U.S. patent application number 16/726708 was filed with the patent office on 2020-04-30 for procedure for the manufacturing of nanostructured platinum.
This patent application is currently assigned to ALBERT-LUDWIGS-UNIVERSITAT FREIBURG. The applicant listed for this patent is ALBERT-LUDWIGS-UNIVERSITAT FREIBURG. Invention is credited to Maria ASPLUND, Christian BOHLER.
Application Number | 20200131655 16/726708 |
Document ID | / |
Family ID | 62784145 |
Filed Date | 2020-04-30 |
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United States Patent
Application |
20200131655 |
Kind Code |
A1 |
BOHLER; Christian ; et
al. |
April 30, 2020 |
PROCEDURE FOR THE MANUFACTURING OF NANOSTRUCTURED PLATINUM
Abstract
A method for the manufacturing of platinum nanostructures
showing improved properties and usable in biomedical appliances is
provided. The method includes providing a solution containing
hexachloroplatinate with the remainder being water and
electrochemical deposition of platinum on a substrate with the
platinum deposited in a nanostructured form.
Inventors: |
BOHLER; Christian;
(Freiburg, DE) ; ASPLUND; Maria; (Freiburg,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ALBERT-LUDWIGS-UNIVERSITAT FREIBURG |
Freiburg |
|
DE |
|
|
Assignee: |
ALBERT-LUDWIGS-UNIVERSITAT
FREIBURG
Freiburg
DE
|
Family ID: |
62784145 |
Appl. No.: |
16/726708 |
Filed: |
December 24, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/EP2018/067222 |
Jun 27, 2018 |
|
|
|
16726708 |
|
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C25D 5/18 20130101; C25D
3/50 20130101 |
International
Class: |
C25D 3/50 20060101
C25D003/50; C25D 5/18 20060101 C25D005/18 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 27, 2017 |
DE |
10 2017 114 200.2 |
Claims
1. A method for the manufacturing of nanostructured platinum, the
method comprising: providing a solution containing
hexachloroplatinate with the remainder water; and electrochemically
depositing platinum on a substrate, wherein the platinum is
deposited in a nanostructured form.
2. The method according to claim 1, wherein the solution comprises
a pH-value between approximately 1.5 and approximately 4.4.
3. The method according to claim 1, wherein a concentration of
hexachloroplatinate is between approximately 0.2 mM and
approximately 3.1 mM.
4. The method according to claim 1, wherein the electrochemical
deposition is carried out in a voltage range between approximately
-0.4 V and approximately +0.4 V vs. Ag/AgCl.
5. The method according to claim 1, wherein the electrochemical
deposition is carried out as a dynamic potential deposition.
6. The method according to claim 5, wherein the electrochemical
deposition is carried out by a single sweep.
7. The method according to claim 5, wherein the electrochemical
deposition is carried out by multiple sweeps in a given potential
range.
8. The method according to claim 1, wherein a grain size of the
deposited platinum is in a range between approximately 1 nm to
approximately 500 nm.
9. The method according to claim 1, wherein a grain size of the
deposited platinum is in a range between approximately 5 nm to
approximately 400 nm.
10. The method according to claim 1, wherein a grain size of the
deposited platinum is in a range between approximately 10 nm to
approximately 200 nm
11. The method according to claim 1, wherein the electrochemical
deposition of the platinum on the substrate comprises a dynamic
potential process with multiple sweeps in a potential range between
approximately 1 mV/s and approximately 200 mV/s.
12. The method according to claim 11, wherein the potential range
is between approximately 2 mV/s and approximately 150 mV/s.
13. The method according to claim 1, wherein the electrochemical
deposition of the platinum on the substrate comprises a total
charge transferred between approximately 0.5 C/cm.sup.2 and
approximately 5 C/cm.sup.2.
14. The method according to claim 1, wherein the electrochemical
deposition of the platinum on the substrate comprises a total
charge transferred between approximately 0.8 C/cm.sup.2 and
approximately 4 C/cm.sup.2.
15. A method for the manufacturing of nanostructured platinum, the
method comprising: preparing a solution containing between
approximately 0.2 mM and approximately 3.1 mM hexachloroplatinate
with the remainder being water, wherein the pH-value of the
solution is between approximately 1.5 and approximately 4.4;
placing a substrate in the solution; and electrochemically
depositing platinum on the substrate using dynamic potential
deposition in a voltage range between approximately -0.4 V and
approximately +0.4 V vs. Ag/AgCl, wherein the deposited platinum
comprises a grain size between approximately 5 nm to approximately
400 nm.
