Stable IR Transparent Conductive Graphene Hybrid Materials and Methods of Making

Abstract

A method of making a transparent conductive graphene hybrid, comprising the steps of providing a PMMA/Graphene hybrid, functionalizing the PMMA/Graphene hybrid, providing a transparent substrate, oxidizing the transparent substrate, treating the oxidized substrate and forming a functionalized substrate, applying the PMMA/Graphene hybrid to the functionalized substrate, removing the PMMA, and forming a transparent conductive graphene hybrid. A transparent conductive graphene hybrid comprising a transparent substrate, wherein the transparent substrate is oxidized, and wherein the transparent substrate is treated with TFPA-NH2 to form a functionalized substrate, and a layer of graphene on the functionalized substrate.

Claims

1. A method of making a transparent conductive graphene hybrid, comprising the steps of: providing a PMMA/Graphene hybrid; functionalizing the PMMA/Graphene hybrid; providing a transparent substrate; oxidizing the transparent substrate and forming an oxidized substrate; treating the oxidized substrate and forming a functionalized substrate; applying the PMMA/Graphene hybrid to the functionalized substrate; removing the PMMA; and forming a transparent conductive graphene hybrid.

2. The method of making a transparent conductive graphene hybrid of claim 1 wherein said step of treating the oxidized substrate comprises TFPA-NH2.

3. The method of making a transparent conductive graphene hybrid of claim 2 wherein said step of oxidizing the transparent substrate and forming an oxidized substrate comprises plasma or chemicals.

4. The method of making a transparent conductive graphene hybrid of claim 3 further including the steps of: functionalizing the graphene layer on the transparent substrate; providing a second PMMA/Graphene layer; functionalizing the second PMMA/Graphene layer; applying the second PMMA/Graphene layer to the functionalized graphene layer; removing the PMMA; and forming a transparent conductive graphene hybrid.

5. The method of making a transparent conductive graphene hybrid of claim 4 wherein said step of functionalizing the second PMMA/Graphene layer comprises TFPA-NH2.

6. The method of making a transparent conductive graphene hybrid of claim 4 wherein said wherein the functionalization comprises target surface modification by self-assembled monolayers.

7. A product of the process of: providing a PMMA/Graphene layer; functionalizing the PMMA/Graphene layer; providing a transparent substrate; oxidizing the transparent substrate and forming an oxidized substrate; treating the oxidized substrate with TFPA-NH2 and forming a functionalized substrate; applying the PMMA/Graphene layer to the functionalized substrate; removing the PMMA; and forming a transparent conductive graphene hybrid comprising a graphene layer on a transparent substrate.

8. A transparent conductive graphene hybrid comprising: a transparent substrate; wherein the transparent substrate is oxidized; and wherein the transparent substrate is treated with TFPA-NH2 to form a functionalized substrate; and a layer of graphene on the functionalized substrate.

Description

DESCRIPTION OF THE DRAWINGS

[0007] The following description and drawings set forth certain illustrative implementations of the disclosure in detail, which are indicative of several exemplary ways in which the various principles of the disclosure may be carried out. The illustrated examples, however, are not exhaustive of the many possible embodiments of the disclosure. Other objects, advantages and novel features of the disclosure will be set forth in the following detailed description when considered in conjunction with the drawings.

[0008] FIG. 1A is a schematic of one step graphene transfer.

[0009] FIG. 1B is a schematic of a modified one step graphene transfer.

[0010] FIG. 2 illustrates electrical and optical properties of graphene/Al.sub.2O.sub.3 hybrid materials after one step graphene transfer of single and multilayer graphene.

[0011] FIG. 3 illustrates comparison of sheet resistance of graphene/Al.sub.2O.sub.3 as a function of number of graphene layers and Al.sub.2O.sub.3 surface induced doping.

[0012] FIG. 4 illustrates transmission of graphene/Al.sub.2O.sub.3 as a function of number of graphene layers and Al.sub.2O.sub.3 surface induced doping.

[0013] FIG. 5 illustrates comparison of sheet resistance of graphene/Ge as a function of number of graphene layers and Ge surface induced doping.

[0014] FIG. 6 illustrates transmission of graphene/Ge as a function of number of graphene layers and Ge surface induced doping in the IR wavelengths 4 μm and 9 μm.

[0015] FIG. 7A is a schematic of sequential graphene transfer.

[0016] FIG. 7B is a schematic of modified sequential graphene transfer.

[0017] FIG. 8 illustrates optical and electrical measurements of Gr/Al.sub.2O.sub.3 hybrid materials obtained using sequential transfer method. Sample 1 was prepared by using 2 L/2 L graphene on Al.sub.2O.sub.3 sample, functionalizing it with TFPA and then transferring 3 L bottom functionalized graphene with HNO.sub.3 onto it. Sample 2 was prepared by using 2 L/2 L graphene on Al.sub.2O.sub.3 sample, functionalizing it with TFPA and then transferring 3 L bottom functionalized graphene with HNO.sub.3 onto it and then functionalizing the top surface with TFPA. Sample 3 was prepared by using 6 L graphene on Al.sub.2O.sub.3 sample, functionalizing it with TFPA and then transferring 1 L bottom functionalized graphene with HNO.sub.3 onto it. Sample 4 was prepared by using 3 L graphene on Al.sub.2O.sub.3 sample, functionalizing it with TFPA and then transferring 2 L bottom functionalized graphene with HNO.sub.3 onto it. Sample 5 was prepared by using 2 L graphene on Al.sub.2O.sub.3 sample, functionalizing it with TFPA and then transferring 3 L bottom functionalized graphene with HNO.sub.3 onto it.

[0018] FIG. 9 illustrates optical and electrical measurements of Gr/Ge hybrid materials obtained using sequential transfer method. Sample 1 was prepared by placing 6 L of graphene Ge, functionalizing graphene on Ge and then transfer 1 L bottom functionalized graphene with HNO.sub.3 onto it. Sample 2 was prepared by using 2 L/2 L graphene on Ge sample, functionalizing it and then transferring 3 L bottom functionalized graphene with HNO.sub.3 onto it. Sample 3 was prepared by using 3 L graphene, functionalizing it by TFPA and then transferring 2 L bottom functionalized graphene with HNO.sub.3 onto it.

[0019] FIG. 10 illustrates transmission of Al.sub.2O.sub.3 and Ge reference and Gr/Al.sub.2O.sub.3 and Gr/Ge hybrid materials in the IR wavelengths.

[0020] FIG. 11 illustrates sheet resistance measurements of Gr/Al.sub.2O.sub.3 nine months after graphene transfer.

DETAILED DESCRIPTION OF THE INVENTION

[0021] A stable IR transparent conductive graphene hybrid material, and methods of making, are disclosed herein.

[0022] The conductive graphene hybrid materials are without loss in electrical properties over time.

[0023] The proof of concept experiments were performed with commercially available graphene (Gr) grown by chemical vapor deposition on Cu foils. Both single and multilayer graphene (2 layers, 3-5 layers, 6-8 layers from ACS Materials) were used. The transparent substrates used were sapphire and germanium wafer (doubly polished). However, the proposed method is applicable to any transparent substrate (organic and inorganic), considering that its surface needs to be oxidized before transfer to enhance adhesion of graphene to it.

[0024] To produce graphene-based hybrid material, graphene must be removed from the Cu foil and placed onto the substrate of interest. Different methods have been developed to achieve this result. They can generally be divided into dry and wet chemical approaches. The wet chemical methods rely on wet chemical etch of the Cu foil, while the top surface of the graphene is preserved by a sacrificial polymeric layers. The main drawback is cleaning of the polymeric residue from the graphene surface on atomic scale. The dry approaches reply on mechanical peeling of the graphene without exposure to chemicals. Lock et. al. discovered a method that relies on differential adhesion with the basic idea that if the graphene's adhesion to the target substrate is higher than the adhesion between graphene and the Cu foil, graphene would be transferred (U.S. patent application Ser. No. 13/466,248). In this work, wet chemical approach was used as explained below. However, the same concept can be applied using a dry transfer approach as well.

