The subject matter pertains generally to laminate structures and the field of electrical connectors and methods of manufacturing electrical connectors.
Electrical connectors can have many forms and applications. Copper and copper alloys are the most widely used base materials for electrical connectors used in switches and brushes. These electrical connectors experience wear due to the mating of contacts and mechanical vibration, thus limiting their longevity. It is known from the study of tribology that a hard material is more wear resistant than a soft material.
It is desirable to develop additional materials for improving the wear properties of electrical connectors while not reducing electrical conductivity.
Provided herein is a layered metal-graphene-metal nanolaminate electrical connector with improved wear performance and reduced friction. Provided is a laminate or electrical connector having a chemical vapor deposition (CVD) monolayer graphene sheet sandwiched between two copper layers resulting in a decrease in friction of coefficient and an improvement in wear resistance of an electrical contact.
Provided is a laminate comprising: a base layer comprising copper; a graphene monolayer disposed on the base layer; and a top layer comprising copper disposed on the graphene monolayer; wherein the laminate exhibits a reduced coefficient of friction in comparison to a copper-copper laminate without a graphene monolayer.
Embodiments of this laminate include:
The laminate wherein the top layer has a thickness from 50 to 500 nm.
The laminate further comprising an additional graphene monolayer disposed on the top layer and an additional copper layer disposed on the additional graphene monolayer.
The laminate further comprising one or more additional substrate layers on which the copper base layer is superimposed.
Also provided is a laminate comprising n graphene monolayers and n+1 copper layers, wherein the graphene monolayers alternate with the copper layers, and n is an integer from 1 to 10.
Embodiments of this laminate include:
The laminate wherein one of the copper layers comprises a thicker substrate layer, and the rest of the copper layers are nanolayers, each independently having a thickness from 50 to 500 nm.
The laminate wherein the substrate layer is a surface layer.
The laminate wherein the substrate layer is the center layer of the laminate.
The laminate comprising at least one additional layer.
Embodiments of either laminate include:
The laminate wherein additional substrate layers comprises a bulking or backing layer wherein the base layer of copper has a thickness from 50 to 500 nm.
The laminate wherein the one or more additional substrate layer comprises a material selected from the group consisting of a metal other than copper, nonconductive materials, or semiconductor materials.
The laminate in the form of a sheet.
The laminate in the form of a three-dimensional shaped object.
The laminate used as an electrical connector.
The laminate wherein the laminate comprises a portion of an electrical circuit.
The laminate wherein the laminate comprises a portion of microcircuit.
The laminate wherein the laminate comprises a portion of a microchip.
The laminate in electrical connectivity to one or more other electrical components to provide a circuit; including wherein the circuit comprises a microcircuit.
The laminate wherein a first laminate is disposed in electrical connectivity with a second laminate of different configuration from the first laminate to provide a portion of an electrical circuit; including the laminate wherein the first and second laminates are in the form of sheets; or the laminate wherein a first shaped laminate is disposed in electrical connectivity with a second shaped laminate of different shape from the first shaped laminate to provide a portion of an electrical circuit.
In one embodiment, the laminate structure is fabricated by growing a continuous monolayer graphene on a copper substrate via chemical vapor deposition process. A thin layer of copper is deposited via physical vapor deposition on the grown graphene to synthesize a Cu-Graphene-Cu laminate.
Also provided is a method for preparing the laminates described above, the method comprising providing a base layer comprising copper; disposing a graphene monolayer on the base layer; and disposing a top layer comprising copper on the graphene monolayer.
Embodiments of the method include:
The method wherein disposing the graphene monolayer on the base layer comprises chemical vapor deposition of carbon atoms on the base layer.
The method wherein disposing the top layer comprising copper on the graphene monolayer comprises physical vapor deposition of copper atoms on the graphene monolayer.
The method further comprising electropolishing the base layer prior to disposing the graphene monolayer on the base layer.
The method further comprising sequentially disposing at least one additional graphene monolayer on the top layer; and disposing at least one additional layer comprising copper on the at least one additional graphene monolayer to provide a laminate comprising alternating graphene monolayer and copper layers on the base layer.
Also provided is a method for improving the wear performance or reducing friction of an electrical connector, the method comprising providing a base layer comprising a copper electrical connector; disposing a graphene monolayer on the base layer; and disposing a top layer comprising copper on the graphene monolayer.