16. The method according to claim 15, wherein electrochemically
depositing the platinum on the substrate comprises multiple sweeps
in a potential range between approximately 1 mV/s and approximately
200 mV/s.
17. The method according to claim 15, wherein electrochemically
depositing the platinum on the substrate comprises a total charge
transferred between approximately 0.5 C/cm.sup.2 and approximately
5 C/cm.sup.2.
18. The method according to claim 15, wherein electrochemically
depositing the platinum on the substrate comprises a deposition
time between approximately 1 s and approximately 60 min.
19. A method for the manufacturing of nanostructured platinum, the
method comprising: preparing a solution containing between
approximately 0.2 mM and approximately 3.1 mM hexachloroplatinate
with the remainder being water, wherein the pH-value of the
solution is between approximately 1.5 and approximately 4.4; and
electrochemically depositing platinum on a substrate using dynamic
potential deposition in a voltage range between approximately -0.4
V and approximately +0.4 V vs. Ag/AgCl and a deposition time
between approximately 10 s and approximately 360 s, wherein the
deposited platinum comprises a grain size between approximately 10
nm to approximately 200 nm.
20. The method according to claim 19, wherein electrochemically
depositing the platinum on the substrate comprises multiple sweeps
in a potential range between approximately 1 mV/s and approximately
200 mV/s.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of International
Application No. PCT/EP2018/067222, filed on Jun. 27, 2018, which
claims priority to and the benefit of DE 10 2017 114 200.2, filed
on Jun. 27, 2017. The disclosures of the above applications are
incorporated herein by reference.
FIELD
[0002] The present disclosure relates to a procedure for the
manufacture of nanostructured platinum as well as the use of a
substrate with deposited nanostructured platinum manufactured in
accordance with the procedure according to the present
disclosure.
BACKGROUND
[0003] The statements in this section merely provide background
information related to the present disclosure and may not
constitute prior art.
[0004] Procedures for the deposition of platinum on substrates are
well-known in the art. In a first alternative procedure, a platinum
containing substance, for example hexachloroplatinate, is dissolved
together with a reducing agent such as formic acid. Due to the
reduction potential of the formic acid, the platinum compound is
reduced, and platinum is deposited on a substrate. These procedures
are known as passive procedures for the depositing of platinum.
Passive procedures for the depositing of platinum are, for example,
used in connection with the manufacturing of platinum catalysts.
Since the reduction of the platinum compound starts immediately
after mixing the same with the reducing agent, the reaction can
only be further influenced by a change of temperature or by the
time the substrate on which the platinum deposits remains in the
solution. The solution prepared can only be used once. The result
is an uncontrolled deposition of platinum on surfaces of a
substrate and on surfaces of the reaction vessel.
[0005] There is another procedure for the deposition of platinum
from platinum containing compounds in a solution. This deposition
procedure is similar to the first passive process described above,
however, in addition to a reducing agent, an electrolyte or a
nucleating agent is used, and this is also known as an
electrochemical process. By this, the deposition is enhanced in
time by the use of an electrical signal. However, the deposition
starts after mixing the platinum containing compound with the
reducing agent, so that at least in part an uncontrolled deposition
of the platinum takes place. However, due to the use of an
additional electrochemically driven step, the platinum is
advantageously deposited on the electrical connected substrate
instead of other surfaces in the reaction vessel, and, in addition,
the deposition time is reduced. Such a procedure is for example
disclosed in WO 2007/050212 A2, where a new kind of a platinum
deposition, called platinum grey, is described to be manufacturable
under certain conditions. In the electrochemical driven process
described therein, a constant voltage is used, and as a platinum
containing compound platinum tetrachloride (PtCl.sub.4) is used. In
addition, sodium dihydrogen phosphate and disodium hydrogen
phosphate as a buffer are used in the platinum containing solution.
The platinum salt concentrations used are from 3 to 30 millimoles
(mM). Similarly, DE 10 2014 006 739 B3 discloses a process for the
deposition of various metals, including platinum, in a solution
containing lead acetate-trihydrate. Lead acetate is used in order
to first deposit lead on a substrate, and afterwards the lead is
substituted by platinum in a further deposition process.
