CN220409858U - Laminate and lithographic stack for transferring graphene-metal bilayer to substrate - Google Patents
Laminate and lithographic stack for transferring graphene-metal bilayer to substrate Download PDFInfo
- Publication number
- CN220409858U CN220409858U CN202320287747.4U CN202320287747U CN220409858U CN 220409858 U CN220409858 U CN 220409858U CN 202320287747 U CN202320287747 U CN 202320287747U CN 220409858 U CN220409858 U CN 220409858U
- Authority
- CN
- China
- Prior art keywords
- graphene
- layer
- polymer layer
- metal
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 102
- 239000002184 metal Substances 0.000 title claims abstract description 102
- 239000000758 substrate Substances 0.000 title claims abstract description 79
- 229920000642 polymer Polymers 0.000 claims abstract description 210
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 112
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims description 314
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 9
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 9
- 229920001721 polyimide Polymers 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 32
- 238000005530 etching Methods 0.000 description 30
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 238000003475 lamination Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 238000010030 laminating Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000013047 polymeric layer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
The present application relates to a laminate and a lithographic stack for transferring graphene-metal bilayers to a substrate. The laminate includes a substrate including one or more polymer layers; and a graphene-metal bilayer laminated over at least a portion of the substrate. The lithographic stack includes a graphene-metal bilayer; a first sacrificial layer on the graphene-metal bilayer; and a second sacrificial layer located under the graphene-metal bilayer. The first sacrificial layer comprises a first continuous polymer layer on the graphene layer of the graphene-metal bilayer; and a first discontinuous polymer layer on the first continuous polymer layer. The second sacrificial layer comprises a second continuous polymer layer underlying the metal layer of the graphene-metal bilayer, the first continuous polymer layer and the second continuous polymer layer of two different materials having a dedicated instability between at least two different etchants; and a second discontinuous polymer layer positioned below the second continuous polymer layer.
Description
Priority
The present application claims priority from U.S. provisional application No. 63/314,219, filed on 25 at 2 months 2022, which is incorporated herein by reference in its entirety.
Technical Field
The present application relates to the field of graphene, and more particularly to a laminate and a lithographic stack for transferring graphene-metal bilayers to a substrate.
Background
Graphene, an allotrope of carbon consisting of a single layer of carbon atoms arranged in a two-dimensional honeycomb-like lattice, has mechanical strength (e.g., tensile strength), chemical stability, transparency, carrier mobility, tunable band gap, and conductivity, which makes it useful for a variety of applications. Indeed, many believe that graphene has an important alternative role in the next generation electronics, enabling the development of smaller and lower power devices.
Chemical Vapor Deposition (CVD) has shown promise as a scalable and economical method of growing graphene over catalysts such as copper and nickel. However, the ability to successfully transfer such graphene onto various substrates has been difficult, often resulting in residual metal or metal etching residues on the graphene or defects (e.g., wrinkles or holes) in the graphene itself. In view of the various applications of graphene, the ability to cleanly and successfully transfer graphene onto a variety of substrates remains an important and active area of research. Thus, new methods, such as those used to transfer graphene to various substrates, are needed to realize the full potential of graphene.
Disclosed herein are methods for transferring graphene to various substrates, and lithographic stacks (lithographic stack) and laminates associated therewith.
Disclosure of Invention
A method of transferring a graphene-metal bilayer to a substrate is disclosed. In some embodiments, the method comprises: a first continuous polymer layer application step; a first discontinuous polymer layer application step; a second continuous polymer layer application step; a second discontinuous polymer layer application step; a first etching step; a laminating step; and a second etching step. The first continuous polymer layer application step includes: a first continuous polymer layer is applied to the exposed face of the graphene layer of the graphene-metal bilayer. The first discontinuous polymer layer application step comprises: the first discontinuous polymer layer is applied to the exposed face of the first continuous polymer layer, thereby forming a first continuous polymer layer and a first sacrificial layer of the first discontinuous polymer layer. The second continuous polymer layer applying step includes: a second continuous polymer layer is applied to the exposed face of the metal layer of the graphene-metal bilayer. The second discontinuous polymer layer applying step comprises: a second discontinuous polymer layer is applied to the exposed face of the second continuous polymer layer, thereby forming a second continuous polymer layer and a second sacrificial layer of the second discontinuous polymer layer. The first etching step includes: the first continuous polymer layer is selectively etched through the first discontinuous polymer layer using a first etchant, thereby removing the first sacrificial layer and again exposing the faces of the graphene layer. The lamination step includes: the substrate is laminated by pressing the face of the graphene layer into the surface of the substrate. The second etching step includes: the second continuous polymer layer is selectively etched through the second discontinuous polymer layer using a second etchant, thereby removing the second sacrificial layer and again exposing the face of the metal layer. Upon completion of the second etching step, the graphene-metal bilayer is transferred to the substrate.
