U.S. patent application number 15/219743 was filed with the patent office on 2017-03-23 for methods and apparatus for transfer for films among substrates.
The applicant listed for this patent is GRAPHENE FRONTIERS. Invention is credited to Bruce Ira WILLNER.
Application Number | 20170080696 15/219743 |
Document ID | / |
Family ID | 50881366 |
Filed Date | 2017-03-23 |
United States Patent
Application |
20170080696 |
Kind Code |
A1 |
WILLNER; Bruce Ira |
March 23, 2017 |
METHODS AND APPARATUS FOR TRANSFER FOR FILMS AMONG SUBSTRATES
Abstract
A method is disclosed which includes: forming at least one layer
of material on at least part of a surface of a first substrate,
wherein a first surface of the at least one layer of material is in
contact with the first substrate thereby defining an interface;
attaching a second substrate to a second surface of the at least
one layer of material; forming bubbles at the interface; and
applying mechanical force; whereby the second substrate and the at
least one layer of material are jointly separated from the first
substrate. Related arrangements are also described.
Inventors: |
WILLNER; Bruce Ira;
(Lawrenceville, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
GRAPHENE FRONTIERS |
PHILADELPHIA |
PA |
US |
|
|
Family ID: |
50881366 |
Appl. No.: |
15/219743 |
Filed: |
July 26, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14445746 |
Jul 29, 2014 |
9427946 |
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15219743 |
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14099032 |
Dec 6, 2013 |
8822308 |
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14445746 |
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61797471 |
Dec 7, 2012 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 21/67092 20130101;
C01B 32/184 20170801; C01B 32/194 20170801; H01L 21/0201 20130101;
B32B 38/10 20130101; B32B 37/24 20130101; B32B 2037/246 20130101;
H01L 21/67132 20130101; B32B 2037/243 20130101; B32B 38/08
20130101 |
International
Class: |
B32B 37/24 20060101
B32B037/24; B32B 38/10 20060101 B32B038/10 |
Claims
1. A method comprising: forming at least one layer of material on
at least part of a surface of a first substrate, wherein a first
surface of the at least one layer of material is in contact with
the first substrate thereby defining an interface; attaching a
second substrate to a second surface of the at least one layer of
material; forming bubbles at the interface; and applying mechanical
force; whereby the second substrate and the at least one layer of
material are jointly separated from the first substrate.
Description
[0001] This application is a continuation of U.S. patent
application Ser. No. 14/445,746, filed Jul. 29, 2014, which is a
continuation of U.S. patent application Ser. No. 14/099,032, filed
Dec. 6, 2013, now U.S. Pat. No. 8,822,308, issued on Sep. 2, 2014,
which claims priority under 35 U.S.C. .sctn.119 to U.S. Provisional
Application No. 61/797,471 entitled Methods and Apparatus for
Transfer of Films Among Substrates, filed Dec. 7, 2012, the entire
contents of which are hereby incorporated by reference.
BACKGROUND
[0002] The present application generally relates to methods and
apparatus for transfer of films from one or more substrates to
another.
[0003] In this specification where a document, act or item of
knowledge is referred to or discussed, this reference or discussion
is not an admission that the document, act or item of knowledge or
any combination thereof was at the priority date, publicly
available, known to the public, part of common general knowledge,
or otherwise constitutes prior art under the applicable statutory
provisions; or is known to be relevant to an attempt to solve any
problem with which this specification is concerned.
[0004] The discovery of graphene has generated widespread interest
for potential use in electronic and other applications due to its
electronic, optical, physical, and mechanical properties. Graphene
is a single atomic layer of carbon atoms, tightly bonded in a
hexagonal lattice. Despite its short history as an experimental
system, graphene has already revealed exciting new physics
including "relativistic" carriers with implications for quantum
electronic transport and charge screening, a width-dependent energy
band gap, extremely high carrier mobility, high elasticity and
electromechanical modulation. The properties of graphene appeal to
many industries, in particular electronics. Graphene's high carrier
mobility and high thermal conductivity make it a potential
alternative to silicon and diamond. Its properties may enable the
creation of next generation solid-state devices (ballistic
transistors, spin transistors, etc.). Graphene is also a candidate
for use as a flexible, optically transparent conductor in
applications such as touch displays and photovoltaics. Other
potential applications include chemical sensors, nanopore filters,
impermeable coatings for corrosion and/or chemical protection,
ultracapacitors, TEM supports, and others.
