US20070029189A1

US20070029189A1 - Combinatorial electrochemical deposition system

Info

Publication number: US20070029189A1
Application number: US11/444,242
Authority: US
Inventors: Michael Zach
Original assignee: University of Chicago
Current assignee: UChicago Argonne LLC
Priority date: 2005-08-02
Filing date: 2006-05-31
Publication date: 2007-02-08

Abstract

A combinatorial electrochemical deposition system enables computer control over multiple parameters and allows for systematic exploration of the parameter space. The combinatorial electrochemical deposition system includes a computer providing system control and data acquisition functions. The computer controls a plurality of pumps; each pump is connected to a respective material supply source. The plurality of pumps is coupled via a mixer and a plurality of distribution valves of a cell and fluidics distribution network to deposit a particular composition of materials or solution concentration to individual electrochemical cells of an electrochemical cell array. The computer controls the mixer and the plurality of distribution valves. The electrochemical cell array includes a plurality of singly addressable flow-through isolatable electrochemical cells with a common working electrode.

Description

This application claims the benefit of U.S. Provisional Application No. 60/704,558, filed on Aug. 2, 2005.

CONTRACTUAL ORIGIN OF THE INVENTION

The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the United States Government and Argonne National Laboratory.

FIELD OF THE INVENTION

The present invention relates to a combinatorial electrochemical deposition system enabling computer control over parameters and allowing for systematic exploration of the parameter space.

DESCRIPTION OF THE RELATED ART

Electrodeposition can be used for making many different materials ranging from bulk materials, films, nanowires, and nanoparticles. The material can be metals, semiconductors, insulators, superconductors or have multiple components. Very importantly the materials can be amorphous, nanocrystalline, or single crystalline which can have very dramatic affect on the properties of the deposit. The deposits and the properties depend upon how the conditions of deposition are controlled.
Literature often cites the conditions used to make a sample with a few of the key parameters, which usually include applied potential, concentration of the ion to be reduced, identity of the supporting electrolyte and temperature. If the system is robust enough, the results can be reproduced from this information.
Often times another lab will have difficulty in reproducing this because not all the parameters are identified. Seldom disclosed information such as exact geometry of the electrochemical cell, the type of isolation from the reference electrode, contamination of the starting reagents water, cleaning method of the equipment, pH, dissolved oxygen content and many other parameters may have a huge impact on the morphology and ultimately on the reproducibility of the system. In addition most publications do not tell the full story because experiments were done one at a time, in a serial manner within a small variation of the parameter space.
Principal aspects of the present invention are to provide a combinatorial electrochemical deposition system enabling computer control over parameters and allowing for systematic exploration of the parameter space.
Other important aspects of the present invention are to provide such combinatorial electrochemical deposition system substantially without negative effect and that overcome some of the disadvantages of prior art arrangements.