[0006] All the known procedures for the deposition of platinum
suffer in that a reducing agent or an additional electrolyte such
as disodium hydrogen phosphate or a kind of a nucleating agent such
as lead acetate are used. In the deposition layer thus created on a
substrate, at least minor amounts of said compounds are
incorporated, limiting the use of such substrates especially for
biomedical applications, but also other uses. Further, as far as
reducing agents are used in the production of a deposition layer of
platinum on a substrate, the procedure is at least in part not
controllable in detail. Further, in most known procedures the
passive reduction of the platinum containing compound could not be
stopped, so that the platin containing solution cannot be used any
further, thereby increasing the costs of said procedures.
[0007] The present disclosure addresses these issues and other
issues related to an alternative method for the deposition of
platinum, especially in a nanostructured form.
SUMMARY
[0008] This section provides a general summary of the disclosure
and is not a comprehensive disclosure of its full scope or all of
its features.
[0009] The present disclosure provides for an advanced procedure
for the manufacturing of nanostructured platinum, which is costly
attractive, controllable and yields in highly purified platinum
deposition layers.
[0010] In one form of the present disclosure, the procedure (also
referred to herein as a "method") in accordance with the present
disclosure for the manufacturing of nanostructured platinum
comprises in a first step providing a solution containing
hexachloroplatinate with the remainder water; and, in a second
step, the electrochemical deposition of platinum on a substrate
such that the platinum is deposited in a nanostructured form. In
some variations, the solution contains only water and
hexachloroplatinate, and no further active agents such as a
reducing agent, a nucleating agent or a buffer solution, among
others. The term "hexachloroplatinate" is to be understood in the
sense of the present disclosure as to refer to the free acid with
the chemical formula H.sub.2PtCl.sub.6, also called hydrogen
hexachloroplatinate. Only very small amounts of impurities may be
present in the solution, containing hexachloroplatinate acid and
water. The concentration of such impurities shall be less than 10
mM, for example less than 3 mM, less than 1 mM, or less that 0.1
mM. As the case may be, an electrolyte as a non-active substance
may be present in the solution, such as sodium or potassium
chloride, especially in small amounts of not more than
approximately 10 nM. In some variations the solution only contains
hexachloroplatinate and water.
[0011] One advantage of using a solution in accordance with the
present disclosure is that highly purified platinum deposition
layers are provided by the procedure in accordance with the present
disclosure, and such layers can be used in biomedical applications
such as the measurement of brain currents and other applications.
Further, due to the electrochemical deposition in the second step,
a completely controlled process is provided for avoiding passive
platinum deposition. Thus, the deposition is truly restricted to
the electrical connected substrate and can be performed for long
times without having an overall passive coating of platinum
structures on the substrate as well as the reaction vessel.
Further, in the absence of any other agent, the pH-value of the
solution used is in a range such that desired substrate materials,
such as polymers or non-noble metals such as steel can be coated
without side effects or the destruction of the substrate itself. In
some variations, the pH-value of the solution provided for in the
first step is in a range between approximately 1.5 and
approximately 4.0. In at least one variation the pH-value is
between approximately 1.8 and approximately 39, for example
approximately 2.0 and approximately 3.0.
[0012] Various materials may be used to form the substrate. As may
be described below in connection with the examples in accordance
with the present disclosure, for example a polyimide substrate may
be used. Polyimide substrates may be provided for in a flexible
form. In the polyimide itself, electrical conductive tracks, e.g.,
tracks made of platinum, can be embedded within the polyimide
material. Such embedded tracks have on their first end region an
active side with a surface being in contact with the deposition
solution, being thus not embedded, whereas on the second end region
an interconnection is provided for by the embedded track, being not
in contact with the depositing solution. Such polyimide substrates
may have, for example, as active sides a circular shape with a
diameter great than ABOUT 5 .mu.m, for example greater than 100
.mu.m, or greater than 2000 .mu.m, and even more. However, also
other polymers may be used as substrate materials, such as silicone
rubber (e.g. PDMS), parylene (e.g. Parylene-C), or epoxy resins
such as SU-8, as well as none-noble metals such as stainless steel
(e.g. 316L), nickel-cobalt-base alloys such as MP35N, or indium tin
oxide (ITO). In addition, also none-noble metals may be used
embedded in polymers such as polyimide, as described before. Other
substrate materials useable in accordance with the present
disclosure are glass or PEM (Polymer Electrolyte Membrane). One PEM
usable is Nafion (registered trademark), obtainable from the
company DuPont. The glass or the PEM are coated with an electrical
conductive material, e.g. with platinum. However, instead of
platinum, also other noble metals such as rhenium, ruthenium,
rhodium, palladium, silver, osmium iridium or gold are usable.