[0005] The goal of low cost graphene sheets has driven recent
research in methods of large area graphene production. Chemical
vapor deposition of graphene on metal substrates is one promising
method for large area, low cost, graphene production. One critical
issue of graphene production is the handling of the graphene films
and the transfer of those films from the deposition substrate to
other substrates for many applications. Accordingly, there is a
need for a large area process to transfer single layer or
multi-layer graphene from one substrate to another substrate.
[0006] One current, widely used graphene transfer process includes
a chemical etching step to remove the metal substrate by
dissolution. Scaling this process to thousands of square meters
production, leads to great expense and waste challenges. The
reclamation or disposal of metal infused etchant constitutes a
major cost and waste handling issue. Since the substrate is
dissolved by the etchant, it cannot be reused for the growth of
graphene films. In addition, the dissolution process is rather
slow. For at least these reasons, this conventional technique is
not well-suited for efficient, large-scale, low cost production of
graphene films.
[0007] While certain aspects of conventional technologies have been
discussed to facilitate disclosure of the invention, Applicants in
no way disclaim these technical aspects, and it is contemplated
that the claimed invention may encompass or include one or more of
the conventional technical aspects discussed herein.
SUMMARY
[0008] The present invention may address one or more of the
problems and deficiencies of the prior art discussed above.
However, it is contemplated that the invention may prove useful in
addressing other problems and deficiencies, or provides benefits
and advantages, in a number of technical areas. Therefore the
claimed invention should not necessarily be construed as being
limited to addressing any of the particular problems or
deficiencies discussed herein.
[0009] The present invention provides methods and apparatus which
provide one or more of the following benefits and advantages:
[0010] elimination or significant reduction of chemical waste and
related environmental and cost benefits; [0011] allows for the
reuse of metal substrates for future graphene formation, thereby
reducing waste and improving the economics of the process; [0012]
allows for a scalable, continuous process for graphene film
creation, substrate transfer and/or multi-layer structure
fabrication; [0013] allows graphene films to be placed on nearly
any smooth surface; [0014] provides a process for transferring
graphene films which are a single atomic layer thickness, as well
as multilayer graphene films; [0015] provides a process which can
transfer Graphene to either flexible or rigid substrates; [0016]
allows for the creation and transfer of large area sheets of
Graphene film.
[0017] Thus, according to one aspect, the present invention
provides a method comprising: forming at least one layer of
material on at least part of a surface of a first substrate,
wherein a first surface of the at least one layer of material is in
contact with the first substrate thereby defining an interface;
attaching a second substrate to a second surface of the at least
one layer of material; forming bubbles at the interface; and
applying mechanical force; whereby the second substrate and the at
least one layer of material are jointly separated from the first
substrate.
[0018] According to a further aspect, there is provided an
arrangement for transferring at least one layer of material from a
first substrate to a second substrate, the arrangement comprising:
a supply roll comprising a roll of a composite material, the
composite material comprising a first substrate, at least one layer
of material in contact with the first substrate thereby defining an
interface, and a second substrate attached to a second surface of
the at least one layer of material; a vessel containing a solution,
the solution comprising water and at least one electrolyte; a
cathode defined at the composite material when disposed in the
solution; an anode disposed in the solution at a location remote
from the cathode; a power source connected to the cathode and
anode; a first pickup roll, the first pickup roll attached to the
second substrate/at least one layer of material; a second pickup
roll, the second pickup roll attached to the first substrate;
wherein the cathode is constructed and arranged so as to produce
bubbles at the interface, and wherein the second pickup roll is
constructed and arranged to pull the first substrate in a first
direction, and the first pickup roll is constructed and arranged to
pull the second substrate along with the at least one layer of
material in a second direction, the first and second directions
diverging from one another, thereby defining an angle of
separation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIGS. 1A-1C' are schematic illustrations of methods
performed according to certain aspects of the present
invention.
