Nanocontact Molding and Casting: from 3D Fingerprint Phantoms to Designed Nanostructures
20200193115 ยท 2020-06-18
Inventors
Cpc classification
B29C33/00
PERFORMING OPERATIONS; TRANSPORTING
B29C59/022
PERFORMING OPERATIONS; TRANSPORTING
G06V40/1376
PHYSICS
B29K2069/00
PERFORMING OPERATIONS; TRANSPORTING
G03F7/0002
PHYSICS
B29C2033/3871
PERFORMING OPERATIONS; TRANSPORTING
B29C33/3878
PERFORMING OPERATIONS; TRANSPORTING
B29C33/3857
PERFORMING OPERATIONS; TRANSPORTING
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
B81C1/0046
PERFORMING OPERATIONS; TRANSPORTING
B29C39/026
PERFORMING OPERATIONS; TRANSPORTING
G06F21/32
PHYSICS
B29K2083/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
A method for fabricating a mold. The mold may comprise mold features with nanometer-scale resolution or minimum dimensions (e.g. the mold replicates nanometer-scale features of a master). The mold may comprise mold features with nanometer to micrometer-scale resolution or minimum dimensions (e.g. the mold replicates nanometer to micrometer-scale features of a master). The method may comprise providing a plate; applying a solvent to a first surface of the plate; allowing the solvent to penetrate from the first surface into the plate to thereby soften a first region of the plate, the first region of the plate including the first surface; pressing a master against the first region of the plate after the first region of the plate has softened to thereby deform at least a portion of the first region into a negative mold; and removing the master from contact with the plate.
Claims
1. A method for fabricating a nanocontact mold, the method comprising: providing a plate; applying a solvent to a first surface of the plate; allowing the solvent to penetrate from the first surface into the plate, to soften a first region of the plate, the first region of the plate including the first surface; pressing a master against the first region of the plate after the first region of the plate has softened to thereby deform at least a portion of the first region into a negative mold; and removing the master from contact with the plate.
2. A method according to claim 1 comprising removing at least some of the solvent from the first region of the plate after allowing the solvent to penetrate from the first surface into the plate to soften the first region of the plate.
3. A method according to claim 1 comprising removing at least some of the solvent from the first region of the plate after pressing the master against the first region of the plate.
4. A method according to claim 1 comprising removing at least some of the solvent from the first region of the plate, wherein removing at least some of the solved from the first region of the plate is effected by pressing the master against the first region of the plate.
5. A method according to claim 2 wherein the at least some of the solvent comprises at least 50% of the solvent applied to the first surface of the plate.
6-7. (canceled)
8. A method according to claim 1 wherein the at least some of the solvent is removed from the first region of the plate between 4 seconds and 120 seconds after applying the solvent to the first surface of the plate.
9. (canceled)
10. A method according to claim 1 wherein the at least some of the solvent is removed from the first region of the plate between 4 seconds and 16 seconds after applying the solvent to the first surface of the plate.
11. A method according to claim 1 wherein the length of time before the at least some of the solvent is removed from the first region is dependent on a desired depth of the first region.
12-14. (canceled)
15. A method according to claim 1 wherein the length of time before the at least some of the solvent is removed from the first region is dependent on a minimum dimension of the features of the master.
16-19. (canceled)
20. A method according to claim 1 wherein the plate comprises a polycarbonate plate.
21. A method according to claim 1 wherein the solvent is acetone.
22. (canceled)
23. A method according to claim 1 wherein the solvent comprises at least 90% acetone (by weight).
24-30. (canceled)
31. A method according to claim 1 wherein a ratio of a volume of solvent applied to the first surface of the plate to a surface area of the first surface of the plate is between 1 mL:300 mm.sup.2 and 1 mL:600 mm.sup.2.
32-33. (canceled)
34. A method according to claim 1 wherein the master comprises a nanometer-scale patterned structure.
35. A method according to claim 1 wherein the master is a finger.
36. (canceled)
37. A method of nanocontact casting, the method comprising; providing a nanocontact mold fabricated according to the method of claim 1; introducing a silicone solution over the first surface of the plate; curing the silicone solution on the first surface of the plate at a curing temperature to make a cured silicone cast; and removing the cured silicone cast from the first surface of the plate.
38. (canceled)
39. A method according to claim 37 comprising fabricating the silicone solution by mixing silicone precursors.
40-42. (canceled)
43. A method according to claim 38 comprising fabricating the silicone solution by mixing the silicone precursors and colour pigment.
44. A method according to claim 38 comprising fabricating the silicone solution by mixing the silicone precursors and conductive particles.
45-54. (canceled)
55. A method according to claim 37 wherein the silicone solution comprises a polydimethylsiloxane (PDMS) solution.
56. A method according to claim 37 wherein the cured silicone cast comprises a nanometer-scale patterned structure.
57. A method according to claim 37 wherein the cured silicone cast comprises a fingerprint phantom.
58-61. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than restrictive.
