U.S. patent application number 15/924721 was filed with the patent office on 2018-07-26 for electrochemical deposition apparatus and methods of using the same.
The applicant listed for this patent is Ashwin-Ushas Corporation. Invention is credited to Prasanna Chandrasekhar, Kyle Hobin, Anthony La Rosa, Richard Modes, Brian J. Zay.
Application Number | 20180209061 15/924721 |
Document ID | / |
Family ID | 58798115 |
Filed Date | 2018-07-26 |
United States Patent
Application |
20180209061 |
Kind Code |
A1 |
Chandrasekhar; Prasanna ; et
al. |
July 26, 2018 |
ELECTROCHEMICAL DEPOSITION APPARATUS AND METHODS OF USING THE
SAME
Abstract
An electrochemical deposition apparatus and methods of using the
same are provided herein.
Inventors: |
Chandrasekhar; Prasanna;
(Holmdel, NJ) ; Zay; Brian J.; (Hamilton, NJ)
; Modes; Richard; (Hopatcong, NJ) ; La Rosa;
Anthony; (Rockaway, NJ) ; Hobin; Kyle;
(Montclair, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Ashwin-Ushas Corporation |
Marlboro |
NJ |
US |
|
|
Family ID: |
58798115 |
Appl. No.: |
15/924721 |
Filed: |
March 19, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
14956493 |
Dec 2, 2015 |
9945045 |
|
|
15924721 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C25D 17/00 20130101;
C25D 9/02 20130101; C25D 17/06 20130101; C25D 17/004 20130101; C25D
17/10 20130101; C25D 17/12 20130101; C25D 21/12 20130101; C25D
17/005 20130101 |
International
Class: |
C25D 17/00 20060101
C25D017/00; C25D 9/02 20060101 C25D009/02; C25D 17/12 20060101
C25D017/12; C25D 21/12 20060101 C25D021/12; C25D 17/10 20060101
C25D017/10 |
Claims
1. An electrochemical deposition apparatus, comprising: a. a
support structure; b. a first electrode mount connected to the
support structure; c. a second electrode mount connected to the
support structure; and d. a deposition chamber frame configured to
receive a deposition solution and disposed proximate to the first
and second electrode mounts, the deposition chamber frame
comprising: i. a first aperture portion configured to face the
first electrode mount, the first aperture portion comprising a
first aperture and a conductive perimeter element; and ii. a second
aperture portion configured to face the second electrode mount, the
second aperture portion comprising a second aperture.
2. The apparatus of claim 1, comprising at least one biasing member
that connects the support structure to at least one of the first
electrode mount and the second electrode mount.
3. The apparatus of claim 2, wherein the at least one biasing
member comprises a spring, a clamp, an actuator, or a combination
thereof.
4. The apparatus of claim 2, wherein the at least one biasing
member connects the support structure to the first electrode mount
and comprises a pneumatic actuator.
5. The apparatus of claim 1, wherein the second aperture is larger
than the first aperture.
6. The apparatus of claim 1, comprising a first electrode connected
to the first electrode mount and configured to be disposed in
electrical communication with the conductive perimeter element.
7. The apparatus of claim 6, wherein the first electrode comprises
a material selected from the group consisting of indium-tin-oxide
(ITO), poly (ethylene terephthalate) (PET), glass, and a
combination thereof.
8. The apparatus of claim 6, wherein the first electrode comprises
a conductive sheet.
9. The apparatus of claim 1, wherein the conductive perimeter
element comprises at least one electrode contact.
10. The apparatus of claim 9, wherein the at least one electrode
contact comprises a plurality of electrode contacts.
11. The apparatus of claim 10, wherein the plurality of electrode
contacts comprises a plurality of spring-loaded contact pins.
12. The apparatus of claim 1, comprising a second electrode
connected to the second electrode mount.
13. The apparatus of claim 12, wherein the second electrode
comprises one or more of graphite, gold, and platinum.
14. The apparatus of claim 12, wherein the second electrode
comprises a conductive sheet.
15. The apparatus of claim 1, comprising a controller in electrical
communication with the conductive perimeter element.
16. The apparatus of claim 1, comprising first and second
electrodes connected to the first and second electrode mounts,
respectively, wherein the first electrode comprises a working
electrode and the second electrode comprises a counter
electrode.
17. The apparatus of claim 16, comprising a controller in
electrical communication with the conductive perimeter element and
the counter electrode.
18. The apparatus of claim 1, comprising a reference electrode
configured to be disposed within the deposition chamber frame.
19. The apparatus of claim 18, wherein the reference electrode
comprises one or more of an Ag/AgCl reference electrode, a Pt wire
quasi-reference electrode, and an Au wire quasi-reference
electrode.
20. The apparatus of claim 1, comprising a container in fluid
communication with the deposition chamber frame; wherein the
container is configured to contain a deposition solution that
comprises a coating material.
21. An electrochemical deposition apparatus comprising an
electroplating vessel, the apparatus comprising: a. a support
structure; b. a frame disposed within the support structure and
comprising a cavity configured to receive a deposition solution,
the cavity comprising: i. a first aperture portion comprising a
first aperture; and ii. a second aperture portion comprising a
second aperture, wherein the second aperture is larger than the
first aperture; c. a working electrode disposed proximate to the
first aperture; and d. a counter electrode disposed proximate to
the second aperture; wherein the frame, the working electrode, and
the counter electrode combine to form the electroplating
vessel.
22. The apparatus of claim 21, wherein the cavity comprises a
telescoped cavity, a tapered cavity, or a combination thereof.
23. The apparatus of claim 21, wherein the second aperture is at
least twice as large as the first aperture.
24. The apparatus of claim 21, comprising a plurality of guides
that are configured to align the frame, the working electrode, and
the counter electrode.
25. A method for electrochemically depositing a coating material on
a working electrode with the electrochemical deposition apparatus
of claim 1, the method comprising the steps of: a. mounting a
working electrode at the first electrode mount; b. mounting a
counter electrode at the second electrode mount; c. preparing a
deposition chamber by: i. biasing the working electrode against the
first aperture portion of the deposition chamber frame; and ii.
biasing the counter electrode against the second aperture portion
of the deposition chamber frame; e. providing a deposition solution
to the deposition chamber, wherein the deposition solution
comprises a coating material; f applying a potential across the
working electrode and the counter electrode to electrochemically
deposit the coating material at the working electrode; and g.
removing the working electrode, having the coating material
deposited thereon, from the first electrode mount.
26. The method of claim 25, wherein the step of providing the
deposition solution to the deposition chamber comprises gravity
flowing the deposition solution to the deposition chamber from a
container that is in fluid communication with the deposition
chamber by raising the container above the deposition chamber.
27. The method of claim 25, wherein the step of removing the
working electrode comprises removing the deposition solution from
the deposition chamber by gravity flowing the deposition solution
to the container from the deposition chamber by lowering the
container below the deposition chamber.
28. The method of claim 25, wherein the step of applying a
potential across the working electrode and counter electrode
comprises applying a linear scan applied potential, which comprises
scanning the applied potential from a pre-determined initial
potential to a pre-determined final potential at a pre-determined
scan rate.
29. The method of claim 25, wherein the step of applying a
potential across the working electrode and counter electrode
comprises applying a fixed applied potential, which comprises
applying a pre-determined fixed potential until: i. a
pre-determined total charge is achieved; or ii. a pre-determined
total deposition time has elapsed.
30. The method of claim 25, wherein the step of preparing the
deposition chamber comprises at least one of: i. pneumatically
biasing the working electrode against the first aperture portion of
the deposition chamber frame; and ii. pneumatically biasing the
counter electrode against the second aperture portion of the
deposition chamber frame.
Description
FIELD OF THE INVENTION
[0001] The present invention relates generally to devices and
methods for the electrochemical deposition of coating materials and
more particularly, but not exclusively, to devices and methods for
the electrochemical deposition of electrochromic polymers for the
preparation of electrochromic lenses.
BACKGROUND OF THE INVENTION
[0002] Electroplating systems are commonly used to electroplate or
electrochemically deposit various materials onto conductive
substrates. Although many types of electroplating systems are
known, a variety of problems exist in the field, as briefly
enumerated below, which are currently in need of solutions.
[0003] Certain problems present in the field include an inability
to make effective electrical contact with substrates while, at the
same time, insulating points of electrical contact from a
deposition or plating solution and maintaining a liquid seal in the
deposition tank, such that there is no leakage. This may be a
problem when using substrates with lower conductivity.
