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Title:
METHODS OF AND APPARATUS FOR MAKING HIGH ASPECT RATIO MICROELECTROMECHANICAL STRUCTURES
Document Type and Number:
WIPO Patent Application WO/2003/071007
Kind Code:
A1
Abstract:
Various embodiments of the invention present techniques for forming structures (e.g. HARMS-type structures) via an electrochemical extrusion (ELEX?TM¿) process. Preferred embodiments perform the extrusion processes via depositions through anodeless conformable contact masks that are initially pressed against substrates that are then progressively pulled away or separated as the depositions thicken. A pattern of deposition may vary over the course of deposition by including more complex relative motion between the mask and the substrate elements. Such complex motion may include rotational components or translational motions having components that are not parallel to an axis of separation. More complex structures may be formed by combining the ELEX?TM¿ process with the selective deposition, blanket deposition, planarization, etching, and multi-layer operations of EFAB?TM¿.

Inventors:
COHEN ADAM L
ZHANG GANG
LE QUI T
Application Number:
PCT/US2002/032943
Publication Date:
August 28, 2003
Filing Date:
October 15, 2002
Export Citation:
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Assignee:
MEMGEN CORP (US)
International Classes:
C25D1/00; C25D5/02; C25D7/12; C25D21/14; H01L21/288; H01L21/768; H05K3/24; (IPC1-7): C25D5/02; C25D5/10; B81C1/00; B81B1/00
Domestic Patent References:
WO1998045504A11998-10-15
Foreign References:
US6027630A2000-02-22
Attorney, Agent or Firm:
Smalley, Dennis R. (1103 West Isabel Street Burbank, CA, US)
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Claims:
We Claim,
1. A method of producing a threedimensional structure, comprising: providing an anode; providing a substrate that functions as a cathode; providing an electrolyte between the anode and the cathode; providing a current source controllably connected to the anode and cathode; providing a mask that comprises an at least partially conformable material and a more rigid support material, the mask having at least one opening extending through the conformable material and extending at least partially through the support material, wherein the opening is defined by mask sidewalls that comprise sidewalls in a region of the support material and sidewalls extending through the conformable material, wherein the opening defines a mask pattern, and wherein the conformable portion of the mask also comprises a face surface; pressing the face surface against the substrate; activating the current source, after performing the pressing operation, to cause deposition of a first deposition material onto the substrate in a first deposition pattern that is at least in part dictated by the mask pattern, wherein the deposition comprises deposition sidewalls ; and after initiating the activating operation, relatively moving the face surface of the mask away from the substrate by a distance that is less than a distance that would cause separation of the mask sidewalls from the deposition sidewalls, and continuing application of the current so as to allow a height of the deposition to increase, wherein sidewalls in the region of the support material are configured or structured so that slippage between the deposition material and the sidewalls in the region of the support material can occur without causing significant damage to either the deposited material or the mask.
2. The method of claim 1 wherein the sidewalls in the region of the support material are passivated.
3. The method of claim 2 wherein the passivation is formed at least in part from a coating placed on the sidewalls of the opening through at least a portion of the support material.
4. The method of claim 3 wherein the coating comprises polytetrafluoroethylene.
5. The method of claim 3 wherein the support comprises silicon.
6. The method of claim 5 wherein the coating is formed, at least in part, during an etching that, at least in part, forms the opening in the silicon.
7. The method of claim 6 wherein the etching comprises deep reactive ion etching (DRIE).
8. The method of claim 1 wherein the sidewalls comprise silicon.
9. The method of claim 8 wherein the silicon is Ptype.
10. A method of producing a threedimensional structure, comprising: providing an anode; providing a substrate that functions as a cathode; providing an electrolyte between the anode and the cathode; providing a current source controllably connected to the anode and cathode; providing a mask that comprises an at least partially conformable material, the mask having at least one opening extending through the conformable material, wherein the opening is defined by mask sidewalls, wherein the opening defines a mask pattern, and wherein the conformable portion of the mask also comprises a face surface; pressing the face surface against the substrate; activating the current source, after performing the pressing operation, to cause deposition of a first material onto the substrate in a first deposition pattern that is at least in part dictated by the mask pattern, wherein the deposition comprises deposition sidewalls ; and after initiating the activating operation, relatively moving the face surface of the mask, away from the substrate by a distance that is less than a distance that would cause separation of the mask sidewalls from the deposition sidewalls, and continuing application of the current so as to allow a height of the deposition to increase, wherein the substrate and the electrolyte act as a corrosion system in absence of a deposition current.
11. The method of claim 10 wherein during the activating operation current is supplied at a variable rate.
12. The method of claim 11 wherein current is initially supplied at a higher rate and then is decreased.
13. The method of claim 12 wherein the initial current is reduced to a desired level after it is known, or it is estimated, that the substrate has been completely coated with first material.
14. The method of claim 13 wherein the initial current is derived based, at least in part on a combination of a desired plating current density and a corrosion current density or current.
15. The method of claim 10 wherein the electrolyte comprises a copper sulfate acid plating solution.
16. The method of claim 14 wherein the substrate comprises nickel.
17. The method of claim 16 wherein the first material comprises copper.
18. A method of producing a threedimensional structure, comprising: providing an anode; providing a substrate that functions as a cathode; providing an electrolyte between the anode and the cathode; providing a current source controllably connected to the anode and cathode; providing a mask that comprises an at least partially conformable material and a more rigid support material, the mask having at least one opening extending through the conformable material and extending through the support material, wherein the opening is defined by mask sidewalls that comprise sidewalls in a region of the support material and in a region of the conformable material, wherein the opening defines a mask pattern, and wherein the conformable portion of the mask also comprises a face surface; pressing the face surface against the substrate; activating the current source, after performing the pressing operation, to cause deposition of a first deposition material onto the substrate in a first deposition pattern that is at least in part dictated by the mask pattern, wherein the deposition comprises deposition sidewalls ; and after initiating the activating operation, relatively moving the face surface of the mask, after initiating the activating operation, away from the substrate by a distance that is less than a distance that would cause separation of the mask sidewalls from the deposition sidewalls, and continuing application of the current so as to allow a height of the deposition to increase, wherein the support material comprises regions of different thicknesses.
19. The method of claim 18 wherein the support material is thinner in the regions surrounding at least a portion of the at least one opening and is thicker in regions separated from the at least one opening.
20. The method of claim 18 wherein the support material has a front side on which the conformable material is placed and a back side opposite to that on which the conformable material is placed and wherein the back side of the support material is etched to thin the support material and thereafter the front side is etched to complete formation of the at least one opening that extends through the support material.
21. The method of claim 18 wherein the support material comprises at least a first support material and a second support material.
22. The method of claim 18 wherein the support material comprises a porous material.
23. The method of claim 18 wherein the support material is less than about 350 um in thickness.
24. The method of claim 18 wherein the support material is less than about 200 um in thickness at least in a region around the at least one opening.
25. A method of producing a threedimensional structure, comprising: providing an anode; providing a substrate that functions as a cathode; providing an electrolyte between the anode and the cathode; providing a current source controllably connected to the anode and cathode; providing a mask that comprises an at least partially conformable material and a more rigid support material, the mask having at least one opening extending through the conformable material and extending through the support material, wherein the opening is defined by mask sidewalls that comprise sidewalls in a region of the support material and in a region of the conformable material, wherein the opening defines a mask pattern, and wherein the conformable portion of the mask also comprises a face surface; pressing the face surface against the substrate; activating the current source, after performing the pressing operation, to cause deposition of a first deposition material onto the substrate in a first deposition pattern at least in part dictated by the mask pattern, wherein the deposition comprises deposition sidewalls ; and after initiating the activating operation, relatively moving the face surface of the mask, away from the substrate by a distance that is less than a distance that would cause separation of the mask sidewalls from the deposition sidewalls, and continuing application of the current so as to allow a height of the deposition to increase, wherein at least one sidewall of the support material is not coincident with a corresponding sidewall of the conformable material.
26. The method of claim 25 wherein an opening associated with the sidewalls of the conformable material is smaller than an opening associated with the sidewalls of the support material.
27. The method of claim 25 wherein an opening associated with the sidewalls of the conformable material, when not compressed against the substrate, is larger than an opening associated with the sidewalls of the support material.
28. A method of producing a threedimensional structure, comprising: providing an anode; providing a substrate that functions as a cathode; providing an electrolyte between the anode and the cathode; providing a current source controllably connected to the anode and cathode; providing a mask that comprises an at least partially conformable material and a more rigid support material, the mask having at least one opening extending through the conformable material and extending through the support material, wherein the opening is defined by mask sidewalls that comprise sidewalls in a region of the support material and in a region of the conformable material, wherein the opening defines a mask pattern, and wherein the conformable portion of the mask also comprises a face surface; pressing the face surface against the substrate; activating the current source, after performing the pressing operation, to cause deposition of a first deposition material onto the substrate in a first deposition pattern that is at least in part dictated by the mask pattern, wherein the deposition comprises deposition sidewalls ; and relatively moving the face surface of the mask, after initiating the activating operation, away from the substrate by a distance that is less than a distance that would cause separation of the mask sidewalls from the deposition sidewalls, and continuing application of the current so as to allow a height of the deposition to increase, wherein the conformable material has a thickness less than about 30% of a thickness of the support material or wherein the conformable material is less than about 30 um in thickness.
29. The method of claim 28 wherein the conformable material has a thickness less than about 20% of a thickness of the support material.
30. The method of claim 28 wherein the conformable material has a thickness less than about 10% of a thickness of the support material.
31. The method of claim 28 wherein the conformable material has a thickness less than about 5% of a thickness of the support material.
32. The method of claim 28 wherein the conformable material is less than about 50 um in thickness.
33. The method of claim 28 wherein the conformable material is less than about 20 um in thickness.
34. The method of claim 28 wherein the conformable material is less than about 10 pm in thickness.
35. A method of producing a threedimensional structure, comprising: providing an anode; providing a substrate that functions as a cathode; providing an electrolyte between the anode and the cathode; providing a current source controllably connected to the anode and cathode; providing a mask that comprises an at least partially conformable material, the mask having at least one opening extending through the conformable material, wherein the opening is defined by mask sidewalls, wherein the opening defines a mask pattern, and wherein the conformable portion of the mask also comprises a face surface; pressing the face surface against the substrate; activating the current source, after performing the pressing operation, to cause deposition of a first deposition material onto the substrate in a first deposition pattern that is at least in part dictated by the mask pattern, wherein the deposition comprises deposition sidewalls ; and after initiating the activating operation, relatively moving the face surface of the mask, away from the substrate by a distance that is less than a distance that would cause separation of the mask sidewalls from the deposition sidewalls, and continuing application of the current so as to allow a height of the deposition to increase; and during or between periods of activation of the current source, causing a flow in at least a portion of the electrolyte or agitation of at least a portion of the electrolyte that is located in proximity to at least a portion of the mask.
36. A method of producing a threedimensional structure, comprising: providing a substrate on which deposition of a material can occur; providing a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and at least partially through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by sidewalls in the region of the conformable material and sidewalls in the region of the support material; selectively depositing material onto the substrate while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the sidewalls of the conformable material and the sidewalls of the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein sidewalls in the region of the support material are configured or structured so that slippage between the deposition material and the sidewalls in the region of the support material can occur without causing significant damage to either the deposited material or the mask;.
37. A method of producing a threedimensional structure, comprising: providing a substrate on which deposition of a material can occur; providing a mask having a pattern comprised of a masking material and at least one opening therein, wherein the masking material has a face surface that can contact the substrate and wherein the masking material surrounding the opening forms mask sidewalls ; selectively depositing material onto the substrate, in the presence of an electrolyte while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the mask sidewalls and the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein the substrate and the electrolyte act as a corrosion system in absence of a deposition current.
38. A method of producing a threedimensional structure, comprising: providing a substrate on which deposition of a material can occur; providing a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by mask sidewalls ; selectively depositing material onto the substrate while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the mask sidewalls and the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein the support material comprises regions of different thicknesses.
39. A method of producing a threedimensional structure, comprising: providing a substrate on which deposition of a material can occur; providing a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by sidewalls in the region of the conformable material and sidewalls in the region of the support material ; selectively depositing material onto the substrate while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the sidewalls in the region of the conformable material and the sidewalls of the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein at least one sidewall of the support material is not coincident with a corresponding sidewall of the conformable material.
40. A method of producing a threedimensional structure, comprising: providing a substrate on which deposition of a material can occur; providing a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by sidewalls in the region of the conformable material and sidewalls in the region of the support material ; selectively depositing material onto the substrate while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the sidewalls in the region of the conformable material and sidewalls of the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein the conformable material has a thickness less than about 30% of a thickness of the support material or wherein the conformable material is less than about 30 um in thickness.
41. A method of producing a threedimensional structure, comprising: providing a substrate on which deposition of a material can occur; providing a mask having a pattern comprised of a masking material and at least one opening therein, wherein the masking material has a face surface that can contact the substrate and wherein the masking material surrounding the opening forms mask sidewalls ; selectively depositing material onto the substrate, in the presence of an electrolyte while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the mask sidewalls and the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; during or between periods of activation of the current source, causing a flow in at least a portion of the electrolyte or agitating at least a portion of the electrolyte that is located in proximity to at least a portion of the mask.
42. An apparatus for producing a threedimensional structure, comprising: a substrate on which deposition of a material can occur; a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and at least partially through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by sidewalls in a region of the conformable material and sidewalls in a region of the support material; means for selectively depositing material onto the substrate while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the sidewalls of the conformable material and the sidewalls of the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein sidewalls in the region of the support material are configured or structured so that slippage between the deposition material and the sidewalls in the region of the support material can occur without causing significant damage to either the deposited material or the mask.
43. An apparatus for producing a threedimensional structure, comprising: a substrate on which deposition of a material can occur ; a mask having a pattern comprised of a masking material and at least one opening therein, wherein the masking material has a face surface that can contact the substrate and wherein the masking material surrounding the opening forms mask sidewalls ; means for selectively depositing material onto the substrate, in the presence of an electrolyte while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the mask sidewalls and the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein the substrate and the electrolyte act as a corrosion system in absence of a deposition current.
44. An apparatus for producing a threedimensional structure, comprising: a substrate on which deposition of a material can occur; a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by mask sidewalls ; means for selectively depositing material onto the substrate while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the mask sidewalls and the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein the support material comprises regions of different thicknesses.
45. An apparatus for producing a threedimensional structure, comprising: a substrate on which deposition of a material can occur; a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by sidewalls in a region of the conformable material and sidewalls in a region of the support material ; means for selectively depositing material onto the substrate while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the sidewalls in the region of the conformable material and the sidewalls of the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein at least one sidewall of the support material is not coincident with a corresponding sidewall of the conformable material.
46. An apparatus for producing a threedimensional structure, comprising: a substrate on which deposition of a material can occur; a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by sidewalls in a region of the conformable material and sidewalls in a region of the support material ; means for selectively depositing material onto the substrate while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the sidewalls in the region of the conformable material and sidewalls of the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; wherein the conformable material has a thickness less than about 30% of a thickness of the support material or wherein the conformable material is less than about 30, um in thickness.
47. An apparatus for producing a threedimensional structure, comprising: a substrate on which deposition of a material can occur; a mask having a pattern comprised of a masking material and at least one opening therein, wherein the masking material has a face surface that can contact the substrate and wherein the masking material surrounding the opening forms mask sidewalls ; means for selectively depositing material onto the substrate, in the presence of an electrolyte while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the mask sidewalls and the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; means for causing at least one of a flow in at least a portion of the electrolyte or agitation of at least a portion of the electrolyte that is located in proximity to at least a portion of the mask.
48. A method of producing a threedimensional structure, comprising: providing a substrate from which a pattern protrudes, where the pattern has pattern sidewalls and the substrate has a face surface that is approximately perpendicular to the side walls ; providing a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and at least partially through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by sidewalls in a region of the conformable material and sidewalls in a region of the support material ;; and mating the mask sidewalls with the pattern sidewalls without mating the face surface of the masking material with the face surface of the substrate and depositing material through the opening onto the substrate wherein sidewalls in the region of the support material are configured or structured so that slippage between the deposition material and the sidewalls in the region of the support material can occur without causing significant damage to either the deposited material or the mask.
49. The method of claim 48 wherein the deposition of material through the opening is accompanied by simultaneous increasing or nonsimultaneous, intermittent increasing of a separation of the face surface of the mask from the face surface of the substrate.
50. A method of producing a threedimensional structure, comprising: providing a substrate from which a pattern protrudes, where the pattern has pattern sidewalls and the substrate has a face surface that is approximately perpendicular to the side walls ; providing a mask, having a pattern, comprised of a masking material and at least one opening therein, wherein the masking material has a face surface that is substantially parallel to the face of the substrate and wherein the masking material surrounding the opening forms mask sidewalls ; and mating the mask sidewalls with the pattern sidewalls without mating the face surface of the masking material with the face surface of the substrate and depositing material through the opening onto the substrate, wherein the substrate and an electrolyte, which participates in the depositing of material, act as a corrosion system in absence of a deposition current.
51. The method of claim 50 wherein the deposition of material through the opening is accompanied by simultaneous increasing or nonsimultaneous, intermittent increasing of a separation of the face surface of the mask from the face surface of the substrate.
52. A method of producing a threedimensional structure, comprising: providing a substrate from which a pattern protrudes, where the pattern has pattern sidewalls and the substrate has a face surface that is approximately perpendicular to the side walls ; providing a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and through the support material, wherein the conformable material has a face surface and wherein the opening is bounded by mask sidewalls ; and mating the mask sidewalls with the pattern sidewalls without mating the face surface of the masking material with the face surface of the substrate and depositing material through the opening onto the substrate, wherein the support material comprises regions of different thicknesses.
53. The method of claim 52 wherein the deposition of material through the opening is accompanied by simultaneous increasing or nonsimultaneous, intermittent increasing of a separation of the face surface of the mask from the face surface of the substrate.
54. A method of producing a threedimensional structure, comprising: providing a substrate from which a pattern protrudes, where the pattern has pattern sidewalls and the substrate has a face surface that is approximately perpendicular to the side walls ; providing a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by sidewalls in a region of the conformable material and sidewalls in a region of the support material ; and mating the mask sidewalls with the pattern sidewalls without mating the face surface of the masking material with the face surface of the substrate and depositing material through the opening onto the substrate. wherein at least one sidewall of the support material is not coincident with a corresponding sidewall of the conformable material.
55. The method of claim 54 wherein the deposition of material through the opening is accompanied by simultaneous increasing or nonsimultaneous, intermittent increasing of a separation of the face surface of the mask from the face surface of the substrate.
56. A method of producing a threedimensional structure, comprising: providing a substrate from which a pattern protrudes, where the pattern has pattern sidewalls and the substrate has a face surface that is approximately perpendicular to the side walls ; providing a mask having a pattern comprised of a conformable material and a more rigid support material and at least one opening that extends through the conformable material and through the support material, wherein the conformable material has a face surface that can contact the substrate and wherein the opening is bounded by sidewalls in a region of the conformable material and sidewalls in a region of the support material; and mating the mask sidewalls with the pattern sidewalls without mating the face surface of the masking material with the face surface of the substrate and depositing material through the opening onto the substrate; wherein the conformable material has a thickness less than about 30% of a thickness of the support material or wherein the conformable material is less than about 30 urn in thickness.
57. The method of claim 56 wherein the deposition of material through the opening is accompanied by simultaneous increasing or nonsimultaneous, intermittent increasing of a separation of the face surface of the mask from the face surface of the substrate.
58. A method of producing a threedimensional structure, comprising: providing a substrate from which a pattern protrudes, where the pattern has pattern sidewalls and the substrate has a face surface that is approximately perpendicular to the side walls ; providing a mask, having a pattern, comprised of a masking material and at least one opening therein, wherein the masking material has a face surface, and wherein the masking material surrounding the opening forms mask sidewalls ; mating the mask sidewalls with the pattern sidewalls without mating the face surface of the masking material with the face surface of the substrate and depositing material through the opening onto the substrate; and, during or between periods of activation of the current source, causing a flow in at least a portion of the electrolyte or agitation of at least a portion of the electrolyte that is located in proximity to at least a portion of the mask.
59. The method of claim 58 wherein the deposition of material through the opening is accompanied by simultaneous increasing or nonsimultaneous, intermittent increasing of a separation of the face surface of the mask from the face surface of the substrate.
Description:
Methods of and Apparatus for Making High Aspect Ratio Microelectromechanical Structures Related Cases: This application claims priority to U. S. Provisional Patent Application No.