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DESCRIPTION
[0062] Throughout the following description specific details are set forth in order to provide a more thorough understanding to persons skilled in the art. However, well known elements may not have been shown or described in detail to avoid unnecessarily obscuring the disclosure. Accordingly, the description and drawings are to be regarded in an illustrative, rather than a restrictive, sense.
[0063] One aspect of the invention provides a method for fabricating a mold. The mold may comprise mold features with nanometer-scale resolution or minimum dimensions (e.g. the mold replicates nanometer-scale features of a master). The mold may comprise mold features with nanometer to micrometer-scale resolution or minimum dimensions (e.g. the mold replicates nanometer to micrometer-scale features of a master). The method may comprise providing a plate; applying a solvent to a first surface of the plate; allowing the solvent to penetrate from the first surface into the plate to thereby soften a first region of the plate, the first region of the plate including the first surface; pressing a master against the first region of the plate after the first region of the plate has softened to thereby deform at least a portion of the first region into a negative mold; and removing the master from contact with the plate. In some embodiments at least some solvent is removed from the first region of the plate.
[0064] Blocks 5-1, 5-2, 5-3 and 5-4 of
[0065] Block 5-1 depicts a plate 10 having a first surface 12. First surface 12 may comprise an entire planar surface of plate 10 or just a portion of a planar surface of plate 10 upon which it is desired to form a negative mold. Plate 10 may comprise, for example, a polycarbonate plate. For example, plate 10 may comprise a polycarbonate material such as Makrolon, Lexan or Tuffak. In some embodiments, plate 10 may comprise polystyrene or molding plastic such as Freeplastic.
[0066] In some embodiments, first surface 12 may be planar. This is not mandatory. First surface 12 may be convex or concave. In some embodiments, a root mean square (RMS) roughness of first surface 12 may be less than 1 m. In some embodiments, a root mean square (RMS) roughness of first surface 12 may be less than 10 nm.
[0067] In some embodiments, first surface 12 of plate 10 may be cleaned. For example, first surface 12 may be cleaned with ethanol and/or deionized water. In some embodiments, first surface 12 may be dried after cleaning to remove the cleaning substances (e.g. ethanol and/or deionized water). For example, in some embodiments, first surface 12 is dried (e.g. any remaining cleaning substances such as ethanol and/or deionized water are allowed to evaporate) in ambient conditions (e.g. 20-24 C. and 26-34% humidity). In other embodiments, first surface 12 is dried with nitrogen or other suitable gas.
[0068] At block 5-2, a solvent 20 is applied to first surface 12. Solvent 20 may be allowed to penetrate from first surface 12 into plate 10 to thereby soften a region 10A of plate 10 (see
[0069] Region 10A may have any desired depth 10B (see
[0070] In some embodiments, solvent 20 is applied to first surface 12 after first surface 12 is cleaned and dried. Solvent 20 may be applied to first surface 12 by, for example, a pipette 22 or a spray bottle (not depicted). This is not mandatory. In some embodiments, solvent 20 is applied to first surface 12 by a spraying, by pouring, by automatic pipette, by misting, and/or by any other suitable technique.
[0071] Solvent 20 may comprise any suitable solvent. Solvent 20 may comprise a liquid at the temperature and pressure associated with the performance of method 5. In some embodiments, solvent 20 may comprise acetone or diluted acetone. In some embodiments, solvent 20 is at least 60% acetone (by weight). In some embodiments, solvent 20 is at least 95% acetone (by weight). In some embodiments, solvent 20 is at least 99% acetone (by weight). In some embodiments, solvent 20 is at least 99.8% acetone (by weight). In some embodiments, solvent 20 comprises ethyl acetate, acetonitrile, diluted hexane, diluted toluene, nail polish remover and/or the like.
[0072] In some embodiments, the volume of solvent 20 applied to first surface 12 may be correlated with and/or proportional to the surface area of first surface 12 and/or a desired volume of region 10A. For example, in some embodiments, a ratio of the volume of solvent 20 applied to first surface 12 of plate 10 to a surface area of first surface of plate 10 is between 1 mL:300 mm.sup.2 and 1 mL:600 mm.sup.2. In some embodiments, a ratio of the volume of solvent 20 applied to first surface 12 of plate 10 to a surface area of first surface of plate 10 is between 1 mL:390 mm.sup.2 and 1 mL:510 mm.sup.2.