SUMMARY OF THE INVENTION

In brief, a combinatorial electrochemical deposition system is provided for enabling computer control over multiple parameters and allowing for systematic exploration of the parameter space. The combinatorial electrochemical deposition system includes a computer providing system control and data acquisition functions. The computer controls a plurality of pumps, each pump is connected to a respective material supply sources. The plurality of pumps is coupled via a mixer and a plurality of distribution valves of a cell and fluidics distribution network to deposit a particular composition of materials or solution concentration to individual electrochemical cells of an electrochemical cell array. The computer controls the mixer and the plurality of distribution valves. The electrochemical cell array includes a plurality of singly addressable flow-through isolatable electrochemical cells with a common working electrode. Each of the electrochemical cells includes a counter electrode and a reference electrode.
In accordance with features of the invention, the combinatorial electrochemical deposition system includes a multi-channel potentiostat coupled to the computer for applying a selected voltage potential to the common working electrode, and to the counter electrode and the reference electrode of each of the electrochemical cells. Demultiplexing electronics are coupled to the computer and the multi-channel potentiostat for applying the selected voltage potential to the counter electrode and the reference electrode of each of the electrochemical cells. The material supply sources include a supporting electrolyte, a selected metal of interest, and predetermined additives. The predetermined additives include, for example, pH modifiers, complexing agents, and surface-active adsorbents.
In accordance with features of the invention, the reference electrode includes a capillary saturated calomel electrode (SCE) reference electrode. The counter electrode includes a platinum counter electrode. The working electrode includes a unitary sheet member supporting a container of each of the electrochemical cells. The working electrode can be implemented by a single crystal silicon wafer or a substantially uniform thin film deposited across a single wafer.
In accordance with features of the invention, the container of each of the electrochemical cells includes a cylindrical container, such as a glass tube, or a glass plate with a plurality of holes. A glass rod is coupled to a set of the electrochemical cells and is selectively moved between a fill position and a bypass position for opening and closing the set of electrochemical cells.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention together with the above and other objects and advantages may best be understood from the following detailed description of the preferred embodiments of the invention illustrated in the drawings, wherein:
FIG. 1 is a schematic and perspective view illustrating an exemplary Combinatoral Electrochemical Deposition system in accordance with the preferred embodiment;
FIG. 2A is a schematic and perspective view illustrating an exemplary single electrochemical cell of the cell and fluidics distribution network of the Combinatoral Electrochemical Deposition system of FIG. 1 in accordance with the preferred embodiment;
FIG. 2B is a side view of the exemplary single electrochemical cell of FIG. 2A;
FIG. 2C is a top view of the exemplary single electrochemical cell of FIG. 2A;
FIG. 3 is a schematic and exploded perspective view illustrating an exemplary fragmentary portion of an electrochemical cell array of the cell and fluidics distribution network of the Combinatoral Electrochemical Deposition system of FIG. 1 in accordance with the preferred embodiment;
FIGS. 4A, 4B, and FIGS. 4C, 4C are respective schematic, side and top views illustrating opening and closing of an electrochemical cell of the cell and fluidics distribution network of the Combinatoral Electrochemical Deposition system of FIG. 1 in accordance with the preferred embodiment;
FIG. 5A is a schematic and plan view illustrating an exemplary electrochemical cell array of the cell and fluidics distribution network of the Combinatoral Electrochemical Deposition system of FIG. 1 in accordance with the preferred embodiment;
FIG. 5B is a schematic and side view illustrating a fragmentary portion of the electrochemical cell array of FIG. 5A;
FIG. 5C is a schematic and plan view illustrating a glass rod of the electrochemical cell array of FIG. 5A;
FIG. 5D is a schematic and plan view illustrating an enlarged fragmentary detail of the glass rod of the electrochemical cell array of FIG. 5C;
FIGS. 6A is a schematic and plan view illustrating another exemplary electrochemical cell array of the cell and fluidics distribution network of the Combinatoral Electrochemical Deposition system of FIG. 1, which can be manufactured in strips for further assembly into the complete array in accordance with the preferred embodiment;
FIG. 6B is a partially schematic side view illustrating a block of the electrochemical cell array of FIG. 6A;