[0013] As far as the terms "approximately", "about" or
"essentially" are used in the present disclosure with respect to
values, value ranges or terms referring to values, they are to be
understood herein to mean what the person skilled in the art would
regard as typical in the given context, and from the perspective of
a person skilled in the art. In particular, deviations of the given
values, value ranges or terms referring to values comprised by the
aforesaid terms amount to +/-10%, for example +/-5% or +/-2%.
[0014] The term "nanostructure(d)" as used in connection with the
deposited platinum on a substrate produced in accordance with the
procedure of the present disclosure refers to grain-like platinum
structures having an irregular outer shell with edges and corners
having a grain size in a range between approximately 1 nm to
approximately 500 nm, for example in a range between approximately
5 nm to approximately 400 nm, or in a range between approximately
10 nm to approximately 200 nm.
[0015] In some variations of the present disclosure, the deposition
time for the electrochemical deposition in the second step of the
procedure is in a range between approximately 1 s and approximately
60 min, for example in a range between approximately 1 s and 1000
s, or in a range between approximately 10 s and approximately 360
s. In at least one variation of the present disclosure, the
temperature at which the deposition takes place is in a range
between approximately 10.degree. C. and approximately 75.degree.
C., for example in a range between approximately 15.degree. C. and
approximately 62.degree. C. In some variations the concentration of
the hexachloroplatinate in the solution before electrochemical
deposition takes place is in a range between approximately 0.2 mM
and approximately 3.1 mM, for example in a range between
approximately 0.25 mM and approximately 3.0 mM, or in a range
between approximately 1.0 mM and approximately 2.9 mM. By using
such low concentrations of hydrogen hexachloroplatinate in the
preparation of the solution in the first step of the procedure in
accordance with the present disclosure, a very controlled
deposition of the platinum and the form of nanostructures on a
substrate are available. If the concentration of hydrogen
hexachloroplatinate would exceed 5 mM, and also 4 mM, controlled
deposition of platinum in the form of nanostructures is reduced or
not possible. IN some variations, highly purified water is used,
especially a highly purified water with a resistance of at least
approximately 15 MOhm*cm, for example at least approximately 18
MOhm*cm, at 25.degree. C., such as Milli-Q (registered trademark)
water of Type 1 in accordance with ASTM D1193-91 provided for by
Millipore Corporation.
[0016] In another form of the present disclosure, the
electrochemical deposition in the second step is carried out in a
voltage range between approximately -0.6 V, for example
approximately -0.4 V, and approximately +0.4 V vs. Ag/AgCl. As far
as in the following voltages or voltage ranges in relation to the
electrochemical deposition in the second step of the procedure in
accordance with the present disclosure are referred to, they are
defined vs. Ag/AgCl. In some variations, the deposition in the
electrochemical step is carried out with a three (3) electrode
set-up. In such a three electrode set-up, a stainless steel counter
electrode is used as well as a Ag/AgCl reference electrode. As a
working electrode, the electrically connected substrate used in the
second step of the procedure in accordance with the present
disclosure is used. However, also a two-electrode setup may be used
for the electrochemical deposition. Although the electrochemical
deposition in the second step in accordance with the present
disclosure may be carried out at a constant potential, in some
variations electrochemical deposition is carried out as a dynamic
potential deposition. Such a dynamic potential deposition leads to
the platinum nanostructures as defined before in form of grain-like
structures with edges and corners. In contrast thereto, an
electrochemical deposition at a constant potential usually leads to
grass-like structures with grass needles with an extension in a
range between approximately 10 nm and approximately 1000 nm, thus,
a range similar to the grain-like nanostructures obtained in
accordance with the procedure of the present disclosure. As a
dynamic potential deposition in accordance with the present
disclosure it is understood that at least over a certain voltage
range with a lower vertex potential and a higher vertex potential
the electrochemical deposition is carried out. In some variations,
the voltage range comprises at least a sweep over a range of
approximately 0.2 V, for example a sweep of a range of at least
approximately 0.5 V. In at least one variation a sweep in a range
between 0.2 V and 0.9 V, in one direction, is used. The dynamic
potential deposition in the sense of the present disclosure may,
thus, be carried out, e. g., as a linear sweep from a lower voltage
to a higher voltage or a linear sweep from a higher voltage to a
lower voltage, or as a cyclic sweep between a lower potential and a
higher potential. Also, the inclination of the sweep may be amended
within one sweep. Besides the aforesaid linear sweeps and cyclic
sweeps, it is also possible to use more complex sweeps using
geometries like exponential signals or sinusoidal signals, square
wave functions and/or saw tooth functions, especially between two
or more potentials. The latter signals or functions are applicable
at frequencies between approximately 5 Hz and approximately 200 Hz.