[0073] The application of solvent in bock 5-2 softens the plate in region 10A of plate 10. In some embodiments, as discussed below, excess solvent may be removed from plate 10 after block 5-2 and prior to block 5-3. At block 5-3, master 30 is pressed against region 10A after region 10A is softened by the application of solvent 20 to thereby deform at least a portion of first region 10A into a negative mold having a deformed surface 12A. Master 30 may comprise any suitable master having any desired shape. For example, in some applications, it is desirable to create a mold of a fingerprint and master 30 is a fingertip (as depicted in block 5-3 of
[0074] Master 30 may be pressed against region 10A with sufficient force or pressure to deform some of the softened material of region 10A. In some embodiments, master 30 is pressed against region 10A with a pressure of between 2 psi to 10 psi. In some embodiments, master 30 is pressed against region 10A with a pressure of between 3 psi to 7 psi. In some embodiments, master 30 is pressed against region 10A with a pressure of approximately 5 psi.
[0075] Swollen polymer chains of plate 10 may be rearranged by the application of force by master 30 to form a highly detailed (e.g. nanometer-scale or micrometer-scale resolution) negative mold 40 of master 30 (see
[0076] Block 5-4 depicts a negative mold 40 and its deformed surface 12A on first surface 12 of plate 10. Negative mold 40 and its deformed surface 12A are formed by pressing master 30 against region 10A. After master 30 is removed from first surface 12 of plate 10, plate 10 may be allowed to dry further (e.g. remaining solvent 20 may be allowed to evaporate). In some embodiments, first surface 12 is allowed to dry in ambient conditions.
[0077] Negative mold 40 and its deformed surface 12A comprise a plurality of mold features 42. Mold features 42 may correspond to (e.g. be complementary to) features 32 of master 30. For example, in the case of a master 30 comprising a fingertip, mold features 42 may correspond to (e.g. be complementary to) ridges and pores of the fingertip. In some embodiments, mold features 42 may have micrometer-scale minimum dimensions. For example, mold features 42 may have dimensions in the range of 20-40 m. In some embodiments, mold features 42 may have nanometer-scale minimum dimensions. For example, mold features 42 may have dimensions in the range of 125-300 nm.
[0078] Mold-fabrication method 5 may comprise removing at least some of solvent 20 (e.g. at least a portion of the applied solvent 20) from region 10A.
[0079] Removing at least some of solvent 20 from region 10A may comprise removing only a portion of the volume of solvent 20 applied at block 5-2. In some embodiments, 50% of solvent 20 applied at block 5-2 is removed from region 10A. In some embodiments, 70% of solvent 20 applied at block 5-2 is removed from region 10A. In some embodiments, 90% of solvent 20 applied at block 5-2 is removed from region 10A. In some embodiments, removing solvent 20 from region 10A comprises removing solvent 20 from first surface 12. In some embodiments, some amount of solvent 20 may remain in region 10A after removing solvent 20 from first surface 12.
[0080] In some embodiments, at least some of solvent 20 is removed from region 10A before master 30 is pressed against first surface 12 of region 10A (e.g. in between blocks 5-2 and 5-3). In some embodiments, at least some of solvent 20 is removed from region 10A while master 30 is pressed against first surface 12 (e.g. during block 5-3). In some embodiments, at least some of solvent 20 is removed from region 10A by master 30 being pressed against first surface 12. In some embodiments, at least some of solvent 20 is removed from region 10A after master 30 is pressed against first surface 12 (e.g. after block 5-3).
[0081] In some embodiments, at least some of solvent 20 is removed from region 10A within between 4 seconds and 120 seconds after the block 5-2 application of solvent 20. In some embodiments, at least some of solvent 20 is removed from region 10A within between 40 seconds and 60 seconds after the block 5-2 application of solvent 20. In some embodiments, at least some of solvent 20 is removed from region 10A within between 4 seconds and 12 seconds after the block 5-2 application of solvent 20.
[0082] In some embodiments, the length of time before at least a portion of solvent 20 is removed from region 10A is dependent on the resolution of features 32 of the master 30. For example, for masters 30 having nanometer-scale features 32, the period of time before at least a portion of solvent 20 is removed from region 10A may between 4 and 16 seconds while for masters having micrometer-scale features 32, the period of time before at least a portion of solvent 20 is removed from region 10A may be between 20 and 40 seconds.
[0083] In some embodiments, the length of time before solvent 20 is removed from first surface 12 is dependent on the time for crystallization (e.g. formation of spherulites) of the material of region 10A (e.g. polycarbonate) to occur. For example, in some embodiments, it is desirable to remove solvent 20 from first surface 12 before crystallization occurs or before substantial crystallization occurs. For example, where masters 30 have nanometer-scale features 32, crystallization may have a negative effect on the resultant mold given that surface features of a spherulite may be on the scale of 200-400 nm and spherulites themselves may be on the scale of 3-8 m. Therefore it may be desirable to remove solvent 20 from first surface 12 before crystallization occurs. In contrast, for a fingerprint mold where features 32 of the master (e.g. fingerprint) are on the scale of 20-40 m (e.g. pores of the fingerprint) or 200-500 m (e.g. ridges of the fingerprint), crystallization may have a less severe negative impact on the resultant mold and it may be acceptable (although not necessarily desirable) for some crystallization to occur. As such, where features 32 of master 30 are on the micrometer scale, it may be acceptable for solvent 20 to remain in contact with first surface 12 for a longer period of time.