60/329,654 which was filed on October 15,2001 and which is incorporated herein by reference as if set forth in full.

US Government Rights: This invention was made with Government support under NSF/SBIR Grant DMI- 0060725 awarded by the National Science Foundation. The Government has certain rights in this invention.

Field of the Invention : The present invention relates generally to the field of Electrochemical Fabrication and the associated formation of three-dimensional structures (e. g. micro-scale or meso- scale structures). In particular, it relates to methods and apparatus for forming such three-dimensional structures using electrochemical deposition techniques, and even more particularly relates to the electrochemical extrusion of such structures via the relative movement of a mask and a substrate.

Background of the Invention : A technique for forming three-dimensional structures/devices from a plurality of adhered layers was invented by Adam L. Cohen and is known as Electrochemical Fabrication. It is being commercially pursued by MEMGenT" Corporation of Burbank, California under the tradename EFAB. This technique was described in US Patent No. 6,027, 630, issued on February 22,2000. This electrochemical deposition technique allows the selective deposition of a material using a unique masking technique that involves the use of a mask that includes patterned conformable material on a support structure that is independent of the substrate onto which plating will occur.

When desiring to perform an electrodeposition using the mask, the conformable portion of the mask is brought into contact with a substrate while in the presence of a plating solution such that the contact of the conformable portion of the mask to the substrate inhibits deposition at selected locations. For convenience, these masks might be

generically called conformable contact masks; the masking technique may be generically called a conformable contact mask plating process. More specifically, in the terminology of MEMGenT" Corporation of Burbank, California such masks have come to be known as INSTANT MASKSTM and the process known as INSTANT MASKING or INSTANT MASK plating. Selective depositions using conformable contact mask plating may be used to form single layers of material or may be used-to form multi-layer structures. The teachings of the'630 patent are hereby incorporated herein by reference as if set forth in full herein. Since the filing of the patent application that led to the above noted patent, various papers about conformable contact mask plating (i. e.