For example, a saw tooth function may be used starting from a
voltage of -0.2 V with a step of +/-0.2 V at a frequency of 20 Hz.
The deposition times for the aforesaid signals and functions are
comparable to the deposition times already mentioned above.
[0017] The teachings of the present disclosure include using a
single sweep or multiple sweeps in a given potential range in the
second step of the electrochemical deposition. That is, in some
variation multiple sweeps are used in a given potential range. In
such variations cyclic multiple sweeps can be used. Such cyclic
multiple sweeps are obtainable by using cyclic voltammetry
technics. In at least one variation cyclic voltammetry in a voltage
range between approximately -0.3 V and 0.3 V is used. When using
multiple cyclic sweeps, at least 5 sweeps back and forth, for
example at least 10 sweeps back and forth, more than approximately
20 sweeps back and forth and less than approximately 1000 sweeps
back and forth are used. In some variations less than or equal to
600 sweeps back and forth are used.
[0018] In some variations of the present disclosure, a scan rate
used for single sweeps or multiple sweeps, especially multiple
cyclic sweeps, in a given potential range are in a range between
approximately 1 mV/s and approximately 200 mV/s, for example in a
range between approximately 2 mV/s and approximately 150 mV/s. In
at least one variation, the total charge transferred is in an
amount between approximately 0.5 C/cm.sup.2 and approximately 5
C/cm.sup.2, for example in a range between approximately 0.8
C/cm.sup.2 and approximately 4 C/cm.sup.2. The charge transferred
can be used to control the deposition process in the second step of
the procedure in accordance with the present disclosure in detail.
The charge transferred is measured by cyclic voltammetry.
[0019] The substrate with deposited nanostructured platinum
thereupon produced in accordance with the procedure of the present
disclosure show very dense, grain-like platinum nanostructures on
the surface of the substrate. The complex impedance Z, that may be
measured by electrochemical impedance spectroscopy, of such a
coated substrate is below the complex impedance of an uncoated
substrate, and is lowered by a factor in a range between
approximately 10 to approximately 100 in the coated substrate
compared to the uncoated substrate. The complex impedance of a
coated substrate produced by multiple cyclic sweeps, especially
produced by cyclic voltammetry, is lower than the complex impedance
of a coating produced with a constant potential process, whereby
all other parameters are hold equal. The lowering of the complex
impedance when using a dynamic potential process, at especially
multiple cyclic sweeps, especially produced by cyclic voltammetry,
compared to a constant potential process, has a magnitude of a
factor between approximately 0.3 and approximately 2.5.
[0020] The present disclosure also refers to use of a substrate
with deposited nanostructured platinum thereupon manufactured in
accordance with the procedure as discussed before as an adhesion
promoter for coatings, as a corrosion protection and/or as a means
for the enhancement of electrochemical properties, such as a
voltage influencing means, an impedance reducing means, or an
enhancement means for charge transfer. Especially, the platinum
nanostructures on a substrate produced in accordance with the
present disclosure may function as an adhesion promoter for a
subsequent deposition of bio-functional coatings for neural probes.
Such coatings may be made, for example, by conducting polymers,
especially in the form of electrodeposited films. Due to the
procedure used for the manufacturing of the platinum nanostructures
on a substrate, a rough layer that provides a higher amount of
nucleation sites as well as a higher degree of mechanical
interaction to a subsequently electrodeposited conducting polymer
layer is obtainable and useable, resulting in a significantly
improved adhesion of the conducting polymer electrodeposited
thereupon. Further, a substrate with an electrocoating of platinum
nanostructures produced in accordance with the present disclosure
is useable as an intermediate layer on none-noble metal surfaces,
that may be used as working electrodes. When used as a voltage
influencing means, one or more layers of electrodeposited platinum
nanostructures produced in accordance with the present disclosure
on a substrate influence the reducing or oxidizing potential of the
original surface, so that the field of use of the original surface
is amended and/or widened. The present disclosure also relates to a
substrate with an electrocoating made of platinum nanostructure,
produced in accordance with the present disclosure, whereby a
mechanical strengthening of the electrodeposited platinum
nanostructure is achieved by filling the platinum nanostructure
with at least one conductive polymer, e.g. PEDOT. This is
especially advantageous in case the platinum nanostructures are
long and/or the deposit will show a weblike structures with holes
therebetween or openings. The substrate may exist of an insulation
layer and a conducting electrode layer, arranged at least on a part
of said insulation layer. The electrocoating of nanostructured
platinum free of ions and salts is arranged at least in part on
said conducting electrode layer.