FIG. 6C is a partially schematic end view illustrating the block of the electrochemical cell array of FIG. 6A;
FIG. 6D is a partially schematic top view illustrating the block of the electrochemical cell array of FIG. 6A;
FIG. 6E is a partially schematic top view illustrating a glass rod of the electrochemical cell array of FIG. 6A;
FIGS. 7A, 7B, and 7C are respective partially schematic opposing side views and a top view illustrating an electrochemical cell of the electrochemical cell array of FIGS. 6A, 6B, 6C, and 6D in accordance with the preferred embodiment;
FIGS. 8A is a schematic and plan view illustrating yet another exemplary electrochemical cell array of the cell and fluidics distribution network of the Combinatoral Electrochemical Deposition system of FIG. 1 in accordance with the preferred embodiment;
FIG. 8B is a partially schematic side view illustrating a bypass position of an electrochemical cell row of the electrochemical cell array of FIG. 8A;
FIG. 8C is a partially schematic end view illustrating a fill or open position of an electrochemical cell row of the electrochemical cell array of FIG. 8A; and
FIGS. 8D, and 8E are respective partially schematic top and side views illustrating an exemplary glass rod of the electrochemical cell array of FIG. 8A.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Having reference now to the drawings, in FIG. 1 there is shown an exemplary Combinatoral Electrochemical Deposition System generally designated by the reference character 100 in accordance with the preferred embodiment. Combinatoral Electrochemical Deposition System 100 includes a computer 102 for providing system control and data acquisition functions.
In accordance with features of the invention, a Combinatoral Electrochemical Deposition System 100 is provided for implementing total computer control over generally all parameters and that allows for systematic exploration of the parameter space. Computer automation is provided for all tasks from mixing of the solutions to rates of filling and controlling the potential and treatment of the sample post deposition.
In accordance with features of the invention, Combinatoral Electrochemical Deposition System 100 enables rapid high throughput for materials synthesis and rapid testing. Combinatoral Electrochemical Deposition System 100 enables systematic exploration of complex multi-dimensional parameter space and automation of multiple tedious tasks. Combinatoral Electrochemical Deposition System 100 typically is an aqueous system that can be implemented with generally inexpensive instrumentation, while Combinatoral Electrochemical Deposition System 100 does not necessarily have to be aqueous. Combinatoral Electrochemical Deposition System 100 implements a programmed self-assembly process.
Computer 102 is coupled to a plurality of pumps 104. Each of the multiple pumps 104 is connected to a respective supply source 106 containing, for example, a supporting electrolyte, a selected metal of interest, a predetermined additive, and a pH modifier. Computer 102 controls an electrochemical deposition of materials of a selected composition.
Combinatoral Electrochemical Deposition System 100 includes an exemplary cell and fluidics distribution network generally designated by the reference character 200 including an array 202 of electrochemical cells 204. A common working electrode (WE) 206 of the preferred embodiment is provided for the multiple cells 204 of the electrochemical cell array 202. The common working electrode (WE) 206 of the preferred embodiment advantageously can be implemented with a single crystal silicon wafer or a substantially uniform thin film deposited across a single wafer.
Cell and fluidics distribution network 200 implements a much different approach to the problem than has been used in conventional arrangements. Most conventional arrangements for combinatorial electrochemistry have utilized a common bath, with a common reference electrode for an array of working electrodes. While this conventional method of manufacture can be much simpler, there are many problems with diffusion from one electrode's environment to another and having separate working electrodes that may differ in composition, unlike a single crystal silicon wafer or a uniform thin film deposited across a single wafer. There are also many problems with systems that are open to the atmosphere allowing contamination. Likewise, systems that perform experiments without being able to control all the parameters like solution mixing and fluidics distribution may suffer from irreproducibility.
Cell and fluidics distribution network 200 is the heart of the Combinatoral Electrochemical Deposition system 100. As shown in FIG. 1, the electrochemical cell array 202 is a 64 electrochemical cell array including 64 parallel singly addressable flow-through isolatable electrochemical (echem) cells 204 with the common working electrode (WE) 206. An exemplary electrochemical cell 204 of the preferred embodiment is illustrated and described with respect to FIGS. 2A, 2B, and 2C.