[0084] In some embodiments, the length of time before at least some of solvent 20 is removed from region 10A is dependent on the desired depth 10B of region 10A. In some embodiments, the length of time before at least some of solvent 20 is removed from region 10A is dependent on the composition of solvent 20. In some embodiments, the length of time before at least some of solvent 20 is removed from region 10A is dependent on the porosity and/or composition of region 10A.
[0085] Solvent 20 may be removed from region 10A and/or first surface 12 by any suitable technique. In some embodiments, solvent 20 is removed from region 10A and/or first surface 12 by evaporation (which may comprise passive removal of solvent 20). In some embodiments, solvent 20 is removed from first surface 12 by blowing it off with air or nitrogen. In some embodiments, solvent 20 is removed from region 10A and/or first surface 12 by the application of pressure by a master 30 which pushes solvent 20 away. In some embodiments, solvent 20 is removed from region 10A and/or first surface 12 by a combination of any two or more of evaporation, blowing and pressure.
[0086] In some embodiments, by pressing master 30 against region 10A, solvent 20 is pushed away from a contact portion 11 of region 10A that is in contact with master 30, as depicted in
[0087] Another aspect of the invention provides a method for casting. The method may comprise providing a mold according to any of the methods described herein (e.g. method 5), introducing (e.g. pouring or the like) a silicone solution over the mold (e.g. over first surface 12 of plate 10); curing the silicone solution on the mold at a curing temperature to make a cured silicone cast; and removing the cured silicone cast from the mold.
[0088] Blocks 105-1, 105-2 and 105-3 of
[0089] At block 105-1, a mold 150 having a negative mold 140 of a master 130 is provided. Mold 150 may be any suitable mold. For example, mold 150 may comprise nanometer-scaled resolution (e.g. the mold may have mold features 142 having nanometer-scale minimum dimensions). Mold 150 may be similar to mold 50 or may comprise mold 50 fabricated according to method 5 described herein.
[0090] Block 105-2 depicts a silicone solution 160 being introduced (e.g. poured or the like) over negative mold 140 on first surface 112 of mold 150. In some embodiments, silicone solution 160 comprises polydimethylsiloxone (PDMS). Silicone solution 160 may comprise a mixture of silicone precursors such as, for example, a silicone elastomer base and a silicone curing agent. In some embodiments, silicone solution 160 may be fabricated by mixing the silicone elastomer base and the silicone curing agent in a ratio of between 5:1 and 20:1 (by weight). In some embodiments, silicone solution 160 may be fabricated by mixing the silicone elastomer base and the silicone curing agent in a ratio of 10:1 (by weight). In some embodiments, the silicone precursors are mixed by stirring and/or vortexing.
[0091] Fingerprint scanners rely on various techniques for detecting ridges (optical, conductivity, ultrasound, thermal) and may use additional measures to verify the authenticity of fingerprints. For use with ultrasound based scanners, silicone (e.g. PDMS) may itself be suitable for a cast, as silicone (e.g. PDMS) possesses a similar density to human tissue. However, while silicone (e.g. PDMS) may be a sufficient physical analog of skin in terms of strength and elasticity, it may be that optical and electrical properties of silicone (e.g. PDMS) are different than those of skin, which can lead to unreadable phantoms for certain types of scanners.
[0092] In some embodiments, silicone solution 160 comprises PDMS mixed with one or more additives. Such additives may impart an eventual silicone cast 170 with desired features (e.g. optical and electrical properties). For example, to approximate optical properties of human tissue, a flesh colored silicone pigment (e.g. pantone 488C) may be added at low weight percent (e.g. less than 10% by weight in some embodiments; less than 5% by weight in some embodiments; about 3% by weight in some embodiments; less than 2% by weight in some embodiments) to silicone solution 160. Pigmentation may provide better scattering and absorption for optical scanners to resolve ridges clearly. Many different pigments can be chosen or combined to mimic a wide range of skin tones.
[0093] In some embodiments, silicone solution 160 may comprise, for example, one or more conductive PDMS precursors (e.g. to produce an electrically conductive fingerprint phantom). In some embodiments, silicone solution 160 may comprise silver coated aluminum nanoparticles dispersed at their percolation threshold. In some embodiments, greater than 15% (by weight) silver nanowires and particles is provided in silicone solution 160. In some embodiments, greater than 18% (by weight) silver nanowires and particles in is provided in silicone solution 160. In some embodiments, greater than 20% (by weight) silver nanowires and particles in PDMS is provided in silicone solution 160. Commercially available conductive PDMS precursors with silver coated aluminum nanoparticles may also be employed. It is desirable for such phantoms to achieve an electrical resistance of 16 M/cm+/10% to properly simulate human tissue. There is a degree of flexibility in achieving readability by capacitive scanners because they are built to detect fingers with a high rate of success by accepting large variations in conductivity.
