Composite patterning devices for soft lithography

• US 20050238967A1
• Filed: 04/27/2005
• Published: 10/27/2005
• Est. Priority Date: 04/27/2004
• Status: Active Grant

• Current Assignee: Board of Trustees of The University of Illinois
• Original Assignee: Board of Trustees of The University of Illinois
• Inventors: Menard, Etienne, Rogers, John A.
• Granted Patent: US 7,195,733 B2
• Time in Patent Office: Days
• US Class Current: 430/5
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C04B 2111/00181 Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
• CPC Class Codes: C04B 24/383 Cellulose or derivatives thereof
• CPC Class Codes: C04B 28/14 containing calcium sulfate cements gypsum-paper plates E04C
• CPC Class Codes: G03F 7/0002 Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

Abstract

The present invention provides methods, devices and device components for fabricating patterns on substrate surfaces, particularly patterns comprising structures having microsized and/or nanosized features of selected lengths in one, two or three dimensions. The present invention provides composite patterning devices comprising a plurality of polymer layers each having selected mechanical properties, such as Young'"'"'s Modulus and flexural rigidity, selected physical dimensions, such as thickness, surface area and relief pattern dimensions, and selected thermal properties, such as coefficients of thermal expansion, to provide high resolution patterning on a variety of substrate surfaces and surface morphologies.

Claims

1. A composite patterning device for generating a pattern on a substrate surface, said device comprising:

a first polymer layer comprising a three-dimensional relief pattern having at least one contact surface disposed thereon, said first polymer layer having a low Young'"'"'s modulus and having an internal surface opposite said contact surface; and

a second polymer layer having an internal surface and an external surface;

said second polymer layer having a high Young'"'"'s modulus;

wherein said first polymer layer and said second polymer layer are arranged such that a force applied to the external surface of said second polymer layer is transmitted to said first polymer layer;

wherein said composite patterning device is capable of establishing conformal contact between at least a portion of said contact surface of said first polymer layer and said substrate surface.

2. The device of claim 1 wherein said internal surface of said first polymer layer is in contact with said internal surface of said second polymer layer.

3. The device of claim 1 wherein said first polymer layer and said second polymer layer are connected by a connecting layer positioned between said internal surface of said first polymer layer and said internal surface of said second polymer layer.

4. The device of claim 1 wherein said connecting layer comprises a thin metal layer.

5. The device of claim 1 wherein said first polymer layer and said second polymer layer are arranged such that a force applied to the external surface of said second polymer layer is transmitted to at least a portion of the contact surface of said first polymer layer.

6. The device of claim 1 wherein said three-dimensional relief pattern has a plurality of contact surfaces.

7. The device of claim 6 wherein said contact surfaces are in substantially the same plane.

8. The device of claim 6 wherein at least a portion of said contact surfaces are in different planes.

9. The device of claim 1 wherein the thickness of said first polymer layer is selected from the range of about 1 micron to about 100 microns.

10. The device of claim 1 wherein the thickness of said first polymer layer is about 5 microns.

11. The device of claim 1 wherein the thickness of said second polymer layer is selected from the range of about 10 microns to about 100 microns.

12. The device of claim 1 wherein the thickness of said second polymer layer is about 25 microns.

13. The device of claim 1 wherein the ratio of the thickness of the first polymer layer and the thickness of the second polymer layer is selected from the range of about 1 to about 10.

14. The device of claim 1 wherein said second polymer layer has a Young'"'"'s modulus selected from the range of about 1 GPa to about 10 GPa.

15. The device of claim 1 wherein said first polymer layer has a Young'"'"'s modulus selected from the range of about 1 MPa to about 10 MPa.

16. The device of claim 1 wherein said first polymer layer has a Young'"'"'s modulus of about 3 MPa.

17. The device of claim 1 wherein said first polymer layer, second layer or both further comprising a fiber material.

18. The device of claim 17 wherein said fiber material is selected from the group consisting of glass fiber, carbon fiber, metal fiber, a ceramic fiber and polymer fiber.