[0021] The working electrodes used as substrates or the substrate
itself may have each kind of geometry, depending also on the
further use of the substrate with an electrodeposited platinum
nanostructure thereupon produced in accordance with the procedure
of the present disclosure. For example, the electrode may have a
needle-like or tip-like structure, a flat structure, as already
disclosed above in connection with polyimide substrates, or may
have any other geometry.
[0022] In some variations cyclic voltammetry is used in a voltage
range between approximately -0.3 V and 0.3 V, whereby more than 20
sweeps, and not more than approximately 1000 sweeps, for example
not more than approximately 500 sweeps back and forth are used with
a scan rate in a range between 1 mV/s and approximately 120 mV/s.
In such variations, a concentration of the hydrogen
hexachloroplatinate is in a range between approximately 1.5 mM and
approximately 2.8 mM and improved mechanical properties especially
when using the platinum nanostructures on the substrate as an
intermediate or enabling layer for bio-functional coatings, for
non-noble metal surfaces and as a voltage-influencing means are
obtainable.
[0023] Further areas of applicability will become apparent from the
description provided herein. It should be understood that the
description and specific examples are intended for purposes of
illustration only and are not intended to limit the scope of the
present disclosure.
DRAWINGS
[0024] In order that the disclosure may be well understood, there
will now be described various forms thereof, given by way of
example, reference being made to the accompanying drawings, in
which:
[0025] FIG. 1 is a time-potential-diagram showing possible linear
sweeps A and B as well as a multiple sweeps C useable in an
electrochemical deposition step, according to the teachings of the
present disclosure;
[0026] FIG. 2 shows cyclic voltammetry diagrams of an uncoated
substrate, a substrate produced in a constant potential process,
and a substrate coated in a dynamic potential process by using
cyclic voltammetry, according to the teachings of the present
disclosure;
[0027] FIG. 3 shows complex impedance of the three substrates shown
in FIG. 2;
[0028] FIG. 4 is a photograph of a polyimide substrate with a
platinum nanostructure deposition carried out by a dynamic
potential process on the left side and by a constant potential
process of the right side, showing overgrowth of the deposited
nanostructures, according to the teachings of the present
disclosure;
[0029] FIGS. 5A to 5C are electron microscopy images of platinum
nanostructures deposited on a substrate by different dynamic
potential process, according to the teachings of the present
disclosure;
[0030] FIG. 5D is an electron microscopy image of platinum
nanostructures deposited on a substrate by a constant potential
process;
[0031] FIGS. 6A and 6B are electron microscopy images of platinum
nanostructures deposited on a polyimide substrate by way of a
constant potential process; and
[0032] FIGS. 7A and 7B are electron microscopy images of platinum
nanostructures deposited on a polyimide substrate by way of a
dynamic potential process, according to the teachings of the
present disclosure.
[0033] The drawings described herein are for illustration purposes
only and are not intended to limit the scope of the present
disclosure in any way.
DETAILED DESCRIPTION
[0034] The following description is merely exemplary in nature and
is not intended to limit the present disclosure, application, or
uses. It should be understood that throughout the drawings,
corresponding reference numerals indicate like or corresponding
parts and features.
[0035] Referring to FIG. 1, three alternatives (A, B, and C) for
carrying out a dynamic potential deposition of platinum
nanostructures on a substrate are shown. A linear sweep A starting
from a low potential of -0.3 volts (V) and ending at a higher
potential of 0.3 V is characterized in a general way, whereas a
linear sweep B starting at a higher potential of 0.3 V and ending
at a lower potential of -0.3 V is also shown. Further, multiple
sweeps C are shown in FIG. 1 with three peaks within the time frame
shown, the multiple sweeps starting at a lower potential of -0.3 V
and running to a higher potential of 0.3 V back and forth. Such
multiple sweeps C may be obtained by using cyclic voltammetry and
is similar to a multiple sweep using a saw tooth function.
