Electrochemical deposition with enhanced uniform deposition capabilities and/or enhanced longevity of contact masks

Abstract

An electrochemical fabrication process for producing multi-layer three-dimensional structures includes selectively electrodepositing one or more building materials using contact masks. In some embodiments, a copper pyrophosphate plating solution is used and is formulated to allow simultaneous deposition to a large area (>=about 1.44 mm 2 ) and to a small area (<=about 0.05 mm 2 ) wherein the thickness of deposition to the smaller area is no less than ½ that to the large area when the deposition to the large area <=about 10 μm in thickness and where the solution contains >=about 30 g/L of copper. In other embodiments contact masks include a support structure that is treated with a corrosion inhibitor (e.g. BTA) prior to attaching or forming a patterned material on it and/or plating baths are operated at low temperature either of which may be useful in extending the life of the masks.

I claim:  
     
         1 . An electrochemical fabrication process for producing a three-dimensional structure from a plurality of adhered layers, the process comprising: 
 (A) supplying a plurality of preformed masks, wherein each mask comprises a patterned dielectric material that includes at least one opening through which deposition can take place during the formation of at least a portion of a layer, and wherein each mask comprises a support structure that supports the patterned dielectric material;    (B) selectively depositing at least a portion of a layer onto the substrate, wherein the substrate may comprise previously deposited material; and    (C) forming a plurality of layers such that each successive layer is formed adjacent to and adhered to a previously deposited layer, wherein said forming comprises repeating operation (B) a plurality of times;    wherein at least a plurality of the selective depositing operations comprise 
 (1) contacting the substrate and the dielectric material of a selected preformed mask or proximately locating the substrate and dielectric material of a selected preformed mask;  
 (2) in presence of a plating solution, conducting an electric current through the at least one opening in the selected mask between an anode and the substrate, wherein the anode comprises a selected deposition material, and wherein the substrate functions as a cathode, such that the selected deposition material is deposited onto the substrate to form at least a portion of a layer; and  
 (3) separating the selected preformed mask and the substrate; and  
   wherein the selected deposition material is copper; and wherein the plating solution comprises a pyrophosphate copper solution that contains more than about 30.0 grams of copper per liter; or    wherein the plating solution comprises a pyrophosphate copper solution that contains more than about 240 grams of pyrophosphate; or    wherein the selected deposition material is copper; and wherein the plating solution comprises a pyrophosphate copper solution that comprises effective amounts of copper and pyrophosphate such that the solution is capable of (1) simultaneously depositing metallic copper to a smaller area (i.e. an area no larger than about 0.05 mm 2 ) and a larger area (i.e. an area no smaller than about 1.4 mm 2 ) such that the height of deposition of the smaller area is no less than one-half the height of deposition of the larger area when the height of deposition of the larger area is greater than 10 μm.    
     
     
         2 . The process of  claim 1  wherein the plating solution comprises a pyrophosphate solution that comprises (1) effective amounts of copper and pyrophosphate such that the solution is capable of simultaneously depositing metallic copper to a smaller area (i.e. an area no larger than about 0.05 mm 2 ) and a larger area (i.e. an area no smaller than about 1.4 mm 2 ) such that the height of deposition of the smaller area is no less than one-half the height of deposition of the larger area when the height of deposition of the larger area is greater than 10 μm, (2) more than 30.0 grams of copper per liter, and (3) more than 240 grams of pyrophosphate per liter.  
     
     
         3 . The process of  claim 1  wherein the solution comprises no less about than 35 grams of copper per liter.  
     
     
         4 . The process of  claim 1  wherein the solution comprises no less about than 40 grams of copper per liter.  
     
     
         5 . The process of  claim 1  wherein the solution comprises no less than about 280 grams of pyrophosphate per liter.  
     
     
         6 . The process of  claim 1  wherein the solution comprises no less than about 320 grams of pyrophosphate per liter.  
     
     
         7 . The process of  claim 1  wherein the plating solution comprises a pyrophosphate solution that comprises (1) effective amounts of copper and pyrophosphate such that the solution is capable of simultaneously depositing metallic copper to a smaller area (i.e. an area no larger than about 0.05 mm 2 ) and a larger area (i.e. an area no smaller than about 1.4 mm 2 ) such that the height of deposition of the smaller area is no less than 65% the height of deposition of the larger area when the height of deposition of the larger area is greater than 10 μm.  
     