19. The device of claim 1 wherein said second polymer layer is selected from the group consisting of a thermoset layer, a polyimide, a thermoplastic layer and a composite polymer layer.

20. The device of claim 1 wherein said second polymer layer comprises a polymer having a coefficient of thermal expansion less than or equal to about 14.5 ppm.

21. The device of claim 1 wherein said first polymer layer is an elastomer layer.

22. The device of claim 1 wherein said first polymer layer comprises poly(dimethylsiloxane) or h-poly(dimethylsiloxane).

23. The device of claim 1 wherein said first polymer layer is a composite polymer layer.

24. The device of claim 1 further comprising a third polymer layer position between said first and second polymer layers, wherein said third polymer is a composite polymer layer comprising a fiber material.

25. The device of claim 1 wherein said composite patterning device has a flexural rigidity selected from the range of about 1×

10<sup>−

7</sup> Nm to about 1×

10<sup>−

5</sup> Nm.

26. The device of claim 1 wherein said relief pattern occupies an area selected from the range of about 10 cm² to about 260 cm².

27. The device of claim 1 wherein said relief pattern comprises a plurality of relief features exhibiting dimensions selected over the range of about 10,000 nanometers to about 50 nanometers.

28. The device of claim 1 wherein said relief pattern comprises a plurality of relief features exhibiting dimensions selected over the range of about 1000 nanometers to about 50 nanometers.

29. The device of claim 1 wherein said first polymer layer is a continuous, unitary layer.

30. The device of claim 1 wherein said first polymer layer is a discontinuous layer.

31. The device of claim 30 wherein said three-dimensional relief pattern comprises a plurality of independent relief features, wherein said independent relief features are in contact with said second polymer layer.

32. The device of claim 1 further comprising a third polymer layer having an internal surface and an external surface, wherein said first, second and third polymer layers are arranged such that a force applied to said external surface of said third polymer layer is transmitted to said first polymer layer.

33. The device of claim 32 wherein said internal surface of said third polymer layer is in contact with said external surface of said second polymer layer.

34. The device of claim 32 wherein said second polymer layer and said third polymer layer are connected by a connecting layer positioned between said external surface of said second polymer layer and said internal surface of said third polymer layer.

35. The device of claim 32 wherein said third polymer layer has a low Young'"'"'s modulus.

36. The device of claim 32 wherein said third polymer layer has a Young'"'"'s modulus selected from the range of about 1 MPa to about 10 MPa.

37. The device of claim 32 wherein the thickness of said third polymer layer is selected from the range of about 1 micron to about 100 microns.

38. The device of claim 32 wherein the thickness of the third polymer layer is within about 10% of the thickness of the first polymer layer.

39. The device of claim 32 wherein the thermal expansion coefficient of said first polymer layer is within about 10% of the thermal expansion coefficient of said third polymer layer.

40. The device of claim 32 wherein said third polymer layer is an elastomeric layer.

41. The device of claim 32 wherein said third polymer layer comprises poly(dimethylsiloxane) or h-poly(dimethylsiloxane).

42. The device of claim 32 wherein said third polymer layer comprises a means of evenly distributing an applied pressure to said contact surface.

43. The device of claim 32 further comprising a fourth layer having an internal surface and an external surface, wherein said first, second, third and fourth polymer layers are arranged such that a force applied to said external surface of said fourth polymer layer is transmitted to said first polymer layer.

44. The device of claim 43 wherein said internal surface of said fourth polymer layer is in contact with said external surface of said third polymer layer.

45. The device of claim 43 wherein said third polymer layer and said fourth polymer layer are connected by a connecting layer positioned between said external surface of said third polymer layer and said internal surface of said fourth polymer layer.

46. The device of claim 43 wherein said fourth polymer layer has a high Young'"'"'s modulus.

47. The device of claim 43 wherein said fourth polymer layer has a Young'"'"'s modulus selected from the range of about 1 GPa to about 10 GPa.