[0004] Moreover, problems may emanate from the resistance increase
(or conductivity drop) from the point of electrical contact to the
interior of the substrate, especially acute for substrates with
lower conductivity. Due to this, the voltage applied at the point
of electrical contact may not be the same as that seen at the
interior of the substrate, leading to non-uniform deposits, with,
in many cases, a greater thickness of the deposit nearer the point
of electric contact than that in the interior of the substrate.
[0005] The field also includes systems that lack an adequate means
of holding electrodes and substrates firmly and maintaining precise
and, preferably, minimal distance between the working electrode
(the substrate upon which a material of interest may be deposited),
the counter electrode, and the reference electrode (if used), for
effective, diffusion-limited control as well as high efficiency of
the electrochemical deposition.
[0006] Issues in the field also include the maintenance of a larger
area for the counter electrode as compared to the working
electrode, so that the limiting electrode processes for the
deposition do not occur at the counter electrode.
[0007] Additional limitations in the field include: (1) use of
pumps and elaborate circulation systems which limit efficiency; (2)
a lack of a hermetic seal of the deposition apparatus or plating
tank such that there is minimal solvent loss, which is especially
pertinent when volatile solvents are used; (3) a lack of accurate
control of the applied potential at the working electrode; (4) a
lack of accurate control of the total charge passed during
electrochemical deposition, so that thickness, morphology, and
other features of the deposit may be well controlled; and (5) a
lack of amenability to automated or semi-automated electrochemical
deposition.
[0008] The present invention answers these and other needs in the
field and provides an electroplating device and methods of using
the same.
SUMMARY OF THE INVENTION
[0009] Generally, the present invention provides an apparatus for
the electrochemical deposition (e.g., electrochemical
polymerization, electrochemical plating, or electroplating) of a
coating material from a deposition solution. In a particular
embodiment, the present invention pertains to an electrochemical
deposition apparatus configured to deposit monomers of
electrochromic conducting polymers at a substrate.
[0010] In a first aspect, the present invention provides an
electrochemical deposition apparatus that may include a support
structure. The apparatus may include a first electrode mount
connected to the support structure and a second electrode mount
connected to the support structure. The apparatus may include a
deposition chamber frame that may be configured to receive a
deposition solution. The deposition chamber frame may be disposed
proximate to the first and second electrode mounts. Moreover, the
deposition chamber frame may include a first aperture portion and a
second aperture portion. The first aperture portion may be
configured to face the first electrode mount and may include a
first aperture and a conductive perimeter element. The second
aperture portion may be configured to face the second electrode
mount and may include a second aperture.
[0011] In certain embodiments of the apparatus of the invention,
the apparatus may include at least one biasing member that may
connect the support structure to at least one of the first
electrode mount and the second electrode mount. The at least one
biasing member may include a spring, a clamp, an actuator, or a
combination thereof. For example, the at least one biasing member
may connect the support structure to the first electrode mount and
may include a pneumatic actuator.
[0012] Regarding certain features of the deposition chamber frame,
the second aperture may be larger than the first aperture.
[0013] The apparatus of the invention may include a first electrode
connected to the first electrode mount. The first electrode may be
configured to be disposed in electrical communication with the
conductive perimeter element at the first aperture portion.
Moreover, the first electrode may include a material selected from
the group consisting of indium-tin-oxide (ITO), poly (ethylene
terephthalate) (PET), glass, and a combination thereof (e.g., a
conductive plastic ITO/PET). Additionally, the first electrode may
include or be provided as a conductive sheet (e.g., a conductive
sheet that includes one or more of ITO, PET, and glass).
[0014] Regarding the conductive perimeter element, the element may
include at least one electrode contact. The at least one electrode
contact may include a plurality of electrode contacts.
Alternatively, the at least one electrode contact be a continuous
electrode contact. In certain embodiments, the conductive perimeter
element may include a plurality of contact pins (e.g.,
spring-loaded contact pins).
[0015] The apparatus of the invention may include a second
electrode connected to the second electrode mount. The second
electrode may include graphite. For example, the second electrode
may include a conductive sheet composed of graphite.
[0016] In another embodiment, the apparatus of the invention may
include first and second electrodes that may be connected to the
first and second electrode mounts, respectively, wherein the first
electrode includes a working electrode and the second electrode
includes a counter electrode.
[0017] The apparatus of the invention may include a reference
electrode that may be disposed within the deposition chamber frame.
The reference electrode of the invention may be a Ag/AgCl reference
electrode or a Pt or Au wire quasi-reference electrode.
[0018] In another aspect, the present invention may include an
electrochemical deposition apparatus that includes an
electroplating vessel. The apparatus may include a support
structure and a frame that may be disposed with the support
structure. The frame may include a cavity that may be configured to
receive a deposition solution and may include: (1) a first aperture
portion having a first aperture; and (2) a second aperture portion
having a second aperture, wherein the second aperture may be larger
than the first aperture. Moreover, the apparatus may include a
working electrode that may be disposed proximate to the first
aperture and/or a counter electrode that may be disposed proximate
to the second aperture. The frame, the working electrode, and the
counter electrode may be combined to form the electroplating vessel
of the apparatus.
[0019] Regarding the cavity of the frame, the cavity may include a
telescoped cavity, a tapered cavity, or a combination thereof.
Additionally, the second aperture may be at least twice as large as
the first aperture. Indeed, the second aperture may be three times
as large as the first aperture.
[0020] In certain embodiments, the apparatus of the invention may
include a plurality of guides that are configured to align the
frame, the working electrode, and/or the counter electrode.
[0021] In certain specific aspects of the devices of the invention,
a counter electrode and a working electrode may be provided that
may be positioned to act as two walls of a deposition chamber. The
counter electrode and working electrode may be placed against a
deposition frame portion which, in combination with the two
electrodes, may act as the deposition chamber, vessel, or tank.
Electrical contact may be made to the counter electrode along its
outside perimeter, which may be sealed off from the deposition
solution. The deposition solution may include a coating material.
Electrical contact may be made to the working electrode along a
portion of the working electrode through the use of a conductive
perimeter element (e.g., spring-loaded contacts) that may also be
sealed off from the deposition solution. The deposition frame
portion, which may be abutted by the working and counter
electrodes, may be tapered or telescoped such that the counter
electrode area is larger than the working electrode area. For
example, the counter electrode area may be significantly larger
(e.g., at least two times larger) than the working electrode area
so that the limiting electrode processes do not occur at the
counter electrode.
[0022] A reference electrode may also be disposed between the
working and counter electrodes. Preferably, the reference electrode
is placed closer to the working electrode, rather than the counter
electrode, such that the applied potential at the working electrode
is more accurately regulated. Prior to filling or charging of the
deposition vessel, the vessel may be sealed pneumatically as the
counter and working electrodes are pneumatically biased against the
deposition frame portion.
[0023] Deposition may be carried out and monitored using an
applied-potential algorithm that may be specifically tailored to
the material to be deposited at the working electrode (e.g., a
conducting polymer (CP) deposited via electropolymerization at the
working electrode from a deposition solution that contains monomers
of the CP). At the completion of the deposition, the deposition
solution may be drained and the deposition chamber may opened, thus
opening the vessel, from which the substrate (i.e., the working
electrode), may be removed for further processing. The exemplary
device described herein, as well as the process related to the use
of the same, may be amenable to automation and provides a solution
to the needs in the field as outlined above.
[0024] In another aspect, the present invention includes a method
for electrochemically depositing a coating material on a working
electrode with an electrochemical deposition apparatus of the
invention. The method may include mounting a working electrode at a
first electrode mount of the apparatus. The method may include
mounting a counter electrode at a second electrode mount. In
addition, the methods of the invention may include preparing a
deposition chamber by (1) biasing the working electrode against a
first aperture portion of a deposition chamber frame; and/or (2)
biasing the counter electrode against a second aperture portion of
the deposition chamber frame. The methods of the invention may also
include the step of providing a deposition solution to the
deposition chamber, where the deposition solution may include the
coating material. The methods of the invention may then include
applying a potential across the working electrode and the counter
electrode to electrochemically deposit the coating material at the
working electrode. Additionally, the methods of the invention may
include removing the working electrode, having the coating material
deposited thereon, from the first electrode mount.
[0025] In one embodiment, the methods of the invention may include
providing the deposition solution to the deposition chamber by
gravity flowing the deposition solution to the deposition chamber
from a container that is in fluid communication with the deposition
chamber by raising the container above the deposition chamber.