INSTANT MASKING) and electrochemical fabrication have been published: 1. A. Cohen, G. Zhang, F. Tseng, F. Mansfeld, U. Frodis and P. Will,"EFAB : Batch production of functional, fully-dense metal parts with micro-scale features", Proc.

9th Solid Freeform Fabrication, The University of Texas at Austin, p161, Aug.

1998.

2. A. Cohen, G. Zhang, F. Tseng, F. Mansfeld, U. Frodis and P. Will,"EFAB : Rapid, Low-Cost Desktop Micromachining of High Aspect Ratio True 3-D MEMS", Proc.

12th IEEE Micro Electro Mechanical Systems Workshop, IEEE, p244, Jan 1999.

3. A. Cohen, "3-D Micromachining by Electrochemical Fabrication", Micromachine Devices, March 1999.

4. G. Zhang, A. Cohen, U. Frodis, F. Tseng, F. Mansfeld, and P. Will,"EFAB : Rapid Desktop Manufacturing of True 3-D Microstructures", Proc. 2nd International Conference on Integrated MicroNanotechnology for Space Applications, The Aerospace Co. , Apr. 1999.

5. F. Tseng, U. Frodis, G. Zhang, A. Cohen, F. Mansfeld, and P. Will,"EFAB : High Aspect Ratio, Arbitrary 3-D Metal Microstructures using a Low-Cost Automated Batch Process", 3rd International Workshop on High Aspect Ratio MicroStructure Technology (HARMST'99), June 1999.

6. A. Cohen, U. Frodis, F. Tseng, G. Zhang, F. Mansfeld, and P. Will,"EFAB : Low- Cost, Automated Electrochemical Batch Fabrication of Arbitrary 3-D Microstructures", Micromachining and Microfabrication Process Technology, SPIE 1999 Symposium on Micromachining and Microfabrication, September 1999.

7. F. Tseng, G. Zhang, U. Frodis, A. Cohen, F. Mansfeld, and P. Will,"EFAB : High Aspect Ratio, Arbitrary 3-D Metal Microstructures using a Low-Cost Automated

Batch Process", MEMS Symposium, ASME 1999 International Mechanical Engineering Congress and Exposition, November, 1999.

8. A. Cohen,"Electrochemical Fabrication (EFABTM) ", Chapter 19 of The MEMS Handbook, edited by Mohamed Gad-EI-Hak, CRC Press, 2002.

9. "Microfabrication-Rapid Prototyping's Killer Application", pages 1-5 of the Rapid Prototyping Report, CAD/CAM Publishing, Inc., June 1999.

The disclosures of these nine publications are hereby incorporated herein by reference as if set forth in full herein.

The electrochemical deposition process may be carried out in a number of different ways as set forth in the above patent and publications. In one form, this process involves the execution of three separate operations during the formation of each layer of the structure that is to be formed: 1. Selectively depositing at least one material by electrodeposition upon one or more desired regions of a substrate.

2. Then, blanket depositing at least one additional material by electrodeposition so that the additional deposit covers both the regions that were previously selectively deposited onto, and the regions of the substrate that did not receive any previously applied selective depositions.

3. Finally, planarizing the materials deposited during the first and second operations to produce a smoothed surface of a first layer of desired thickness having at least one region containing the at least one material and at least one region containing at least the one additional material.

After formation of the first layer, one or more additional layers may be formed adjacent to the immediately preceding layer and adhered to the smoothed surface of that preceding layer. These additional layers are formed by repeating the first through third operations one or more times wherein the formation of each subsequent layer treats the previously formed layers and the initial substrate as a new and thickening substrate.

Once the formation of all layers has been completed, at least a portion of at least one of the materials deposited is generally removed by an etching process to expose or release the three-dimensional structure that was intended to be formed.

The preferred method of performing the selective electrodeposition involved in the first operation is by conformable contact mask plating. In this type of plating, one or more conformable contact (CC) masks are first formed. The CC masks include a support structure onto which a patterned conformable dielectric material is adhered or

formed. The conformable material for each mask is shaped in accordance with a particular cross-section of material to be plated. At least one CC mask is needed for each unique cross-sectional pattern that is to be plated.

The support for a CC mask is typically a plate-like structure formed of a metal that is to be selectively electroplated and from which material to be plated will be dissolved. In this typical approach, the support will act as an anode in an electroplating process. In an alternative approach, the support may instead be a porous or otherwise perforated material through which deposition material will pass during an electroplating operation on its way from a distal anode to a deposition surface. In either approach, it is possible for CC masks to share a common support, i. e. the patterns of conformable dielectric material for plating multiple layers of material may be located in different areas of a single support structure. When a single support structure contains multiple plating patterns, the entire structure is referred to as the CC mask while the individual plating masks may be referred to as"submasks". In the present application such a distinction will be made only when relevant to a specific point being made.

In preparation for performing the selective deposition of the first operation, the conformable portion of the CC mask is placed in registration with and pressed against a selected portion of the substrate (or onto a previously formed layer or onto a previously deposited portion of a layer) on which deposition is to occur. The pressing together of the CC mask and substrate occur in such a way that all openings, in the conformable portions of the CC mask contain plating solution. The conformable material of the CC mask that contacts the substrate acts as a barrier to electrodeposition while the openings in the CC mask that are filled with electroplating solution act as pathways for transferring material from an anode (e. g. the CC mask support) to the non-contacted portions of the substrate (which act as a cathode during the plating operation) when an appropriate potential and/or current are supplied.

An example of a CC mask and CC mask plating are shown in Figures 1 (a) -1 (c).

Figure 1 (a) shows a side view of a CC mask 8 consisting of a conformable or deformable (e. g. elastomeric) insulator 10 patterned on an anode 12. The anode has two functions. Figure 1 (a) also depicts a substrate 6 separated from mask 8. One is as a supporting material for the patterned insulator 10 to maintain its integrity and alignment since the pattern may be topologically complex (e. g. , involving isolated "islands"of insulator material). The other function is as an anode for the electroplating operation. CC mask plating selectively deposits material 22 onto a substrate 6 by simply pressing the insulator against the substrate then electrodepositing material

through apertures 26a and 26b in the insulator as shown in Figure 1 (b). After deposition, the CC mask is separated, preferably non-destructively, from the substrate 6 as shown in Figure 1 (c). The CC mask plating process is distinct from a"through- mask"plating process in that in a through-mask plating process the separation of the masking material from the substrate would occur destructively. As with through-mask plating, CC mask plating deposits material selectively and simultaneously over the entire layer. The plated region may consist of one or more isolated plating regions where these isolated plating regions may belong to a single structure that is being formed or may belong to multiple structures that are being formed simultaneously. In CC mask plating as individual masks are not intentionally destroyed in the removal process, they may be usable in multiple plating operations.

Another example of a CC mask and CC mask plating is shown in Figures 1 (d)- 1 (f). Figure 1 (d) shows an anode 12'separated from a mask 8'that comprises a patterned conformable material 10'and a support structure 20. Figure 1 (d) also depicts substrate 6 separated from the mask 8'. Figure 1 (e) illustrates the mask 8'being brought into contact with the substrate 6. Figure 1 (f) illustrates the deposit 22'that results from conducting a current from the anode 12'to the substrate 6. Figure 1 (g) illustrates the deposit 22'on substrate 6 after separation from mask 8'. In this example, an appropriate electrolyte is located between the substrate 6 and the anode 12'and a current of ions coming from one or both of the solution and the anode are conducted through the opening in the mask to the substrate where material is deposited. This type of mask may be referred to as an anodeless INSTANT MASK (AIM) or as an anodeless conformable contact (ACC) mask.

Unlike through-mask plating, CC mask plating allows CC masks to be formed completely separate from the fabrication of the substrate on which plating is to occur (e. g. separate from a three-dimensional (3D) structure that is being formed). CC masks may be formed in a variety of ways, for example, a photolithographic process may be used. All masks can be generated simultaneously, prior to structure fabrication rather than during it. This separation makes possible a simple, low-cost, automated, self- contained, and internally-clean"desktop factory"that can be installed almost anywhere to fabricate 3D structures, leaving any required clean room processes, such as photolithography to be performed by service bureaus or the like.

An example of the electrochemical fabrication process discussed above is illustrated in Figures 2 (a) -2 (f). These figures show that the process involves deposition of a first material 2 which is a sacrificial material and a second material 4

which is a structural material. The CC mask 8, in this example, includes a patterned conformable material (e. g. an elastomeric dielectric material) 10 and a support 12 which is made from deposition material 2. The conforma portion of the CC mask is pressed against substrate 6 with a plating solution 14 located within the openings 16 in the conformable material 10. An electric current, from power supply 18, is then passed through the plating solution 14 via (a) support 12 which doubles as an anode and (b) substrate 6 which doubles as a cathode. Figure 2 (a), illustrates that the passing of current causes material 2 within the plating solution and material 2 from the anode 12 to be selectively transferred to and plated on the cathode 6. After electroplating the first deposition material 2 onto the substrate 6 using CC mask 8, the CC mask 8 is removed as shown in Figure 2 (b). Figure 2 (c) depicts the second deposition material 4 as having been blanket-deposited (i. e. non-selectively deposited) over the previously deposited first deposition material 2 as well as over the other portions of the substrate 6. The blanket deposition occurs by electroplating from an anode (not shown), composed of the second material, through an appropriate plating solution (not shown), and to the cathode/substrate 6. The entire two-material layer is then planarized to achieve precise thickness and flatness as shown in Figure 2 (d). After repetition of this process for all layers, the multi-layer structure 20 formed of the second material 4 (i. e. structural material) is embedded in first material 2 (i. e. sacrificial material) as shown in Figure 2 (e). The embedded structure is etched to yield the desired device, i. e. structure 20, as shown in Figure 2 (f).

Various components of an exemplary manual electrochemical fabrication system 32 are shown in Figures 3 (a) -3 (c). The system 32 consists of several subsystems 34, 36,38, and 40. The substrate holding subsystem 34 is depicted in the upper portions of each of Figures 3 (a) to 3 (c) and includes several components: (1) a carrier 48, (2) a metal substrate 6 onto which the layers are deposited, and (3) a linear slide 42 capable of moving the substrate 6 up and down relative to the carrier 48 in response to drive force from actuator 44. Subsystem 34 also includes an indicator 46 for measuring differences in vertical position of the substrate which may be used in setting or determining layer thicknesses and/or deposition thicknesses. The subsystem 34 further includes feet 68 for carrier 48 which can be precisely mounted on subsystem 36.

The CC mask subsystem 36 shown in the lower portion of Figure 3 (a) includes several components: (1) a CC mask 8 that is actually made up of a number of CC masks (i. e. submasks) that share a common support/anode 12, (2) precision X-stage 54, (3) precision Y-stage 56, (4) frame 72 on which the feet 68 of subsystem 34 can

mount, and (5) a tank 58 for containing the electrolyte 16. Subsystems 34 and 36 also include appropriate electrical connections (not shown) for connecting to an appropriate power source for driving the CC masking process.