In some embodiments, the graphene layer is a monolayer graphene.
In some embodiments, the graphene layer is bilayer graphene.
In some embodiments, the graphene layer is a multilayer graphene having three or more graphene layers.
In some embodiments, the first continuous polymer layer applying step comprises: a first continuous polymer layer is sprayed or spin coated (spin coating) onto the exposed face of the graphene layer.
In some embodiments, the first continuous polymer layer is about 1-2 μm thick after the first continuous polymer layer is applied to the exposed face of the graphene layer in the first continuous polymer layer applying step.
In some embodiments, the first continuous polymer layer is polymethyl methacrylate (PMMA).
In some embodiments, the first discontinuous polymer layer applying step comprises: the first discontinuous polymer layer is pressed into the exposed face of the first continuous polymer layer with heat.
In some embodiments, the first discontinuous polymer layer is penetrated by an array of perforations therethrough. The perforations allow the first etchant to penetrate through the first discontinuous polymer layer during the first etching step.
In some embodiments, the second continuous polymer layer applying step comprises: a second continuous polymer layer is sprayed or spin-coated onto the exposed face of the metal layer.
In some embodiments, the second continuous polymer layer is about 1-2 μm thick after the second continuous polymer layer is applied to the exposed face of the metal layer in the second continuous polymer layer applying step.
In some embodiments, the second continuous polymer layer is polyvinyl alcohol (PVA).
In some embodiments, the second discontinuous polymer layer applying step comprises: the second discontinuous polymer layer is pressed into the exposed face of the second continuous polymer layer with heat.
In some embodiments, the second discontinuous polymer layer is penetrated by an array of perforations therethrough. The perforations allow the second etchant to penetrate through the second discontinuous polymer layer during the second etching step.
In some embodiments, each of the first and second discrete polymeric layers is independently a Polyimide (PI), polyethylene terephthalate (PET), or polyethylene naphthalate (PEN).
In some embodiments, the first etchant is acetone.
In some embodiments, the method further comprises an adhesive applying step. The adhesive applying step includes: an adhesive is applied to the surface of the substrate prior to the lamination step.
In some embodiments, the substrate is a catheter tube or luer connector of a catheter.
In some embodiments, the substrate is a Thermoplastic Polyurethane (TPU).
In some embodiments, the second etchant is water.
Another method of transferring a graphene-metal bilayer to a substrate is also disclosed. In some embodiments, the method includes a first continuous polymer layer application step; a first discontinuous polymer layer application step; a second continuous polymer layer application step; a second discontinuous polymer layer application step; a first etching step; a laminating step; and a second etching step. The first continuous polymer layer application step includes: a first continuous polymer layer of PMMA having a thickness of about 1-2 μm is sprayed or spin-coated onto the exposed face of the graphene layer of single-layer graphene, double-layer graphene or more graphene of the graphene-metal bilayer. The first discontinuous polymer layer application step comprises: a first discontinuous polymer layer of PI, PET or PEN having a thickness of about 25-50 μm is pressed with heat into the exposed face of the first continuous polymer layer. The first discontinuous polymer layer is penetrated by an array of perforations therethrough. The second continuous polymer layer applying step includes: a second continuous polymer layer of PVA having a thickness of about 1-2 μm is sprayed or spin-coated onto the exposed face of the metal layer of the graphene-metal bilayer. The second discontinuous polymer layer applying step comprises: a second discontinuous polymer layer of PI, PET or PEN having a thickness of about 25-50 μm is pressed with heat into the exposed face of the second continuous polymer layer. The second discontinuous polymer layer is penetrated by an array of perforations therethrough. The first etching step includes: the first continuous polymer layer is selectively etched through the perforations of the first discontinuous polymer layer using a first etchant of acetone to again expose the faces of the graphene layer. The lamination step includes: the substrate of TPU is laminated by pressing the face of the graphene layer into the surface of the substrate. The surface of the substrate optionally includes an adhesive applied thereto. The second etching step includes: the second continuous polymer layer is selectively etched through the perforations of the second discontinuous polymer layer using a second etchant of water to again expose the face of the metal layer. Upon completion of the second etching step, the graphene-metal bilayer is transferred to the substrate.
In some embodiments, the substrate is a catheter tube or luer connector of a catheter.