[0026] In another embodiment, the methods of the invention may
include the step of removing the deposition solution from the
deposition chamber by gravity flowing the deposition solution to
the container from the deposition chamber by lowering the container
below the deposition chamber.
[0027] The step of applying a potential across the working
electrode and the counter electrode, according to the methods of
the invention may include applying a linear scan applied potential,
which may include scanning the applied potential from a
pre-determined initial potential to a pre-determined final
potential at a pre-determined scan rate. Alternatively, or in
addition thereto, the step of applying a potential across the
working electrode and counter electrode, according to the methods
of the invention, may include applying a fixed applied potential or
multiple fixed applied potentials, which may include applying (a)
pre-determined fixed potential(s) until: (1) a pre-determined total
charge is achieved; or (2) a pre-determined total deposition time
has elapsed.
[0028] The step of preparing the deposition solution chamber may
include at least one of: (1) pneumatically biasing the working
electrode against the first aperture portion of the deposition
chamber frame; and (2) pneumatically biasing the counter electrode
against the second aperture portion of the deposition chamber
frame.
[0029] The present application incorporates several references that
describe certain aspects of electrochromic technology,
specifically, U.S. Pat. Nos. 5,995,273; 6,033,592; and 8,902,486;
and U.S. Patent Application Publication Nos. 2013/0120821 and
2014/0268283, the entirety of which are incorporated herein by
reference.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] The foregoing summary and the following detailed description
of the exemplary embodiments of the present invention may be
further understood when read in conjunction with the appended
drawings, in which:
[0031] FIG. 1 schematically illustrates a perspective view of an
exemplary electrochemical deposition apparatus of the
invention.
[0032] FIG. 2 schematically illustrates an exploded view of an
exemplary electrochemical deposition apparatus of the
invention.
[0033] FIG. 3 schematically illustrates a perspective view of a
tank support member.
[0034] FIG. 4 schematically illustrates a perspective view of an
exemplary working electrode.
[0035] FIG. 5 schematically illustrates a perspective view of an
exemplary counter electrode.
[0036] FIG. 6 schematically illustrates a view of the second
aperture portion on the deposition chamber frame of the
invention.
[0037] FIG. 7 schematically illustrates a view of the first
aperture portion on the deposition chamber frame of the
invention.
[0038] FIG. 8 schematically illustrates a method of using an
electrochemical deposition apparatus of the invention to deposit a
coating material on a working electrode (i.e., a substrate).
DETAILED DESCRIPTION OF THE INVENTION
[0039] The present invention relates generally to electrochemical
deposition (e.g., electrochemical polymerization or
"electroplating") of coating materials from deposition solutions
onto desired substrates in a tank or vessel. More particularly, the
present invention relates to the electrochemical deposition of
electrochromic conducting polymers from their monomer containing
solutions onto a conductive substrate using a tank or vessel that
facilitates automation of an electrochemical deposition process.
These features include, by way of example, but not limited to,
pneumatic opening/closing and sealing of the tank or vessel,
minimization of monomer solution volume, and devices for electrical
connection to substrates that minimize or reduce resistive
drop.
[0040] Referring now to the figures, wherein like elements are
numbered alike throughout, FIGS. 1 and 2 provide an exemplary
electrochemical deposition apparatus 1. The apparatus 1 includes a
support structure 10. A first electrode mount 20 and second
electrode mount 30 may be connected to the support structure 10.
The first electrode mount 20 and second electrode mount 30 may be
used to mount electrodes upon which electrochemical deposition may
occur. A deposition chamber frame 40 may be placed proximate to the
first electrode mount 20 and the second electrode mount 30. The
deposition chamber frame 40 may be placed between the first
electrode mount 20 and second electrode mount 30 such that when the
first electrode mount 20 and the second electrode mount 30 are
biased against the sides of the deposition chamber frame 40, they
may combine to form a deposition chamber or vessel, which may
receive a deposition solution.
[0041] When the first electrode mount 20 and second electrode mount
30 are separated from the deposition chamber frame 40, the
apparatus 1 is in its "open" configuration, during which an
electrode may be placed on the first electrode mount 20 or second
electrode mount 30. When the first electrode mount 20 and second
electrode mount 30 are biased against the sides of the deposition
chamber frame 40, thereby forming a deposition chamber or vessel,
the apparatus 1 is in its "closed" configuration, during which the
vessel may be filled with a deposition solution as described
herein.
[0042] The support structure 10 may include several components that
support one or more of the first electrode mount 20, the second
electrode mount 30, and the deposition chamber frame 40. The
support structure 10 may include a base 11, support plates 13 and
14, a support member 15, and brackets 12. As shown in FIG. 1, the
support plates 13 and 14 may be positioned on the base 11 and
supported by brackets 12. The support member 15 may be positioned
at the base 11, proximate to the support plates 13 and 14.
Specifically, the support member 15 may be placed between the
support plates 13 and 14 and may support one or more of the first
support mount 20, the second electrode mount 30, and the deposition
chamber frame 40. In particular embodiments, the support member 15
is fixed to the base 11 and is provided to support first electrode
mount 20 and/or the deposition chamber frame 40 when the apparatus
1 is in its closed configuration. As shown in FIG. 3, the support
member 15 may include a basin 151 and a drain 152. The basin 151
may catch any deposition solution that escapes the deposition
chamber frame 40 during operation of the apparatus 1. Moreover, the
drain 151 may allow any deposition solution caught within the basin
151 to be removed or collected.
[0043] The components of the support structure 10 may be composed
of a metal (e.g., aluminum), a polymeric material (e.g., high
density polyethylene (HDPE)), or a combination thereof. In certain
preferred aspects, the components of the support structure 10 may
be composed of aluminum. For example, the base 11, support brackets
12, support plates 13 and 14, and vessel support member 15 may be
composed of aluminum.
[0044] The first electrode mount 20 may be connected to the support
plate 13 and the second electrode mount 30 may be connected to the
support plate 14. One or both of the first electrode mount 20 and
second electrode mount 30 may be connected to support plates 13 and
14, respectively, through a biasing member 16. For example, both
the first and second electrode mounts 20 and 30, respectively, may
be connected to the support plates 13 and 14, respectively, through
a biasing member 16. In contrast, one of the first and second
electrode mounts 20 and 30, respectively, may be connected to the
support plate 13 or 14 via a biasing member 16 while the other
electrode mount is connected to the other support plate by a
fastener. As used herein, the term "fastener" refers to something
that attaches or joins two or more parts together. In some
embodiments, a fastener may be a mechanical fastener that
mechanically joins or affixes two or more objects together (e.g., a
screw, a pin, a rivet, and the like). In other embodiments, a
fastener may be a chemical fastener that that chemically joins or
affixes two or more objects together (e.g., glue, epoxy, adhesive,
solder, and the like). In an exemplary embodiment, the first
electrode mount 20 may be connected to the support plate 13 via one
or more biasing members 16 and the second electrode mount 30 may be
connected to support plate 14 with one or more fasteners.
[0045] As shown in FIGS. 1 and 2, the present invention may include
several biasing members 16. The term "biasing member" may represent
a spring, a clamp, an actuator, or a combination thereof. When the
biasing member is an actuator, the actuator may be a hydraulic
actuator, a pneumatic actuator, or a combination thereof. In
certain embodiments, the biasing member 16 is a pneumatic actuator
as shown in FIGS. 1 and 2. In accordance with the present
invention, hydraulic and/or pneumatic actuators may be connected to
a source of hydraulic and/or pneumatic pressure and a switch that
may activate (extend) and/or deactivate (retract) such hydraulic
and/or pneumatic actuators.
[0046] Moreover, the apparatus 1 may include 1 to 10 biasing
members. Preferably, the apparatus 1 may include 4 to 6 biasing
members, where the biasing members are pneumatic actuators. The
biasing members 16 of the invention may be used to open and close
the apparatus 1 as described above.
[0047] The first electrode mount 20 and the second electrode mount
30 may be composed of a chemically inert polymeric material, such
as HDPE. Moreover, each of the first electrode mount 20 and the
second electrode mount 30 may include a flexible backing material
on their respective mounting faces 22 and 32. The flexible backing
materials may be a sheet that includes ethylene propylene diene
monomer (EPDM), silicone rubber, or a combination thereof.
[0048] A first electrode 25 may be mounted on the first electrode
mount 20. An exemplary first electrode 25 is provided in FIG. 4.