Embodiments of the method include:
The method wherein disposing the graphene monolayer on the base layer comprises chemical vapor deposition of carbon atoms on the base layer.
The method wherein disposing the top layer comprising copper on the graphene monolayer comprises physical vapor deposition of copper atoms on the graphene monolayer.
The method further comprising electropolishing the base layer prior to disposing the graphene monolayer on the base layer.
The method further comprising sequentially disposing at least one additional graphene monolayer on the top layer; and disposing at least one additional layer comprising copper on the at least one additional graphene monolayer to provide a laminate comprising alternating graphene monolayer and copper layers on the base layer.
Experiments demonstrate that graphene incorporated into the contact improves the reliability of the electrical connectors while reducing wear and failure.
Described herein are materials and methods for improving the wear performance of electrical contacts and connectors.
Copper (Cu) and copper alloys are the most widely used base material for electrical contacts and connectors. As shown in
An alternative material may involve graphene. Graphene (abbreviated Gr) is a two-dimensional material consisting of an atomically thin sheet of carbon atoms covalently bonded in a honeycomb (hexagonal) lattice. Graphene exhibits exceptional mechanical properties. It is the strongest material in the world, with a maximum strength of 100 GPa. This is demonstrated through the nano-indentation of free-standing circular membranes.
Graphene also acts as a solid lubricant to reduce wear.
A matrix composite of graphene platelets in a metal (Cu) matrix is shown schematically in
A structure such as shown in
Provided herein is a laminate having a chemical vapor deposition (CVD) monolayer graphene sheet sandwiched between two copper layers resulting in a decrease in friction of coefficient and an improvement in wear resistance of the laminate compared to structures without an embedded graphene layer. In one embodiment the laminate is used as an electrical connector.
Chemical vapor deposition (CVD) can be used to prepare monolayer (one atom thick) graphene on substrates in an industrially scalar method. CVD facilitates the growth of large areas of graphene that conforms to a metal substrate of choice such as copper. CVD is conducted by passing methane through a quartz tube equipped with gas inlets at high heat where the methane reacts to provide atomic carbon, which is deposited on the substrate. The resulting graphene film is polycrystalline and may have defects in the form of a one dimensional grain boundary such as bilayer or trilayer patches. CVD of the graphene may be conducted at temperatures from about 800° C. to about 1200° C. for about 15 to 45 minutes. Shorter CVD periods may result in gaps in the monolayer and longer periods may increase the incidence of bilayer, trilayer and multilayer patch defects in the graphene sheet. A second copper layer can be deposited onto the graphene layer by physical vapor deposition, such as by sputtering, in nanolayer thickness, such as from about 50 to about 500 nm, or from about 100 nm to 400 nm.
Physical vapor deposition (PVD) includes a variety of vacuum deposition methods that can be used to produce thin films and coatings. PVD is characterized by a process in which the material goes from a condensed phase to a vapor phase and then back to a thin film condensed phase. The most common PVD processes are sputtering and evaporation. Examples of PVD include cathodic arc deposition, in which a high-power electric arc discharged at a target (source) material blasts away some into highly ionized vapor to be deposited onto the workpiece; electron beam physical vapor deposition, in which the material to be deposited is heated to a high vapor pressure by electron bombardment in high vacuum and is transported by diffusion to be deposited by condensation on the (cooler) workpiece; evaporative deposition in which the material to be deposited is heated to a high vapor pressure by electrical resistance heating in high vacuum; pulsed laser deposition in which a high-power laser ablates material from a target into a vapor for subsequent deposition; and sputter deposition, in which a glow plasma discharge (usually localized around a source target by a magnet) bombards the material, sputtering some away as a vapor for subsequent deposition; and pulsed electron deposition, in which a highly energetic pulsed electron beam ablates material from the source target generating a plasma stream under nonequilibrium conditions.
A flow scheme of the fabrication of the fabrication process is shown in
The result is a three-layer laminate comprising a graphene monolayer sandwiched between two copper layers, at least one of which is a nanolayer having thickness from about 50 nm to about 500 nm.
