laser beams employed to carry out the lithographic process. In one embodiment, although differing orientations and alignments of beams are possible, one beam is situated perpendicular to the substrate supporting the patternable photoresist and three beams are situated about 120° apart and directed at an acute angle, generally, but not necessarily, less than about 40° to the central beam and intersecting with the central beam at an air or inert gas-photoresist interface. The central perpendicular beam can be of greater intensity, for example, about four times the intensity, of the other three beams, individually or collectively. By using this geometry and a reflective substrate, the dose required for pattern formation can be achieved with a very short irradiation period, for example, less than about 0.3 seconds using a 5W laser. The laser interference provides a sufficient dose for patterned initiator generation throughout the photoresist in constructive volumes with this relatively short irradiation, but the reflected light is of insufficient intensity to generate an insoluble mass in the destructive regions as the irradiation geometry and the light dose is set to avoid photoinitiation to a degree required for gelation in those volumes where voids are to be formed after development of the photoresist composition. By fixing the laser intensity, modification of the process requires manipulation of only the exposure time. In this manner, a three-dimensional photonic crystal template can be constructed where the proportion of constructive volume to destructive volumes and the gradient of voids can be controlled by varying only the irradiation time used when a thickness and photoinitiator concentration is established.
[0026] As detailed herein, the method for making periodic photonic crystal templates uses a fixed, though not equal, laser intensity for all beams. The fraction of the final three-dimensional photonic crystal templates that are void varies as a gradient along the depth of the template and the direction of the gradient is controllable by the irradiation period for a given laser power. In this manner, the smaller an irradiation time, the lesser quantity of an active species is generated and the greater the solid volume near the irradiated surface relative to the solid volume at the substrate for a fixed laser beams' intensity and using a fixed development procedure. In this manner, the manufacturing process can be readily altered by only the exposure time to bias the nature of the density gradient of the three-dimensional photonic crystal template. As the exposure period is controlled by effectively switching the light on and off, the void portion of the template can be altered as desired from template to template, even during a production run of multiple templates.
[0027] The three-dimensional photonic crystal templates of the present disclosure can be used as a template for processes that require a sufficiently conductive substrate, such as a silicon substrate, to allow electrodeposition or other processes requiring using the substrate as an electrode. In this manner, a relatively large area template with nanometer to micrometer features can be formed with a short burst of laser light. The three-dimensional photonic crystal template can be of various negative photoresists, when the initiation of polymerization can be generated photolytically by the laser wavelengths employed. In general, but not necessarily, the polymerization is a living or controlled diffusion polymerization, such as a photo-cationic, photo-anionic, or a photo-generated reversibly stabilized radical polymerization. For example, the negative photoresist can be SU-8, a multi-epoxy monomer that is polymerized via a cationic photoinitiator activated by the light projected on the surface with an interference pattern of initiating cations formed within the glassy photoresist. By appropriate choice of the angle of the laser beams to the substrate, the reflected light from the reflective substrate can be complementary to the incident light for generating a desirable three-dimensional photonic crystal template.