[0020] FIGS. 2-3 are schematic illustrations of methods performed
according to further aspects of the present invention.
[0021] FIG. 4 is a schematic illustration of an arrangement, and
related methods, configured according to the principles of the
present invention.
[0022] FIG. 5 is a schematic illustration of further optional
aspects of methods and arrangements of the present invention.
[0023] FIG. 6 is a schematic illustration of arrangements and
methods according to additional aspects of the present
invention.
DETAILED DESCRIPTION
[0024] As used herein, the singular forms "a", "an" and "the" are
intended to include the plural forms as well, unless the context
clearly indicates otherwise. Additionally, the use of "or" is
intended to include "and/or", unless the context clearly indicates
otherwise.
[0025] According to certain aspects of the present invention there
are provided methods of transferring graphene from a substrate on
which it is formed to a second substrate. These methods attach the
second substrate to the graphene, as described later, immerse the
layers in a solution, and then use a mechanical pulling action to
separate the graphene and second substrate from the original
substrate with the aid of bubbles, formed electrolytically at the
interface between the graphene and the metal, to push the two
layers apart. An electrolysis cell is configured in the solution by
electrically contacting the graphene and metal structure and a
second electrode. This process is suitable for graphene films grown
on conductive substrate. This process is especially suitable for
scaling to larger area graphene films.
[0026] Certain illustrative, non-limiting embodiments of methods
and arrangements according to the principles of the present
invention are schematically depicted in FIGS. 1-6.
[0027] As illustrated, for example, in FIG. 1A, at least one layer
of material 12 can be formed on at least part of a surface of a
first substrate 10 thereby forming an interface 16 between a first
surface 14 of the at least one layer of material 12 and the
substrate 10. The at least one layer material can be formed on part
of a surface of the first substrate, for example, as a periodic
pattern. Alternatively, the at least one layer of material 12 can
cover the entire surface of the first substrate 10. The layer of
material 12 can be formed as a single layer of material, or as
multiple layers of material. The layer of material 12 can have any
suitable thickness. The methods and arrangements of the present
invention are advantageous with respect to thin layers, such as
layers having a total thickness less than 10 nm. The at least one
layer of material 12 can be formed from any suitable material, or
combination of materials. According to certain embodiments, the at
least one layer of material 12 comprises graphene. The graphene may
be present as a single atomic layer of graphene, or as layers of
graphene having a multiple-atom thickness. The graphene can be
combined with one or more additional materials. For example, the
graphene can be doped with one or more dopants. The dopant(s) can
comprise iodine, nitrogen, boron, potassium, arsenic, gallium,
aluminum, indium, or others. Graphene can be formed according to
any suitable technique, generally known to those skilled in the
art, such as exfoliation of graphite, epitaxial growth, oxide
reduction of graphite, etching or division of carbon nanotubes,
sonication of graphite, and carbon dioxide reduction reactions.
According to certain embodiments of the present invention, graphene
is grown on a substrate by chemical vapor deposition. According to
further alternative embodiments, the graphene may be grown onto a
planarized substrate under relatively low temperature, near
atmospheric pressure, conditions. For example, the substrate 10 can
be planarized by any suitable technique, such as electropolishing,
mechanically polishing, and/or chemically polishing the surface
thereof upon which graphene is to be grown. This surface of the
substrate 10 is then contacted with a hydrocarbon gas (e.g.,
methane) at a temperature of about 250.degree. C. to about
2000.degree. C., and at a pressure of about 10.sup.-7 atmospheres
to about ambient pressure. One suitable technique of forming
graphene as the at least one layer material 12 upon the substrate
10 according to certain illustrative and non-limiting embodiments
of the present invention is described in WO 2012/021677, the entire
contents of which is incorporated herein by reference.