A method of transferring a graphene layer to a substrate is also disclosed. In some embodiments, the method includes a first continuous polymer layer application step; a first discontinuous polymer layer application step; a second continuous polymer layer application step; a second discontinuous polymer layer application step; a first etching step; a laminating step; and a second etching step. The first continuous polymer layer application step includes: a first continuous polymer layer is applied to a first exposed face of the graphene layer. The first discontinuous polymer layer application step comprises: the first discontinuous polymer layer is applied to the exposed face of the first continuous polymer layer, thereby forming a first continuous polymer layer and a first sacrificial layer of the first discontinuous polymer layer. The second continuous polymer layer applying step includes: a second continuous polymer layer is applied to the second exposed face of the graphene layer. The second discontinuous polymer layer applying step comprises: a second discontinuous polymer layer is applied to the exposed face of the second continuous polymer layer, thereby forming a second continuous polymer layer and a second sacrificial layer of the second discontinuous polymer layer. The first etching step includes: the first continuous polymer layer is selectively etched through the first discontinuous polymer layer using a first etchant, thereby removing the first sacrificial layer and again exposing the first face of the graphene layer. The lamination step includes: the substrate is laminated by pressing the first face of the graphene layer into the surface of the substrate. The second etching step includes: the second continuous polymer layer is selectively etched through the second discontinuous polymer layer using a second etchant, thereby removing the second sacrificial layer and again exposing the second face of the graphene layer. Upon completion of the second etching step, the graphene layer is transferred to the substrate.
Also disclosed is a laminate, in some embodiments, comprising a substrate comprising one or more polymer layers, and a graphene-metal bilayer laminated over at least a portion of the substrate.
In some embodiments, the substrate has two dimensions.
In some embodiments, the substrate is a sheet comprising one or more polymer layers.
In some embodiments, the substrate has three dimensions.
In some embodiments, the substrate is a medical device or a portion of a medical device that includes the one or more polymer layers.
In some embodiments, the substrate is a luer connector of a catheter.
In some embodiments, the substrate is a catheter tube of a catheter.
In some embodiments, the graphene-metal bilayer is patterned into one or more electronic devices.
In some embodiments, the one or more electronic devices include at least one single material graphene thermocouple as a temperature sensor.
In some embodiments, the polymer is a TPU.
In some embodiments, the laminate further comprises an adhesive layer between the substrate and the graphene-metal bilayer.
In some embodiments, the graphene-metal bilayer comprises a metal layer on the graphene layer.
In some embodiments, the metal layer is formed of copper or nickel.
In some embodiments, the graphene layer is a monolayer graphene.
In some embodiments, the graphene layer is bilayer graphene.
In some embodiments, the graphene layer is a multilayer graphene having three or more graphene layers.
A lithographic stack for transferring a graphene-metal bilayer to a substrate is also disclosed. In some embodiments, the lithographic stack includes a graphene-metal bilayer, a first sacrificial layer on the graphene-metal bilayer, and a second sacrificial layer under the graphene-metal bilayer. The first sacrificial layer includes a first continuous polymer layer on the graphene layer of the graphene-metal bilayer, and a first discontinuous polymer layer on the first continuous polymer layer. The second sacrificial layer includes a second continuous polymer layer under the metal layer of the graphene-metal bilayer, and a second discontinuous polymer layer under the second continuous polymer layer. The first continuous polymer layer and the second continuous polymer layer of two different materials have exclusive instability between at least two different etchants.
In some embodiments, the graphene layer is a monolayer graphene.
In some embodiments, the graphene layer is bilayer graphene.
In some embodiments, the graphene layer is a multilayer graphene having three or more graphene layers.
In some embodiments, the first continuous polymer layer is about 1-2 μm thick.
In some embodiments, the first continuous polymer layer is PMMA.
In some embodiments, the first discontinuous polymer layer is penetrated by an array of perforations therethrough. The array of perforations allows a first etchant of the at least two etchants to permeate through the first discontinuous polymer to selectively etch the first continuous polymer layer.
In some embodiments, the first etchant is acetone.
In some embodiments, the second continuous polymer layer is about 1-2 μm.
In some embodiments, the second continuous polymer layer is PVA.
In some embodiments, the second discontinuous polymer layer is penetrated by an array of perforations therethrough. The array of perforations allows a second etchant of the at least two etchants to permeate through the second discontinuous polymer to selectively etch the second continuous polymer layer.
In some embodiments, the second etchant is water.
In some embodiments, each of the first discontinuous polymer layer and the second discontinuous polymer layer is independently PI, PET, or PEN.