The blanket deposition subsystem 38 is shown in the lower portion of Figure 3 (b) and includes several components: (1) an anode 62, (2) an electrolyte tank 64 for holding plating solution 66, and (3) frame 74 on which the feet 68 of subsystem 34 may sit. Subsystem 38 also includes appropriate electrical connections (not shown) for connecting the anode to an appropriate power supply for driving the blanket deposition process.

The planarization subsystem 40 is shown in the lower portion of Figure 3 (c) and includes a lapping plate 52 and associated motion and control systems (not shown) for planarizing the depositions.

In the last decade or so, there has been interest in creating MEMS devices whose overall height is comparable to or greater than their lateral extents; such structures are called high aspect ratio microstructures, or"HARMS". Two processes have emerged to dominate the manufacture of HARMS. They are LIGA and deep reactive ion etching (DRIE). LIGA is used to form metal structures and via secondary molding operations it may be used to produce polymer and ceramics structures. DRIE is used for etching deep holes into silicon.

The LIGA process is illustrated in Figures 4 (a) -4 (f). The process is essentially based on"through-mask plating"using a very thick patterned resist (e. g., 100s of microns to a centimeter or more). The resist is patterned using extremely high energy X-rays (e. g. , > 1 GeV) which allows the radiation to penetrate through the thick resist without significant attenuation or scattering. This, combined with a highly-collimated synchrotron beam, makes possible the fabrication of structures with very straight and parallel sidewalls having very smooth surfaces.

In Figure 4 (a), a substrate 102 is prepared (e. g. , by planarizing, cleaning, and depositing a conductive plating base (not shown). In Figure 4 (b), a thick layer of polymer 104 serving as an X-ray resist (typically poly (methylmethacrylate), or PMMA), is bonded to the plating base. As shown in Figure 4 (c), the resist 104 is exposed to energetic X-rays 106 through a specially-fabricated patterned mask 108 that may for example include gold patterning 112 on a silicon or graphite base 114. The exposure renders certain areas of the resist soluble in a developing chemical. Figure 4 (d) shows the patterned resist after development yielding mask 116, which has openings that extend to the plating base on the substrate 102. Next a through-mask selective

electroplating operation occurs. Figure 4 (e) shows the substrate 102 with mask 116 immersed in a deposition bath 118 held in a deposition tank 120, an anode 122; electrical connections 124 and 126 connecting the anode and substrate to a power supply 128. When current is applied, a metal 132' (or other electrodepositable material) is deposited onto the exposed plating base of substrate 102. If a low-stress formulation and deposition parameters are employed, the deposition can be continued to yield a thick deposit of metal (or other material) 132 as shown in Figure 4 (f). Then, as is shown in Figure 4 (g), the mask 116 can be removed (usually chemically) to yield the released deposited structure 132. If desired, this microstructure can then be used for molding other materials such as polymers or ceramics, for example, using injection molding or embossing techniques, for mass production.

Materials typically electrodeposited in LIGA are pure metals such as Ni, Cu, and Au, or metal alloys such as Ni-Fe (e. g., Permalloy). The latter is challenging due to limited mass transfer in the high aspect ratio mask. Also composite materials such as Ni and SiC can be deposited.

Because of the high cost of LIGA and an associated shortage of infrastructure, efforts have been made recently to develop alternative methods of fabricating through- mask electrodeposition masks with reasonably high aspect ratios (though much lower than those attainable with LIGA). One such effort is"UV-LIGA", in which a UV-curable resist is used (e. g. , the negative-working photoresist called SU-8 from an epoxy based photopolymer that has been available commercially for several years). Though SU-8 can achieve reasonably vertical sidewalls and thicknesses up to several hundred microns, it is extremely difficult to remove after the electrodeposition process is completed.

Another method that has been explored is sometimes known as Laser LIGA : it involves the use of a laser (typically a UV excimer laser) to machine cavities in a polymer to form a mask. This technique can create masks up to several tens of microns thick, but the sidewalls tend to be tapered (i. e. , not parallel) and somewhat rough.

A need exists for a more cost effective HARMS technology. A need exists for a HARMS technology that is compatible with the formation of HARMS devices on substrates containing microelectronic devices (e. g. , a CMOS wafer). A need exists for a HARMS technology that results in structures having more uniform properties throughout their heights. This is particularly true when deposition of alloying materials is to occur (inhibition of ionic transport into deep through-masks can vary by ionic

specifies and by depth level in the mask). A need exists for a HARMS technology that allows formation of more complex structures.

Summary of the Invention It is an object of various aspects of the present invention, or of variations thereof, to provide a more cost effective HARMS-type technology.

It is an object of various aspects of the present invention, or of variations thereof, to provide a HARMS-type technology that is compatible with the formation of HARMS devices on substrates containing microelectronic devices.

It is an object of various aspects of the present invention, or of variations thereof, to provide a HARMS-type technology that results in structures having more uniform properties throughout their heights.

It is an object of various aspects of the present invention, or of variations thereof, to provide a HARMS-type technology that allows formation of more complex structures.

It is an object of various aspects of the present invention, or of variations thereof, to provide enhanced electrochemical fabrication techniques that can be used to supplement the formation capabilities associated with CC mask plating.

It is an object of various aspects of the present invention, or of variations thereof, to provide enhanced electrochemical formation capabilities It is an object of various aspects of the present invention, or of variations thereof, to expand the range of materials that can be used in HARMS-type applications.

Other objects and advantages of various aspects of the invention will be apparent to those of skill in the art upon review of the teachings herein. The various aspects of the invention, set forth explicitly herein or otherwise ascertained from the teaching herein, may address any one of the above objects alone or in combination, or alternatively may address some other object of the invention ascertained from the teachings herein. It is not intended that all of these objects be addressed by any single aspect of the invention even though that may be the case with regard to some aspects.

In the 1St through 6th aspects of the invention, a method of producing a three- dimensional structure, includes: providing an electrode that functions as an anode; providing a substrate that functions as a cathode; providing an electrolyte between the anode and the cathode; providing a current source controllably connected to the anode and cathode; providing a mask that comprises an at least partially conformable material, the mask having at least one opening extending through the conformable material, wherein the opening is defined by mask sidewalls, wherein the opening

defines a mask pattern, and wherein the conformable portion of the mask also comprises a face surface; pressing the face surface against the substrate; activating the current source, after performing the pressing operation, to cause deposition of a first material onto the substrate in a first deposition pattern that is at least in part dictated by the mask pattern, wherein the deposition comprises deposition sidewalls ; and after initiating the activating operation, relatively moving the face surface of the mask away from the substrate by a distance that is less than a distance that would cause separation of the mask sidewalls from the deposition sidewalls, and continuing application of the current so as to allow a height of the deposition to increase; and wherein one of the following is included: (1) the mask includes a support structure that is more rigid than the conformable material, the opening extends at least partially through the support material, the mask sidewalls include sidewalls in a region of the support material and sidewalls that extend through the conformable material, and the sidewalls in the region of the support material are configured or structured so that slippage between the deposition material and the sidewalls in the region of the support material can occur without causing significant damage to either the deposited material or the mask;.

(2) the substrate and the electrolyte act as a corrosion system in absence of a deposition current; (3) the mask includes a support structure that is more rigid than the conformable material, the opening extends through the support material, the mask sidewalls include sidewalls in a region of the support material and in a region of the conformable material, and the support material includes regions of different thicknesses; (4) the mask includes a support structure that is more rigid than the conformable material, the opening extends through the support material, the mask sidewalls include sidewalls in a region of the support material and in a region of the conformable material, and at least one sidewall of the support material is not coincident with a corresponding sidewall of the conformable material ; (5) the conformable material has a thickness less than about 30% of a thickness of the support material or wherein the conformable material is less than about 30 um in thickness; or (6) during or between periods of activation of the current source, causing a flow in at least a portion of the electrolyte or agitation of at least a portion of the electrolyte that is located in proximity to at least a portion of the mask.

In the 7th through 12th aspects of the invention, a method of producing a three- dimensional structure, includes: providing a substrate on which deposition of a material can occur; providing a mask having a pattern comprised of a masking material and at least one opening therein, wherein the masking material has a face surface that can contact the substrate and wherein the masking material surrounding the opening forms mask sidewalls ; selectively depositing material onto the substrate, while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the mask sidewalls and the deposited material and continuing the deposition of material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; and wherein one of the following is included : (7) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and at least partially through the support material, the face surface of the masking material includes a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls in a region of the conformable material, and the sidewalls in the region of the support material that are configured or structured so that slippage between the deposition material and the sidewalls in the region of the support material can occur without causing significant damage to either the deposited material or the mask; (8) the selective depositing of material occurs in the presence of an electrolyte, and the substrate and the electrolyte act as a corrosion system in absence of a deposition current; (9) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and through the support material, the face surface of the masking material includes a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls that extend through the conformable material, and the sidewalls in the region of the support material are configured or structured so that slippage between the deposition material and the sidewalls in the region of the support material can occur without causing significant damage to either the deposited material or the mask; (10) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and at least partially through the support material, the face surface of the masking material includes

a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls in a region of the conformable material, and wherein the sidewalls in the region of the support material and in the region of the conformable material are not coincident; (11) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and at least partially through the support material, the face surface of the masking material includes a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls in a region of the conformable material, and wherein the conformable material has a thickness less than about 30% of a thickness of the support material or wherein the conformable material is less than about 30 um in thickness; or (12) the selective depositing of material occurs in the presence of an electrolyte, and causing a flow in at least a portion of the electrolyte or agitating at least a portion of the electrolyte that is located in proximity to at least a portion of the mask.

In the 1 3th through 18th aspects of the invention, an apparatus for producing a three-dimensional structure, includes: a substrate on which deposition of a material can occur; a mask having a pattern comprised of a masking material and at least one opening therein, wherein the masking material has a face surface that can contact the substrate and wherein the masking material surrounding the opening forms mask sidewalls ; means for selectively depositing a first material onto the substrate, in the presence of an electrolyte while the mask is pressed against the substrate and thereafter relatively separating the mask from the substrate while maintaining contact between the mask sidewalls and the deposited material and continuing the deposition of the first material so that a height of deposition increases beyond what it was prior to beginning the separation of the mask and the substrate; and wherein one of the following is included: (13) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and at least partially through the support material, the face surface of the masking material includes a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls in a region of the conformable material; and wherein sidewalls in the region of the support material are configured or structured so that slippage between the deposition material and the sidewalls in the region of the support

material can occur without causing significant damage to either the deposited material or the mask (14) the substrate and the electrolyte act as a corrosion system in absence of a deposition current; (15) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and through the support material, the face surface of the masking material includes a surface of the conformable material ; and wherein the support material comprises regions of different thicknesses.

(16) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and at least partially through the support material, the face surface of the masking material includes a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls in a region of the conformable material ; wherein at least one sidewall of the support material is not coincident with a corresponding sidewall of the conformable material ; (17) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and at least partially through the support material, the face surface of the masking material includes a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls in a region of the conformable material ; wherein the conformable material has a thickness less than about 30% of a thickness of the support material or wherein the conformable material is less than about 30, um in thickness; or (18) means for causing at least one of a flow in at least a portion of the electrolyte or agitation of at least a portion of the electrolyte that is located in proximity to at least a portion of the mask.