The first electrode 25 may include a conductive sheet or film upon
which a coating material may be deposited during an electrochemical
reaction. The first electrode 25 may include a metallic material, a
non-metallic material, or a combination thereof, provided that the
electrode is conductive. For example, the first electrode 25 may
include a material selected from the group consisting of indium tin
oxide (ITO), poly ethylene terephthalate (PET), glass, or a
combination thereof. In a specific embodiment, the first electrode
25 may include a sheet or film of ITO/PET or ITO/glass. Moreover,
the first electrode 25 may have a surface resistivity of about 20
to 100 Ohms per square.
[0049] In another embodiment of the invention, the first electrode
25 may be shaped in the form of a lens, such as an eyeglass lens,
in preference to a simple rectangular, circular, or oval shape,
such that it is prepared for assembly into a lens without the need
for further cutting or shaping.
[0050] The second electrode 35 may be mounted on the second
electrode mount 30. An exemplary second electrode 35 is provided in
FIG. 5. The second electrode 35 may include a conductive sheet or
film. The second electrode 35 may include a metallic material, a
non-metallic material, or a combination thereof, provided that the
electrode is conductive. By way of non-limiting example, the second
electrode 35 may include graphite, gold, or platinum. In a specific
embodiment, the second electrode 35 may be a conductive sheet of
graphite. Moreover, as shown in FIG. 5, the second electrode 35 may
include contact site 37. The contact site 37 may be a tab or
portion of the second electrode 35 that is amenable to attaching a
clip, clamp, wire, or a combination thereof.
[0051] As described herein, the first electrode 25 is preferably
the working electrode. In the present invention, the working
electrode is the substrate upon which a coating material may be
deposited during an electrochemical reaction. The second electrode
35 is preferably the counter electrode. In the present invention,
the counter electrode is provided to complete the electrochemical
cell. Accordingly, where the working electrode is configured to be
a cathode, the counter electrode will be the anode, and vice
versa.
[0052] The first electrode 25 and second electrode 35 may include
guide holes 26 and 36, respectively. The guide holes 26 and 36 may
be aligned with guide holes 24 and 31 on the first electrode mount
20 and second electrode mount 30, respectively. Additionally, the
deposition chamber frame 40 may include guide holes 44. Through the
listed guide holes (i.e., guide holes 24, 26, 31, 36, and 44) may
be placed guide pins 80. As shown in FIG. 2, the apparatus 1 may
include four guide pins 80 that may be provided through guide holes
24, 26, 31, 36, and 44 in order to align the various components of
the apparatus 1.
[0053] The deposition chamber frame 40 is shown in FIGS. 1, 2, 6
and 7. The deposition chamber frame 40 may be disposed proximate to
the first electrode mount 20 and the second electrode mount 30.
More particularly, the deposition chamber frame 40 may be placed
between the first electrode mount 20 and the second electrode mount
40, such that when the apparatus 1 is in its closed configuration,
the first electrode mount 20, the second electrode mount 30, and
the deposition chamber frame 40 may form a deposition chamber or
vessel. For example, deposition chamber frame 40 may have a hollow
interior as shown in FIG. 7 as cavity 401. The volume of cavity 401
may be filled with a deposition solution when the apparatus 1 is in
the closed configuration.
[0054] The deposition chamber frame 40 may have a first aperture
portion 41 and a second aperture portion 45.
[0055] First aperture portion 41 may be the portion of the
deposition chamber frame 40 that may face the first electrode mount
20 and/or the first electrode 25. When the apparatus 1 is in its
closed configuration, the first aperture portion 41 may abut the
first electrode mount 20 or the first electrode 25 when the first
electrode 25 is mounted at the first electrode mount 20. The first
aperture portion 41 may include a first aperture 411 and a
conductive perimeter element 90. The conductive perimeter element
90 may contact, and electrically communicate with, a portion of the
first electrode 25. The conductive perimeter element 90 may include
at least one conductor or electrode contact that may electrically
communicate with a portion of the first electrode 25. For example,
the conductive perimeter element 90 may be a continuous conductor
or electrode contact that may have a rectangular shape, a square
shape, a circular shape, an oval shape, or a combination thereof.
Moreover, the conductive perimeter element 90 may be a continuous
conductor or electrode contact that may have a shape configured to
match a lens (e.g., an electrochromic lens) or a shape suited to
match the application for which the coated or plated substrate is
to be used.
[0056] In another embodiment, the conductive perimeter element 90
may encompass a plurality of conductor or electrode contacts that
may be arranged to provide a rectangular shape, a square shape, a
circular shape, an oval shape, or a combination thereof. Moreover,
the conductive perimeter element 90 may be a plurality of conductor
or electrode contacts that may be arranged to provide a shape
configured to match a lens (e.g., an electrochromic lens) or a
shape suited to match the application for which the coated or
plated substrate is to be used. In a preferred embodiment of the
invention, the conductive perimeter element 90 may be a plurality
of conductor or electrode contacts as set forth in FIGS. 2 and
6.
[0057] As shown in FIGS. 2 and 6, the conductive perimeter element
90 may be set into the first aperture portion 41 of the deposition
chamber frame 40. The conductive perimeter element 90 may include a
plurality of electrode contacts 91. Electrode contacts 91 may be
deformable or biased conducting pins. For example, electrode
contacts 91 may be spring loaded conducting pins (e.g., POGO
pins).
[0058] The conductive perimeter element 90 may also include a
conductive base 93 upon which the plurality of electrode contacts
91 may be connected. The conductive base 93 may be set into a base
channel 94 on the first aperture portion 41 of the deposition
chamber frame 40. The conductive base 93 may be connected to the
deposition chamber frame 40 with one or more fasteners. As shown in
FIGS. 2 and 7, the conductive base 93 may be fastened to the
deposition chamber frame 40 in the base channel 94 with one or more
screws, such as screws 92.
[0059] As shown in FIGS. 2 and 7, the deposition chamber frame 40
includes an electrical connection tunnel 49 (see, e.g., inset 491
of FIG. 7). The electrical connection tunnel 49 communicates with a
conductor 941 that electrically communicates with the conductive
base 93. Accordingly, a wire that may be connected to a power
source or controller, as described herein, may be passed through
the electrical connection tunnel 49 to contact the conductor 941
and allow a power source and/or a controller to electrically
communicate with the conductive base 93. Alternatively, element 941
may be an aperture through which a wire may be passed to contact
the conductive base 93.
[0060] The first aperture portion 41 may also include a gasket 42
that may be set into a gasket channel 43. The gasket 42 may be
composed of a flexible, chemically inert material such as EPDM,
silicone rubber, or a combination thereof. The gasket 42 may be
provided to maintain a seal that prevents leakage of deposition
solution when the apparatus 1 is in its closed configuration (e.g.,
when the first electrode 25 is biased against the first aperture
portion 41 of deposition chamber frame 40). Moreover, the gasket 42
prevents contact between the conductive perimeter element 90 and
the deposition solution when the apparatus 1 is in its closed
configuration. Accordingly, the perimeter of the conductive
perimeter element 90 is preferably greater than the perimeter of
the gasket 42.
[0061] In certain embodiments of the invention, the design of the
the first aperture 411 and the gasket 42 may be modified to act as
a mask on the first electrode 25 to control the manner in which a
coating or plating material is deposited at the first electrode 25.
For example, the first aperture 411 and the gasket 42 may be sized
to provide a rectangular shape, a square shape, a circular shape,
an oval shape, or a combination thereof. Moreover, the first
aperture 411 and the gasket 42 may be sized to provide a shape
configured to match a lens (e.g., an electrochromic lens) or a
shape suited to match the application for which the coated or
plated material is to be used. For example, the first aperture 411
and the gasket 42 may be sized to provide the shape of a motorcycle
helmet visor or spectacle lens. Indeed, the first electrode contact
25 may be used as a film or layer in an electrochromic device that
may be applied to a motorcycle helmet visor. Accordingly, the first
aperture 411 and the gasket 42 may be sized to match the shape of
the visor to simplify production where the first electrode is also
sized to match the application for which the coated or plated
substrate is to be used.
[0062] Second aperture portion 45 may be the portion of the
deposition chamber frame 40 that may face the second electrode
mount 30 and/or the second electrode 35. When the apparatus 1 is in
its closed configuration, the second aperture portion 45 may abut
the second electrode mount 30 or the second electrode 35 when the
second electrode 35 is mounted at the second electrode mount 30. As
shown in FIG. 7, the second aperture portion 45 may include a
second aperture 451. The second aperture 451 may be larger than the
first aperture 411. For example, the second aperture 451 may be at
least about two times larger than the first aperture 411. In
addition, the second aperture 451 may be about three times larger
than the first aperture 411.