These and other features of the concepts provided herein will become more readily apparent to those skilled in the art in view of the drawings and the following description, which describe in more detail certain embodiments of such concepts.
Drawings
Fig. 1 illustrates a method of transferring graphene to a substrate, according to some embodiments.
Fig. 2 illustrates a laminate laminated with graphene-metal bilayers as part of a catheter having a catheter tube, according to some embodiments.
Fig. 3 illustrates another laminate with a graphene-metal bilayer patterned into an electronic device as part of a catheter with a catheter tube, according to some embodiments.
Detailed Description
Before some specific embodiments are disclosed in greater detail, it is to be understood that the specific embodiments disclosed herein are not limiting the scope of the concepts provided herein. It should also be understood that a particular embodiment disclosed herein may have features that are readily separable from the particular embodiment and that are optionally combined with or substituted for features of any of the many other embodiments disclosed herein.
With respect to the terms used herein, it is also to be understood that these terms are for the purpose of describing some particular objects and that these terms do not limit the scope of the concepts provided herein. Ordinal numbers (e.g., first, second, third, etc.) are generally used to distinguish or identify different features or steps in a set of features or steps, and do not provide a sequential or numerical limitation. For example, the "first," "second," and "third" features or steps need not necessarily occur in that order, and particular embodiments including such features or steps need not necessarily be limited to three features or steps. In addition, any of the foregoing features or steps may in turn further comprise one or more features or steps, unless otherwise indicated. For convenience, labels such as "left", "right", "top", "bottom", "front", "rear", etc. are used, and are not intended to imply any particular fixed position, orientation or direction, for example. Rather, such indicia are used to reflect, for example, relative position, orientation, or direction. The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.
Reference to, for example, "proximal", "proximal portion" or "proximal section" of a catheter includes a portion or section of the catheter that is intended to be in close proximity to a clinician when the catheter is used with a patient. Likewise, for example, the "proximal length" of the catheter includes the length of the catheter that is intended to be proximal to the clinician when the catheter is used on a patient. For example, the "proximal end" of a catheter includes the end of the catheter that is intended to be close to the clinician when the catheter is used on a patient. The proximal portion, proximal section, or proximal length of the catheter may include the proximal end of the catheter; however, the proximal portion, proximal section, or proximal length of the catheter need not include the proximal end of the catheter. That is, unless the context suggests otherwise, the proximal portion, proximal section, or proximal length of the catheter is not the tip portion or tip length of the catheter.
Reference to, for example, "distal", "distal portion" or "distal section" of a catheter includes a portion or section of the catheter that is intended to be near or within a patient when the catheter is used with the patient. Likewise, for example, the "distal length" of a catheter includes the length of the catheter that is intended to be near or within the patient when the catheter is used with the patient. For example, the "distal end" of a catheter includes the end of the catheter that is intended to be near or within the patient when the catheter is used with the patient. The distal portion, distal section, or distal length of the catheter may include the distal end of the catheter; however, the distal portion, distal section, or distal length of the catheter need not include the distal end of the catheter. That is, the distal portion, distal section, or distal length of the catheter is not the tip portion or tip length of the catheter unless the context suggests otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.
As described above, CVD has shown promise as a scalable and economical method of growing graphene on catalysts such as copper and nickel. However, the ability to successfully transfer such graphene onto various substrates has been difficult, often resulting in residual metal or metal etching residues on the graphene or defects (e.g., wrinkles or holes) in the graphene itself. In view of the various applications of graphene, the ability to cleanly and successfully transfer graphene onto a variety of substrates remains an important and active area of research. Thus, new methods, such as those used to transfer graphene to various substrates, are needed to realize the full potential of graphene.
Methods for transferring graphene to a substrate, and lithographic stacks and laminates related thereto, are disclosed. For example, one method includes transferring a graphene-metal bilayer to a substrate to form a laminate thereof. The method may include: applying a first continuous polymer layer to a graphene layer of a graphene-metal bilayer; applying a first discontinuous polymer layer to the first continuous polymer layer; applying a second continuous polymer layer to the metal layer of the graphene-metal bilayer; applying a second discontinuous polymer layer to the second continuous polymer layer; etching the first continuous polymer layer through the first discontinuous polymer layer using a first etchant; laminating the substrate by pressing the face of the graphene layer into the surface of the substrate; the second continuous polymer layer is etched through the second discontinuous polymer layer using a second etchant, thereby transferring the graphene-metal bilayer to the substrate to form a laminate.