In the 19th through 24th aspects of the invention, a method of producing a three- dimensional structure, includes: providing a substrate from which a pattern protrudes, where the pattern has pattern sidewalls and the substrate has a face surface that is approximately perpendicular to the side walls ; providing a mask, having a pattern, including a masking material having a face surface and at least one opening therein, and wherein the masking material surrounding the opening forms mask sidewalls ; mating the mask sidewalls with the pattern sidewalls without mating the face surface of the masking material with the face surface of the substrate and depositing material through the opening onto the substrate; and wherein on the following is included:

(19) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and at least partially through the support material, the face surface of the masking material includes a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls in a region of the conformable material ; wherein sidewalls in the region of the support material are configured or structured so that slippage between the deposition material and the sidewalls in the region of the support material can occur without causing significant damage to either the deposited material or the mask (20) wherein the substrate and an electrolyte, which participates in the depositing of material, act as a corrosion system in absence of a deposition current.

(21) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material through the support material, the face surface of the masking material includes a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls in a region of the conformable material ; (22) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and at least partially through the support material, the face surface of the masking material includes a surface of the conformable material, wherein at least one sidewall of the support material is not coincident with a corresponding sidewall of the conformable material.

(23) the masking material includes a conformable material and a more rigid support material, the opening extends through the conformable material and through the support material, the face surface of the masking material includes a surface of the conformable material, mask sidewalls include sidewalls in a region of the support material and sidewalls in a region of the conformable material ; and wherein the conformable material has a thickness less than about 30% of a thickness of the support material or wherein the conformable material is less than about 30 um in thickness.

(24) during or between periods of activation of the current source, causing a flow in at least a portion of the electrolyte or agitation of at least a portion of the electrolyte.

In a variation of the 19th through 24th aspects, the method additionally includes the face of the masking material facing the face of the substrate and both faces being substantially parallel to one another.

In variations of the 1St aspect, methods include one or more of: (1) sidewalls in the region of the support material being passivated, (2) at least a portion of the

sidewalls are, at least in part, passivated by a coating placed on the sidewalls of the opening; (3) at least a portion of the sidewalls are passivated with a polytetrafluoroethylene coating; (4) the support including silicon, (5) at least a portion of the sidewalls are passivated by a coating that is formed, at least in part, during an etching operation that, at least in part, forms the opening in support material; (6) the opening being formed in the support material by deep reactive ion etching; (7) the support material includes a P-type silicon.

In variations of the 2nd aspect, methods include one or more of: (1) the current being supplied at a variable rate; (2) the current being initially supplied at a higher rate and then being decreased, (3) an initial current being reduced to a desired level after it is known, or it is estimated, that the substrate has been completely coated with the first material; (4) an initial current being derived based, at least in part on a combination of a desired plating current density and a corrosion current density or current; and (5) the electrolyte includes a copper sulfate acid plating solution, the first material includes copper, and/or the substrate includes nickel.

In variations of the 3rd aspect, methods include one or more of: (1) the support material being thinner in the regions surrounding at least a portion of the at least one opening and is thicker in regions separated from the at least one opening; (2) the support material has a front side on which the conformable material is placed and a back side opposite to that on which the conformable material is placed, and wherein the back side is etched to thin the support material and thereafter the front side is etched to complete formation of the at least one opening that extends through the support material; (3) the support material including at least a first support material and a second support material ; (4) the support material including a porous material; (5) the support material being less than about 350 um in thickness and more preferably less than about 200 um in thickness at least in a region around the at least one opening.

In variations of the 4th aspect, methods include one or more of: (1) an opening associated with the sidewalls of the conformable material being smaller than an opening associated with the sidewalls of the support material, and/or (2) an opening associated with the sidewalls of the conformable material, when not compressed against the substrate, being larger than an opening associated with the sidewalls of the support material.

In variations of the 5th aspect, methods include one or more of: (1) the conformable material having a thickness less than about 20% of a thickness of the support material, more preferably less than about 10% of a thickness of the support

material, and most preferably less than about 5% of a thickness of the support material ; and/or (2) the conformable material having a thickness less than about 20 microns, more preferably less than about 10 microns, and most preferably less than about 5 microns.

Further aspects of the invention will be understood by those of skill in the art upon reviewing the teachings herein. Other aspects of the invention may involve combinations of the above noted aspects of the invention. Other aspects of the invention may involve apparatus that can be used in implementing one or more of the above method aspects of the invention. These other aspects of the invention may provide various combinations of the aspects presented above as well as provide other configurations, structures, functional relationships, and processes that have not been specifically set forth above.

Brief Description of the Drawings Figures 1 (a) -1 (c) schematically depict a side view of various stages of a CC mask plating process, while Figures 1 (d) - (g) depict a side view of various stages of CC mask plating process using a different type of CC mask.

Figures 2 (a) -2 (f) schematically depict side views of various stages of an electrochemical fabrication process as applied to the formation of a particular structure where a sacrificial material is selectively deposited while a structural material is blanket deposited.

Figures 3 (a) -3 (c) schematically depict side views of various example subassemblies that may be used in manually implementing the electrochemical fabrication method depicted in Figures 2 (a) -2 (f).

Figures 4 (a) -4 (g) depict side views of various stages in a LIGA process for forming a HARMS-type structure.

Figures 5 (a) -5 (f) depict side views of various stages in a process according to a preferred embodiment of the present invention.

Figure 6 depicts a side view of a structure formed according to a preferred embodiment where the motion between the mask and the substrate included both perpendicular movement and parallel movement such that a desired amount of lateral variation in the deposit occurred.

Figures 7 (a) -7 (c) depict side views of various stages in a process according to a preferred embodiment of the present invention while Figure 7 (d) depicts an alternate configuration for sealing the mask and reservoir 304.

Figure 8 (a) -8 (d) depict side views of various stages of a process for forming a mold that can be used for forming a CC mask.

Figures 9 (a) -9 (f) depict side views of various stages of a CC mask formation process using the mold of figures 8 (a) -8 (d).

Figure 10 depicts a side view of an alternate CC mask configuration that includes a porous support.

Figures 11 (a) -11 (d) depict side views of various stages of a mask formation process that includes selective thinning of a substrate.

Figures 12 (a) -12 (d) depict various masks with non-coincident support and conformable materials regions.

Figures 13-15 depict various embodiments that include electrolyte flow or agitation.

Detailed Description of Preferred Embodiments of the Invention Figures 1 (a) -1 (g), 2 (a) -2 (f), and 3 (a) -3 (c) illustrate various aspects of electrochemical fabrication that are known. Other electrochemical fabrication techniques are set forth in the'630 patent referenced above, in the various previously incorporated publications, in patent applications incorporated herein by reference, still others may be derived from combinations of various approaches described in these publications, patents, and applications, or are otherwise known or ascertainable by those of skill in the art. All of these techniques may be combined with those of the present invention to yield enhanced embodiments.

Various embodiments of the invention present techniques for forming structures (e. g. HARMS-type structures) via an electrochemical extrusion (ELECT"') process.

Some preferred embodiments perform the extrusion process via depositions through an anodeless conformable contact mask that is initially pressed against a substrate and is then progressively pulled away from the substrate as the deposition thickens. The pattern of deposition may vary over the course of deposition by including relative motion between the mask and the substrate that includes translational or rotational components. More complex structures may be formed by combining the extrusion process with the selective deposition, blanket deposition, planarization, etching, and multi-layer operations of the electrochemical fabrication processes set forth in the U. S.

Patent 6,027, 630. In other embodiments, there may be no need for an initial face-to- face contact between the mask and the substrate particularly if the extrusion is to be added to an existing deposition where the contact can begin with a mating of side walls.

In still other embodiments the mask may be placed in proximity to the substrate and an initial deposition can be used to seal the mask and he substrate such that the initial gap is at least partially filled with a deposition material.

In a first preferred embodiment, the mask is initially pressed against the substrate so that the face of its conformable material (e. g. elastomeric surface) conforms to the substrate as in CC mask plating illustrated in Figures 1 (a)- (1 g). This contact positioning of the conformable contract mask prevents any deposition of material in contacted regions. An expandable bellows chamber is provided that surrounds the substrate and prevents the deposition bath from contacting the sides or rear of the substrate as well as the sides of later deposits, and thus prevents deposition in those regions. When the deposit has begun to grow in thickness, the substrate (or mask) is withdrawn at a controlled rate that on average closely matches the deposition rate, such that the progressing"working surface" (i. e. the surface at which the deposition is occurring) remains relatively fixed with respect to the mask. During the movement when the face of the mask no longer contacts the substrate, the sidewalls of the mask remain in intimate contact with the deposit, thus forming a seal which prevents deposition other than in the open areas of the mask. Eventually, a high aspect ratio structure, or at least a structure having a height in excess of that normally allowed by a mask of given dimensions, may be generated which is easily separated from the mask which can then be reused.

A first preferred embodiment is illustrated in Figures 5 (a) -5 (f). This embodiment uses a relatively thin mask (i. e. much thinner than the masks used in LIGA) that is independent of the substrate, and which is moved relative to the substrate during deposition to extrude a structure.

Figures 5 (a) -5 (f) illustrate side views of various stages in the process of this embodiment along with the various components that are used in the embodiment.

Figure 5 (a) illustrates a mask 102 that includes a support portion 104 (e. g. a rigid or dimensionally stable structure) and a conformable portion 106, an electrode 108 that may function as an anode, a substrate 110, and a bellows 120 and bellows chamber 112 that are located within a deposition tank 114 that can hold an electrolyte 116 (shown in Figure 5 (b) ). The open side of the bellows 120 connects to and seals with a perimeter region of the mask 102. This sealing makes the openings through the mask the only paths between the inside and outside of the bellows. Next, as shown in Figure 5 (b), the substrate 110 and the mask 102 are pressed against each other and the tank 114 is filled with electrolyte 116 in such a manner that the electrolyte does not become

located in the region 112 between the substrate and the bellows. As shown in Figure 5 (c) a potential is applied between the anode 108 and the substrate 110 (which acts as a cathode) via power source 122 and wires 124 and 126. The potential is supplied with a polarity and current that allows a deposition 138 to begin forming on the substrate at an appropriate rate. The primary source of the deposition material is preferably the anode 108 with potentially some deposition material being supplied directly by the electrolyte.

After the deposition thickens to a desired height, the substrate and the mask begin to separate at a desired rate. The average rate of separation is preferably approximately equal to the average rate of deposition such that a deposition zone and a location on the mask surface stay in the same approximate position throughout the deposition operation with the exception of the initial portion of the deposition that occurs before movement begins. During separation, the sidewalls 132 of the mask seal with the sidewalls 134 of the growing deposit 138 such that the electrolyte does not enter the bellows chamber 112. In one embodiment the deposition rate and the movement occur in such a manner that the position of the deposition stays at a position 140 relative to the face surface 136 of the mask resulting in a separation of"L". In other embodiments though the average deposition rate and the separation rate are approximately equal, actual separation may occur in discrete and discontinuous steps while the deposition may occur in a continuous manner, or in a discontinuous manner.

Deposition and movement may occur in an alternating manner at different times. In some embodiments the working surface may extend into the support region of the mask.

