Pattern transfer by solid state electrochemical stamping

Abstract

The present invention provides an electrochemical fabrication platform for making structures, arrays of structures and functional devices having selected nanosized and/or microsized physical dimensions, shapes and spatial orientations. Methods, systems and system components of the present invention use an electrochemical stamping tool for generating patterns of relief and/or recessed features exhibiting excellent reproducibility, pattern fidelity and resolution on surfaces of solid state ionic conductors and in metal. Electrochemical stamping tools of the present invention are capable high throughput patterning of large substrate areas and, thus, enable a robust and commercially attractive manufacturing pathway to a range of functional systems and devices including nano- and micro-electromechanical systems, sensors, energy storage devices and integrated electronic circuits.

1 . A method of making a structure comprising: 
 a. providing a first electrode in electrical contact with a solid state ionic conductor;    b. providing a second electrode in electrical contact with a metal;    c. establishing electrical contact between at least a portion of said solid state ionic conductor and said metal; and    d. generating an electric field between said first and second electrodes, wherein a portion of the metal is oxidized thereby generating metal ions and free electrons, wherein said metal ions migrate through the solid state ionic conductor to the first electrode where they are reduced and wherein said free electrons migrate to said second electrode, thereby making said structures;    wherein said solid state ionic conductor or said first electrode is a stamping tool that generates a pattern of electrical contacts between said stamping tool and said solid state ionic conductor or said metal.    
     
     
         2 . The method of  claim 1  wherein the metal comprises a metal layer, a bulk metal, metal particles, metal cluster or a metal substrate.  
     
     
         3 . The method of  claim 1  wherein the solid state ionic conductor comprises metal atoms that are the same as metal atoms in said metal.  
     
     
         4 . The method of  claim 1  wherein said electric field is generated by applying a potential difference between said first and second electrodes, wherein said second electrode has a higher electrical potential than said first electrode.  
     
     
         5 . The method of  claim 4  wherein said potential difference between first and second electrodes has a value selected from the range of about 100 mV to about 2000 mV.  
     
     
         6 . The method of  claim 1  wherein said first electrode is a cathode and wherein said second electrode is an anode.  
     
     
         7 . The method of  claim 1  wherein physical contact is established between at least a portion of said stamping tool and said solid state ionic conductor or said metal.  
     
     
         8 . The method of  claim 1  wherein said stamping tool comprises a pattern of relief features, wherein physical or electrical contact between at least a portion of said relief features and said solid state ionic conductor or said metal generates said pattern of electrical contacts.  
     
     
         9 . The method of  claim 8  wherein said pattern of said stamping tool is at least partially transferred to said ionic conductor via electrochemical etching or said metal via electrochemical deposition.  
     
     
         10 . The method of  claim 1  further comprising the step of applying a force to said stamping tool.  
     
     
         11 . The method of  claim 10  wherein said force is applied uniformly to one or more surfaces of said stamping tool such that electrical contact between at least a portion of said stamping tool and said solid state ionic conductor or said metal is maintained during processing.  
     
     
         12 . The method of  claim 1  wherein said ionic conductor is said stamping tool, wherein said stamping tool has a selected pattern of relief features, wherein physical contact between at least a portion of said relief features and said metal generates said pattern of electrical contacts.  
     
     
         13 . The method of  claim 12  wherein metal atoms are oxidized in regions of said metal in physical contact with at least a portion of said relief features of said stamping tool.  
     
     
         14 . The method of  claim 12  wherein localized electrochemical etching of said metal occurs at regions of said metal in physical contact with said relief features of said stamping tool.  
     
     
         15 . The method of  claim 12  wherein at least a portion of said pattern of said stamping tool is transferred to said metal via electrochemical etching.  
     
     
         16 . The method of  claim 12  wherein at least a portion of said relief features of said stamping tool are nanosized relief features, microsized relief features or both nanosized features and microsized relief features.  
     
     
         17 . The method of  claim 1  wherein said first electrode is said stamping tool, wherein said stamping tool has a shape selected such that electrical contact between said stamping tool and said solid state ionic conductor generates said pattern of electrical contacts.  
     