     
         8 . The process of  claim 1  wherein the plating solution comprises a pyrophosphate solution that comprises (1) effective amounts of copper and pyrophosphate such that the solution is capable of simultaneously depositing metallic copper to a smaller area (i.e. an area no larger than about 0.05 mm2) and a larger area (i.e. an area no smaller than about 1.4 mm2) such that the height of deposition of the smaller area is no less than 80% the height of deposition of the larger area when the height of deposition of the larger area is greater than 10 μm.  
     
     
         9 . The process of  claim 1  wherein the plating bath is at a temperature below about 43° C. when conduction of the electric current begins.  
     
     
         10 . The process of  claim 1  wherein the plating bath is at a temperature below about 38° C. when conduction of the electric current begins.  
     
     
         11 . The process of  claim 1  wherein the plating solution is not agitated during selective deposition.  
     
     
         12 . The process of  claim 1  wherein the formation of each of a number of layers comprise at least one blanket deposition as well as the selective deposition wherein for a given layer the selectively deposited material is different from a material deposited by blanket deposition.  
     
     
         13 . The process of  claim 1  wherein the plurality of selective depositions comprise the deposition of a plurality of different materials.  
     
     
         14 . The process of  claim 1  wherein at least a portion of one layer is formed by a non-electroplating deposition process.  
     
     
         15 . The process of  claim 1  wherein a plurality of depositions occur during the formation of each of a number of layers wherein at least one of the depositions on each of the number of layers deposits copper and at least one of the other depositions on the number of layers deposits nickel.  
     
     
         16 . The process of  claim 1  wherein a number of the plurality of layers are each formed by depositing at least one structural material using at least one deposition and by depositing at least one sacrificial material by using at least one other deposition.  
     
     
         17 . The process of  claim 16  wherein at least a portion of the at least one sacrificial material is removed after formation of a plurality of layers to reveal a three-dimensional structure comprised of at least one structural material.  
     
     
         18 . The process of  claim 1  wherein the dielectric comprises a conformable material and a thickness of the conformable material of at least one selected mask is less than 100 μm and is more preferably less than 50 μm.  
     
     
         19 . The process of  claim 1  wherein the formation of at least a plurality of layers additionally comprises removing a portion of the deposited material such that a desired surface level is obtained.  
     
     
         20 . An electrochemical fabrication process for producing a three-dimensional structure from a plurality of adhered layers, the process comprising: 
 (A) supplying a plurality of preformed masks, wherein each mask comprises a patterned dielectric material that includes at least one opening through which deposition can take place during the formation of at least a portion of a layer, and wherein each mask comprises a support structure that supports the patterned dielectric material;    (B) selectively depositing at least a portion of a layer onto the substrate, wherein the substrate may comprise previously deposited material; and    (C) forming a plurality of layers such that each successive layer is formed adjacent to and adhered to a previously deposited layer, wherein said forming comprises repeating operation (B) a plurality of times;    wherein at least a plurality of the selective depositing operations comprise 
 (1) contacting the substrate and the dielectric material of a selected preformed mask;  
 (2) in presence of a plating solution, conducting an electric current through the at least one opening in the selected mask between an anode and the substrate, wherein the anode comprises a selected deposition material, and wherein the substrate functions as a cathode, such that the selected deposition material is deposited onto the substrate to form at least a portion of a layer; and  
 (3) separating the selected preformed mask from the substrate; and  
   wherein prior to the dielectric material and support structure being joined together, the support structure undergoes a treatment with a corrosion inhibitor, or    wherein the plating solution is a copper solution that is at a temperature of less than about 43° C.    
     
     
         21 . The process of  claim 20  wherein the support structure comprises copper and wherein the corrosion treatment comprises exposing a surface of the support structure to BTA.  
     
     
         22 . A contact mask for use in electroplating operations, comprising: 
 a preformed mask that comprises a patterned dielectric material that includes at least one opening through which deposition can take place during the formation of at least a portion of a layer, and wherein the at least one mask comprises a support structure that supports the patterned dielectric material; and    wherein the patterned dielectric material is bonded to the support structure, which support structure comprises the anode for current flow through the plating solution during selective deposition, and    wherein a surface of the support structure that is bonded to the dielectric material comprises a modified chemical structure that enhances the corrosion resistance of the preformed mask.    
     
     
         23 . The apparatus of  claim 22  wherein the modified chemical structure comprises a polymerized structure.  
     
     
         24 . The apparatus of  claim 23  wherein the modified chemical structure comprises BTA.