Combinatoral Electrochemical Deposition System 100 includes demultiplexing electronics 108 and a multi-channel potentiostat 110, both coupled to and controlled by computer 102. Computer 102 controls the potentiostat 110 which controls the potential applied to a particular cell 204 and period of time the selected potential is applied to each cell 204 within the electrochemical cell array 206 and records the data generated which is relayed back to the computer 102 for storage and further analysis. Multi-channel potentiostat 110 is operatively controlled by computer 102 to provide a“virtual ground” to the working electrode 206 by connection to the ports labeled W via a connection 112.
Multi-channel potentiostat 110 and demultiplexing electronics 108 are operatively controlled by computer 102 to provide a plurality of selected reference electrode potentials indicated by ports labeled R via the demultiplexing electronics 108 to the electrochemical cell array 206. Multi-channel potentiostat 110 and demultiplexing electronics 108 are operatively controlled by computer 102 to provide one or a plurality of controlled counter electrode potentials indicated by multiple ports labeled C via the demultiplexing electronics 108 to the electrochemical cell array 206.
Combinatoral Electrochemical Deposition System 100 includes a mixer 114 and a plurality of distribution valves 116 coupled between the pumps 104 and the electrochemical cell array 202, and coupled to computer 102. Computer 102 controls the mixing of solutions and rates of filling of the electrochemical cell array 202. An output waste flow from the electrochemical cell array 202 is collected in a waste vessel 120. After an electrochemical deposition process is completed, a gas, such as argon, is blown through the electrochemical cell array 202 to empty all the multiple cells 204
Various computers can be used to implement computer 102, such as personal computer using the commercial program Labview® functioning as a data acquisition computer system by executing two way communication with the system 100 via serial port, parallel port, GPIB, TCP/IP or a data acquisition (DAQ) interface. A commercially available multi-channel potentiostat manufactured and sold by Princeton Applied Research, Ametek® can be used for the multi-channel potentiostat 110. Masterflex® computer controlled peristaltic pumps can be used for the plurality of pumps 104.
Referring also to FIG. 2A, 2B, and 2C, each electrochemical cell 204 includes a reference electrode 210, a counter electrode 212, the common working electrode 206, an inlet port 214 and an outlet port 216.
A capillary SCE (saturated calomel electrode) reference electrode can be used to implement reference electrode 210, while other reference electrode types such as MSE (mercurous sulfate electrode), Ag/AgCI electrode, quasi-reference electrode also can be used. The counter electrode 212 includes a generally circular disk 220 having a pair of generally centrally disposed, spaced apart openings 222, 224 respectively for receiving the cell input 214 and cell outlet 216. A third opening 226 in the circular disk 220 of the counter electrode 212 is provided for receiving the reference electrode 210. The wire attached 212 to the circular disk 220 provides electrical contact to the counter electrode.
For example, a platinum counter electrode can implement the counter electrode 212, while the counter electrode 212 may also be implemented by a platinized titanium, gold or any other metal inert to modification or dissolution under the conditions being studied.
In accordance with features of the invention, the independent electrochemical cells 204 of Combinatoral Electrochemical Deposition System 100 avoid cross contamination and mass transport from adjacent electrodes. The electrochemical cells 204 being constructed of inert materials enables consistent results to be obtained after aggressive cleaning with reagents known to clean contaminants to the highest degree possible such as concentrated sulfuric acid and concentrated nitric acid. Avoidance of materials such as base metals, polyethylene, silicone, nylon and other non-fluorinated plastics prevents trace contamination of the solutions or electrode surfaces, which can be problematic for obtaining pure, consistent electrochemistry. Combinatoral Electrochemical Deposition System 100 combines both synthesis and characterization in the single system. The separate electrochemical cells 204 of Combinatoral Electrochemical Deposition System 100 allow systematic exploration of solution concentration, which is a very important parameter affecting conditions of growth and are necessary to change for characterization. Combinatoral Electrochemical Deposition System 100 enables ease of connection and allows experimentation with generally any parameter within, for example, more than a 20 dimensional parameter space. Combinatoral Electrochemical Deposition System 100 includes sealed and integrated robotic mixing and fluidic distribution network 200 enabling cleanliness without requiring a clean room environment.