Fig. 1 illustrates a method of transferring graphene to a substrate 100 according to some embodiments. Notably, the method may include one or more steps selected from those shown in fig. 1 or described below. In addition, while many possible steps of a method of transferring graphene to substrate 100 are named herein, it should be understood that the method may include steps described herein but not named. Finally, any of the many possible steps of the methods of transferring graphene to substrate 100 named or described herein may in turn further comprise one or more steps (e.g., sub-steps), unless otherwise indicated.
Although not shown, the method may begin with a graphene growth step. The graphene growth step includes growing a graphene layer 102 on a metal layer 104 by CVD or the like to form a graphene-metal bilayer 106. However, the metal layer 104 on which the graphene layer 102 is grown may be the same or different from the metal layer 104 set forth below, depending on whether one or more additional steps are performed to effectively exchange the metal layers. For example, in the graphene growth step, the graphene layer 102 may be grown on a nickel or copper layer as the metal layer 104, and the nickel or copper layer may actually be exchanged with a palladium or gold layer, which becomes the metal layer 104 set forth below. That is, the metal layer 104 on which the graphene layer 102 is grown may alternatively be removed entirely in one or more additional steps, thereby replacing the graphene-metal bilayer 106 set forth below with the graphene layer 102 alone. Regardless, when present, the metal layer 104 may be formed of gold, silver, palladium, copper, or nickel; copper, however, is generally preferred for use in one or more of the electronic devices described below. The graphene layer 102 grown on the metal layer 104 may be a single-layer graphene, a double-layer graphene, or a multi-layer graphene including three or more graphene layers.
Although not shown, the method may include a first continuous polymer layer application step. The first continuous polymer layer application step includes: a first continuous polymer layer 108 (e.g., polymethyl methacrylate [ PMMA ]) is applied to the exposed face of the graphene layer 102 of the graphene-metal bilayer 106, for example, by spraying or spin coating the first continuous polymer layer 108 onto the exposed face of the graphene layer 102 until it is about 1-2 μm thick, to form a lithographic stack of the graphene-metal bilayer 106 and the first continuous polymer layer 108. Notably, the first continuous polymer layer application step can be distinguished from the second continuous polymer layer application step (step a) shown in fig. 1 starting from the opposite side of the graphene-metal bilayer 106.
Although not shown, the method may include a first discontinuous polymer layer application step, optionally after a first perforation step, to form a first discontinuous polymer layer 110. The first discontinuous polymer layer application step comprises: a first discontinuous polymer layer 110 (e.g., polyimide [ PI ], polyethylene terephthalate [ PET ], or polyethylene naphthalate [ PEN ] of about 25-50 μm, but independent of the second discontinuous polymer layer 120) is applied to the exposed face of the first continuous polymer layer 108, e.g., by pressing the first discontinuous polymer layer 110 into the exposed face of the first continuous polymer layer 108 with heat, to form a lithographic stack 112 of graphene-metal bilayer 106 and first sacrificial layer 114, wherein the first sacrificial layer 114 comprises the first continuous polymer layer 108 and the first discontinuous polymer layer 110. The pressure and temperature applied during the first discontinuous polymer layer application step should be sufficient to bond the graphene-metal bilayer 106 and the first sacrificial layer 114 with sufficient integrity to hold the lithographic stack 112 together for subsequent roll-to-roll or batch processing. Notably, the first discontinuous polymer layer application step can be distinguished from the second discontinuous polymer layer application step (step B) shown in fig. 1 starting from the opposite side of the graphene-metal bilayer 106 having the first continuous polymer layer 108 thereon.
As shown, the method may include a second continuous polymer layer application step (step a). The second continuous polymer layer applying step includes: a second continuous polymer layer 116 (e.g., polyvinyl alcohol [ PVA ]) is applied to the exposed face of the metal layer 104 of the graphene-metal bilayer 106, for example, by spraying or spin coating the second continuous polymer layer 116 onto the exposed face of the graphene layer 102 until it is about 1-2 μm thick, to form a lithographic stack 118 of the graphene-metal bilayer 106, the first sacrificial layer 114, and the second continuous polymer layer 116. Notably, the first continuous polymer layer 108 and the second continuous polymer layer 116 are each made of two different materials, such as PMMA and PVA, which have dedicated (exclusive) instability between at least two different etchants, such as acetone and water, described below.