[0028] Regardless of the nature of the at least one layer of
material 12, the first substrate 10 can be formed from any suitable
material. The first substrate 10 can be flexible or rigid.
According to certain illustrative examples, the substrate 10 can be
formed of a metal. Specific non-limiting examples of metals that
could be used to form the substrate 10 include copper, rhodium,
ruthenium, iridium, platinum, cobalt, nickel, or any combination
thereof. According to one illustrative non-limiting example, the
substrate 10 is formed from copper.
[0029] As illustrated, for example, in FIG. 1A, the first substrate
10 may have an optional layer or coating 11 applied to a surface
thereof before or after the formation of material 12. The layer or
coating 11 can be formed any suitable material or materials. For
example, it can be formed of a polymer, such as polyethylene
terephthalate (PET), Poly(methyl methacrylate) (PMMA), Polyethylene
naphthalate (PEN), polyamide, polytetrafluoroethylene (PTFE),
polyethylene, and others. The layer or coating may be applied by
any suitable technique, such as adhesive attachment, laminating,
coating, spraying, spin coating, dipping, and the like.
[0030] As further illustrated, for example, in FIG. 1B, a second
substrate 18 can be attached to a second surface of the at least
one layer of material. The second substrate 18 can be formed from
any suitable material, or combination of materials. According to
certain non-limiting examples, the second substrate 18 can be
formed from poly(methyl methacrylate) (PMMA) or polyethylene
terephthalate (PET). Alternatively, the second substrate 18 could
be formed from polyethylene (PE), polyvinylchloride (PVC), glass,
silica, silicon dioxide, silicon, MgO, and others. The second
substrate can be applied to the at least one layer of material by
any suitable technique. Suitable techniques include, but not
limited to adhesive attachment, laminating, coating, spraying, spin
coating, dipping, and the like.
[0031] Next, the above described combination of materials can be
separated or delaminated. This separation or delamination is
achieved through a combination of the application of mechanical
forces, with the assistance of bubbles 22 formed along the
separation interface 16. This mechanism is schematically
illustrated in FIGS. 1C-1C'. The bubbles 12 can be formed by any
suitable mechanism. According to one illustrative embodiment, the
bubbles 22 are formed by the emission of hydrogen due to the
electrolysis of water. This mechanism should be familiar to those
skilled in the art. In water at the negatively charged cathode, a
reduction reaction takes place, with electrons (e-) from the
cathode being given to hydrogen cations to form hydrogen gas (the
half reaction balanced with acid): Reduction at cathode: 2H.sup.+
(aq)+2e.sup.- .fwdarw.H.sub.2 (g). At the positively charged anode,
an oxidation reaction occurs, generating oxygen gas and giving
electrons to the anode to complete the circuit: Anode (oxidation):
2H.sub.2O (l).fwdarw.O.sub.2 (g)+4H.sup.+ (aq)+4e.sup.-.
[0032] Specific optional embodiments for carrying out the
electrolysis reaction noted above will be described later
herein.
[0033] As further noted above, the other component utilized
according to the principles of the present invention to delaminated
or separate the aforementioned materials involve the application of
mechanical force or pressure. This is schematically illustrated by
the block arrows appearing in FIG. 1C-1C'. As illustrated therein,
these forces are applied in directions which diverge from one
another thereby defining a separation angle .alpha.. The
effectiveness and efficiency of the delamination operation can be
influenced through careful selection of the appropriate separation
angle .alpha., as well as the quantity of force applied. According
to certain embodiments of the present invention, the separation
angle .alpha. is about 1 degree to about 90 degrees, or about 5
degrees to about 60 degrees.