[0063] Furthermore, the first aperture 411 and the second aperture
451 may define the front and back, respectively, of the cavity 401.
The cavity 401, between the first aperture 411 and the second
aperture 451, may be telescoped, tapered, or a combination thereof.
In certain specific embodiments, the cavity 401 tapers from the
second aperture 451 to the first aperture 411 as shown, at least,
in FIG. 7. More broadly, the deposition chamber frame 40 may have a
tapered or telescoped cavity 401, such that the counter electrode
area is larger and/or significantly larger (e.g., at least twice as
large) than the working electrode area, so that limiting electrode
processes do not occur at the counter electrode.
[0064] The second aperture portion 45 may include a gasket 46 that
may be set into a gasket channel 47. The gasket 46 may be composed
of a flexible, chemically inert material such as EPDM, silicone
rubber, or a combination thereof. The gasket 46 may be provided to
maintain a seal that prevents leakage of deposition solution when
the apparatus 1 is in its closed configuration (e.g., when the
second electrode 35 is biased against the second aperture portion
45 of the deposition chamber frame 40).
[0065] As shown in FIG. 7, the deposition chamber frame 40 may
include a frame inlet/outlet 48. The frame inlet/outlet 48 may be
in fluid communication with a container 50. Specifically, the
apparatus 1 may include a tube 51 that connects the container 50 to
the frame inlet/outlet 48. The frame inlet/outlet 48 allows the
deposition chamber frame 40 to receive a deposition solution during
a deposition process when the apparatus 1 is in its closed
configuration. Moreover, the frame inlet/outlet 48 allows the
deposition chamber frame 40 to empty of the deposition solution
after a deposition process and before the apparatus 1 is reset to
its open configuration.
[0066] The deposition chamber frame 40 may also include one or more
vent apertures 61. The vent apertures 61 may communicate with the
cavity 401 of the deposition chamber frame 40. Moreover, the
present invention may include one or more stoppers 60 that may be
placed into the vent apertures 61. The stoppers 60 may be composed
of a flexible, chemically inert material such as EPDM, silicone
rubber, or a combination thereof.
[0067] The present invention may also include a reference electrode
62 that may be placed within the cavity 401 of the deposition
chamber frame 40. For example, as shown in FIG. 2, at least one of
the stoppers 60 may include a hole through which the reference
electrode 62 may be provided. Therefore, when passing through a
stopper 60, the reference electrode 62 may be placed within the
cavity 401 while maintaining the integrity of the cavity 401 and
the deposition chamber frame 40. The reference electrode 60 may be
any type of electrochemical reference or quasi-reference electrode
known to those persons having ordinary skill in the art. However,
in preferred embodiments, the reference electrode 60 is a Ag/AgCl
reference electrode or a Pt or Au wire quasi-reference electrode.
Moreover, in particular embodiments, the reference electrode 60 is
configured to be placed within the cavity 401 of the deposition
chamber frame 40 such that it may be proximate to the first
electrode 25 and the second electrode 35 when the apparatus 1 is in
its closed configuration. Preferably, the reference electrode 60 is
configured to be placed within the cavity 401 of the deposition
chamber frame 40 such that it may be closer to the first electrode
25 as compared to the second electrode 35 when the apparatus 1 is
in its closed configuration. Indeed, the reference electrode 60 may
be preferably disposed at a position that is closer to the working
electrode (i.e., the first electrode 25), compared to the counter
electrode (i.e., the second electrode 35), such that the applied
potential at the working electrode is more accurately
regulated.
[0068] As described herein, the apparatus 1 may include a container
50 that may be fluidly connected to the deposition chamber frame 40
through a tube 51. Specifically, a bottom portion of the container
50 may be connected through the tube 51 to the frame inlet/outlet
48, which is preferably placed at the bottom of the deposition
chamber frame 40, as shown in FIG. 7. The present invention allows
for gravity flowing a deposition solution contained in the
container 50 from the container 50 in order to the fill the cavity
of the deposition chamber frame 40 when the apparatus 1 is in its
closed configuration. As used herein, the term "gravity flowing,"
relates to a flow of fluid that is driven by gravity from a higher
location to a lower location. For example, filling the deposition
chamber frame 40 requires raising the container 50 above a desired
fluid level in the deposition chamber frame 40. In contrast,
emptying the deposition chamber frame 40 requires lowering the
container 50 below a desired fluid level in the deposition chamber
frame 40. Due to this arrangement, no pumps are required to fill or
empty the cavity 401 of the deposition chamber frame 40 when the
apparatus 1 is in its closed configuration.
[0069] The deposition solution used in the processes of the
invention may include a solvent and one or more coating materials
that may be deposited or electroplated onto a first electrode 25
(i.e., the substrate). In certain embodiments, the coating material
may include an inorganic coating material (e.g., one or more metal
salts) or an organic coating material (e.g., one or more monomers).
Where the coating material includes an organic coating material,
such as a monomer, deposition at the first electrode 25 (i.e., the
substrate) may include electropolymerization. In preferred
embodiments, the deposition solution may include monomers of
electrochromic conducting polymers, for example, as may be
described in U.S. Pat. Nos. 5,995,273 and 6,033,592; and U.S.
Patent Application Publication Nos. 2013/0120821 and
2014/0268283.
[0070] The solvent of the deposition solution may include a polar
aprotic solvent, a non-polar solvent, a polar protic solvent, or a
combination thereof, that may be known to a person having ordinary
skill in the art provided that the coating material is
substantially miscible with the solvent. In certain embodiments,
the solvent of the deposition solution is selected from the group
consisting of acetonitrile, N,N'-dimethylformamide, and a
combination thereof.
[0071] The present invention may also include a controller 70 that
may be in electrical communication with or otherwise may be
configured to be electrically connected to one or more of the first
electrode 25, the second electrode 35, and the reference electrode
62. In certain preferred embodiments, the controller 70 is provided
to be connected to the first electrode 25 (i.e., the working
electrode) through the conductive perimeter element 90, the second
electrode 35 (i.e., the counter electrode) through the contact site
37, and the reference electrode 62. The controller 70 may be a
potentiostat, a galvanostat, a DC power supply, or a combination
thereof.
[0072] Preferably, the controller 70 may be a
potentiostat/galvanostat as described in pending U.S. patent
application Ser. No. 14/844,367, the entirety of which is
incorporated herein by reference.
[0073] Indeed, the controller 70 may be an electrochemical
instrument that may be provided for conducting electrochemical
analysis of materials. The electrochemical instrument may be in the
form of a potentiostat/galvanostat for conducting electrochemical
analysis of materials positioned between a counter electrode and a
working electrode of the instrument. The electrochemical instrument
may include a microcontroller, for controlling operation of the
circuitry of the instrument. The microcontroller may function to
operate pursuant to a computer program as well as various inputs
from a user to provide various or selected parameters or modes of
operation. The microcontroller may produce desired digital control
signals. A digital-to-analog converter (DAC) may be provided in
electrical communication with the microcontroller for generating an
analog output signal in response to digital control signals from
the microcontroller. A high current driver may be provided in
electrical communication with the DAC to produce a high current
range output in response to the analog output signal from the DAC.
For example, the high current driver may produce a high current
range output in the range of about a fraction of milliAmpere mA or
a mA to about amperes As. As a specific optional example, the high
current driver may produce current in the range of about 0.25 mA to
about 2.5 A. A high current monitor may be provided in electrical
communication with the high current driver to monitor the high
current range output from the high current driver. The high current
monitor may produce a feedback signal for the high current driver
in response to the current monitored by the high current monitor to
control the current produced by the high current driver. The high
current monitor may also supply an output dependent on the current
supplied from the high current driver for monitoring by the
microcontroller. The high current monitor may also supply a working
output signal at a working output for performing analysis of a
selected material. For this purpose, a counter electrode contact
may be provided for electrical communication with the counter
electrode (e.g., second electrode 35) and connectable in electrical
communication with the working output of the high current monitor.
A working electrode contact may be provided for electrical
communication with a working electrode (e.g., first electrode 25)
and may be electrically connectable with a fixed stable voltage
potential (for example, ground or virtual ground) for enabling
electrochemical analysis of material at or between the counter
electrode and the working electrode. For example, a selected
working output signal from the high current monitor may be applied
from the counter electrode at or through the material being
analysed or tested and then to the working electrode.