48. The device of claim 43 wherein thickness of said fourth polymer layer is selected from the range of about 10 microns to about 100 microns.

49. The device of claim 43 wherein the thickness of said fourth polymer layer is within about 10% of the thickness of said second polymer layer.

50. The device of claim 43 wherein the thermal expansion coefficient of said fourth polymer layer is within about 10% of the thermal expansion coefficient of said second polymer layer.

51. The device of claim 43 wherein said fourth layer comprises a material selected from the group consisting of:

a polymer;

a glass;

a ceramic; and

a metal.

52. The device of claim 1 further comprising an actuator connected to said external surface of said second polymer layer, wherein said actuator is capable of providing a force to said external surface of said second polymer layer.

53. The device of claim 32 further comprising an actuator connected to said external surface of said third polymer layer, wherein said actuator is capable of providing a force to said external surface of said third polymer layer.

54. The device of claim 43 further comprising an actuator connected to said external surface of said fourth polymer layer, wherein said actuator is capable of providing a force to said external surface of said fourth polymer layer.

55. The device of claim 1 comprising a stamp, a mold or a photomask.

56. The device of claim 1 wherein said composite patterning device transmits electromagnetic radiation in the ultraviolet region of the electromagnetic spectrum, the visible region of the electromagnetic spectrum or both the ultraviolet region and visible region of the electromagnetic spectrum.

57. The device of claim 1 wherein said composite patterning device transmits a pattern of electromagnetic radiation having a selected two dimensional spatial distribution of intensities.

58. The device of claim 1 wherein the composite patterning device has a net thermal expansion coefficient that is within 10% of the thermal expansion coefficient of said substrate.

59. A composite patterning device for generating a pattern on a substrate surface, said device comprising:

a first layer comprising a three-dimensional relief pattern having at least one contact surface disposed thereon, said first layer having a low Young'"'"'s modulus and having an internal surface opposite said contact surface;

a second layer having an internal surface and an external surface;

said second layer having a high Young'"'"'s modulus; and

a third layer having an internal surface and an external surface;

wherein said first, second and third polymer layers are arranged such that a force applied to the external surface of said third polymer layer is transmitted to said first polymer layer; and

wherein the thicknesses and thermal expansion coefficients of said first and third layers are selected to provide a substantially symmetrical distribution of the coefficients of thermal expansion about the center of said patterning device along a layer alignment axis extending through said patterning device, and wherein said composite patterning device is capable of establishing conformal contact between at least a portion of said contact surface of said first layer and said substrate surface.

60. The device of claim 59 wherein said internal surface of said first layer is in contact with said internal surface of said second layer and wherein said external surface of said second layer is in contact with said internal surface of said third layer.

61. The device of claim 59 wherein said first polymer layer and said second polymer layer are connected by a connecting layer positioned between said internal surface of said first polymer layer and said internal surface of said second polymer layer and wherein said third polymer layer and said fourth polymer layer are connected by a connecting layer positioned between said external surface of said third polymer layer and said internal surface of said fourth polymer layer.

62. The device of claim 59 wherein said layer alignment axis is oriented orthogonal to a plane containing at least one contact surface.

63. A patterning device for generating a pattern on a substrate surface, said device comprising:

an polymer layer comprising a three-dimensional relief pattern and a base, wherein said three-dimensional relief pattern has at least one contact surface disposed thereon, wherein said base has an external surface positioned opposite to said contact surface, wherein said contact surface is orthogonal to a layer alignment axis extending through said layer, and wherein the Young'"'"'s modulus of said polymer layer varies continuously along said layer alignment axis from a said contact surface to said external surface.

wherein said patterning device is capable of establishing conformal contact between at least a portion of said contact surface and said substrate surface.

64. The device of claim 63 wherein the Young'"'"'s modulus of said polymer layer varies continuously along said layer alignment axis from a low modulus value at said contact surface to a high modulus value at a mid point along said layer alignment axis between said contact surface and said external surface.