Each electrochemical cell 204 is singly addressable flow-through isolatable electrochemical cell. For example, different selected potentials are applied via the demultiplexing electronics 108 to the respective counter electrode 212 of the singly addressable electrochemical cells 204 with respect to the respective reference electrode 210 for each cell. The potentiostat connection 112 to the working electrode (WE) 206 hold the WE at virtual ground, while the potential is sensed by the individual reference electrodes 210 of respective electrochemical cells 204 which provides a feedback mechanism and allows the potentiostat 110 to raise or lower the potential of the counter electrode 212 until the desired potential is achieved at the working electrode 206. Because a single common working electrode 206 is used for the electrochemical cell array 202 allows a homogenous single silicon wafer to be used to define the working electrode 206 for all the singly addressable electrochemical cells 204. This is an important feature of Combinatoral Electrochemical Deposition System 100.
The electrochemical cell 204 including a generally cylindrical, stepped container 230 mounted on the common WE 206 within a masked off area 232 of a wafer defining the common WE 206. It should be understood that the container 230 is not necessarily stepped. For example, the container 230 can be defined by a single diameter container, such as shown in FIG. 7A. The cylindrical, stepped container 230 includes an enlarged upper portion 234. For example, a glass, Viton or Teflon, stepped tube can implement the cylindrical container 300.
As shown in FIG. 2B, the enlarged upper portion 234 of the cell container 230 including a pair of aligned openings 236 for receiving an inert tube (High Purity PFA tubing) 238. A second glass rod 240 is received through a second offset pair of openings 242 as indicated in the top view of FIG. 2C.
Referring to FIG. 3, there is shown an exploded perspective view of an exemplary fragmentary portion of an electrochemical cell array generally designated by the reference character 300 of the cell and fluidics distribution network 200 of the Combinatoral Electrochemical Deposition system 100 in accordance with the preferred embodiment. The same reference characters used in FIG. 2A, 2B, and 2C, with respect to electrochemical cell 204 are used for similar or identical components in FIG. 3 and following description.
As shown, electrochemical cell array portion 300 includes multiple electrochemical cells 204 with one shown mounted within a support structure 302. Support structure 302 includes a base member 304 supporting an upper member 306. The base member 304 is a glass member that is bonded with the upper member 306, for example, formed of Teflon. Support structure 302 includes a plurality of stepped openings 308, each for receiving a respective electrochemical cell 204. An opening extends through the upper Teflon member 306 for receiving the fluid pathway 238 that is received through the multiple electrochemical cells 204.
Referring to FIGS. 4A, 4B, and FIGS. 4C, 4C, there are shown respective schematic, side and top views illustrating opening and closing of the electrochemical cell 204 of the cell and fluidics distribution network 200 in accordance with the preferred embodiment. As shown in FIGS. 4A and 4B, the electrochemical cell 204 is provided in the filling position with the glass rod 240 having respective flow-through notches 242 aligned to admit inflow to the cell from upstream flow path channel 238A through the inflow channel 214 and outflow from the cell through outflow channel 216 to the downstream flow channel 238B. As shown in FIGS. 4C and 4D, the electrochemical cell 204 is provided in the bypass position with the glass rod 240 moved to aligned bypass opening 244 relative to the openings of channels and provide a direct pathway between the upstream flow path and outflow channels 238A and 238B.
Referring to FIG. 5A, 5B, and 5C, there is shown an exemplary electrochemical cell array generally designated by the reference character 500 used with the Combinatoral Electrochemical Deposition system 100 in accordance with the preferred embodiment. Electrochemical cell array 500 includes an 8 cell by 8-cell array. A plurality of input valves 502, 1-8 couple a particular composition of materials or solution concentration via channel 238 to a respective fill input 214 to the electrochemical cell 204 of the electrochemical cell array 500. A respective air cylinder or solenoid 504 (one shown) is coupled to each glass rod 240 to selectively move the glass rod for opening and closing the individually addressable electrochemical cells 204. Valves 502 and air cylinders 504 are operatively controlled by computer 102.
As shown in FIG. 5A, in the array 500 a third glass rod 240 is moved by the illustrated air cylinder or solenoid 504 and valve 502, 3 is opened to fill the corresponding electrochemical cell 204 indicated by reference character A. Each of the electrochemical cells 204 can be sequentially filled or by-passed by opening each valve 502, 1-8 and selectively moving the glass rod 240 between the fill and bypass positions. The air cylinder or solenoid 504 can be implemented with a commercially available air cylinder, such as, manufactured and sold by Clippard and Minimatics.