[0094] Silicone thinner may be added at between 2-7% by weight (e.g. 5% by weight) to decrease viscosity and ensure complete molding of fingerprints impressions.
[0095] In some embodiments, silicone solution 160 comprises polyurethane, Ecoflex, or another suitable polymer or elastomer. In some embodiments, silicone solution 160 comprises a PDMS solution purchased from Sylgard. Silicone solution 160 may be chosen to have a sufficiently low viscosity for silicone solution 160 to completely fill mold 150 and ensure complete molding. In some embodiments, lower viscosity silicone solution 160 is used where mold 150 has smaller (e.g. nanometer-scale) features as compared to when mold 150 has larger (e.g. micrometer-scale) features.
[0096] In some embodiments, mold walls 152 may be provided to contain silicone solution 160 as it is introduced atop mold 150. Mold walls 152 may form a perimeter around first surface 112 or around negative mold 140.
[0097] After silicone solution 160 is introduced over negative mold 140 and/or first surface 112, silicone solution 160 may optionally be degassed to remove any dissolved gases from silicone solution 160. Any suitable degassing technique may be employed. For example, silicone solution 160 may be placed under reduced pressure. In some embodiments, membrane degasification, sparging by inert gas, addition of a reductant, freeze-pump-thaw cycling and/or any other suitable degassing technique may be employed.
[0098] After silicone solution 160 is introduced over negative mold 140 and/or first surface 112 and after optional degassing of silicone solution 160, silicone solution 160 may be cured on negative mold 140 at a curing temperature to form a cured silicone cast 170. In some embodiments, curing time and curing temperature are dependent on the composition of silicone solution 160. In some embodiments, the curing temperature is between 60 C. and 100 C. In some embodiments, the curing temperature is between 75 C. and 85 C. In some embodiments, silicone solution 160 is cured on first surface 112 and/or negative mold 140 at the curing temperature for between 1 hour and 3 hours to make cured silicone cast 170. In some embodiments, silicone solution 160 is cured on first surface 112 and/or negative mold 140 at the curing temperature for between 1.5 hour and 2.5 hours to make cured silicone cast 170. In some embodiments the curing time is dependent on the temperature. For example, as the curing temperature increases, the curing time may decrease and as the curing temperature decreases, the curing time may increase. In some embodiments, the curing temperature is at or near ambient temperature (e.g. between 20 C. to 30 C.) and the curing time is between 24 hours and 48 hours.
[0099] At block 105-3, after silicone solution 160 is sufficiently cured and cured silicone cast 170 is formed, cured silicone cast 170 may be removed from mold 150. In some embodiments, cured silicone cast 170 is removed by cutting and/or peeling. In some embodiments, mold 150 remains substantially intact after silicone cast 170 is removed from mold 150 and mold 150 may be re-used.
[0100] In some embodiments, such as where master 30 is a finger, silicone cast 170 may be a fingerprint phantom. In some embodiments, the fingerprint phantom may be wrapped around a finger of a glove or an actual finger to give the fingerprint phantom a desired shape.
Experimental Results
[0101] The inventors conducted various experiments to evaluate method 5 and method 105. In some experiments, a 1.5 inch by 1.5 inch piece of polycarbonate (e.g. plate 10) was cut from a large sheet and the protective film removed from one side. The polycarbonate surface (e.g. first surface 12) was washed with deionized water and ethanol and then dried with nitrogen. 1.0 mL of acetone (e.g. solvent 20) was dispensed onto the polycarbonate surface (e.g. first surface 12) with an automatic pipette and left for 45 seconds. A finger (e.g. master 30) was then either pressed with mild force or rolled to produce a fingerprint impression (e.g. negative mold 40) on the surface. The polycarbonate plate was left to dry (e.g. any remaining solvent 20 was allowed to evaporate) in ambient conditions to solidify the fingerprint impression and form a mold (e.g. mold 50, 150).
[0102] Fingerprint phantoms (e.g. casts 170) were constructed by casting PDMS using the polycarbonate mold (e.g. mold 150) according to method 105. Two precursors to PDMS: an elastomer base (part A) and a curing agent (part B) were mixed in a 10:1 ratio (by weight) by manual stirring and vortexing. The precursor solution (e.g. silicone solution 160) was poured over the polycarbonate mold 150, degassed for 45 minutes in a vacuum chamber, and then cured in an oven at 80 C. for 2 hours. The PDMS phantom was then cut and peeled from the mold.