As shown, the method may include a second discrete polymeric layer application step (step B), optionally after a second perforation step, to form a second discrete polymeric layer 120. The second discontinuous polymer layer applying step (step B) includes applying a second discontinuous polymer layer 120 (e.g., PI, PET, or PEN of about 25-50 μm, but independent of the first discontinuous polymer layer 110) to the exposed face of the second continuous polymer layer 116, e.g., by pressing the second discontinuous polymer layer 120 into the exposed face of the second continuous polymer layer 116 with heat, to form a lithographic stack 122 of graphene-metal bilayer 106, first sacrificial layer 114, and second sacrificial layer 124, wherein the second sacrificial layer 124 includes the second continuous polymer layer 116 and the second discontinuous polymer layer 120. In practice, the lithographic stack 122 includes the graphene-metal bilayer 106, the first sacrificial layer 114 on the graphene-metal bilayer 106, and the second sacrificial layer 124 under the graphene-metal bilayer 106. The pressure and temperature applied during the second discontinuous polymer layer application step should be sufficient to bond the graphene-metal bilayer 106 and the second sacrificial layer 124 with sufficient integrity to hold the lithographic stack 122 together for subsequent roll-to-roll or batch processing.
As shown, the method may include a first etching step (step C). The first etching step (step C) includes selectively etching the first continuous polymer layer 108 through the first discontinuous polymer layer 110 using a first etchant (e.g., acetone at about 40-50 ℃) to remove the first sacrificial layer 114 and again expose the faces of the graphene layer 102 to form the lithographic stack 126 of graphene-metal bilayer 106 and the second sacrificial layer 124. Notably, the first discontinuous polymer layer 110 is permeable to the first etchant. In practice, the first discontinuous polymer layer 110 is perforated by an array of regular or irregular perforations 128, which is up to at least 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of the first discontinuous polymer layer 110. For example, up to at least 33% of the first discontinuous polymer layer 110 may be perforated in the first discontinuous polymer layer 110. The array of perforations 128 allows a first etchant to penetrate through the first discontinuous polymer layer 110 during the first etching step to selectively etch the first continuous polymer layer 108 over the second continuous polymer layer 116 or any other layer present.
Although not shown, the method may include an adhesive applying step. The adhesive applying step includes: adhesive 130 is applied to the surface of substrate 100 prior to the lamination step described below. Notably, depending on the surface chemistry between the face of the graphene layer 102 and the surface of the substrate 100, the laminate 132 described below may or may not benefit from the adhesive 130.
As shown, the method may include a lamination step (step D). The laminating step (step D) includes laminating at least a portion of the substrate 100 by pressing the face of the graphene layer 102 into the surface of the substrate 100 or a portion thereof, optionally with an adhesive 130, to form a laminate 132 of the substrate 100 and the graphene-metal bilayer 106 with the remainder of the lithographic stack 126, i.e., the second sacrificial layer 124, thereon. Notably, the substrate 100 can have two dimensions of a two-dimensional substrate, such as a sheet of polymer layer 134 comprising one or more polymers, such as Thermoplastic Polyurethane (TPU). Alternatively, the substrate 100 may have three dimensions for a three-dimensional substrate, such as a medical device (e.g., catheter, probe, cannula, syringe, etc.) including the one or more polymer layers 134 of the aforementioned polymers. The three-dimensional substrate, or portion thereof, laminated with the graphene-metal bilayer 106 may be non-planar, e.g., curved. In fact, the portion of the three-dimensional substrate laminated with the graphene-metal bilayer 106 may be curved like the conduit tube member 140 of the conduit 139 described below.
As shown, the method may include a second etching step (step E). The second etching step (step E) includes selectively etching the second continuous polymer layer 116 through the second discontinuous polymer layer 120 using a second etchant (e.g., water or deionized water at about 60-80 ℃) to remove the second sacrificial layer 124 and again expose the face of the metal layer 104 to form the laminate 136 of the substrate 100 and the graphene-metal bilayer 106. Notably, the second discontinuous polymer layer 120 is permeable to the second etchant. In practice, the second discontinuous polymer layer 120 is perforated by an array of regular or irregular perforations 138, which is up to at least 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of the second discontinuous polymer layer 120. For example, up to at least 33% of the second discontinuous polymer layer 120 may be perforated in the second discontinuous polymer layer 120. The array of perforations 138 allows a second etchant to penetrate through the second discontinuous polymer layer 120 during the second etching step to selectively etch the second continuous polymer layer 116 over any other layers present.
Notably, the foregoing method of transferring graphene to substrate 100 advantageously enables mass production, such as in a roll-to-roll or batch process.