[0074] A low current driver may also be optionally provided in
electrical communication with the DAC to produce a low current
range output in response to the analog output signal from the DAC.
For example, a low current range output may be in the range of
about nanoAmperes nAs, and perhaps even as small as picoAmperes
pAs, to about a mA or a fraction of a mA. As a specific optional
example, the low current driver may produce current in the range of
about 2.5 nA to 0.25 mA. The low current driver may be in
electrical communication with the counter electrode contact so that
the low current range output may be supplied by the low current
driver to the counter electrode. A low current monitor may be
connectable in electrical communication with the working electrode
contact for detecting current at the working electrode contact. In
a low current mode of operation, the low current range output from
the low current driver may be supplied to the counter electrode
through or at the material being analysed or tested and then to the
working electrode. The low current monitor in electrical
communication with the working electrode may supply an output
dependent on the current detected at the working electrode contact
for monitoring by the microcontroller. The low current monitor may
also provide a feedback signal for the low current driver in order
to control the output of the low current driver to control the
current between the counter electrode contact and the working
electrode contact. The low current monitor may optionally include a
monitor amplifier having an amplifier input connectable in
electrical communication with the working electrode contact and
having an amplifier output. The low current monitor may also
include an array of feedback resistors connected between the output
of the monitor amplifier and the input of the monitor amplifier.
The low current monitor may also include a monitor multiplexer, for
example, an analog multiplexer, in electrical communication with
the microcontroller for selecting at least one of the feedback
resistors in the array for electrical communication between the
output and input of the monitor amplifier to control the output of
the monitor amplifier.
[0075] The high current monitor may optionally include a first high
current range monitoring circuit for monitoring current in a first
high current range and a second high current monitoring circuit for
monitoring current in a second high current range. As an optional
example, the first high current monitoring circuit may operate in a
range of about mAs to about an A whereas the second high current
monitoring circuit may operate in a range of about a fraction of a
mA to about mAs. As a more specific optional example, the high
current monitoring circuit may operate in a range of about 25 mA to
2.5 A and the second high current monitoring circuit may operate in
a range of about 0.25 mA to 25 mA. Of course, the two ranges need
not precisely overlap at a common end point and such common end
point can be altered to a different magnitude.
[0076] The instrument may also include a reference electrode
contact for electrical communication with a reference electrode
(e.g., reference electrode 62) for positioning relative to the
working electrode and counter electrode in communication with the
material, and a buffer in electrical communication with the
reference electrode contact for detecting voltage at the reference
electrode contact. The buffer may supply an output dependent on the
voltage detected at the reference electrode contact that is
buffered from the reference electrode contact for monitoring by the
microcontroller. The buffer may also selectively provide a feedback
signal for the high current driver to control the output produced
by the high current driver when operating in voltage mode at a high
current or high power mode of operation in order to control the
voltage at the reference electrode contact. The buffer may also
supply the feedback signal from the buffer to the low current
driver to control the output produced by the low current driver to
control the voltage at the reference electrode contact when
operating in voltage mode at a low current or low power mode of
operation. In order to accommodate such an optional arrangement
having both a high current driver and a low current driver, the
instrument may also include a high current switch for switchably
connecting the high current driver in and out of electrical
communication with the counter electrode contact and a low current
switch for switchably connecting the low current driver in and out
of electrical communication with the counter electrode contact. The
microcontroller may function to enable or disable output from
either or both of the high current or low current drivers to
respectively provide a type of high current switch and a low
current switch, respectively, to connect and disconnect from the
counter electrode contact. The microcontroller may operate to
control the high current switch and the low current switch so that
when the high current switch electrically connects the high current
driver into electrical communication with the counter electrode
contact, the microcontroller causes the low current switch to
switch the lower current driver out of electrical communication
with the counter electrode contact. Likewise, when the low current
switch switches the low current driver into electrical
communication with the counter electrode contact, the high current
switch electrically disconnects the high current driver from
electrical communication with the counter electrode contact. For an
optional arrangement in which the high current monitor includes
both a first high current monitoring circuit and a second high
current monitoring circuit, the high current switch may include a
first high current monitor switch for electrically connecting the
first high current range monitoring circuit in and out of
electrical communication with the counter electrode contact and a
second high current monitoring switch for electrically connecting
the second high current monitoring circuit in and out of electrical
communication with the counter electrode contact. In operation, the
microcontroller may be in electrical communication with the first
and second high current monitoring switches such that when one of
the high current monitoring switches is turned on the other high
current monitoring switch is turned off and when at least one of
the high current monitoring switches is turned on then the low
current switch is turned off under the control of the
microcontroller.
[0077] The instrument may also include a ground switch under the
control of the microcontroller for electrically connecting the
working electrode contact in and out of electrical communication
with a fixed stable voltage potential such as ground or virtual
ground. When the high current driver is switched by the high
current switch to be in electrical communication with the counter
electrode contact, such as when operating in a high power or high
current mode of operation, the microcontroller may control the
ground switch to connect the working electrode contact to
ground.
[0078] The instrument may also include a low current monitor switch
under the control of the microcontroller for switchably connecting
the working electrode contact in and out of electrical
communication with the low current monitor. In a low power or low
current mode of operation, the low current monitor switch
electrically connects the working electrode contact into electrical
communication with the low current monitor and the low current
switch operates to connect the low current driver in electrical
communication with the counter electrode contact. In a high current
or high power mode of operation, the low current monitor switch may
also function to disconnect the working electrode contact out of
electrical communication with the low current monitor, and the low
current switch may function to disconnect the low current driver
out of electrical communication with the counter electrode
contact.
[0079] Next, the instrument may also include a feedback
multiplexer, for example, an analog multiplexer, in electrical
communication with the microcontroller and in electrical
communication with the high current monitor for receiving the
feedback signal from the high current monitor, the buffer for
receiving the feedback signal from the buffer, and the low current
monitor for receiving the feedback signal from the low current
monitor, and for switchably selecting which of the feedback
signals, or a signal dependent thereon, is output by the feedback
multiplexer under the control of the microcontroller. In this
regard, the microcontroller may operate to control the feedback
multiplexer to supply the feedback signal from the high current
monitor for the high current driver when operating in high current
mode and to supply the feedback signal from the low current monitor
for the low current driver when operating in low current mode, and
to supply the feedback signal from the buffer for at least one of
the high current driver or low current driver when operating in
voltage mode. For example, the feedback multiplexer may supply the
feedback signal from the buffer for the high current driver when
operating in voltage mode at a high power mode of operation and for
the low current driver when operating in voltage mode at a low
power mode of operation. Optionally, the first high current range
monitoring circuit may provide a first high current feedback signal
for the feedback multiplexer and the second high current monitoring
circuit may supply a second high current feedback signal for the
feedback multiplexer. When operating in the high current mode, the
multiplexer under the control of the microcontroller may
selectively supply the first high current feedback signal from the
first high current range monitoring circuit for the high current
driver when operating in first high current range and selectively
supply the second high current feedback signal from the second high
current range monitoring circuit for the high current driver when
operating in the second high current range. The first high current
range monitoring circuit may include a first sense resistor
connected in series between the high current driver and the counter
electrode contact and a first differential amplifier, such as an
instrumentation amplifier, connected across the first sense
resistor to detect the voltage produced by the current flow through
the first sense resistor to provide the first high current feedback
signal. Likewise, the second high current range monitoring circuit
may include a second sense resistor connected in series between the
high current driver and the counter electrode and a second
differential amplifier, such as an instrumentation amplifier,
connected across the second sense resistor to detect the voltage
produced by current flow through the second sense resistor to
provide the second high current feedback signal. Preferably, the
first and second sense resistors are connected in parallel circuits
and have different magnitudes of resistance, optionally such as a
10.sup.2 magnitude difference such as 0.1 and 10 ohms for
example.
[0080] The instrument may also include an analog-to-digital
converter (DAC) in electrical communication with the outputs of the
low current monitor, the buffer and the high current monitor to
convert the output signals of the low current monitor, the buffer
and the high current monitor to digital signals for the
microcontroller.
[0081] In an optional arrangement, the buffer may also be in
electrical communication with the counter electrode contact for
detecting a voltage at the counter electrode contact and for
supplying a buffered output indicating the voltage at the counter
electrode contact for electrical communication with the
microcontroller.
