The present invention relates to thin membranes (such as graphene) and methods of aligned transfer of such thin membranes to substrates. The present invention further relates to devices that include such thin membranes.
Graphene sheets—one-atom-thick two-dimensional layers of sp2-bonded carbon—have a range of unique electrical, thermal and mechanical properties. Just as glass windows are supported on all sides by a stronger frame structure (such as a wall), a “graphene window” is graphene supported on all sides by a much thicker material (typically metal). Graphene windows can be any shape, such as a round shape like a drum. The graphene of a graphene window generally is grown on its supporting metal (such as Cu).
An advantage of graphene windows is that they can be transferred to another substrate (such as the metal-oxide portion of a graphene-drum switch) without the use of liquid (which tends to tear the graphene when the liquid dries). A reason the graphene windows of the present invention are larger and cleaner than any known to be reported in the literature is because a production method has been developed that among other improvements, uses very pure metal foils as a starting point. In addition to graphene-drum switches, graphene windows can be used to make graphene pumps and other NEM devices. As the terms “thin membrane window,” “graphene windows,” and the like are used herein, once these have been transferred to another substrate, they are still referred to as “thin membrane window,” “graphene windows,” etc.
In addition to graphene windows that are larger and cleaner, it has been found that coating at least one side of the graphene with a few nanometer thick layer of metal can lower the membrane's electrical resistance by an order of magnitude, which is advantageous when making electrical devices out of graphene (such as graphene-based low-loss switches).
Graphene windows, method for making same, and devices containing same are described in co-pending U.S. Patent Appl. No. 61/427,011 to Everett et al. (“the '011 Patent Application”), which is incorporated herein in its entirety.
The present invention relates to thin membranes (such as graphene windows) and methods of aligned transfer of such thin membranes to substrates. The present invention further relates to devices that include such thin membranes.
The present invention relates to an efficient, facile method for transferring thin membranes to substrates following alignment of the membranes to substrate features. In embodiments of the present invention, this method has been used to transfer arrays of single-layer graphene windows onto silicon target test chips. The transfer method of the present invention has advantages over other transfer methods in that it eliminates steps that chemically or physically modify the thin membrane when transferred onto the target substrate, such as the need to immerse one or both sides of the transferred thin membrane in a liquid. The present invention also provides for the ability to control the composition of the ambient environment during the thin membrane transfer. Such environmental control is useful for systems where, for example, effective transfer yield, particulate contamination, oxidative corrosion processes, and/or gaseous dielectric strength need to be controlled.
In general, in one aspect, the invention features a method that includes back etching a first thin membrane substrate to form a first thin membrane window array. The first thin membrane substrate has a first side and a second side. The first thin membrane window array is formed on the second side of the first thin membrane substrate. The method further includes adhering a first side of a flexible substrate to the first side of the first thin membrane substrate. The method further includes aligning the first thin membrane window array to a first side of a target substrate. The first side of the target substrate includes a first target feature array to which the first thin membrane window array is aligned. The method further includes contacting the first thin membrane window array to the first side of the target substrate while maintaining alignment. The method further includes transferring the first thin membrane window array to the first target feature array on the first side of the target substrate.
Implementations of the inventions can include one or more of the following features:
The method can further include adhering a first side of a rigid substrate to a second side of the flexible substrate.
The rigid substrate can be transparent.
The rigid substrate can include glass.
The flexible substrate can be transparent.
The flexible substrate can be an elastomer.
The elastomer can include cross-linked polydimethylsiloxane.
The method can further include removing the flexible substrate and the first thin membrane substrate while maintaining the first thin membrane window array on the first target feature array of the target substrate.
The first thin membrane substrate can be a metal.
The mean surface roughness can be less than 0.5 microns.
The metal can be copper.
The first thin membrane window array can include graphene.
The first thin membrane window array can include graphene oxide.
The first thin membrane window array can include a graphene/thin metal film composite.
The first thin membrane window array can have no more than one thin membrane window.
The first thin membrane window array can include more than one thin membrane windows.
The first thin membrane substrate can include a first set of alignment marks. The target substrate can include a second set of alignment marks. The step of aligning the first thin membrane window array to a first side of a target substrate can include aligning the first set of alignment marks with the second set of alignment marks.
The method can further include transferring a second thin membrane window array to the first side of the target substrate.
The step of transferring the second thin membrane window array to the first side of the target substrate can include aligning the second thin membrane window array to the first side of a target substrate. The second thin membrane window array can be located on a second side of the second thin membrane window substrate. The first side of the target substrate can include a second target feature array to which the second thin membrane window array is aligned. The step of transferring the second thin membrane window array to the first side of the target substrate can include contacting the second side of the second thin membrane window array against the first side of the target substrate while maintaining alignment. The step of transferring the second thin membrane window array to the first side of the target substrate can include transferring the thin membranes of the second thin membrane window array to the second target feature array on the first side of the target substrate.