65. The device of claim 63 wherein the Young'"'"'s modulus of said polymer layer varies continuously from said high modulus value at a mid point along said layer alignment axis to a low modulus value at said external surface.

66. The device of claim 63 wherein said polymer layer has a substantially symmetrical distribution of the coefficients of thermal expansion about the center of said patterning device along said layer alignment axis.

67. A method of generating a pattern on a substrate surface, said method comprising the steps of:

providing a composite patterning device comprising;

a first polymer layer comprising a three-dimensional relief pattern having at least one contact surface disposed thereon, said first polymer layer having a low Young'"'"'s modulus and having a internal surface opposite said contact surface; and

a second polymer layer having an internal surface and an external surface;

said second polymer layer having a high Young'"'"'s modulus;

wherein said first polymer layer and said second polymer layer are arranged such that a force applied to the external surface of said second polymer layer is transmitted to said first polymer layer;

depositing a transfer material onto said contact surface of said first polymer layer, thereby generating a layer of transfer material on the contact surface;

contacting said composite patterning device and said substrate surface in a manner establishing conformal contact between at least a portion of said contact surface and said substrate surface, wherein said layer of transfer material is exposed to said substrate surface; and

separating said composite patterning device and said substrate surface, thereby transferring at least a portion of said transfer material to said substrate surface and generating said pattern on said substrate surface.

68. The method of claim 67 wherein said depositing step comprises depositing said transfer material onto said contact surface via vapor deposition.

69. The method of claim 67 wherein said depositing step comprises depositing said transfer material onto said contact surface via sputtering deposition.

70. The method of claim 67 wherein said depositing step comprises depositing said transfer material onto said contact surface via bringing said contact surface into contact with a reservoir of said transfer material.

71. A method of generating a pattern on a substrate surface, said method comprising the steps of:

providing a composite patterning device comprising;

a first polymer layer comprising a three-dimensional relief pattern having at least one contact surface disposed thereon, said first polymer layer having a low Young'"'"'s modulus and having a internal surface opposite said contact surface; and

a second polymer layer having an internal surface and an external surface;

said second polymer layer having a high Young'"'"'s modulus;

wherein said first polymer layer and said second polymer layer are arranged such that a force applied to the external surface of said second polymer layer is transmitted to said first polymer layer;

contacting said composite patterning device and said substrate surface in a manner establishing conformal contact between at least a portion of said contact surface and said substrate surface, thereby generating a mold comprising the space separating said three-dimensional relief pattern and said substrate surface;

introducing a transfer material into said mold; and

separating said composite patterning device and said substrate surface, thereby generating said pattern on said substrate surface.

72. A method of generating a pattern on the surface of a substrate comprising a photosensitive material, said method comprising the steps of:

providing a composite patterning device comprising;

a first polymer layer comprising a three-dimensional relief pattern having at least one contact surface disposed thereon, said first polymer layer having a low Young'"'"'s modulus and having a internal surface opposite said contact surface; and

a second polymer layer having an internal surface and an external surface;

said second polymer layer having a high Young'"'"'s modulus;

wherein said first polymer layer and said second polymer layer are arranged such that a force applied to the external surface of said second polymer layer is transmitted to said first polymer layer;

contacting said composite patterning device and said surface of said substrate in a manner establishing conformal contact between at least a portion of said contact surface and said surface of said substrate; and

directing electromagnetic radiation through said composite patterning device and onto said surface of said substrate, thereby generating a pattern of electromagnetic radiation having a selected two-dimensional distribution of intensities on said substrate surface;

wherein interaction of said electromagnetic radiation and said radiation sensitive material generates chemically modified regions of said radiation sensitive material, thereby generating said pattern on said substrate surface.

73. The method of claim 72 further comprising the step of removing at least a portion of said chemically modified regions of said substrate.

74. The method of claim 72 further comprising the step of removing at least a portion of said substrate that is not chemically modified.