[0082] The controller 70 may include an electrochemical instrument
for conducting an electrochemical analysis of selected materials
that may be configured, adjusted or set to operate in a high power
or high current mode of operation and as such may be in the
configuration of potentiostat and/or galvanostat for providing
selected electrical signals to a counter electrode (e.g., second
electrode 35) and a working electrode (e.g., first electrode 25).
As configured for a high power or high current mode of operation,
the electrochemical instrument may include a microcontroller for
providing digital control signals and a digital-to-analog converter
(DAC) in electrical communication with the microcontroller for
generating an analog output signal in response to digital control
signals from the microcontroller. A high current driver may be in
electrical communication with the DAC to produce a high current
range output in response to the analog output signal from the DAC.
For example, the high current range output may be in the ranges
previously indicated. A high current monitor may be used in
electrical communication with the high current driver to monitor
the current output by the high current driver. The high current
monitor may produce a current feedback signal for the high current
driver in response to the current monitored by the high current
monitor to control the current produced by the high current driver.
The high current monitor may also supply an output dependent on the
current produced by the high current driver for monitoring by the
microcontroller. The high current monitor may also supply a working
output signal at a work output for application to a material, such
as a material under test or analysis. For this purpose, a counter
electrode contact for electrical communication with a counter
electrode is connectable in electrical communication with the work
output of the high current monitor. A working electrode contact for
electrical communication with a working electrode may be connected
in electrical communication with a fixed stable voltage potential,
such as ground or virtual ground, for enabling electrochemical
analysis of material at or between the counter electrode and the
working electrode. The high current monitor may optionally include
a first high current range monitoring circuit for monitoring
current in a first high current range and a second high current
monitoring circuit for monitoring current in a second high current
range. For example, the first and second high current ranges may be
in the ranges previously indicated. The high current monitor may
also include a first high current monitor switch for electrically
connecting the first high current range monitoring circuit in and
out of electrical communication with the counter electrode and a
second high current monitoring switch for electrically connecting
the second high current monitoring circuit in and out of electrical
communication with the counter electrode contact, optionally under
the control of the microcontroller which may be in electrical
communication with the first and second high current monitoring
switches.
[0083] The instrument may also include a reference electrode
contact for electrical communication with a reference electrode
(e.g., reference electrode 62) for positioning relative to the
working electrode and the counter electrode in communication with
the material. A buffer may be provided for electrical communication
with the reference electrode contact for detecting voltage at the
reference electrode contact and for supplying an output dependent
on the voltage at the reference electrode contact that is buffered
from the reference electrode contact for monitoring by the
microcontroller. The buffer may also provide a feedback signal for
the high current driver to control the output produced by the high
current driver to control the voltage at the reference electrode
contact.
[0084] The instrument may also include a feedback multiplexer,
optionally in the form of an analog multiplexer, in electrical
communication with the microcontroller, and both in electrical
communication with the high current monitor for receiving the
feedback signal from the high current monitor and in electrical
communication with the buffer for receiving the feedback signal
from the buffer for switchably selecting under the control of the
microcontroller which of the feedback signals, or a signal
dependent thereon, is output by the feedback multiplexer for the
high current driver. In current mode, the microcontroller will
switch the feedback multiplexer to output the feedback signal from
the high current monitor for feedback for the high current driver.
In voltage mode, the microcontroller will switch the feedback
multiplexer to output the feedback signal from the buffer for
feedback for the high current driver. Optionally, the first high
current range monitoring circuit may provide a first high current
feedback signal for the feedback multiplexer and the second high
current range monitoring circuit may provide a second high current
feedback signal for the feedback multiplexer. The feedback
multiplexer may operate under the control of the microcontroller to
selectively supply the first high current feedback signal, or a
signal dependent thereon, from the first high current range
monitoring circuit for the high current driver when operating in
the first high current range and to selectively supply the second
high current feedback signal, or a signal dependent thereon, from
the second high current range monitoring circuit for the high
current driver when operating in the second high current range.
[0085] Optionally, the first high current range monitoring circuit
may include a first sense resistor connected in series between the
high current driver and the counter electrode contact, and a first
differential amplifier, such as an instrumentation amplifier,
connected across the first sense resistor to detect the voltage
generated by current flow through the first sense resistor to
produce the first high current feedback signals and an output for
monitoring by the microcontroller. Likewise, the second high
current range monitoring circuit may optionally include a second
sense resistor connected in series between the high current driver
and the counter electrode contact, and a second differential
amplifier, such as an instrumentation amplifier, connected across
the second sense resistor to detect the voltage generated by the
current flow through the second sense resistor to produce the
second high current feedback signal and an output for monitoring by
the microcontroller. Preferably, the first and second sense
resistors are connected in parallel circuits and have different
magnitudes of resistance, optionally such as a 10.sup.2 magnitude
difference such as 0.1 and 10 ohms for example.
[0086] The instrument may also include an analog-to-digital
converter (ADC) in electrical communication with the
microcontroller and in electrical communication with the outputs of
the buffer and the high current monitor to convert the output
signals of the buffer and the high current monitor to a digital
signal for the microcontroller.
[0087] Optionally, the buffer may also be connectable in electrical
communication with the counter electrode contact for detecting a
voltage at the counter electrode contact for supplying a buffered
output representing the voltage at the counter electrode contact
for electrical communication with the microcontroller.
[0088] The controller 70 may include an electromechanical
instrument that may be configured, adjusted, or set to operate, for
example, as a potentiostat or a galvanostat in a low current or low
power mode of operation. When so configured, the instrument
includes a microcontroller for providing digital control signals,
and a digital-to-analog converter (DAC) in electrical communication
with the microcontroller for generating an analog output signal in
response to digital control signals from the microcontroller. A low
current driver may be positioned in electrical communication with
the DAC to produce a low current range output in response to the
analog output signal from the DAC. For example, a low current range
may be in the range previously indicated. A counter electrode
contact may be provided for electrical communication with a counter
electrode (e.g., second electrode 35) and for electrical
communication with the output of the low current driver. A working
electrode contact may also be provided in electrical communication
with a working electrode (e.g., first electrode 25) for enabling
electrochemical analysis of material between the counter electrode
and the working electrode. In operation, current from the low
current driver may be supplied to the counter electrode for
application at or through the material to be analyzed or tested and
then to the working electrode.
[0089] The instrument may also include a low current monitor
connectable in electrical communication with the working electrode
contact for detecting current at the working electrode contact and
for supplying an output dependent on the current detected at the
working electrode contact for monitoring by the microcontroller.
The low current monitor may also provide a feedback signal for the
low current driver in order to control the output of the low
current driver to control the current between the counter electrode
contact and the working electrode contact. The low current monitor
may optionally include a monitor amplifier, such as a current
feedback amplifier or transimpedance amplifier, having an input
connectable in electrical communication with the working electrode
contact and providing an output. The low current monitor may also
include an array of feedback resistors connected between the output
of the monitor amplifier and the input of the monitor amplifier to
provide a feedback loop between the output and the input of the
monitor amplifier. The low current monitor may also include a
monitor multiplexer, for example, an analog multiplexer, in
electrical communication with the microcontroller for selecting at
least one of the feedback resistors in the array for electrical
connection between the output and the input of the monitor
amplifier to control the output of the monitor amplifier.
[0090] The instrument may optionally include a reference electrode
contact for electrical communication with a reference electrode
(e.g., reference electrode 62) for positioning relative to the
working electrode and the counter electrode in communication with
the material. The instrument may also include a buffer for
electrical communication with the reference electrode contact for
detecting voltage at the reference electrode contact. The buffer
may function to supply an output dependent on the voltage at the
reference electrode contact that is buffered from the reference
electrode contact for monitoring by the microcontroller. The buffer
may also provide a feedback signal for the low current driver to
control the output produced by the low current driver to control
the voltage at the reference electrode contact. In a voltage mode
of operation, the voltage at the reference electrode contact may be
monitored relative to voltage at the working electrode contact,
which may, for example, be a virtual ground.
[0091] The instrument may also include a feedback multiplexer, for
example, an analog multiplexer, in electrical communication with
the microcontroller. The feedback multiplexer may also be in
electrical communication with the buffer for receiving the feedback
signal from the buffer and in electrical communication with the low
current monitor for receiving the feedback signal from the low
current monitor for switchably selecting which of the feedback
signals input to the feedback multiplexer, or a signal dependent
thereon, will be output for the low current driver under the
control on the microcontroller. In this regard, the microcontroller
may function to control the feedback multiplexer to supply the
feedback signal from the low current monitor for the low current
driver when operating in low current mode and to selectively supply
the feedback signal from the buffer for the low current driver when
operating in voltage mode.