FIGS. 5B, 5C, and 5D illustrate electrochemical cells 204 and the glass rod 240 of the electrochemical cell array 500. As described above, the notches 242 are respectively aligned with the cell inlet 214 and cell outlet 216 for filling any electrochemical cells 204 in the array 500. The bypass 244 of the glass rod 240 is moved relative to the channel 238 so that electrochemical cell 204 is provided in the closed or bypass position.
FIGS. 6A, 6B, 6C, 6D and 6E there is shown another exemplary electrochemical cell array generally designated by the reference character 600 used with the Combinatoral Electrochemical Deposition system 100 in accordance with the preferred embodiment. Electrochemical cell array 600 includes a five by five (5 by 5) array of electrochemical cells 602. Electrochemical cells 602 are illustrated and described with respect to FIGS. 7A, 7B, and 7C.
Electrochemical cell array 600 is defined by a plurality of identical blocks 604 secured together by a pair of tie rods 606. Each block 604 contains five electrochemical cells 602, as shown in FIGS. 7A, 7B, and 7C. As shown in FIG. 6A, a plurality of inert tubes (high purity PFA tubing) 608 extend horizontally through the blocks 604 that together define respective corresponding rows of electrochemical cells 602 within the electrochemical cell array 600. A glass rod 610 extends through the electrochemical cells 602 within each of the multiple blocks 604 defining the electrochemical cell array 600. As shown in FIG. 6A, the respective second glass rods 610 extend vertically through respective corresponding columns of electrochemical cells 602 within the electrochemical cell array 600.
Referring also to FIGS. 7A, 7B, and 7C, each electrochemical cell 602 of the electrochemical cell array 600 includes a reference electrode 620, a counter electrode 622, the common working electrode 206 as shown in FIG. 2A, an input 624 and an outlet 626. The container for each electrochemical cell 602 is defined by a respective one of a plurality of openings 630 extending from top to bottom through each block 604 as shown in FIGS. 6A and 6D. A pair of openings or holes 632 extending from side to side through each block 604 is defined near opposite ends of the block as shown in FIGS. 6A and 6B for receiving the tie rods 606. A respective one of a plurality of spaced apart openings 634 defined near an upper portion of the block 604 as shown in FIGS. 6A and 6B for receiving a respective glass rod 608. An elongated opening 636 is defined near the upper portion of the block 604 as shown in FIGS. 6A and 6C for receiving a respective glass rod 610.
The glass rods 610 include notches 612 respectively positioned relative to the channels 608 to admit inflow to the cell 602 from flow path channel 608 and outflow from the cell 602 to the channel 608. Then the notches 612 of glass rods 610 are selectively moved to position bypass grooves 614 into a bypass position for the cells 602, operatively controlled by computer 102 via an air cylinder or solenoid (not shown in FIG. 6A).
Referring to FIGS. 8A, 8B, 8C, and 8D, there is shown yet another exemplary electrochemical cell array generally designated by the reference character 800 used with the Combinatoral Electrochemical Deposition system 100 in accordance with the preferred embodiment. Electrochemical cell array 800 includes a hexagonal shaped spacing for group of 61 electrochemical cells 802 to maximize utilization of a wafer defining a common working electrode (WE) 206.
Electrochemical cell array 800 includes a plurality (nine) of glass rods 804 extending horizontally and a plurality (nine) of flow path channels 806 extending diagonally, at 60° from the glass rods 804, as shown in FIG. 8A. A plurality of input valves 810, 1-9 couple a particular composition of materials or solution concentration via channel 806 to a respective electrochemical cell 802 of the electrochemical cell array 800. A respective air cylinder or solenoid 812 (one shown) is coupled to each glass rod 804 to selectively move the glass rod for opening and closing the individually addressable electrochemical cells 802. Computer 102 operatively controls valves 810 and air cylinders 812.
FIG. 8B illustrates a bypass position of a row electrochemical cells of the electrochemical cell array 800 with the glass rod 804 positioned at a bypass position with notches 816 in the glass rod 804 offset from cell flow paths indicated by 814.
FIG. 8C illustrates a fill or open position of the electrochemical cell row with the glass rod 804 positioned at an aligned position with notches 816 in the glass rod 804 aligned with the cell flow paths 814. FIGS. 8D, and 8E provide top and side views of the glass rod 804 the electrochemical cell array 800.
While the present invention has been described with reference to the details of the embodiments of the invention shown in the drawing, these details are not intended to limit the scope of the invention as claimed in the appended claims.