     
         18 . The method of  claim 17  wherein said metal ions are reduced at regions of said solid state ionic conductor in electrical contact with said stamping tool, thereby generating one or more deposited metal layers on a surface of said solid state ionic conductor in electrical contact with said stamping tool.  
     
     
         19 . The method of  claim 17  wherein localized electrochemical deposition of metal occurs at regions of said solid state ionic conductor in electrical contact with said stamping tool.  
     
     
         20 . The method of  claim 17  wherein said stamping tool comprises a plurality of features arranged in a selected pattern, and wherein at least a portion of said pattern of said stamping tool is transferred to a surface of said solid state ionic conductor via localized electrochemical deposition.  
     
     
         21 . The method of  claim 20  wherein said features of said stamping tool are nanosized features, microsized features or both.  
     
     
         22 . The method of  claim 20  wherein said features of said stamping tool have substantially the same voltages.  
     
     
         23 . The method of  claim 20  wherein at least a portion of said features of said stamping tool have substantially different voltages.  
     
     
         24 . The method of  claim 20  wherein said stamping tool comprises an array of individually addressable electrodes in electrical contact with said solid state ionic conductor, wherein the voltage on each electrode in the array is independently selectable.  
     
     
         25 . The method of  claim 24  wherein said stamping tool is capable of transferring a pattern to a surface of said solid state ionic conductor that is programmable, scalable or both programmable and scalable.  
     
     
         26 . An electrochemical patterning system for making one or more structures, comprising: 
 a first electrode in electrical contact with a solid state ionic conductor; and    a second electrode in electrical contact with a metal, wherein at least a portion of said solid state ionic conductor and said metal are in electrical contact, wherein said solid state ionic conductor or said first electrode is a stamping tool that generates a pattern of electrical contacts between said stamping tool and said solid state ionic conductor or said metal.    
     
     
         27 . The system of  claim 26  wherein said wherein solid state ionic conductor and said metal are in electrical contact such that generation of an electric field between said first and second electrodes results in oxidation of a portion of said metal, thereby generating metal ions and free electrons, wherein said metal ions migrate through the solid state ionic conductor to the first electrode where they are reduced and wherein said free electrons migrate to said second electrode.  
     
     
         28 . The system of  claim 26  wherein at least a portion of said solid state ionic conductor and said metal are in physical contact.  
     
     
         29 . The system of  claim 26  wherein said metal layer is said second electrode.  
     
     
         30 . The system of  claim 26  further comprising an actuator operationally connected to said stamping tool such that it is capable of providing a force to said stamping tool that maintains electrical contact between said stamping tool and said solid state ionic conductor or metal.  
     
     
         31 . The system of  claim 26  wherein said stamping tool has a Young's modulus selected from the range of about 20 GPa to about 200 GPa.  
     
     
         32 . The system of  claim 26  wherein said first electrode is a cathode and said second electrode is an anode.  
     
     
         33 . The system of  claim 26  wherein said ionic conductor is said stamping tool, wherein said stamping tool has a selected pattern of relief features, wherein at least a portion said relief features of said stamping tool are provided in physical contact with said metal, thereby generating said pattern of electrical contacts.  
     
     
         34 . The system of  claim 33 , wherein application of an electric field between said first and second electrodes transfers at least a portion of said pattern of said stamping tool to said metal layer via electrochemical etching.  
     
     
         35 . The system of  claim 33  wherein at least a portion of said relief features of said stamping tool are nanosized relief features, microsized relief features or both nanosized features and microsized relief features.  
     
     
         36 . The system of  claim 26  wherein said first electrode is said stamping tool, wherein said stamping tool comprises a plurality of features arranged in a selected pattern, wherein at least a portion of said features are in electrical contact with said solid state ionic conductor thereby generating said pattern of electrical contacts.  
     
     
         37 . The method of  claim 36  wherein application of an electric field between said first and second electrodes transfers at least a portion of said pattern of said stamping tool to said solid state ionic conductor via electrochemical deposition.  
     