[0028] In one aspect, the laser beams may be oriented in the manner illustrated in
[0029] In one aspect, the method does not require any modification of an established development protocol for initiation, polymerization, crosslinking, and developing to form the cured photoresist resin. A traditional process for forming and developing a photoresist is outlined in the flow chart provided in
[0030] In the development of the polymer, which further effects the dissolving of the unpolymerized or insufficiently polymerized regions, diffusion rates of the generated active species and propagation rates of the photoresist polymer must be considered. As the degrees of initiation and propagation affect the diffusing species structures, controlling the three-dimensional photonic crystal template structure becomes a complicated problem where a functional window is easily missed. Modification of the post irradiation process does not readily lend to achieving an easily modified route to a desired specific structures where small difference in time, temperature, and concentration all can promote a loss of structural control. The control of the dosing rate has little error associated with its implementation as the control is exclusively of the amount of initiator generated, particularly with photoinitiators with a high quantum yield, such as, but not limited to, iron-arene salts, such as, cyclopentadienyl(fluorene) iron (III) hexafluorophosphate as a cationic initiator. Photoinitiators that do not act as thermal initiators at temperatures employed for deposition on the substrate or baking during development are advantageous. Other iron-are salts that can be used include Irgacure 261, [Cp-Fe-Naph]PF.sub.6, CFC, and CFA. Other photoinitiators include diaryliodonium salts and triarylsulfonium salts. The anion coupled to the cation of these photoinitiators can be, but are not limited to, PF.sub.6, SbF.sub.6, BF.sub.4, triflate, and tosylate. A photosensitizer can be included with the photoinitiator. Useful photosensitizers include DIEF, RBAX, TIHF, Acridine Orange, and Erythrosin B. In this manner, the method is implemented by fine control of only one variable, the photonic dose, and does not require a consideration of the complicated multiple processes that occur during a development bake and void forming dissolving process.
[0031] Portions of the process of
[0032] The exemplary structure of
[0033] The post irradiation processing is represented by the transition of
[0034] After baking, development continues with the dissolving of the monomer and non-crosslinked polymer in the destructive volumes that will generate the voids of the three-dimensional photonic crystal template. As shown in
[0035] To avoid structural collapse of the voids during a final drying of the three-dimensional photonic crystal template due to surface tension effects, drying can be carried out using supercritical CO2 where the liquid-vapor interface is beyond the critical point. The wet three-dimensional photonic crystal template is placed in liquid CO2 followed by heating past the critical point and releasing the pressure until ambient pressure and temperature is achieved. The resulting three-dimensional photonic crystal template is isolated with distinct constructive volumes of cross-linked photoresist polymer and destructive volumes void of condensed matter.
[0036] Modification of the irradiation profile during the formation of the three-dimensional photonic crystal template or by decorating the deposited photoresist surface with reflective or absorbing particles allows the formation of uniform, patterned or gradient periodic structures along any axis and bias the proportion of void volume in the template. This permits the formation of a metal matrix device that displays the negative of the template, where the void volumes result in the metal features and the resin features of the template generate the voids of the metal matrix upon degradation.
[0037] The resulting polymeric three-dimensional photonic crystal template, when situated on a substrate with sufficient conductivity, can be used to fill the voids with a metal or other material that can be deposited by an electrodeposition process. In this manner, the avoidance of defects is critical to assure that the necessary percolation of voids through the template allows the growth throughout the entire template formed from the photoresist layer. Removal of the template allows development of a metallic device, where the positive features of the device are formed in the voids in the template. The device has a gradient of features that match the gradient void structure of the template. Other non-metal devices can be prepared, such as a high surface area catalytic supports, where the three-dimensional photonic crystal template is a scaffold for the deposition of a catalyst layer on the template.