Upon completion of the second etching step of the method of transferring graphene to substrate 100 described above, graphene-metal bilayer 106 is successfully transferred to at least a portion of substrate 100, forming laminate 136. As described above, the substrate 100 may be a two-dimensional substrate (e.g., a sheet). The resulting laminate from such a two-dimensional substrate comprises a graphene-metal bilayer 106 laminated over at least a portion of the substrate 100 for the two-dimensional laminate. As described above, the substrate 100 may alternatively be a three-dimensional substrate (e.g., a medical device). The laminate resulting from such a three-dimensional substrate includes a graphene-metal bilayer 106 laminated over at least a portion of the substrate 100 for the three-dimensional laminate.
Fig. 2 and 3 illustrate a laminate 136 as part of a catheter 139 having a catheter tube 140, laminated with a graphene-metal bilayer 106, according to some embodiments.
As shown, the laminate 136 includes a portion of the conduit 139 laminated with the graphene-metal bilayer 106. Although the portion of the catheter 139 shown in fig. 2 laminated with the graphene-metal bilayer 106 is at least a proximal portion of the catheter tube 140 (up to the entirety of the catheter tube 140), the portion of the catheter 139 laminated with the graphene-metal bilayer 106 may additionally or alternatively be a hub 142, one or more extension legs 144, or one or more luer connectors 146. As shown in fig. 3, catheter tube 140 may be advantageously laminated in at least a distal portion thereof to include one or more electronics. Indeed, the graphene-metal bilayer 106 may be patterned in one or more patterning steps, either before or after the lamination step, which in turn may include various masking and etching steps to create one or more electronic devices. The one or more electronic devices may include at least one single material graphene thermocouple 148 as a temperature sensor. Such thermocouples may be similar to those described in the following documents: harzheim, a.,F.,Gotsmann,B.,van der Zant,H.,&gehring, P. (2020) & single material graphene thermocouple, & advanced functional materials,30 (22) 2000574 (original reference: harzheim, A., & gt>F.,Gotsmann,B.,van der Zant,H.,&Gehring, p. (2020). Single-Material Graphene thermo-couplings, advanced Functional Materials,30 (22), 2000574), thermocouple 148 includes: for example, a graphene layer 102 patterned into a narrower leg 150 and a wider leg 152, having different seebeck coefficients, coupled together with a thermocouple junction therebetween; and a metal layer 104 patterned into electrical contacts 154 and leads extending therefrom.
Although certain embodiments have been disclosed herein, and although specific embodiments have been disclosed in considerable detail, these specific embodiments are not intended to limit the scope of the concepts provided herein. Additional adaptations and/or modifications will occur to those skilled in the art and are, in a broader aspect, contemplated. Accordingly, changes may be made to the specific embodiments disclosed herein without departing from the scope of the concepts presented herein.
Claims (25)
1. A laminate, comprising:
a substrate comprising one or more polymer layers; and
a graphene-metal bilayer laminated over at least a portion of the substrate,
wherein the substrate is a medical device or a part of a medical device comprising the one or more polymer layers.
2. The laminate of claim 1, wherein the substrate is a luer connector of a catheter.
3. The laminate of claim 1, wherein the substrate is a conduit tube of a conduit.
4. The laminate of claim 1, wherein the graphene-metal bilayer is patterned into one or more electronic devices.
5. The laminate of claim 4, wherein the one or more electronic devices comprise at least one single material graphene thermocouple as a temperature sensor.
6. The laminate of claim 1, wherein the polymer is a thermoplastic polyurethane.
7. The laminate of claim 1, further comprising an adhesive layer between the substrate and the graphene-metal bilayer.
8. The laminate of claim 1, wherein the graphene-metal bilayer comprises a metal layer on a graphene layer.
9. The laminate of claim 8, wherein the metal layer is formed of copper or nickel.
10. The laminate of claim 8, wherein the graphene layer is a monolayer graphene.
11. The laminate of claim 8, wherein the graphene layer is bilayer graphene.
12. The laminate of claim 8, wherein the graphene layer is a multi-layer graphene having three or more graphene layers.
13. A lithographic stack for transferring a graphene-metal bilayer to a substrate, comprising:
a graphene-metal bilayer;
a first sacrificial layer on the graphene-metal bilayer, the first sacrificial layer comprising:
a first continuous polymer layer on the graphene layer of the graphene-metal bilayer; and
a first discontinuous polymer layer on the first continuous polymer layer; and a second sacrificial layer under the graphene-metal bilayer, the second sacrificial layer comprising:
a second continuous polymer layer under the metal layer of the graphene-metal bilayer, the first and second continuous polymer layers of two different materials having a proprietary instability between at least two different etchants; and
a second discontinuous polymer layer positioned below the second continuous polymer layer.