[0034] According to a further alternative embodiment of the
technique described above, the at least one layer of material 12
can be further transferred to an additional third substrate. An
example of this alternative procedure is schematically illustrated
in FIGS. 2-3. As illustrated therein, the second substrate acts as
a transfer film 18'. This transfer film 18' can be formed from any
suitable material or combination of materials. It can be formed
from the same material as the second substrate 18, as previously
described above. Alternatively, the transfer film 18' can be formed
from a different material such as heat transfer tape, PET, PE, PVC,
PTFE, PMMA, and others. According to one specific, non-limiting
example, the transfer film 18' can be formed from a
thermally-sensitive adhesive which breaks down upon exposure to
elevated temperatures. This permits a relatively simple mechanism
for releasing the transfer film 18' from the at least one layer
material 12. Subsequent to the separation of the first substrate 10
and optional layer or coating 11 from the at least one layer of
material 12 and transfer film 18', a third substrate 24 is attached
to a surface of the at least one layer material 12. See, e.g., FIG.
2. Next, the transfer film 18' is removed from the at least one
layer of material 12, leaving the at least one layer material 12
disposed upon the end-use substrate 24 (FIG. 3). This removal can
be accomplished by any suitable technique, such as the
above-mentioned heating of a thermally-sensitive adhesive,
mechanical force, chemical separation techniques, chemical
dissolution, chemical etching, photoinduced degradation, and
depolymerization. One advantage of this alternative technique is
that the at least one layer of material 12 can be transferred to a
rigid substrate 24. Of course, the substrate 24 may also be
flexible. The substrate 24 can be formed of any suitable material,
such as a ceramic, metal or polymer. Specific illustrative, and
non-limiting examples, include: silicon, glass, quartz,
semiconductor films on rigid substrates.
[0035] The present invention also encompasses arrangements, which
can be, for example, utilized to carry out the aforementioned
methods. Arrangements constructed according to the principles of
the present invention are illustrated in FIGS. 4-6. Those features
illustrated therein which are also described above in connection
with the aforementioned methods are identified using the same
reference numerals utilized in FIGS. 1-3. As illustrated, for
example, in FIG. 4, the aforementioned method can be implemented as
a roll-to-roll process. The arrangement depicted in FIG. 4 is
suitable for such roll-to-roll processes, but is not limited in
this manner. As illustrated therein, the arrangement can comprise a
number of different combinations of the illustrated features. For
example, a supply roll 26 comprising a roll of composite material
28 can be provided. The composite material can comprise a first
substrate 10, at least one layer material 12 in contact with the
first substrate thereby defining interface 16, a second substrate
18 attached to a second surface of the at least one layer of
material 12, and an optional additional layer or coating 11
disposed on a surface of the first substrate 10. These materials
can take the specific forms or compositions previously mentioned
above.
[0036] This composite material 28 is fed into what amounts to
electrolytic cell by any suitable arrangement, such as one or more
guide rollers 44, 46. The electrolytic cell comprises a vessel 30
containing a solution 32 the solution 32 comprises water and at
least one electrolyte. Any suitable electrolyte, or combination of
electrolytes, can be utilized. According to certain optional
embodiments, the electrolyte comprises, for example, sodium
hydroxide, potassium hydroxide, sulfuric acid, and/or sodium
chloride. The solution comprises a 0.05 mole to 1 mole electrolyte
per liter of water. Alternatively, the solution contains one or
more dopant materials. Suitable dopants include, but are not
limited to, iodine, nitrogen, boron, potassium, arsenic, gallium,
aluminum, indium, chromium, or a number of organic molecules such
as 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane,
7,7,8,8-Tetracyano-2,3,5,6-tetrafluoroquinodimethane (F4-TCNQ). The
solution may contain any suitable amount of dopant, which is highly
dependent upon the dopant used.
[0037] For certain applications (e.g., a transparent conductor),
important properties of the film may be refined and improved by
doping the graphene. For example, with the proper doping, the
electronic carrier density in the graphene will be increased,
increasing conductivity for a transparent contact. As a two
dimensional material, in which all the material is an exposed
surface, graphene may be doped after deposition because there is no
need for the dopant to diffuse to deeper layers (as there are
none).
[0038] Doping of the graphene can be achieved during the transfer
process by incorporating the dopant into the electrolyte solution.
As the graphene is separated from the metal deposition substrate,
it is exposed to the solution. The electrolyte in the solution or
another additive serves as the dopant, adhering to the surface of
the graphene during the process. The separation process does not
require a particular electrolyte to function. The electrolyte
increases the conductivity of the solution to enable charge
transfer through the solution. There are many electrolyte additives
which will increase the solution conductivity. Accordingly,
solution additives may be selected and mixed to achieve a targeted
doping density and an effective graphene-metal separation. The
process can be controlled and refined through control of the
electrolyte makeup and the exposure duration through the geometry
of the separation bath.
[0039] The electrical bias on the graphene, which is part of one of
the electrodes in the electrolysis cell, can be used to draw
dopants to the graphene surface, where it bonds or is adsorbed.
[0040] The process may use more than one electrolyte. Multiple
electrolytes can be used to control doping while maintaining the
solution conductance for the separation process.
[0041] The cell is completed by forming a cathode 34 at the
composite material, and anode 36 located at a distance from the
cathode, or "remotely" relative thereto. In order to optimize the
accuracy and efficiency of the delamination process, the anode can
be located near the point of separation 16. Through placement of
the anode, the formation of hydrogen bubbles can be focused toward
the separation interface 16. In addition, the presence of the
optional coating 11 on the first substrate 10 can serve to prevent
electrolytic reaction on those surfaces of the first substrate 10
which is covered by the coating or layer 11, thereby effectively
focusing the reaction at the interface 16 during the delamination
or separation procedure. The cathode is negatively biased, and the
anode is positively biased, and both are connected to a power
source 38 which provides electrical current flows through the
solution 32. Any suitable power source can be utilized and any
appropriate voltage and current conditions can be applied. For
example, the power source can be constructed and arranged to
generate electrical current having a current density of 0.5
A/cm.sup.2 and voltage of 10V. The voltage is highly dependent upon
the positioning of the electrodes. The essential location for gas
formation to occur is at the point of separation 16. Gas bubbling
will occur at every exposed conductive surface of the composite
material cathode that is immersed in the solution. Power source
construction should account for all current flow at the point of
separation and elsewhere. As a result, hydrogen is emanated in
gaseous form at the cathode 34 (which is the composite material
28), specifically bubbles 22 are formed at least at the interface
16 between the first substrate 10 and the at least one layer of
material 12.
[0042] Alternatively, the gas formation aiding the separation can
be of a different composition by use of different chemistry and
placement of anode and cathode. Other gas bubbling which may be
employed by electrolysis or other electrochemical reactions
include, for example, oxygen, nitrogen, or chlorine.
[0043] As further illustrated in FIG. 4, the arrangement may
further comprise a first pickup roll 40 the first pickup roll is
attached to the second substrate 18 and the at least one layer
material 12 disposed on a surface thereon. Connection of these
materials to the pickup roll 40 can be facilitated by the use of a
leader film 50, as illustrated in FIG. 5. The leader film 50 can be
formed from any suitable material, such as a polymer. Suitable
polymers include PET, PMMA, polyamide, PTFE, and polyethylene.
Through location of the first pickup roll 40, the second substrate
18 and material 12 is mechanically pulled in a first direction. The
first substrate 10, and optional additional layer or coating 11,
can be connected to a second pickup roll 42. As illustrated in FIG.
4, and optional guide roll 48 can be utilized to affect the
direction by which the first substrate 10 and optional additional
layer or coating 11 is pulled by the pickup roll 42. Therefore, as
clearly illustrated in FIG. 4, the at least one layer of material
12 and the second substrate 18 travel away from the separation
roller 46 in different directions. More specifically, according to
the embodiment illustrated in FIG. 4, the first substrate 10 and
optional coating 11 separate from the curved path of the separation
roller 46 surface, while the at least one layer of material 12 and
the second substrate 18 continue to follow the curved surface of
the separation roller 46 for an additional distance before
traveling away from the separation roller 46. Of course this
arrangement can be modified according to alternative embodiments.
For example, the relative position of the rollers and/or layers of
the composite could be switched such that the at least one layer of
material 12 and the second substrate 18 separate from the curved
path of the separation roller 46 surface, while the first substrate
10 and optional coating 11 continued to follow the curved surface
of the separation roller 46 for an additional distance before
traveling away from the separation roller 46.
[0044] Again, the first substrate 10 and optional additional layer
or coating 11 can be attached to the pickup roll 42 by a connection
through a leader film 52, as illustrated in FIG. 5. The leader film
52 can be formed from any suitable material. One such material as a
polymer, for example, any of the materials mentioned above in
connection with the description of leader film 50 will suffice. As
previously explained herein, the direction by which the second
substrate 18 and at least one layer material 12 is pulled diverges
from the direction in which the first substrate 10, and optional
additional layer or coating 11, is pulled. This divergence defines
a separation angle .alpha.. The separation angle can have any
suitable value, depending on the nature of the delamination
procedure, the amount of hydrogen gas or bubbles created at the
interface, and a number of different factors. According to certain
illustrative embodiments, an appropriate separation angle .alpha.
is about 5 degrees to about 60 degrees. Thus, the combination of
diverging mechanical forces and the creation of bubbles 22 at the
separation interface 16 allows for the separation of layers from
the composite material 28. According to the illustrated
non-limiting embodiment, this technique is utilized to separate the
second substrate 18 and at least one layer material 12 from the
first substrate 10 and the optional coating or additional layer
11.
[0045] According to additional alternative aspects of the present
invention, methods and arrangements are provided which constitute
an in-line process. One non-limiting example of such methods and
arrangements is schematically illustrated in FIG. 6. Those features
illustrated therein which are also described above in connection
with the aforementioned methods and arrangements are identified
using the same reference numerals utilized in FIGS. 1-5. The
various materials and components previously described and also
identified in FIG. 6 can have any of the previously described
characteristics compositions and/or configurations. As illustrated,
for example, in FIG. 6, the methods and arrangements can begin with
a first substrate 10. This first substrate 10 can be provided,
optionally, in the form of a supply roll 8. At least one layer of
material 12 is formed on at least part of a surface of the first
substrate 10. The at least one layer of material 12 can be formed
by any suitable technique, as previously described herein.
According to one optional embodiment, the at least one layer of
material 12 can comprise graphene can be deposited by a chemical
vapor deposition technique. The specifics of this technique have
been previously described above in connection with other
embodiments and are incorporated herein by reference. In order to
carry out the chemical vapor deposition of graphene, a chemical
vapor deposition apparatus 54 is provided. The first substrate 10
can be continually fed through the chemical vapor deposition
chamber 54 in order to deposit the at least one layer of material
12 thereon in a continuous manner.
[0046] The first substrate 10 and at least one layer material 12
exits the chemical vapor deposition chamber 54, and the first
substrate 10 is optionally provided with an additional layer or
coating 11 on another surface of the first substrate 10. This
additional layer or coating 11 can be applied by any suitable
technique as previously described herein. The appropriate apparatus
for applying the additional layer or coating 11 schematically
illustrated in FIG. 6 at element 56.
[0047] The first substrate 10 along with the at least one layer of
material 12, and the optional additional layer or coating 11 is
then combined with the second substrate 18. The second substrate 18
can be applied to a second surface of the at least one layer
material in a continuous manner, utilizing any suitable technique.
Exemplary techniques for application of the second substrate have
been previously described above, and are incorporated herein by
reference. The suitable apparatus for the application of the second
substrate 18 according to the aforementioned suitable techniques is
schematically illustrated in FIG. 6 at element 58.
[0048] After application of the second substrate 18, the resulting
composite material 28 comprises a first substrate 10, at least one
layer of material 12, second substrate 18, and optionally, the
additional layer or coating 11. This composite material 28 is then
subjected to a delamination or separation procedure. According to
the illustrative embodiment, the first substrate 10, and optional
additional layer or coating 11 is separated from the at least one
layer of material 12 and the second substrate 18. While any
suitable technique can be utilized for this delamination or
separation, the methods and arrangements of the present invention
described herein are particularly effective in this regard. Thus,
for example, the arrangement of FIG. 4, and its related methods
previously described herein, can be utilized to provide the
continuous delamination or separation noted above. This arrangement
is schematically illustrated in FIG. 6 at element 60. These
delaminated or separated portions can be continually taken up on
pickup rolls, as previously described herein.