Figure 5 (d) depicts the state of deposition after the deposit thickness has grown to several times the thickness of the original mask and even more times the thickness of the conformable material portion 104 of the mask. Figure 5 (e) depicts the state of the process after the deposit 138 has grown to become the completed structure142 has been completed to form the completed structure 142. Figure 5 (f) depicts the combined substrate 110 and structure 142 after being removed from the apparatus of Figures 5 (a) - 5 (e) Figure 6 illustrates a side view of a structure 242 formed by electrochemical extrusion of material onto substrate 210 via mask 202. During the formation of the structure 242 not only was there a perpendicular separation of the planes of the mask 202 and substrate 210 surfaces but there was also motion that had a component parallel to the planes of the mask and substrate surfaces. The parallel component of

motion may include translational motion or may include rotational motion around an axis that has a component that is perpendicular to a plane of the mask surface (i. e. the face of the conformable material) or of a contact face of the substrate surface.

Figures 7 (a) -7 (c) illustrate another preferred embodiment where the bellows of the first embodiment are removed in favor of other structural components that inhibit deposition of material onto the sidewalls of the structure and onto the substrate (other than where initial openings in the mask expose selected portions of the substrate to electrolyte).

Figure 7 (a) depicts a base structure 300 on which an electrolyte reservoir 304 sits. A mask 302 sits on a gasket 308 located on a lower lip 306 at the bottom of the electrolyte reservoir 304. Of course, as opposed to just sitting on one another, in some embodiments the mask may be attached to the reservoir in any appropriate manner and similarly the reservoir may be attached to the base. On lip 306 and gasket 308, a support portion 312 of mask 302 sits while a conformable portion 322 of the mask is located on a lower surface of the support portion 312. One or more openings for the desired deposition pattern (in this example three are depicted) extend through both the conformable material and the support portion of the mask. A substrate 324 on which deposition is to occur is located below the mask on stage 332. Stage 332 is shown as having Z-movement capability 334 (i. e. movement capability in a direction substantially perpendicular to the plane of the substrate) but it is to be understood that for alignment purposes prior to beginning deposition or for varying the deposition pattern in the a plane parallel to the plane of the substrate, stage 332 could offer X and/or Y motion capability or rotational motion capability. Figure 7 (a) further shows that the apparatus includes an anode 334 that is located in electrolyte reservoir 304, electrical connections 336,338, and 340 that connect the anode 334, the substrate 324, and the stage 332 to controller 344. During operation, the controller supplies appropriate power to the anode and the substrate such that deposition onto the substrate occurs at a desirable rate and such that the motion of the substrate 324 relative to the mask 302 is appropriately controlled.

As shown in Figure 7 (b) the conformable portion 322 of the mask 302 contacts the substrate 324, the electrolyte reservoir 304 is filled with electrolyte 342 such that anode 334 and substrate 324 are connected by a conductive path. Deposition begins formation of structure 352 prior to initiating any movement of the substrate 324. In Figure 7 (c), a further stage of the process is shown where a deposition of significant height has been formed.

In some alternative embodiments the process may not begin with a face-to-face mating of the substrate and the mask (where the faces are considered to be the surfaces of the mask and the substrate that are substantially perpendicular to a direction of the height of the deposition). Instead the process may begin with a mating between the sidewalls of the mask and sidewalls of a protrusion that extends from the face of the substrate. Such an alternative process may be considered an add-on process, as the depositions that occur simply add to an existing structure. The initial protrusion may originate in many ways. For example, it may be from a molding operation, a previous extrusion operation, or a non-extrusion based conformable contact mask plating operation.

It is believed that these alternatives can be understood with reference to Figures 5 (e), 6, or 7 (c) where the state of deposition in each may be considered a protrusion that extends from the substrate and onto which one or more further depositions will occur. As such these figures may be considered to be the starting point of the process.

These starting points are achieved by mating the protrusion to the mask either in the presence of an electrolyte or subsequently surrounding the mated combination with electrolyte. After mating and electrolyte immersion, follow-on deposition occurs.

The follow-on deposition is preferably accompanied by relative movement between the mask and the substrate. However, in some embodiments the follow-on deposition may not be accompanied by such movement as the act of performing the deposition on an existing protrusion may be considered as a type of extrusion. In some embodiments, depositions may occur multiple times between mating and unmating operations where unmating and mating operations always occur between relative movements of the mask and the substrate.

The controller 344 may take various forms. For example it may be a computer programmed to control deposition time, current level for the electrodeposition operations, start time for initiating relative movement between the substrate and the mask, or the rate of such movement or the amount and timing of discrete movements, and the like. In less automated embodiments the controller may be two or more discrete devices and independent devices. For example, it may include a separate power supply for the deposition operation and a separate power supply and/or controller for the stage. The deposition power supply may include an adjustment for setting current to a desired value (e. g. based on a desired current density). The movement of the stage may be controlled to begin after a predetermined deposition time, after a predetermined amount of charge as flowed or been transferred through the

deposition system, or after a determined or estimated deposition height has been achieved. In some tests performed, it was found that a deposition thickness of about 20 microns before allowing the extrusion motion to begin resulted in reasonable sealing between the mask and the deposit during movement (i. e. no extraneous deposits or at least no excessive extraneous deposits were observed). Tests with a 10 micron thick deposition prior to initiating extrusion motion produced unsatisfactory results in those specific experiments. It is possible that in a given situation, thinner depositions prior to beginning extrusion motion could yield satisfactory results. It is within the level of skill in the art to determine a required minimum or at least a workable deposition thickness in a given situation.

Deposition may be terminated after a predetermined deposition time (a time estimated to produce the desired deposition height or a minimum deposition height to which the total deposition can be planed), after a predetermined amount of charge has flowed or been transferred through the deposition system, or after a determined or estimated deposition height has been achieved. In some alternative embodiments, deposition height may be periodically checked to ensure that movement and deposition are progressing as anticipated, corrective action may be taken as needed, and/or build parameters may be updated based on devised performance data. In some embodiments, the current may be set based on a desired current density and a known or estimated surface area for the deposition.

In some alternative embodiments, the movement between the mask and the substrate will be controlled in a manner that inhibits the deposition material from reaching a height within the mask that allows the deposited material to contact the support material. In other embodiments the deposition material will be allowed to contact the sidewalls of the support material The movement of stage 332 may be manually controlled, semi-automatically controlled, or automatically controlled (e. g. by a programmable device).

In some alternative embodiments, sealing between the mask and the reservoir may occur via the conformable material that forms part of the mask. For example, the conformable material may have an outer diameter that mates with the opening through the bottom of the reservoir 304 (e. g. the inside dimension of lip 306) or it may extend complete across the support structure such that an outer ring of conformable material rest on the lip of the reservoir thereby potentially obviating the need for the gasket 308.

This final alternative is shown in Figure 7 (d).

In the most preferred embodiments the anode includes an erodable material that supplies the deposition material but in other embodiments the deposition material may be provided by other means (e. g. solely by the solution) in which case the anode may not need to be erodable.

In the most preferred embodiments the mask is of the anodeless type while in other embodiments the anode may form part of the mask. In some anodeless type embodiments, the openings through the support material may be identical in size and configuration to the opening holes through the support portion while in other embodiments the opening sizes in the conformable material may be larger or smaller than the openings through the support material.

In still other embodiments, the support material may include a porous material and openings through the support portion may be paths through the pores. An example of a mask 500 with a porous support is shown in Figure 10. A conformable portion 504 (e. g. PDMS) of the mask 500 is patterned and attached to a relatively thin solid support structure 502 (e. g. a thin silicon wafer) that is in turn bonded to a porous structure 506 (e. g. a glass frit). In the most preferred embodiments each of these three components would be dielectrics but in other embodiments the solid support and the porous structure can be conductive. It is believed that a p-type silicon material may be particularly advantageous as the solid support structure as it is believed to resist acceptance of deposits of material if the deposition height and relative motion of the mask and substrate allow the deposit to contact the solid support 502.

In some preferred embodiments the substrate material will be the same as the deposition material while in other embodiments the materials may be different. For example, the deposition material may be copper, nickel, gold, silver, an alloy, or the like, while the substrate material may be any of these materials or some other material and even a material that isn't readily depositable. As a further example, the substrate may be composed of pure nickel (99.98%) while the deposition material may come from an electrode (i. e. anode) of pure OFHC copper (99.95%). In some embodiments where copper is the deposition material, the electrolyte may be a copper plating bath, such as a copper sulfate acid bath (e. g. Techni Copper U or Techni Copper FB from Technic Inc. of Cranston, Rhode Island) or a copper pyrophosphate bath (e. g. Unichrome from Atotech USA Inc. of Somerset, New Jersey).

The embodiment of Figure 5 illustrated a sideways extrusion of the material while the embodiment of Figure 7 illustrated a vertical extrusion of material where newly deposited material is added on top of previously deposited material. In still other

embodiments the mask and substrate may take on other orientations, for example the substrate may be located above the mask. If the substrate is located above the mask any bubbles resulting from the deposition process may tend to get stuck within the mask against the substrate or previously deposited material and a method to remove such bubbles may be desirable (e. g. flowing of electrolyte, agitation of electrolyte, periodic separation with or without associated agitation or flow, and the like).

In some embodiments, the structures may take on more complex forms. For example, the deposition material may be changed so that a portion of the extruded structure is formed from one material while another extruded portion is formed from a different material. A first portion of the extruded structure may be formed with one mask pattern while another extruded portion may be formed with a different mask pattern. In still other embodiments one or more breaks in deposition may occur, followed by one or more planarization operations. In other embodiments one or more extrusion operations may be performed in combination with one or more non-extrusion type deposition operations (e. g. depositions operations that do not include relative movement between a mask and the substrate).

In some embodiments, a second material may be deposited either selectively or by blanket deposition. In some embodiments, single or multiple materials may be planarized (e. g. by lapping, grinding, chemical mechanical polishing, and the like) as a basis for further deposition operations either of the extrusion type or of the non- extrusion type. In some embodiments multiple deposition operations may not occur in a repeated registration with each other but may occur in a desired shifted or rotated registration with respect to each other. In some multiple material embodiments, the material deposited by extrusion may be a sacrificial material while in other embodiments it may be a structural material. In some embodiments selective and/or non-selective depositions may be performed by electroplating, electrophoretic deposition, CVD, PVD, and/or any other technique capable of locating a material in a desired pattern on a substrate.

In some embodiments, for example to allow clearing of bubbles or to allow refreshing of electrolyte, the deposition current may be shut off one or more times, the mask and deposition may be separated, the mask and the deposition realigned and contacted, and then the current reactivated. In some embodiments this shutting off, separating, re-contacting, and re-depositing may be accompanied by an intermediate planarization operation (e. g. lapping) so as to allow reestablishment of planarity of the deposit prior to continuing with further deposition. In still other embodiments, fresh

electrolyte may be made to flow between the anode and the back side (i. e. the support side) of the mask and/or some agitation of the electrolyte may occur to help ensure maintenance of electrolyte properties. In embodiments where electrolyte is refreshed, replenished, or agitated, control of any pump or agitation actuator may occur via the same controller that handles deposition and separation.

In some embodiments, the mask may only include the conformable portion of the mask. The conformable portion of the mask preferably has sufficient conformability to allow easy separation of the mask and the deposit and to inhibit excessive amounts of electrolyte leakage between both the mask and the substrate and the mask and the deposit. In some embodiments, it may be found that sufficient conformability for such purposes is achieved without resorting to the need for a more rigid support structure.