[0103] Specifically,
[0104]
[0105] The quality of various PDMS fingerprint phantoms made using method 5 and 105 was first examined for fidelity with the original fingerprints (e.g. masters 30) from which they were made.
[0106] As can be seen by comparing
[0107] In the binarized representations (e.g.
[0108] Several fingerprint matching algorithms are currently available which operate on the principle of comparing fingerprint minutiae. Particularly, the software identifies the location and direction of minutiae (e.g. ridge ends or splits) and compares them. The output is a similarity score (see the top right corner of each of
[0109] The quality of phantoms (e.g. casts 170) fabricated using methods 5 and 105 was further validated based on the reproduction (from master to mold and from mold to cast/phantom) of three different levels of physical details that exist within a fingerprint pattern. The first level of details is the location and arrangement of fingerprint ridges in relation to each other. The second level details (also referred to as minutiae) are unique ridge formations (e.g. patterns) formed where ridges come together and differentiate. The third level of details may comprise dimensional attributes of fingerprint ridges, including the width, edge contours, shape, location and size of pore and other permanent details such as creases or scars. Highly distinctive third level features are an excellent source of information for examining partial prints. In some circumstances, as few as 20-40 pores (e.g. the size and location of 20-40 pores) of a fingerprint are adequate for positive identification.
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[0112] In general, the minimal size and depth of third level details such as sweat pores can make third level details difficult to identify and define. Third level features, however, can be accurately recorded in the polycarbonate mold using method 5 and reproduced in PDMS fingerprint phantoms using method 105, as best shown by comparing
[0113] The inventors undertook experiments to determine what solvents could be employed as solvent 20 in method 5. Ethyl acetate was tested and was found to effectively swell and soften polycarbonate. However, it was found that polycarbonate hardens quickly after softening. Ethanol was also test. However, ethanol was found not to effectively swell and soften polycarbonate. Finally, while nail polish remover was successfully employed to fabricate a fingerprint mold, the resolution of the fingerprint mold was not ideal.
[0114] The inventors undertook experiments to study the capability of recording the depth of fingerprint ridges on a polycarbonate mold (e.g. mold 50) fabricated using method 5 (see
[0115] Along the ridges of the polycarbonate mold (see
[0116] Polycarbonate fingerprint molds fabricated using method 5 described herein and PDMS phantoms fabricated using method 105 described herein were imaged with a scanning electron microscope (SEM) to study microstructural details and examine how such microstructural details are transferred during molding method 5 and casting method 105.
[0117] When swollen with a solvent 20 (e.g. acetone), polycarbonate not only forms a malleable surface, but also undergoes rearrangement at the molecular level. Solvent molecules penetrate between polymer chains, which push them apart and increase their free volumes. Greater free volumes allow polycarbonate which originally existed in an amorphous state (polymer chains are too rigid to crystallize from melt) to adopt ordered configurations and crystallize into spherulites (e.g. spherical semi-crystalline regions inside non-branched linear polymers). Spherulites in polycarbonate range in size between 5-10 m in size. Spherulites comprise 100 nm crystalline polycarbonate tendrils which grow and branch outward from a central nucleation point with amorphous polycarbonate filling space between the tendrils. Evidence of polycarbonate spherulite impressions in PDMS would indicate that PDMS can mold features at least as small as spherulites or their tendrils (at micrometer and nanometer-scale, respectively).
[0118]
[0119] The inventors observed that the shape of an individual spherulite can be cast on the PDMS phantom with the details corresponding to protruding tendrils using method 105. For example, see
[0120] Methods 5 and 105 for molding and casting have applications beyond fingerprint phantoms. For example, methods 5 and 105 can be applied to mold and cast microstructures and nanostructures. Traditional micro/nanofabrication techniques require costly materials (e.g. high-grade silicon wafers, photoresists) and equipment (e.g. electron beam or UV lithography facilities) and previous molding techniques require well controlled molding parameters and conditions. For example, many prior art molding methods require a heated compression molding press to supply consistent heating and/or pressure. In contrast, molds described herein can be fabricated from an unmodified sheet of polycarbonate rapidly under ambient laboratory conditions on a benchtop by method 5.
[0121] In one exemplary experiment, a DVD-R was delaminated by wedging a razor blade between the middle layers and separating them manually to expose the polycarbonate base with the data layer atop, which contains a nanometer-scale periodic diffraction grating (e.g. a pattern with a series of repeating ridges with a periodic width of 740 nm). The data (dye) layer was removed from the polycarbonate base by sonicating and washing with ethanol. A 1.5 inch by 1.5 inch piece of the polycarbonate base adorned with the diffraction grating was used to prepare a PDMS master for testing molding and casting according to method 5 and method 105.