[0036] Now referring to FIG. 2, the cyclic voltammetry properties
of an uncoated substrate, a substrate coated by way of a dynamic
potential process, and a substrate obtained by constant potential
process are shown. For the constant potential process, a potential
of -0.3 V is used, whereas for the dynamic potential process,
cyclic voltammetry with a voltage range between -0.3 V to 0.3 V
back and forth is used. For the dynamic potential process, 300
multiple cyclic sweeps back and forth between -0.3 V and 0.3 V are
used with a scan rate of 12 millivolts per second (mV/s) to deposit
the nanostructures. The total charge transferred was about 2
Coulombs per centimeter squared (C/cm.sup.2). An identical charge
is transferred with respect to the constant potential process to
the substrate. The potential was held constant for 2310 seconds (s)
at -0.3 V. The hydrogen hexachloroplatinate aqueous solution used
with respect to the constant potential process as well as the
dynamic potential process was identical and contained 2.5
millimoles (mM) hydrogen hexachloroplatinate. As shown in FIG. 2,
the electrochemical active area of the substrate produced with the
dynamic potential process is greater than the electrochemical
active are of the substrate produced with a constant potential
process. For the cyclic voltammetry measurements done with respect
to FIG. 2, an aqueous solution of highly purified water with a
phosphate buffered saline (PBS) at a concentration of 0.01 moles
(M) without hydrogen hexachloroplatinate (as well as any other kind
of agents) is used. The cyclic voltammetry is carried out at room
temperature (25.degree. C.).
[0037] Referring to FIG. 3, the complex impedance measured by
electrochemical impedance spectroscopy of the substrates is shown,
as defined in connection with FIG. 2 above. One may determine from
FIG. 3 that the complex impedance (with symbol |Z| and unit S2) of
the coated substrates is lowered by a factor of 35 to 50 compared
to the uncoated substrate. Further, the complex impedance of the
substrate having platinum nanostructures electrodeposited thereupon
by way of a dynamic potential process show a lowered impedance by a
factor of around 1.5 compared to the substrate obtained by a
constant potential process, as defined before in connection with
FIG. 2. Thus, one may obtain from FIGS. 2 and 3 that the
electrodeposition of platinum nanostructures by way of a dynamic
potential process, especially by multiple sweeps provides a
substrate with at least one layer of platinum nanostructures with
desirable properties. In one form, multiple cyclic sweeps
obtainable by cyclic voltammetry provide a substrate with at least
one layer of platinum nanostructures with desirable properties.
Indeed, as shown in FIGS. 5A to 5D (see discussion below), by way
of a dynamic potential process a more homogeneous and thinner
electrodeposition of platinum nanostructures on substrates is
obtainable. Due to the increased homogeneity, such layers of
platinum nanostructures on substrates show improved properties
especially when used as intermediate layers or adhesion promotion
layers as discussed before.
[0038] Now referring to FIG. 4, the coated substrates produced in
accordance with the solutions and the electrochemical deposition
are shown, as defined with respect to FIG. 2 above, whereby on the
left-handed side of FIG. 4 the substrate with platinum
nanostructures produced by way of a dynamic potential process as
described above is shown, and on the right-handed side platinum
nanostructures deposited on the substrate produced by the constant
potential process as defined above is shown. The right-handed side
of FIG. 4 shows an overgrowth of the platinum nanostructures over
the rim of the active area of a substrate, whereas no such
overgrowth takes place by the dynamic potential process as
evidenced by the left-handed side platinum nanostructures deposited
on the active area of the polyimide substrate.
[0039] FIGS. 5A to 5C show electronic microscopy images of
substrates with electrocoated platinum nanostructures obtained by
various dynamic potential processes, whereas FIG. 5D shows the
result of a constant potential process. In FIG. 5A, the
electrodeposition of platinum nanostructures was carried out using
a dynamic potential process, namely a linear voltage ramp starting
from a negative potential of -0.3 V and ending at a positive
potential of 0.3 V. The scan rate was 2 mV/s and the total
deposition time was 300 s. In contrast, FIG. 5B shows a linear
voltage ramp starting from a higher potential of 0.3 V and ending
at a lower potential at -0.3 V. The other conditions are identical
to the linear voltage ramp as used for the deposition of platinum
nanostructures shown in FIG. 5A. FIG. 5C shows platinum
nanostructures deposited by a dynamic potential process using
cyclic voltammetry in a potential range between -0.3 V and 0.3 V at
a scan rate of 120 mV/s and fifty-eight (58) sweeps back and forth.
Conversely, FIG. 5D shows the electrodeposited platinum
nanostructures produced by using a constant potential of -0.3 V.
The charge transferred in FIGS. 5A, 5B, and 5D was 1.1 C/cm.sup.2,
whereas the charge transferred in FIG. 5C was doubled to 2.2
C/cm.sup.2. As shown for the dynamic potential process of FIGS. 5A
to 5C a more homogeneous and denser surface structure of the
electrodeposited layer of platinum nanostructures is obtained
compared to the electrodeposited layer produced by a constant
potential process in accordance with FIG. 5D. Moreover, FIG. 5D
shows very coarse and grass-like platinum nanostructures with
extensions between approximately 20 nanometers (nm) to
approximately 700 nm, whereas the platinum nanostructures obtained
by the dynamic potential process in accordance with FIGS. 5A to 5C
show a grain-like structure with corners and edges, with dimensions
for the grain size between approximately 25 nm to approximately 150
nm (FIG. 5A), between approximately 10 nm to approximately 100 nm
(FIG. 5B), and between approximately 20 nm to approximately 200 nm
(FIG. 5C). The finest nanostructures were obtained by the linear
voltage ramp starting from the higher potential in accordance with
FIG. 5B, whereas the most homogeneous surface structure was
obtainable by using a linear voltage ramp starting from the lower
potential in accordance with FIG. 5A. The structure of the platinum
nanostructures produced in accordance with cyclic voltammetry as
shown in FIG. 5C is in the middle between the structures of the
platinum nanostructures shown in FIGS. 5A and 5B.
[0040] Referring to FIGS. 6A and 6B, electron microscopy images of
an active area of a polyimide substrate coated with platinum
nanostructures by way of a constant potential process are shown.
The potential was held constant at -0.3 V over 220 s. The
concentration of the hexachloroplatinate was 2.5 mM. From the
enlargement shown in FIG. 6A one clearly sees the needle-like or
grass-like structure of the platinum nanostructures produced by the
constant potential process. The constant potential process further
shows undefined and substantially larger structures at the edge of
the substrate as a consequence of an inhomogeneous growth.
[0041] In contrast, FIG. 7 shows an active area coated with
platinum nanostructures produced by the process using a dynamic
potential process, namely cyclic voltammetry in a range between
-0.3 V and 0.3 V at a scan rate of 120 mV/s and a total of three
hundred (300) sweeps back and forth. The total charge transfer was
2.1 C/cm.sup.2, identical to the total charge transferred in the
example shown in FIGS. 6A and 6B. The homogeneous and dense
grain-like structure of the platinum nanostructures deposited on
the polyimide substrate material shown in FIG. 7A is an enlargement
of FIG. 7B. Further, the deposition area as shown in FIGS. 7A and
7B is more homogeneous and shows well defined nanostructures at the
rim of the substrate in contrast to the undefined large structures
resulting from the constant potential process as illustrated in
FIGS. 6A and 6B.
[0042] By way of the present disclosure, it is provided a procedure
for the manufacturing of platinum nanostructures from a solution
containing only water and hexachloroplatinate, and yielding
substrates coated with platinum nanostructures that are also usable
in biomedical applications. The solution may be used at various
times as no active agents such as reducing agents are present. The
electrodeposited platinum nanostructures, especially when using a
dynamic potential process, have a dense and homogeneous appearance
with a grain-like structure with edges and corners on the grains.
The deposition process is definable in detail, so that depositions
of platinum nanostructures in one or more layers are obtainable
with predefined properties.
[0043] Unless otherwise expressly indicated herein, all numerical
values indicating mechanical/thermal properties, compositional
percentages, dimensions and/or tolerances, or other characteristics
are to be understood as modified by the word "about" or
"approximately" in describing the scope of the present disclosure.
This modification is desired for various reasons including
industrial practice, material, manufacturing, and assembly
tolerances, and testing capability.
[0044] As used herein, the phrase at least one of A, B, and C
should be construed to mean a logical (A OR B OR C), using a
non-exclusive logical OR, and should not be construed to mean "at
least one of A, at least one of B, and at least one of C."
[0045] The description of the disclosure is merely exemplary in
nature and, thus, variations that do not depart from the substance
of the disclosure are intended to be within the scope of the
disclosure. Such variations are not to be regarded as a departure
from the spirit and scope of the disclosure.
* * * * *