[0092] The instrument may also include an analog-to-digital
converter (ADC) in electrical communication with the
microcontroller and in electrical communication with the outputs of
the low current monitor and the buffer to convert the output of the
low current monitor and the buffer to a digital signal for supply
to the microcontroller for monitoring by the microcontroller.
[0093] Optionally, the buffer may also be connectable in electrical
communication with the counter electrode contact for detecting a
voltage at the counter electrode contact and for supplying a
buffered output representing the voltage at the counter electrode
contact for electrical communication with the microcontroller.
[0094] The controller 70 may include or be connected to a power
source 75. The power source 75 may include any source of direct
current (DC) to the controller 70. In certain embodiments, the
power source 75 could include a source of alternating current (AC)
that is converted to DC, as is known in the art. The power source
75 may include a battery. As used herein, the term "battery" refers
to an electro-chemical device comprising one or more
electro-chemical cells and/or fuel cells, and so a battery may
include a single cell or plural cells, whether as individual units
or as a packaged unit.
[0095] The present invention also includes method 1000, shown in
FIG. 8, of using the apparatus 1 to produce a working electrode
(e.g., first electrode 25) having a coating material deposited or
otherwise electroplated thereon.
[0096] The apparatus 1 may be provided in the open configuration
(step 1010) so that a first electrode 25 (i.e., the working
electrode) may be mounted on the first electrode mount 20 (step
1020) and a second electrode 35 (i.e., the counter electrode) may
be mounted on the second electrode mount 30 (step 1030).
[0097] Prior to providing the deposition solution, a deposition
chamber may be prepared by activating the biasing members 16 to
bias (1) the working electrode against the first aperture portion
41 of the deposition chamber frame 40; and (2) the counter
electrode against second aperture portion 45 of the deposition
chamber frame 40, and thereby hermetically sealing the deposition
chamber (step 1040). As noted above, the counter and working
electrodes (i.e., first and second electrodes 25 and 35,
respectively) then form the two walls of the deposition chamber. In
certain embodiments, the deposition chamber may be prepared and
hermetically sealed by with pneumatic actuators 16, which may apply
about 75 psi of pressure on the back of the working electrode. Step
1040 may further include providing a reference electrode 62 (e.g.,
a Ag/AgCl reference electrode or Pt or Au wire quasi reference
electrode) to the deposition chamber at the deposition chamber
frame 40.
[0098] A deposition solution may then be provided to the deposition
chamber by gravity flowing the deposition solution into the
deposition chamber (step 1050). Gravity flowing the deposition
solution eliminates pumps and extensive circulation tubing that may
ordinarily be required. A container 50 that holds the deposition
solution is connected to the deposition chamber frame 40, which
forms a portion of the deposition chamber, and is raised above the
level of the deposition chamber to gravity flow the deposition
solution into the deposition chamber.
[0099] A controller 70, which may be a potentiostat, galvanostat,
or combination thereof, may then be connected to the working
electrode, counter electrode, and reference electrode and a
potential may be applied across the working electrode and the
counter electrode (step 1060). Through the application of a
potential across the working and counter electrodes in a
galvanostatic or potentiostatic mode, electrochemical deposition
may occur at the working electrode wherein the coating material in
the deposition solution may be deposited at the working electrode.
Electrochemical deposition may be carried out preferably in a
potentiostatic (i.e., with controlled voltage) rather than a
galvanostatic (i.e., controlled current) mode for electrochromic
CPs of the invention as described, for example, in U.S. Patent
Application Publication No. 2013/0120821, the entirety of which is
incorporated herein by reference.
[0100] In certain embodiments of the invention, the manner in which
the potential may be applied may be dependent upon the specific
electrochromic CP being deposited and may be tailored thereto. For
example, in the case of poly (aromatic amine) CPs, generally, a
potentiostatic method with coulometric monitoring of the total
charge deposited (i.e., step 1070), may be preferred. In this
manner, the charge deposited per unit area may be used to control
the thickness, morphology, and other parameters of the film of
electrochromic CP deposited. In the case of thiophene-based CPs,
generally, a repeated-potential-sweep method, starting and stopping
at preferred, predetermined voltages, is preferred.
[0101] Therefore, step 1060 may include applying a linear scan
applied potential, which may include scanning the applied potential
from a pre-determined initial potential to a pre-determined final
potential at a pre-determined scan rate. Step 1060 may,
alternatively, include applying a fixed applied potential or
several fixed applied potentials across the working electrode and
the counter electrode. The fixed applied potential(s) may be
applied until (1) a pre-determined total charge is achieved, or (2)
a pre-determined total deposition time has elapsed.
[0102] Accordingly, the controller 70 may be provided to control
the application of potential across the working and counter
electrodes. The controller 70 may terminate or halt the
electrochemical deposition process when the desired voltage, number
of linear potential sweeps, total charge, or a combination of
selected parameters, is achieved (step 1080).
[0103] After halting the application of potential across the
working electrode and counter electrode (step 1080), the deposition
solution may be removed from the deposition chamber (step 1090). To
remove the deposition solution from the deposition chamber, the
container 50 is lowered below the level of the deposition chamber.
The fill/empty process may be automated using an actuator that may
be provided to automatically raise the container or lower the
container when actuated to fill or empty the vessel,
respectively.
[0104] After the deposition solution is removed from the deposition
chamber (step 1090), the biasing members 16 may be deactivated
(e.g., releasing the pneumatic pressure at pneumatic actuators 16)
and the first electrode mount 20, second electrode mount 30, and
deposition chamber frame 40 may be separated to open the deposition
chamber (step 1100). When the apparatus 1 is in its open
configuration, the working electrode with coating material
deposited thereon may be removed for further processing (step
1110).
[0105] Upon removing the working electrode with the coating
material deposited thereon, the apparatus 1 may be recycled and
returned to step 1020 to repeat the process in order to produce
another coated or electroplated substrate. Moreover, when repeating
the method 1000, the counter electrode may be cleaned before
remounting the counter electrode at the second electrode mount 30
in step 1030. Alternatively, when repeating the method 1000, step
1030 may be omitted and the counter electrode need not be removed
between cycles of the method.
[0106] The entire deposition process, including, for example, the
steps such as loading of the substrate (i.e., working electrode),
charging of the deposition solution, deposition via an
applied-potential, draining of the deposition solution, and removal
of the deposited substrate, is amenable to and is easily automated
or semi-automated.
[0107] A number of patent and non-patent publications are cited
herein in order to describe the state of the art to which this
invention pertains. The entire disclosure of each of these
publications is incorporated by reference herein.
[0108] While certain embodiments of the present invention have been
described and/or exemplified above, various other embodiments will
be apparent to those skilled in the art from the foregoing
disclosure. The present invention is, therefore, not limited to the
particular embodiments described and/or exemplified, but is capable
of considerable variation and modification without departure from
the scope and spirit of the appended claims.
[0109] Moreover, as used herein, the term "about" means that
dimensions, sizes, formulations, parameters, shapes and other
quantities and characteristics are not and need not be exact, but
may be approximate and/or larger or smaller, as desired, reflecting
tolerances, conversion factors, rounding off, measurement error and
the like, and other factors known to those of skill in the art. In
general, a dimension, size, formulation, parameter, shape or other
quantity or characteristic is "about" or "approximate" whether or
not expressly stated to be such. It is noted that embodiments of
very different sizes, shapes and dimensions may employ the
described arrangements.
[0110] Furthermore, the transitional terms "comprising",
"consisting essentially of" and "consisting of", when used in the
appended claims, in original and amended form, define the claim
scope with respect to what unrecited additional claim elements or
steps, if any, are excluded from the scope of the claim(s). The
term "comprising" is intended to be inclusive or open-ended and
does not exclude any additional, unrecited element, method, step or
material. The term "consisting of" excludes any element, step or
material other than those specified in the claim and, in the latter
instance, impurities ordinary associated with the specified
material(s). The term "consisting essentially of" limits the scope
of a claim to the specified elements, steps or material(s) and
those that do not materially affect the basic and novel
characteristic(s) of the claimed invention. All devices,
apparatuses, and methods described herein that embody the present
invention can, in alternate embodiments, be more specifically
defined by any of the transitional terms "comprising," "consisting
essentially of," and "consisting of."
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