The 3-step fabrication process can be repeated to provide additional graphene monolayer(s) and copper nanolayer(s) in the laminate. For instance, repeating the process one additional time provides a 5-layer laminate as shown in
In some embodiments, the laminate may further comprise one or more additional substrate layers on which the copper substrate or base layer is superimposed. The additional substrate layers may comprise a bulking or backing layer that allows the first copper layer to be thinner. For example, a layer of copper can be sputtered onto an additional substrate layer to provide a nanolayer of copper on the additional substrate layer. The additional substrate layer(s) may comprise a metal other than copper, such as gold, silver, platinum, steel, etc., nonconductive (insulating) materials, or semiconductor materials. The substrate may comprise silicon and/or silicon dioxide. The additional substrate layer may be a sacrificial layer that is not included in the final laminate, or it may be included in the final laminate.
The embodiments shown in the figures are shown schematically in the form of sheets, but the laminate is not limited to sheets. In some embodiments, the substrate and the resulting laminate may be a three-dimensional shaped object. The shaped object may be molded, machined, 3D printed or otherwise shaped to provide the desired shape. The shaped object may comprise a conventional metal (copper) electrical connector of any desired shape to match its intended use in an electrical circuit or device. Provided is a method for improving the wear performance or reducing friction of an electrical connector, the method comprising providing a base layer comprising a copper electrical connector; disposing a graphene monolayer on the base layer; and disposing a top layer comprising copper on the graphene monolayer. Application of a graphene monolayer and a nanolayer of copper as described herein can provide additional wear prevention to the connector without adding significant thickness or reducing conductivity.
The Cu-Gr-Cu laminates described herein may be particularly suitable for use in microcircuits, such as in microchips. An initial copper nanolayer may be applied by PVD, such as by sputtering, onto a substrate layer, followed by application of a graphene monolayer by CVD and a copper nanolayer by PVD as described herein. Additional graphene monolayer(s) and copper nanolayer(s) may be applied to provide multilayer laminates. The substrate may be masked to provide a layout for the laminate that corresponds to the desired conductivity pathway for at least a portion of the microcircuit.
The laminate may be in electrical connectivity to one or more other electrical components to provide a circuit, such as a microcircuit. In some embodiments, a first laminate, such as on a substrate, can be disposed in electrical connectivity with a second shaped laminate of different configuration from the first shaped laminate to provide a portion of an electrical circuit, such as a microcircuit. The first and second laminates may be in the form of sheets or three-dimensional shaped objects.
In a specific embodiment, the laminate structure was fabricated by growing a continuous graphene monolayer on a 1-mm thick Cu sheet (Alpha Aesar, 99.9999%) via chemical vapor deposition process at 1000° C. for 30 minutes. During the growth process, methane and hydrogen flow at 5 sccm and 10 sccm respectively while maintaining a pressure of 0.2-0.3 Torr. Next, a 100 nm layer of Cu was deposited via physical vapor deposition on the grown graphene monolayer to synthesize a Cu-Graphene-Cu laminate.
The frictional properties of the composite were measured using a scratch test method on a nanoindenter, such as a G200 Agilent nanoindenter, shown schematically in
The scratch test was performed on two different samples, a Cu-Gr-Cu laminate, and a graphene-free Cu—Cu laminate. A plot of the load compared to the scratch distance for the samples is shown in
Scratch tests along the face orientation have a higher CoF compared to the edge orientation for a similar average displacement into the surface, as shown in
A Cu-Gr-Cu laminate structure shows an increased resistance to wear compared to a bare copper structure (no graphene) and a graphene-coated structure. The schematic of this test is shown in
The load displacement curve for a series of shallow indents is shown in
While the disclosed subject matter has been described in terms of particular variations and illustrative figures, those of ordinary skill in the art will recognize that the disclosed subject matter is not limited to the variations or figures described. In addition, where methods and steps described above indicate certain events occurring in certain order, those of ordinary skill in the art will recognize that the ordering of certain steps may be modified and that such modifications are in accordance with the variations of the disclosed subject matter. Additionally, certain of the steps may be performed concurrently in a parallel process when possible, as well as performed sequentially as described above. Therefore, to the extent there are variations of the disclosed subject matter, which are within the spirit of the disclosure or equivalent to the disclosed subject matter found in the claims, it is the intent that this patent will cover those variations as well.
This Non-provisional Application claims priority from U.S. Provisional Application No. 62/506,402, filed May 15, 2017, and U.S. Provisional Application No. 62/518,844, filed Jun. 13, 2017, both of which are incorporated by reference in their entirety herein.
This invention was made with government support under grant 1363093 awarded by the NSF. The government has certain rights in the invention.
Number | Date | Country | |
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62506402 | May 2017 | US | |
62518844 | Jun 2017 | US |