[0049] According to another embodiment, the process may be
performed using a first substrate 10, as in the previous
embodiment, except the first substrate 10 can be rigid. The first
rigid substrate 10 can be fed through the chemical vapor deposition
chamber 54 in order to deposit the at least one layer of material
12 thereon, as described earlier (e.g., FIG. 1A. FIG. 6). The first
rigid substrate 10 along with the at least one layer of material
12, and the optional additional layer or coating 11 is then
combined with the second substrate 18 (e.g., FIG. 1B). The second
substrate 18 is composed of a flexible material can be applied to a
second surface of the at least one layer material in a continuous
manner, utilizing any suitable technique. This composite material
28 is then subjected to a delamination or separation procedure as
illustrated in FIG. 1C'. According to the illustrative embodiment,
the first rigid substrate 10, and optional additional layer or
coating 11 is separated from the at least one layer of material 12
and the second substrate 18. According to a further optional
embodiment, the process may continue so as to transfer the at least
one layer of material 12 to a third substrate 24. In this
alternative embodiment, the second substrate 18 acts as a transfer
film 18'. This additional optional procedure and its associated
components of the arrangement contained within the area delineated
by the broken line in FIG. 6. As further illustrated therein, a
third substrate 24 is applied to a surface of the at least one
layer material 12 (see, e.g., FIGS. 2-3). The third substrate 24
can be applied by any suitable technique, as previously described
herein. The apparatus associated with the application of the third
substrate 24 is schematically illustrated in FIG. 6 by element 62.
Subsequently, the transfer film 18' is removed from the at least
one layer of material by any suitable technique. These techniques
include the delamination procedure of the present invention
previously described herein, one embodiment of which being
illustrated in FIG. 4. Additional removal techniques previously
described may also be utilized and are incorporated herein by
reference. The apparatus associated with removal of the transfer
film 18' is schematically illustrated in FIG. 6 by element 64. The
resulting structure is composed of the third substrate 24 and the
at least one layer of material 12 disposed thereon. This
alternative embodiment can be useful in the event that end-use
substrate to which the at least one layer of material 12 is to be
applied is relatively rigid and nature. Thus, the third substrate
24 can be a relatively rigid material formed from any suitable
substance, as previously described in connection with the
description of FIGS. 2-3 above.
[0050] Other embodiments within the scope of the claims herein will
be apparent to one skilled in the art from consideration of the
specification or practice of the invention as disclosed herein. It
is intended that the specification be considered exemplary only,
with the scope and spirit of the invention being indicated by the
claims.
[0051] In view of the above, it will be seen that the several
advantages of the invention are achieved and other advantages
attained.
[0052] As various changes could be made in the above methods and
compositions without departing from the scope of the invention, it
is intended that all matter contained in the above description
shall be interpreted as illustrative and not in a limiting
sense.
[0053] All references cited in this specification are hereby
incorporated by reference. The discussion of the references herein
is intended merely to summarize the assertions made by the authors
and no admission is made that any reference constitutes prior art.
Applicants reserve the right to challenge the accuracy and
pertinence of the cited references.
[0054] Any numbers expressing quantities of ingredients,
constituents, reaction conditions, and so forth used in the
specification are to be understood as being modified in all
instances by the term "about." Notwithstanding that the numeric al
ranges and parameters setting forth, the broad scope of the subject
matter presented herein are approximations, the numerical values
set forth are indicated as precisely as possible. Any numerical
value, however, may inherently contain certain errors or
inaccuracies as evident from the standard deviation found in their
respective measurement techniques. None of the features recited
herein should be interpreted as invoking 35 U.S.C. .sctn.112, 6,
unless the term "means" is explicitly used.
* * * * *