Claims

1. A combinatorial electrochemical deposition system comprising:

a computer providing system control and data acquisition functions;

a plurality of pumps coupled to said computer, each pump being connected to a respective material supply source;

a fluidics distribution network including a mixer and a plurality of distribution valves coupled to said computer and said plurality of pumps;

an electrochemical cell array coupled to said plurality of distribution valves, said fluidics distribution network being controlled by said computer for depositing a particular composition of materials or solution concentration to individual electrochemical cells of said electrochemical cell array;

said electrochemical cell array includes a plurality of singly addressable flow-through isolatable electrochemical cells with a common working electrode, each of said electrochemical cells including a counter electrode and a reference electrode.

2. A combinatorial electrochemical deposition system as recited in claim 1 includes a multi-channel potentiostat coupled to said computer for applying a selected voltage potential to said common working electrode, and to said counter electrode and said reference electrode of each of said electrochemical cells.

3. A combinatorial electrochemical deposition system as recited in claim 2 includes demultiplexing electronics coupled to said computer and said multi-channel potentiostat for applying said selected voltage potential to said counter electrode and said reference electrode of each of said electrochemical cells.

4. A combinatorial electrochemical deposition system as recited in claim 1 wherein said reference electrode includes a capillary SCE reference electrode.

5. A combinatorial electrochemical deposition system as recited in claim 1 wherein said counter electrode includes a platinum counter electrode.

6. A combinatorial electrochemical deposition system as recited in claim 1 wherein said working electrode includes a unitary sheet member supporting a container of each of said electrochemical cells.

7. A combinatorial electrochemical deposition system as recited in claim 6 wherein said container of each of said electrochemical cells includes a cylindrical container.

8. A combinatorial electrochemical deposition system as recited in claim 7 wherein said containers of said electrochemical cells are defined by a plurality of through holes in a single glass plate.

9. A combinatorial electrochemical deposition system as recited in claim 7 wherein said cylindrical container includes a glass tube.

10. A combinatorial electrochemical deposition system as recited in claim 1 wherein said computer controls each of said pumps connected to said respective material supply source and said mixer for mixing of the solution concentration.

11. A combinatorial electrochemical deposition system as recited in claim 10 wherein said respective supply sources include a supporting electrolyte, a selected metal of interest, and a predetermined additive.

12. A combinatorial electrochemical deposition system as recited in claim 1 wherein said computer controls a rate of filling of said electrochemical cells in said electrochemical cell array.

13. A combinatorial electrochemical deposition system as recited in claim 1 wherein said electrochemical cells of said electrochemical cell array include said common working electrode defined by a single crystal silicon wafer.

14. A combinatorial electrochemical deposition system as recited in claim 1 wherein said electrochemical cells of said electrochemical cell array include said common working electrode defined by a generally uniform thin film supported on a single wafer.

15. A combinatorial electrochemical deposition system as recited in claim 1 wherein said electrochemical cells of said electrochemical cell array include a glass rod coupled to a set of electrochemical cells, said glass rod selectively moved between a fill position and a bypass position for opening and closing said set of electrochemical cells.

16. A combinatorial electrochemical deposition system as recited in claim 15 include an air cylinder coupled to said glass rod for controlling movement of said glass rod between said fill position and said bypass position.