The second thin membrane window array can be aligned with the first thin membrane window array.
The second thin membrane window array can be aligned with the first thin membrane window array to create an array of transferred two-layer membrane features.
The second thin membrane window array can be offset from the first thin membrane window array.
The method can further include utilizing a gas pressure differential to assist in the transfer of the thin membranes to the first target feature array.
The can further include utilizing a vapor contained within a gas during transfer. The gas can be air. The ratio of partial pressure of the vapor to the saturation pressure can be in excess of 0.2. The vapor can include water in an amount that is at least about 20% relative humidity.
The method can further include aligning a first side of the second target substrate to the first thin membrane window array on the first side of the target substrate. The first side of the second target substrate can have a second target feature array on the first side of the second target substrate. The method can further include contacting the first thin membrane window array to the first side of the second target substrate while maintaining alignment such that the first thin membrane window array is sandwiched between the target substrate and the second target substrate.
The first target substrate can include an array of electromechanical switches.
The first target substrate can include an array of electromechanical sensors.
The second target substrate can include an array of electromechanical switches.
The second target substrate can include an array of electromechanical sensors.
The graphene windows transferred to the target substrate can be used in a graphene pump.
The graphene windows transferred to the target substrate can be used in a NEMS device.
The present invention relates to thin membranes (such as graphene windows) and methods of aligned transfer of such thin membranes to substrates. The present invention further relates to devices that include such arrays.
The '011 Patent Application describes methods to produce graphene and methods for making graphene windows and devices containing such graphene windows. In the methods described herein, the free standing thin membranes utilized are free standing graphene windows prepared following the methods described in the '011 Patent Application. While graphene windows are discussed and described herein, the thin membranes utilized in the present invention are not limited to only graphene windows. Rather, the thin membrane can be made of any thin material that is sufficiently mechanically robust (such as, for example, a thin membrane of graphene oxide or any combination of materials that form a sufficiently robust composite material, such as a thin membrane of graphene and graphene oxide) to span the lateral dimensions of the target substrate feature. Thus, the discussion of graphene windows is for exemplary purposes and is not intended to limit the scope of the present invention.
Furthermore, the thin membrane is generally a membrane that is atomically thin. For single-layer graphene membranes, the thickness is sub-nanometer; membranes containing multiple graphene layers, graphene/graphene oxide composites, and graphene/metal films are typically on the order of about 1 to about 25 nanometers.
As shown by arrows 109, the graphene window/elastomeric substrate 205 is paired with a second substrate 107 (such as a chip). Second substrate 107 has target features (target features 108a, 108b, and 108c). During the pairing of the graphene window/elastomeric substrate 205 with the second substrate 107, the individually addressable chambers (addressable chambers 206a, 206b, and 206c) are aligned with the target features (target features 108a, 108b, and 108c, respectively) and then brought in contact with one another.
This liquid-less transfer method is useful because the elastomeric substrate conforms to the metal foil/graphene window array and also to the underlying substrate/chip during transfer, thereby providing uniform contact. Additionally, with respect to the method depicted in
In the orientation shown in
Using lateral translation (including rotation), alignment between assembly 406 and substrate 407 is achieved. As depicted in
The assembly 406 can then be removed from the assembly/substrate 413 with the graphene window 404 remaining on substrate 407 and in contact with target feature 408 (as depicted in
By this method, a thin membrane window array (such as a graphene window array) can be transferred onto the substrate with alignment/registry to the substrate. The thin membrane window array can be one thin membrane window or can be more than one thin membrane window. Thus, by this process, multiple thin membranes can be transferred while aligned to the substrate target features by simultaneously transferring an array of multiple thin membranes onto the substrate (such as by using Cu foil having multiple thin membrane windows).
Alignment marks patterned into the Cu foil and on the target chip allow translation of each surface relative to the other using standard translation stages (x, y, z, and θ) before bringing the thin membranes into direct contact with the underlying target features on the substrate/chip.
Multiple thin membrane windows arrays can be transferred by a series of aligned transfers, which can be used to increase the density of the thin membranes transferred onto the substrate beyond what is capable through creation of a thin membrane window array on the supporting metal foil.
As depicted in
Similar to as shown in
Similar to as shown in
Additional alignment and transfer steps can be performed to further increase transfer density. Thus, by this approach, a higher density of graphene windows is attainable.
Using the alignment and transfer methods discussed above, this results in transferred graphene windows (i) 601a, (ii) 601b, and (iii) 601c on the on substrate target features (i) 607a and 607aa, (b) 607b, and (c) 607c, respectively (assembly 612 in
As depicted in
A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
While embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described and the examples provided herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Accordingly, other embodiments are within the scope of the following claims. The scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims.
The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated herein by reference in their entirety, to the extent that they provide exemplary, procedural, or other details supplementary to those set forth herein.