Example 1

[0025] In the wet chemical approach both one step transfer and multiple sequential transfers were used. Schematics of the one step graphene transfer (OSGT) and the modified one step graphene transfer (MOSGT) methods are shown in FIG. 1. In the one step graphene transfer, graphene surfaces was coated by PMMA at 4000 rpm for 1 min, then placed in APS 100 Cu etchant for 8 hours. Then the PMMA/Gr hybrid was placed in deionized water for 12 hours to rinse the metal residues from the graphene surface. Separately, the surface of the transparent substrate was treated chemically or by plasma to produce highly oxidized surface. Germanium surface was plasma functionalized using microwave Plasma Preen System in argon or oxygen environment for 1 minute. The sapphire was first immersed into sc1 solution for 10 minutes (DI H.sub.2O:H.sub.2O.sub.2:NH.sub.4OH 6:1.5:1 80° C.), followed by HF etch for 1 minute (49% HF in H.sub.2O 1:100) and sc2 incubation (H.sub.2O:H2O.sub.2:HC17:1.5:1 80° C.) for 10 minutes. Then, the PMMA/Gr hybrid was scooped with the modified target surface. Then, the PMMA/Gr/substrate was placed on hot plate at 60° C. for a few minutes, followed by bake at 120° C. for 1 minute. The PMMA film was removed by acetone dip for 1 minute, followed by rinse in isopropanol and dried with nitrogen. In the MOSGT transfer, the effect of functionalization of target surface on graphene's electrical properties was explored. The oxidized target substrates (UHMW PE, sapphire and germanium) were further functionalized with TFPA-NH.sub.2 solution in methanol by dip coating for two hours. This functionalization can be expanded to other chemical, plasma-based functionalizations as well as target surface modification by self assembled monolayers (e.g. silane-based).

[0026] The electrical and optical properties of graphene/Al.sub.2O.sub.3 hybrids produced by the one step transfer of single and multilayer graphene are shown in FIG. 2. It should be noted that the graphene surface is very sensitive to polymeric residues after the transfer, as well as to its post-treatment. Methanol rinse increased the sheet resistance of the single and double layer graphene surfaces. Additional annealing step in Ar/H.sub.2 mixture was needed to reduce their resistance values. The obtained resistance values were in the kΩ/sq range. The lowest values were obtained using 6 layers graphene 800 Ω/sq. The transmission of the Gr/Al.sub.2O.sub.3 hybrid was reduced proportional to the number of the graphene layers.

[0027] Multiple attempts were made to optimize the OSGT by use of different PMMA resists, and methods for PMMA removal. The best results are shown in FIG. 3—lower resistivity values were obtained for the transfer of single and double layers of graphene (1.5 kΩ/sq). The multilayers (3 L, 6 L) were not affected. In further attempt to minimalize the resistance of the Gr/Al.sub.2O.sub.3 hybrids the MOSGT method was applied. As shown in FIG. 3, the resistance of double layer graphene sample was further reduced. The transmission values of the graphene/Al.sub.2O.sub.3 produced by this method are shown in FIG. 4 suggest that substrate functionalization dos not significantly affect the optical properties of the hybrids.

[0028] FIG. 5 shows the results from the OSGT and MOSGT transfer of single and multilayer graphene to germanium. The obtained resistance values were in the kΩ/sq range with the lowest value achieved when 6 L of graphene was used consistent with previous results. The functionalization of germanium did not decrease the sheet resistance values of graphene as was the case with Al.sub.2O.sub.3. Transmission of germanium and Gr/germanium hybrids after the OSGT and MOSGT methods at two wavelengths (4 and 9 μm) are shown in FIG. 6—insignificant decrease of transmission (3-4%) was observed in Gr/Ge hybrids compared to Ge reference. In summary single layer transfer of graphene resulted in obtaining conductive Gr/Al.sub.2O.sub.3 and Gr/Ge hybrids with the sheet resistance 1-3 kΩ/sq.