     
         38 . The system of  claim 36  wherein said features of said stamping tool have substantially the same voltages.  
     
     
         39 . The system of  claim 36  wherein at least a portion of said features of said stamping tool have substantially different voltages.  
     
     
         40 . The system of  claim 36  wherein said stamping tool comprise a grid electrode.  
     
     
         41 . The system of  claim 36  wherein said stamping tool comprises an array of individually addressable electrodes in electrical contact with said solid state ionic conductor, wherein the voltage on each electrode in the array is independently selectable.  
     
     
         42 . The system of  claim 36  wherein said stamping tool is programmable, scalable or both programmable and scalable.  
     
     
         43 . The system of  claim 26  wherein said metal has a thickness selected from the range of about a few nanometers to about 100 mm, and wherein said solid state ion conductor has a thickness selected from the range of about 50 nanometers to about 100 mm.  
     
     
         44 . The system of  26  wherein said solid state ion conductor has an ionic conductivity selected from the range of about 0.001 S/cm to about 440 S/cm.  
     
     
         45 . The system of  26  wherein said solid state ion conductor is selected from the group consisting of Ag 2 S, Cu 2 S, AgI, RbAg 4 l 5 , Ag 3 SI, AgCuS, AgCuSe, Br 4 Cu 16 I 7 Cl 13 , and Cu 2 S.  
     
     
         46 . The system of  claim 26  wherein said solid state ion conductor is an amorphous solid, a semicrystalline solid, a single crystalline solid, or a composite material.  
     
     
         47 . The system of  claim 26  wherein said solid state ion conductor is a superionic conductor.  
     
     
         48 . The system of  26  wherein said metal is selected from the group consisting of Ag, Cu, Au, Zn, and Pb.  
     
     
         49 . An electrochemical stamping tool for etching structures into a metal comprising: 
 a first electrode having a first electric potential;    an ionic conductor having a selected pattern of relief features, wherein said ionic conductor is in electrical contact with said first electrode and wherein at least a portion of said relief features are capable of establishing electrical contact with said metal; and    a second electrode in electrical contact with said metal having a second electric potential that is higher than said first electrode.    
     
     
         50 . An electrochemical stamping tool for generating structures on a solid state ionic conductor comprising: 
 a first electrode comprising a plurality of features arranged in a selected pattern, wherein at least a portion of said features are capable of establishing electrical contact with said solid state ionic conductor; and a metal in electrical contact with said solid state ionic conductor.    
     
     
         51 . The electrochemical stamping tool of  claim 50  wherein said first electrode is an array of electrodes, wherein at least a portion of the electrodes in the array are in electrical contact with said solid state ionic conductor.  
     
     
         52 . A method of making a structure comprising: 
 a. providing a first electrode in electrical contact with a metal and in electrical contact with a solid state ionic conductor, wherein said metal covers at least a portion of a surface of said solid state ionic conductor;    b. providing a second electrode in electrical contact with said solid state ionic conductor;    c. establishing electrical contact between at least a portion of said solid state ionic conductor and said metal; and    d. generating an electric field between said first and second electrodes, wherein metal atoms in said metal are oxidized, thereby generating metal ions and free electrons, wherein said metal ions migrate through said solid state ionic conductor to said second electrode where they are reduced and wherein said free electrons migrate to said first electrode, thereby making said structures.    
     
     
         53 . The method of  claim 52  wherein said metal comprises a metal surface, bulk metal, metal substrate, metal cluster or metal particles.  
     
     
         54 . The method of  claim 52  wherein the electrical contact between said first electrode and said metal is a single point contact.  
     
     
         55 . The method of  claim 52  wherein the electrical contact between said first electrode and said metal is an electrical contact pattern.  
     
     
         56 . The method of  claim 55  wherein said electrical contact pattern is generated by a stamping tool.  
     
     
         57 . The method of  claim 55  wherein said electrical contact pattern is generated by said first electrode having a plurality of features arranged in a selected pattern, and wherein at least a portion of said pattern is transferred to a surface of said metal via localized electrochemical etching.