[0122] To replicate the PDMS master made from the DVD-R grating, a 1.5 inch by 1.5 inch piece of polycarbonate (e.g. plate 10) was cut from a large sheet and the protective film removed from one side. The polycarbonate surface was washed with deionized water and ethanol and then dried with nitrogen. 1.0 mL of acetone was dispensed onto the polycarbonate surface with an automatic pipette and left for 10 seconds. Excess acetone was removed from the polycarbonate surface by holding it upside down after the 10 seconds acetone treatment. The polycarbonate substrate was placed onto and gently pressed into the PDMS master. After allowing it to dry for 10 minutes the polycarbonate was removed from the PDMS master. The polycarbonate plate was left to dry in ambient conditions to solidify the fingerprint impression and form a mold (e.g. mold 50, 150).
[0123] Casts (e.g. casts 170) were made using the polycarbonate mold. Two precursors to PDMS: an elastomer base (part A) and a curing agent (part B) were mixed in a 10:1 ratio (by weight) by manual stirring and vortexing. The precursor solution (e.g. silicone solution 160) was poured over the polycarbonate mold, degassed for 45 minutes in a vacuum chamber, and then cured in an oven at 80 C. for 2 hours. The PDMS cast was then cut and peeled from the mold.
[0124] As shown in
[0125] Small pieces of polycarbonate (1.51.5) were cut from a large sheet to be employed as plates 10 for fingerprint molding. The protective film was removed from one side (e.g. first surface 12), but left on the other side (backside) during the solvent treatment. The polycarbonate surface was first washed with deionized water and ethanol (95%), then dried under nitrogen. To prepare for fingerprinting, the finger was cleaned by washing with warm water and then dried by dabbing with a Kimwipe.
[0126] 1.0 mL of 99.8% acetone (by weight) (e.g. solvent 20) was deposited onto the polycarbonate plate with an automatic micropipette and left on first surface for 45 seconds. The finger was then either pressed with mild force or rolled on the surface to produce a fingerprint impression. Rolling was done in a similar manner as to with ink printing: one edge of the finger was pressed then the digit was rolled to the other edge producing a flat print that includes both the edges and center of the fingerprint. Once dried, the protective coating was removed from the backside of polycarbonate plate 10. The plastic fingerprint replicas (e.g. negative molds 40) were imaged using an Epson Perfection 1250 scanner or a Nikon D5300 DSLR camera equipped with a micro lens. In both cases, the fingerprints were recorded with a black paper background underneath the polycarbonate plate for better contrast. Fingerprint impressions (e.g. negative molds 40) were also imaged using an Olympus BX50 polarized light microscope to examine the fingerprinting-related recrystallization process on the polycarbonate surface.
[0127]
[0128] To further confirm the transformation of polycarbonate from amorphous into a semi-crystalline state, wetting properties of the surface of polycarbonate were investigated. As shown in the inset of
[0129] The inventors examined the quality of fingerprint replicas (e.g. negative molds 40) based on the three levels of physical details that exist in human fingerprints. When a fingerprint is molded onto polycarbonate plate 10 treated with acetone (e.g. solvent 20), the solvated polymer chains (the swollen top layer) form opaque regions between fingerprint ridges. Underneath the fingerprint ridges, most of the swollen polycarbonate chains are displaced during fingerprinting, which appeared transparent in the molded fingerprints (see
[0130] A complete fingerprint image obtained with a desktop scanner and a black background is displayed in
[0131] Conventionally, sweat pores and other third level details are difficult to replicate due to their small size and depth. These highly distinctive features however, can be resolved in the fingerprints molded on polycarbonate, as can be seen in
[0132] A unique feature of methods 5, 105 is the capability of recording the depth of fingerprint features (e.g. mold features 42). The depth of fingerprint features provides insight into the wear and tear of finger ridges, often associated with age and occupation. Like sweat pores, ridge depth has the potential to allow for positive identification with a much smaller portion of a fingerprint as compared to two dimensional fingerprint replicas. To illustrate this unique feature, a fingerprint-molded polycarbonate plate, as shown in
[0133] Polycarbonate is of low cost and is chemically stable. It is useful as a fingerprinting substrate because of the rapid and distinct optical property change upon solvent treatment. During the molding process, the surface layer of polycarbonate is softened by solvent 20 (e.g. acetone) to the point that the swollen polymer chains can physically rearrange. When pressed with a master, the swollen polymer is squeezed between features of the master (e.g. squeezed into fingerprint ridges and into sweat pores). Generally polycarbonate is produced in the amorphous state as the polymer chains are rigid, making them difficult to crystallize from melt. Once swollen, the polycarbonate chains can adopt a more energetically favorable conformation and rearrange into spherulites (e.g. spherical formation of crystalline polycarbonate regions that grow radially from a central point with amorphous polycarbonate filling in between these nanostructured crystalline domains). The crystallization process occurs rather fast, which is consistent with the observation for the fingerprint replica being stabilized within minutes. The spherulites of semi-crystalline polycarbonate create a rough surface that scatters incoming light; hence it is opaque in appearance. Crystalline polycarbonate is birefringent, which scatters polarized light directionally depending on the incident angle.