The conformable contact masks of various embodiments may be formed in many different ways. The conformable material for some masks may be an elastomeric material, such as a rubber material, a urethane, or the like. A rubber material may be a silicone rubber, such as polydimethylsiloxane (PDMS). The supporting substrate may be a metal, silicon wafer, a relatively hard plastic or the like.

Some masks may be formed in a three step process that includes: (1) Design and fabrication of a photomask, (2) fabrication of a mold, and (3) fabrication of the mask. As some masks have feature sizes on the order of tens to hundreds of microns, the molds that may be used in patterning them may be considered micromolds.

Micromold fabrication may employ photolithography of a photoresist (such as is used in IC fabrication), to realize features on the microscale. One such photoresist is SU-8 (from Microchem Inc. of Newton, Massachusetts). SU-8 is a negative photoresist.

It has good mechanical properties, can be adhered to silicon, and can be coated (e. g. from 1 lim to more than 500 ! lu) in a single operation to a desired thickness (e. g. 25 m to 100 , m). Silicon wafers offer excellent flatness and smoothness which can be transferred to the contact surface of a conformable material that is patterned by an SU- 8/silicon micromold.

A process that can be used to fabricate an SU-8/silicon micromold is illustrated in Figures 8 (a) -8 (d). Figure 8 (a) depicts a side view of a silicon wafer 402. Figure 8 (b) shows that a coating of photoresist 406 (e. g. SU-8) of desired thickness is applied to the surface of the wafer 402. Figure 8 (c) illustrates the use of a photomask 412 in combination with a source (not shown) of UV radiation 416 can be used to selective expose 418 the coating of photoresist 406. Figure 8 (d) depicts mold 424 that results from the development of the photoresist 406 that was patterned via of the exposure of

Figure 8 (c). In Figure 8 (d) a region of photoresist 426 (the portion of the resist that was exposed) remains on the silicon wafer 402.

A process for using a mold, such as that shown in Figures 8 (d) to form a silicon/silicone mask, is depicted in Figures 9 (a) -9 (f). The process includes the following: (0) Start with a mold 424 as shown in Figure 9 (a) which includes base 402 and patterned photoresist 426, (1) Pour liquid PDMS 452 over photoresist pattern 426 of the mold 424 as shown in Figure 9 (b), (2) degas the PDMS to remove air bubbles, (3) place an Si wafer 454 onto the PDMS 452, pressing it down as indicated by arrows 454 as shown in Figure 9 (c) and holding it in position (e. g. with a molding fixture), and putting the fixture in an oven at an elevated temperature (e. g. 65 °C) for a period of time sufficient to cure the PDMS (e. g. for about 6 hours) to form a pattern 456 of cured PDMS, (4) de-mold the partially formed mask 458 from the mold as shown in Figure 9 (d). The partially formed mask may include a silicone residue 464 on the silicon 452 that is exposed in the opening 462 in the silicone, (5) use an etching operation (e. g.

RIE) to remove any silicone residue from the silicon surface in the opening to yield a partially formed mask 458 with an opening that is free of silicone as shown in Figure 9 (e), and (6) use deep reactive ion etching (DRIE) to etch through the silicon wafer as shown in Figure 9 (f) to yield a completed anodeless mask 472. Prior to performing the coating operation of step (2) above, the surface of the photoresist and silicon wafer of the mold may be treated with a release agent that may aid in the de-molding process of step (4). Experiments have produced masks by this process where the resulting conformable material thickness is about 25, um with a silicon thickness of about 300 urn.

In some embodiments, the silicon thickness could be reduced so as to reduce the required time to etch through it. For example, SOI wafers could be used. In other embodiments, a sacrificial film may be used to protect the conformable material (e. g.

PDMS) during DRIE operations.

In some embodiments, sidewalls of an opening that extend through or into a mask and more particularly into the region of a rigid material that forms part of a mask may be configured or structured so that slippage between a deposition material and the sidewalls of the region can occur without causing significant damage to either the deposited material or the mask (e. g. damage that makes the structure being formed unusable for its intended purpose or damage that makes the mask unusable for continuing the extrusion process). A first example of such a configuration or structure involves forming the mask such that the openings through the conformable material are

partially blocked by the support material (e. g. the openings through the support material are larger than the openings through the support material. A side view of a mask having such a configuration is shown in a Figure 12 (b). A second example of such a configuration or structure involves forming a coating on the sidewalls. For example, such a coating might include polytetrafluoroethylene, e. g. TEFLON. Such coatings may be applied by any appropriate technique from PVD, i. e. physical vapor deposition, CVD, i. e. chemical vapor deposition, immersion in a solvent containing the coating material and removing the solvent (e. g. by evaporation). Such coatings may be applied to the sidewalls of surfaces during a DRIE, i. e. deep reactive ion etching, process.

In some embodiments, the selected electrolyte and the substrate may react with one another such that the electrolyte begins dissolving the substrate (e. g. via a corrosion process). Sulfate acid copper plating baths, a preferred electrolyte for the present invention when copper is to be selectively deposited, can react with nickel substrates in such a manner. When using such combinations, it may be desirable to plate a first coating of material over the substrate relatively quickly to avoid excess damage to the substrate. As the corrosion effect, may be considered to be a current flowing in the opposite direction as that normally used in plating, it may be desirable to begin plating with a somewhat elevated plating current, such that the net current flow more closely approximates deposition using a desired current density than it otherwise would. In some embodiments, regardless of corrosion phenomena, the use of a higher initial current might be used solely for the purpose of getting a deposit down as quickly as possible. Once it is believed or known that the corrodible material (e. g. the substrate) is completed coated with the deposition material, the current may be lowered to yield a more desirable current density and associated plating rate.

In some embodiments, it may be desirable to minimize the thickness of the support material. For example it may be done to lower an etching process time for the sake of speeding the process. It may be done to lower an etching (e. g. DRIE) process time so that etching induced peripheral damage and structural changes are minimized.

It may also be done to improve the transfer between a volume of electrolyte within the openings of the masks and a larger volume of electrolyte outside the openings. Of course, thinning the entire support structure may be most beneficial in terms of improving electrolyte/ion transfer and for minimizing etching time (while the conformable material is present) but such global thinning may be impractical in some embodiments as it may excessively weaken the support structure. In some embodiments, selective thinning may be performed. An example of such a process is

set forth in Figures 11 (a) -11 (d). Figure 11 (a) starts with a structure 452 that is to be selectively thinned (e. g. a silicon wafer). Figure 11 (b) illustrates the structure 452 of 11 (a) after selective thinning. Selective thinning may have occurred via an etching operation, e. g. such as DRIE. Figure 11 (c) illustrates a partially completed mask structure 458'after bonding of the thinned support structure 452 and a patterned conformable material 456. Figure 11 (d) depicts, a completed mask 472'after etching through the opening in the conformable material opens a hole through the support structure 452.

As noted above, masks can be formed with non-coincident sidewalls (i. e. sidewalls that do not meet at the same line or do not meet with parallel surfaces).

Several such masks are illustrated in Figures 12 (a) -12 (d). Figure 12 (a) depicts a side view of a mask having a support material 552 and a conformable material 556. In Figure 12 (b) the support material 552 is shown as having several extended portions 558 that overhang the conformable material 556. Figure 12 (c) shows the opposite situation of that shown in Figure 12 (b) where the conformable material has extended regions 568 that extend or overhang beyond the support material. Figure 12 (d) shows a mask that contains regions with no overhang 462, support material overhang 558, and conformable material overhang 568.

In some embodiments the thicknesses of the support material and conformable material are important and/or their relative thicknesses are important. As noted above, it is desirable to make the mask as thin as possible but practical reasons limit this ability. The conformable material should be thick enough to allow an adequate seal to form between its sidewalls and the sidewalls of any deposition. If it is desired that deposited material not extend far enough into the mask to contact the support material or some other material that is located beyond the conformable material, the conformable material must have additional thickness to account for variations in deposition depth, errors in matching mask movement to deposit grow and the like. On the other hand, to enhance resolution in the plane of the depositions, it is advantageous to minimize the thickness of the conformable material. Furthermore as noted above, the support material must be thick enough to provide adequate structure integrity for the mask. In this regard, in some embodiments, it is preferred that the conformable material having a thickness less than about 20% of a thickness of the support material, more preferably less than about 10% of a thickness of the support material, and most preferably less than about 5% of a thickness of the support material ; and/or it is preferred that the conformable material have a thickness less than about 50 microns,

more preferably less than about 20 microns, and most preferably less than about 10 microns. In some preferred embodiments the support material may be thinner than about 350 microns (urn) and even more preferably less than about 200 urn at least in a region around the at least one opening.

In other embodiments the thicknesses and/or ratios may be greater while in still other embodiments they may be smaller.

In some embodiments to maintain a desired freshness of the electrolyte, it may be advantageous to have a flow of fresh electrolyte through the reservoir and more preferably to flow in proximity to openings in the masks in hopes of enhancing the exchange of electrolyte between the cell openings (e. g. pockets) and the bulk of the electrolyte outside the openings. This is illustrated in Figure 13 where an inlet 560 and outlet 562 can be used with appropriate tubing (not shown) and a pump (not shown) to cause a flow as indicated by the arrows that sweep between inlet and outlet and above the mask 302. In alternative embodiments the flow of material can be concentrated more directly on the mask. This is illustrated in Figure 14, where nozzle 570 directs a flow of material in directions that have components not only parallel to the back surface of the mask but also perpendicular thereto as well. Outlet 572 functions to remove excess material from the reservoir 304. In still other embodiments, adequate refreshment may be gained from a recirculating flow of material or by an agitation of the electrolyte. Figure 15 illustrates an embodiment where an agitation or vibration transducer 580, having a ring-like shape, and operating at an appropriate frequency and power level is located within reservoir 304. Line 582 is a control line that connects the transducer to controller 344. In some embodiments pumps, or the like that control flow may be also controlled by controller 344. In other embodiments, flow and agitation may be used.

The patent applications in the following table are hereby incorporated by reference herein as if set forth in full. The gist of each patent application is included in the table to aid the reader in finding specific types of teachings. It is not intended that the incorporation of subject matter be limited to those topics specifically indicated, but instead the incorporation is to include all subject matter found in these applications.