75. A method of making a composite patterning device, said method comprising the steps of:

providing a master relief pattern having a selected three-dimensional relief pattern;

contacting said master relief pattern with a prepolymer of a low modulus polymer;

contacting said prepolymer material with an high modulus polymer layer;

polymerizing said prepolymer, thereby generating a low modulus polymer layer in contact with said high modulus polymer layer and in contact with said master relief pattern;

said low modulus polymer layer having a three-dimensional relief pattern; and

separating said low modulus polymer layer from said master relief pattern, thereby making said composite pattering device.

76. A fiber reinforced composite patterning device for generating a pattern on a substrate surface, said device comprising:

a first polymer layer comprising a three-dimensional relief pattern having at least one contact surface disposed thereon, said first polymer layer having a low Young'"'"'s modulus and having an internal surface opposite said contact surface; and

a second polymer layer having an internal surface and an external surface;

said second polymer layer comprising an array of fibers in a polymer, wherein said internal surface of said second polymer layer is in contact with said external surface of said first polymer layer;

a third polymer layer having an internal surface and an external surface;

said third polymer layer comprising an mesh of fibers in a polymer, wherein said internal surface of said third polymer layer is in contact with said external surface of said second polymer layer;

a fourth polymer layer having an internal surface and an external surface;

said fourth polymer layer comprising an mesh of fibers in a polymer, wherein said internal surface of said fourth polymer layer is in contact with said external surface of said third polymer layer;

a fifth polymer layer having an internal surface and an external surface;

said fifth polymer layer comprising an array of fibers in a polymer, wherein said internal surface of said fifth polymer layer is in contact with said external surface of said fourth polymer layer;

wherein said composite patterning device is capable of establishing conformal contact between at least a portion of said contact surface of said first polymer layer and said substrate surface.

77. An alignment system for aligning a conformable patterning device and a substrate, said system comprising:

said conformable patterning device comprising a first polymer layer having a contact surface with a first alignment element, said first polymer layer having a low Young'"'"'s modulus, said first alignment element comprising either a recessed region or a relief feature;

said substrate having an external surface;

wherein said external surface comprises a second alignment element comprising either a recessed region or a relief feature that is complementary to said first alignment element;

a patterning agent present between said contact surface of said conformable patterning device and said external surface of said substrate;

wherein said contact surface is capable of establishing conformal contact with said external surface such that said first and second alignment features engage.

78. The system of claim 77 wherein said conformable patterning device further comprises additional relief features, recessed regions or both relief features and recessed regions, wherein conformal contact of said contact surface and said external surface generates spaces occupied by said patterning agent.

79. The system of claim 78 wherein said patterning agent absorbs, scatters or reflects electromagnetic radiation directed onto said conformable patterning device, thereby generating electromagnetic radiation having a selected two dimensional spatial distribution of intensities that is transmitted to said external surface.

80. The system of claim 77 wherein said patterning agent is a lubricant capable of lowering the friction between said contact surface and said external surface of said substrate.

81. The system of claim 77 wherein said first and second alignment elements are relief features or recessed regions having shapes selected from the group consisting of pyramidal, cylindrical, polygonal, triangular, rectangular, square, conical, trapezoidal and spherical.

82. The system of claim 77 wherein the conformable patterning device is a composite patterning device further comprising one or more additional polymer layers connected to said first polymer layer.

83. A method of aligning a conformable patterning device and a substrate, said method comprising:

providing said conformable patterning device comprising a first polymer layer having a contact surface with a first alignment element, said first polymer layer having a low Young'"'"'s modulus, said first alignment element comprising either a recessed region or a relief feature;

providing said substrate having an external surface;

wherein said external surface comprises a second alignment element comprising either a recessed region or a relief feature that is complementary to said first alignment element;

providing a patterning agent between said contact surface of said conformable patterning device and said external surface of said substrate; and

establishing conformal contact between said contact surface and said external surface such that said first and second alignment features engage.

84. The method of claim 83 wherein said patterning agent is a lubricant capable of lowering the friction between said contact surface and said external surface of said substrate.