Example 2

[0029] To further lower the resistance of the hybrid materials, the sequential transfer protocols were developed. First, graphene layers were sequentially placed on top of each other (SGT) following the OSGT protocols explained above. However, this approach did not yield the desired results. For this reason, in the modified sequential transfer protocol shown in FIG. 7, an additional step after the water rinsing of graphene to functionalize the bottom of the graphene in 2M HNO.sub.3 solution in water (note the top graphene surface is protected with PMMA layer). Then, this functionalized surface is contacted with functionalized transparent surface (with TFPA-NH.sub.2 molecules) and hydrogen bonds between the oxygen functional groups of graphene and NH.sub.2 functionalities of the substrates are created. For sequential placement, the top graphene surface is functionalized by TFPA-NH.sub.2 as well.

[0030] The electrical and optical results of sequential graphene transfer to Al.sub.2O.sub.3 are shown in FIG. 8 respectively. The sheet resistance values below 300 W/sq were achieved. Also, we found that the order in which graphene is layered mattered (2 L/3 L vs. 3 L/2 L; 2 L/2 L/3 L vs 6 L/1 L). Even though the total number of layers is the same—five layers—3 L/2 L had 250 Ohm/sq resistance vs. 100 Ohm/sq of 2 L/3 L. Similarly 2 L/2 L/3 L had 300 Ohm/sq resistance vs. 200 Ohm/sq resistance 6 L/1 L. The overall reduction of transmission was less than 10%, however the resistance values of Gr/Al.sub.2O.sub.3 approach ITO/Al.sub.2O.sub.3 values. The lowest obtained value was 100 Ohm/Sq.

[0031] To show to broad applicability of the proposed above approach, similar graphene layering experiments were conducted using germanium as well. Sheet resistance values below 600 Ohm/sq were achieved as well. The dependence of the way graphene layers were placed on the final resistance values was observed as well. Even though the total number of layers is the same (seven), when 6 L/1 L layered, the hybrid resistance was halves from 600 to 300 Ohm/in comparison to the 2 L/2 L/3 L combination (FIG. 9). The transmission difference for these samples was insignificant, as shown in FIG. 9.

[0032] In transmission spectra of insulators Al.sub.2O.sub.3 and Ge and the conducting Gr/Al.sub.2O.sub.3 and Gr/Ge are shown in FIG. 10. It is obvious, that the price in transmission is less than 10% over the whole IR range. The lowest obtained sheet resistance for the Al.sub.2O.sub.3 case was 100 Ohm/sq and for Ge 300 Ohm/sq. Applying the same method using different graphene layering combinations could further reduce these resistance values.

[0033] The same strategy can be applied in combination with the Lock et al. developed dry graphene transfer approach. The modified target substrates can be placed to HNO.sub.3 modified graphene/Cu foil in the Nanoimprinter. After transfer print at 500 psi and 30 minutes, graphene can be removed from Cu foil. Then, graphene's top surface can be modified by TFPA-NH.sub.2 to yield NH.sub.2 functionalized surface and contacted again to HNO.sub.3 modified graphene/Cu foil in the Nanoimprinter for sequential print.

[0034] The main drawback of the technologies developed to date is that the electrical resistance of chemically modified substrates degrades with time (seconds to minutes) after functionalization. To evaluate the stability of our samples, nine months after preparation, electrical and optical measurements on small subset of the Gr/Al.sub.2O.sub.3 and Gr/Ge was conducted. The results of electrical measurements are summarized in FIG. 11. It is clear that the sheet resistance values are similar to their original values. Thus, the hybrid materials, prepared using this methodology, have surfaces with stable electrical properties. The optical transparent properties were not changed as well.

[0035] Disclosed herein are conductive IR transparent substrates with electrical properties that do not degrade over time.

[0036] The above examples are merely illustrative of several possible embodiments of various aspects of the present disclosure, wherein equivalent alterations and/or modifications will occur to others skilled in the art upon reading and understanding this specification and the annexed drawings. In addition, although a particular feature of the disclosure may have been illustrated and/or described with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular application. Also, to the extent that the terms “including”, “includes”, “having”, “has”, “with”, or variants thereof are used in the detailed description and/or in the claims, such terms are intended to be inclusive in a manner similar to the term “comprising”.