[0038] The use of a short irradiation times of less than about 1 second using, for example, a 5W laser can generate three-dimensional photonic crystal templates having a proportion of constructive volume that is directly proportional to the irradiation time with thin layers of photoresist compositions are used. The light dose determines the nature of the pattern, and herein, the recitation of a time must be considered in view of the laser power. Readily discernable gradients are not observed for three-dimensional photonic crystal templates formed from thin photoresist layers, for example those less than about 10 μm in thickness. With thick layers, a gradient of pores or void volumes results in a three-dimensional photonic crystal template having a percolating periodic matrix of voids is formed with a gradient displaying increasingly greater void volume while approaching the substrate, as shown in
[0039] Methods
[0040] A diode pump solid state laser, Verdi 5W (Coherent Inc.), a frequency doubled Nd:YVO.sub.4 laser, was used at 532 nm for multi-beam interference lithograph. The Verdi 5W has a maximum power of 5.5 W and a beam diameter of 2.25 mm. It was used with the beam expanded to 9 mm using a spatial filter and sub-second exposure times. The optical platform employed a rigid table-top (Newport RS-4000) and pneumatic isolators (Newport 1-2000) for vibration dampening. The beam was split into four beams and arranged by the mirrors into an umbrella geometry, as shown in
[0041] The photoresist composition of SU-8 octafunctional monomer with cyclopentadienyl(fluorene) iron (III) hexafluorophosphate photoinitiator was prepared in cyclopentanone and spin coated on a silicon wafer. Solvent evaporation from the photoresist composition was carried out on a hot plate to a temperature of about 65 □ C. for ten minutes and about 95 □ C. for twenty minutes. After cooling to room temperature, exposure was set using an electric shutter. Immediately after exposure, development was started with a bake at 85 □ C. for twenty minutes. After cooling to room temperature, propylene glycol monomethyl ether acetate (PGMEA) was used with gentle stirring to dissolve the destructive volumes and form the periodic structure of the three-dimensional photonic crystal template. Immersion into isopropanol results in the extraction of residual PGMEA from the cured SU-8 resin. Supercritical drying was carried out by immersion of the SU-8 resin on the Si wafer in liquid CO2 using ae critical point dryer (Samdri 790) at about 0° C. and slowly heated through the critical point followed by the slow release of pressure to ambient and cooling to ambient temperature to yield the three-dimensional photonic crystal template that displayed a gradient depending only on the period or irradiation and the thickness of the layer.
[0042] The preceding description is merely illustrative in nature and is in no way intended to limit the disclosure, its application, or uses. As used herein, the phrase at least one of A, B, and C should be construed to mean a logical (A or B or C), using a non-exclusive logical “or.” It should be understood that the various steps within a method may be executed in different order without altering the principles of the present disclosure. Disclosure of ranges includes disclosure of all ranges and subdivided ranges within the entire range.
[0043] The headings (such as “Background” and “Summary”) and sub-headings used herein are intended only for general organization of topics within the present disclosure, and are not intended to limit the disclosure of the technology or any aspect thereof. The recitation of multiple embodiments having stated features is not intended to exclude other embodiments having additional features, or other embodiments incorporating different combinations of the stated features.
[0044] As used herein, the terms “comprise” and “include” and their variants are intended to be non-limiting, such that recitation of items in succession or a list is not to the exclusion of other like items that may also be useful in the devices and methods of this technology. Similarly, the terms “can” and “may” and their variants are intended to be non-limiting, such that recitation that an embodiment can or may comprise certain elements or features does not exclude other embodiments of the present technology that do not contain those elements or features.
[0045] As used herein, the term “about” includes exactly the term or number that it modifies and slight variations therefrom. “Slight variations therefrom” can include within 15 degrees/percent/units or less, within 14 degrees/percent/units or less, within 13 degrees/percent/units or less, within 12 degrees/percent/units or less, within 11 degrees/percent/units or less, within 10 degrees/percent/units or less, within 9 degrees/percent/units or less, within 8 degrees/percent/units or less, within 7 degrees/percent/units or less, within 6 degrees/percent/units or less, within 5 degrees/percent/units or less, within 4 degrees/percent/units or less, within 3 degrees/percent/units or less, within 2 degrees/percent/units or less, or within 1 degree/percent/unit or less. In some instances, “about” can include being within normal manufacturing tolerances.
[0046] The broad teachings of the present disclosure can be implemented in a variety of forms. Therefore, while this disclosure includes particular examples, the true scope of the disclosure should not be so limited since other modifications will become apparent to the skilled practitioner upon a study of the specification and the following claims. Reference herein to one aspect, or various aspects means that a particular feature, structure, or characteristic described in connection with an embodiment or particular system is included in at least one embodiment or aspect. The appearances of the phrase “in one aspect” (or variations thereof) are not necessarily referring to the same aspect or embodiment. It should be also understood that the various method steps discussed herein do not have to be carried out in the same order as depicted, and not each method step is required in each aspect or embodiment.
[0047] The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations should not be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.