The teachings in these incorporated applications can be combined with the teachings of the instant application in many ways. For example, the various apparatus configurations disclosed in these referenced applications may be used in conjunction with the novel features of the instant invention to provide various alternative apparatus that include the functionality disclosed herein: US Application No. Title Filing Date Brief Description US App. No. 09/488,142 Method for Electrochemical Fabrication January 20,2000 This application is a divisional of the application that led to the above noted'630 patent. This application describes the basics of conformable contact mask plating and electrochemical fabrication including various alternative methods and apparatus for practicing EFAB as well as various methods and apparatus for constructing conformable contact masks US App. No. 09/755,985 Microcombustor and Combustion-Based Thermoelectric January 5,2001 Microgenerator Describes a generally toroidal counterflow heat exchanger and electric current microgenerator that can be formed using electrochemical fabrication. US App. No. 60/379,136 Selective Electrochemical Deposition Methods Having Enhanced May 7,2002 Uniform Deposition Capabilities Describes conformable contact mask processes for forming selective depositions of copper using a copper pyrophosphate plating solution that allows simultaneous deposition to at least one large area (greater than about 1.44 mm2) and at least one small area (smaller than about 0.05 mm2) wherein the thickness of deposition to the smaller area is no less than one-half the deposition thickness to the large area when the deposition to the large area is no less than about 10 um in thickness and where the copper pyrophosphate solution contains at least 30 g/L of copper. The conformable contact mask process is particularly focused on an electrochemical fabrication process for producing three-dimensional structures from a plurality of adhered layers. US App. No. 60/379,131 Selective Electrodeposition Using Conformable Contact Masks May 7,2002 Having Enhanced Longevity Describes conformable contact masks that include a support structure and a patterned elastomeric material and treating the support structure with a corrosion inhibitor prior to combining the support and the patterned elastomeric material to improve the useful life of the mask. Also describes operating the plating bath at a low temperature so as to extend the life of the mask. US App. No. 60/379,132 Methods and Apparatus for Monitoring Deposition Quality During May 7,2002 Conformable Contact Mask Plating Operations Describes an electrochemical fabrication process and apparatus that includes monitoring of at least one electrical parameter (e. g. voltage) during selective deposition using conformable contact masks where the monitored parameter is used to help determine the quality of the deposition that was made. If the monitored parameter indicates that a problem occurred with the deposition, various remedial operations are undertaken to allow successful formation of the structure to be completed. US App. No. 60/329, 654"Innovative Low-Cost Manufacturing Technology for High Aspect October 15,2001 Ratio Microelectromechanical Systems (MEMS)" This is the parent application for the present application and describes a conformable contact masking technique where the depth of deposition is enhanced by pulling the mask away from the substrate as deposition is occurring in such away that the seal between the conformable portion of the mask and the substrate shifts from the face of the conformal material and the opposing face of the substrate to the inside edges of the conformable material and the deposited material. US App. No. 60/379,129 Conformable Contact Masking Methods and Apparatus Utilizing May 7, 2002 In Situ Cathodic Activation of a Substrate Describes an electrochemical fabrication process benefiting from an in situ cathodic activation of nickel where prior to nickel deposition, the substrate is exposed to the desired nickel plating solution and a current less than that capable of causing deposition is applied through the plating solution to the substrate (i. e. cathode) to cause activation of the substrate, after which, without removing the substrate from the plating bath, the current is increased to a level which causes deposition to occur. US App. No. 60/379,134 Electrochemical Fabrication Methods With Enhanced Post May 7,2002 Deposition Processing Describes an electrochemical fabrication process for producing three-dimensional structures from a plurality of adhered layers where each layer includes at least one structural material (e. g. nickel) and at least one sacrificial material (i. e. copper) that will be etched away from the structural material after the formation of all layers have been completed. A copper etchant containing chlorite (e. g. Enthone C-38) is combined with a corrosion inhibitor (e. g. sodium nitrate) to prevent pitting of the structural material during removal of the sacrificial material. US App. No. 60/364,61 Electrochemical Fabrication Method and Apparatus for March 13,2002 Producing Three-Dimensional Structures Having Improved Surface Finish Describes an electrochemical fabrication (e. g. EFABTM) process and apparatus provided that remove material deposited on at least one layer using a first removal process that includes one or more operations having one or more parameters, and remove material deposited on at least one different layer using a second removal process that includes one or more operations having one or more parameters, wherein the first removal process differs from the second removal process by inclusion of at least one different operation or at least one different parameter. US App. No. 60/379,133 Method of and Apparatus for Forming Three-Dimensional May 7,2002 Structures Integral With Semiconductor Based Circuitry Describes an electrochemical fabrication (e. g. by EFAB) process and apparatus that can form three- dimensional multi-layer structures using semiconductor based circuitry as a substrate. Electrically functional portions of the structure are formed from structural material (e. g. nickel) that adheres to contact pads of the circuit. Aluminum contact pads and silicon structures are protected from copper diffusion damage by application of appropriate barrier layers. In some embodiments, nickel is applied to the aluminum contact pad via solder bump formation techniques using electroless nickel plating. US App. No. 60/379,176 Selective Electrochemical Deposition Methods Using May 7,2002 Pyrophosphate Copper Plating Baths Containing Citrate Salts Describes an electrochemical fabrication (e. g. by EFABTM) process and apparatus that can form three- dimensional multi-layer structures using pyrophosphate copper latin solutions that contain a citrate salt. In preferred embodiments the citrate salts are provided in concentrations that yield improved anode dissolution, reduced formation of pinholes on the surface of deposits, reduced likelihood of shorting between anode and cathode during deposition processes, and reduced plating voltage throughout the period of deposition. A preferred citrate salt is ammonium citrate in concentrations ranging from somewhat more that about 10 g/L for 10 mA/cm2 current density to as high as 200 g/L or more for a current density as high as 40 mA/cm2. US App. No. 60/379,135 Methods of and Apparatus for Molding Structures Using May 7,2002 Sacrificial Metal Patterns Describes molded structures, methods of and apparatus for producing the molded structures. At least a portion of the surface features for the molds are formed from multilayer electrochemically fabricated structures (e. g. fabricated by the EFABw formation process), and typically contain features having resolutions within the 1 to 100 um range. The layered structure is combined with other mold components, as necessary, and a molding material is injected into the mold and hardened. The layered structure is removed (e. g. by etching) along with any other mold components to yield the molded article. In some embodiments portions of the layered structure remain in the molded article and in other embodiments an additional molding material is added after a partial or complete removal of the layered structure. US App. No. 60/379,177 Electrochemically Fabricated Structures Having Dielectric Bases May 7,2002 and Methods of and Apparatus for Producing Such Structures Describes multilayer structures that are electrochemically fabricated (e. g. by EFABTM) on a temporary conductive substrate and are thereafter are bonded to a permanent dielectric substrate and removed from the temporary substrate. The structures are formed from top layer to bottom layer, such that the bottom layer of the structure becomes adhered to the permanent substrate. The permanent substrate may be a solid sheet that is bonded (e. g. by an adhesive) to the layered structure or the permanent substrate may be a flowable material that is solidified adjacent to or partially surrounding a portion of the structure with bonding occurs during solidification. The multilayer structure may be released from a sacrificial material prior to attaching the permanent substrate or more preferably it may be released after attachment. US App. No. 60/379,182 Electrochemically Fabricated Hermetically Sealed May 7,2002 Microstructures and Methods of and Apparatus for Producing Such Structures Describes multilayer structures that are electrochemically fabricated (e. g. by EFABTM) from at least one structural material (e. g. nickel), at least one sacrificial material (e. g. copper), and at least one sealing material (e. g. solder). The layered structure is made to have a desired configuration which is at least partially and immediately surrounded by sacrificial material which is in turn surrounded almost entirely by structural material. The surrounding structural material includes openings in the surface through which etchant can attack and remove trapped sacrificial material found within. Sealing material is located near the openings. After removal of the sacrificial material, the box is evacuated or filled with a desired gas or liquid. Thereafter, the sealing material is made to flow, seal the openings, and resolidify. US App. No. 60/379,184 Multistep Release Method for Electrochemically Fabricated May 7,2002 Structures Describes multilayer structures that are electrochemically fabricated (e. g. by EFABTM) from at least one structural material (e. g. nickel), that is configured to define a desired structure and which may be attached to a support structure, and at least a first sacrificial material (e. g. copper) that surrounds the desired structure, and at least one more material which surrounds the first sacrificial material and which will function as a second sacrificial material. The second sacrificial material is removed by an etchant and/or process that does not attack the first sacrificial material. Intermediate post processing activities may occur, and then the first sacrificial material is removed by an etchant or process that does not attack the at least one structural material to complete the release of the desired structure. US App. No. 60/392531 Miniature RF and Microwave Components and Methods for June 27,2002 Fabricating Such Components RF and microwave radiation directing or controlling components describes that are monolithic, that are formed from a plurality of electrodeposition operations, that are formed from a plurality of deposited layers of material, that include inductive and capacitive stubs or spokes that short a central conductor of a coaxial component to the an outer conductor of the component, that include non-radiation-entry and non-radiation- exit channels that are useful in separating sacrificial materials from structural materials and that are useful, and/or that include surface ripples on the inside surfaces of some radiation flow passages. Preferred formation processes use electrochemical fabrication techniques (e. g. including selective depositions, bulk depositions, etching operations and planarization operations) and post-deposition processes (e. g. selective etching operations and/or back filling operations. US App. No. TBD Multi-cell Masks and Method and Apparatus for Using Such Dkt No. P-US018-B-MG Masks October 1,2002 To Form Three-Dimensional Structures Describes multilayer structures that are electrochemically fabricated via depositions of one or more materials in a plurality of overlaying and adhered layers. Selectivity of deposition is obtained via a multi-cell controllable mask. Alternatively, net selective deposition is obtained via a blanket deposition and a selective removal of material via a multi-cell mask. Individual cells of the mask may contain electrodes comprising depositable material or electrodes capable of receiving etched material from a substrate. Alternatively, individual cells may include passages that allow or inhibit ion flow between a substrate and an external electrode and that include electrodes or other control elements that can be used to selectively allow or inhibit ion flow and thus inhibit significant deposition or etching. US App. No. TBD Monolithic Structures Including Alignment andlor Retention Dkt No. P-US025-A-MG Fixtures October 1, 2002 for Accepting Components Describes permanent or temporary alignment and/or retention structures for receiving multiple components. The structures are preferably formed monolithically via a plurality of deposition operations (e. g. electrodeposition operations). The structures typically include two or more positioning fixtures that control or aid in the positioning of components relative to one another, such features may include (1) positioning guides or stops that fix or at least partially limit the positioning of components in one or more orientations or directions, (2) retention elements that hold positioned components in desired orientations or locations, and (3) positioning and/or retention elements that receive and hold adjustment modules into which components can be fixed and which in turn can be used for fine adjustments of position and/or orientation of the components.

Various other embodiments of the present invention exist. Some of these embodiments may be based on a combination of the teachings herein with various teachings incorporated herein by reference. Some embodiments may not use any blanket deposition process and/or they may not use a planarization process. Some embodiments may involve the selective deposition of a plurality of different materials on a single layer or on different layers. Some embodiments may use blanket depositions processes that are not electrode position processes. Some embodiments may use selective deposition processes on some layers that are not conformable contact masking processes and are not even electrode position processes. Some embodiments may use nickel as a structural material while other embodiments may use different materials such as gold, silver, or any other electrodepositable materials that can be separated from copper and/or some other sacrificial material. Some embodiments may use copper as the structural material with or without a sacrificial material. Some embodiments may remove a sacrificial material while other embodiments may not. In some embodiments the anode may be different from the conformable contact mask support and the support may be a porous structure or other perforated structure. Some embodiments may use multiple conformable contact masks with different patterns so as to deposit different selective patterns of material on different layers and/or on different portions of a single layer.

In view of the teachings herein, many further embodiments, alternatives in design and uses of the instant invention will be apparent to those of skill in the art. As such, it is not intended that the invention be limited to the particular illustrative embodiments, alternatives, and uses described above but instead that it be solely limited by the claims presented hereafter.