[0134] It was demonstrated that the polycarbonate surface has been structurally altered by imaging fingerprint-molded and unmodified polycarbonate with a polarized optical microscope (see
[0135] The above proposed structural changes of polycarbonate surface upon solvent-assisted molding of fingerprints were further evaluated with SEM imaging. If no external force is applied, acetone-treated polycarbonate should form a homogeneous multi-layered network of spherulites. Physical force applied by molding motion may disrupt the spherulite formation.
[0136] With even higher resolution in
[0137] Based on the SEM and polarized microscopy images described above, a hypothetic diagram for the surface morphology of fingerprint-molded polycarbonate is proposed in
[0138] Methods 5, 105 have extended applications beyond reproducing fingerprints. In other words, the high fidelity with which methods 5, 105 create fingerprint replicas may be applied to produce highly engineered surfaces. Microfluidic channels have been produced in polycarbonate by methods 5, 105 in place of previously used techniques such as milling or molding with extreme pressure. Using methods 5, 105 may reduce or negate a need for high heat and/or extreme pressure to produce microfluidic devices, which reduces the cost and fabrication complexity. By combining control over surface properties with the tools to imprint micro/nanostructure, various microfluidic devices can be fabricated through the solvent-assisted molding processes described herein.
[0139]
[0140] As discussed herein, methods 5 and 105 are not limited to molding fingerprints and/or fingerprint phantoms. For example, micrometer-scaled and nanometer-scaled structures (e.g. nanostructured templates) can be replicated from masters (e.g. pre-fabricated templates) onto polycarbonate replicas.
[0141] The PDMS stamp was used to produce a polycarbonate replica master (see
[0142] In another experiment, a prefabricated nickel nanostructure bearing a nanoscale array of pits and tracks etched with electron/ion beam technology that produces a holographic security image was used as a nanostructured template. Features on the nickel nanostructure ranged in size from 400 nm to 100 nm depending on the desired optical properties. A PDMS cast of the nickel nanostructure was constructed by pouring 2 grams of h-PDMS (1:1 ratio of parts A and B) over the nickel nanostructure. After the h-PDMS was degassed and cured for 30 minutes at 60 C., a layer of regular PDMS was poured on top to form a flexible backing. The PDMS was degassed for 30 min, cured in the oven at 80 C. for 2 hours, then peeled from the nickel nanostructure.
[0143] To replicate the nickel master a thin film of acetone (e.g. solvent 20) in the amount of 0.5 ml for each 1 cm.sup.2 was applied to the surface (e.g. first surface 12) of a polycarbonate plate (e.g. plate 10) for 10 seconds. Then the PDMS cast was gently placed onto the polycarbonate and 5 PSI of pressure was applied to maintain conformal contact. After the acetone had evaporated the cast and polycarbonate replica were separated by hand.
[0144] As shown in
[0145] A polycarbonate replica fabricated using method 5 (shown in
[0146] Significant crystallization (formation of spherulites) on the surface of the polycarbonate was not observed as spherulite formation was prevented by the short acetone treatment time (10 seconds) and the spatial limitation. Large spherulites would jeopardize the resolution of pattern transfer into polycarbonate at the nanoscale by deforming the surface morphologies. Particularly,
[0147] Fourier-transform infrared spectroscopy analysis of PDMS after casting and SEM imaging of polycarbonate after molding further reinforce that material is not transferred during molding. As such, polycarbonate replicas can be reused as masters multiple times without any apparent damage or contamination. The robust nature of this approach is clear; numerous polycarbonate replicas can be prepared without the need of any sophisticated instrumentation and clean-room facilities.
[0148] Applications of method 5 for fabricating molds and method 105 for casting are varied. For example, method 5 of fabricating molds and method 105 of casting described herein may reduce the cost of producing nanostructures that can help broaden the applications of micrometer-scale and nanometer-scale devices generally. Non-limiting exemplary fields of application include optical filters, micro electromechanical systems, sensors and microfluidic devices. Nanometer-scale molded surfaces fabricated by the methods 5, 105 may be adapted to enhance many applications such as, for example low-flow-resistance and low-fluid-loss microfluidic devices, microfluidics devices that perform protein separations which rely on modified surfaces to localize and control surface adhesion, and PDMS stamps (templates) for micro-contact printing which rely on embedded nanostructures to improve ink transfer and reduce residual contamination.
[0149] While a number of exemplary aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub-combinations thereof. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations as are consistent with the broadest interpretation of the specification as a whole.