14. The lithographic stack of claim 13, wherein the graphene layer is a monolayer graphene.
15. The lithographic stack of claim 13, wherein the graphene layer is bilayer graphene.
16. The lithographic stack of claim 13, wherein the graphene layer is a multi-layer graphene having three or more graphene layers.
17. The lithographic stack of claim 13, wherein the first continuous polymer layer is 1-2 μιη thick.
18. The lithographic stack of claim 13, wherein the first continuous polymer layer is polymethyl methacrylate.
19. The lithographic stack of claim 13, wherein the first discontinuous polymer layer is penetrated by an array of perforations therethrough, thereby allowing a first etchant of the at least two different etchants to penetrate through the first discontinuous polymer in order to selectively etch the first continuous polymer layer.
20. The lithographic stack of claim 19, wherein the first etchant is acetone.
21. A lithographic stack according to claim 13, wherein said second continuous polymer layer is 1-2 μm.
22. The lithographic stack of claim 13, wherein the second continuous polymer layer is polyvinyl alcohol.
23. The lithographic stack of claim 13, wherein the second discontinuous polymer layer is penetrated by an array of perforations therethrough, thereby allowing a second etchant of the at least two different etchants to penetrate through the second discontinuous polymer in order to selectively etch the second continuous polymer layer.
24. The lithographic stack of claim 23, wherein the second etchant is water.
25. The lithographic stack of claim 13, wherein each of the first and second discontinuous polymer layers is independently a polyimide, polyethylene terephthalate, or polyethylene naphthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202320287747.4U CN220409858U (en) | 2023-02-21 | 2023-02-21 | Laminate and lithographic stack for transferring graphene-metal bilayer to substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202320287747.4U CN220409858U (en) | 2023-02-21 | 2023-02-21 | Laminate and lithographic stack for transferring graphene-metal bilayer to substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN220409858U true CN220409858U (en) | 2024-01-30 |
Family
ID=89643859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202320287747.4U Active CN220409858U (en) | 2023-02-21 | 2023-02-21 | Laminate and lithographic stack for transferring graphene-metal bilayer to substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN220409858U (en) |
-
2023
- 2023-02-21 CN CN202320287747.4U patent/CN220409858U/en active Active
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101652787B1 (en) | Method of fabricating large-scale graphene and transfering large-scale graphene | |
| CN103477399B (en) | Possess with Graphene be main constituent the transfer sheet of nesa coating and manufacture method, transparent conductor | |
| JP5097172B2 (en) | Graphene layer peeling method, graphene wafer manufacturing method, and graphene element manufacturing method | |
| US20200170108A1 (en) | Scalable, Printable, Patterned Sheet Of High Mobility Graphene On Flexible Substrates | |
| KR101716468B1 (en) | Tranfering method for graphene using self-adhesive film | |
| US10857773B2 (en) | System for transfer of nanomembrane elements with improved preservation of spatial integrity | |
| KR20120054383A (en) | Method for transferring grapheme and apparatus for transferring grapheme | |
| WO2011024539A1 (en) | Expansion device using carbon nanotube and method for manufacturing same | |
| TW201039297A (en) | Method for isolating a flexible substrate from a carrier and method for fabricating an electric device | |
| CN113701926B (en) | Flexible pressure sensor based on fold and crack structure and preparation method thereof | |
| TWI379625B (en) | Conductor-clad laminate, wiring circuit board, and processes for producing the same | |
| TW201627247A (en) | Transfer of monolayer graphene onto flexible glass substrates | |
| CN220409858U (en) | Laminate and lithographic stack for transferring graphene-metal bilayer to substrate | |
| JP2011066057A (en) | Thermal diffusion sheet, and method and device for manufacturing the same | |
| CN116653374A (en) | Method for transferring graphene to a substrate and related lithographic stacks and laminates | |
| KR101579935B1 (en) | Method and apparatus for forming and transfering pattern of nanofilm using imprint | |
| KR101926488B1 (en) | Method of manufacturing grapheme film | |
| KR20130138877A (en) | Method for manufacturing pattern, pattern manufactured by the same and application using the same | |
| TW201247422A (en) | Method of transferring a graphene film | |
| EP2519964A2 (en) | Method of using a mask to provide a patterned substrate | |
| KR102211774B1 (en) | Method of preparing a Touch screen panel and Touch screen panel prepared by using the same | |
| Yang et al. | “Cut-and-paste” method for the rapid prototyping of soft electronics | |
| KR101867377B1 (en) | Nanofilm transfer method and apparatus | |
| KR101915192B1 (en) | Method for gaining graphene | |
| WO2015064481A1 (en) | Method for producing carbon nanotube sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |