None.
The invention generally concerns nanomaterials. In particular certain embodiments are directed to methods and compositions related to quantum wires.
Nanoelectronic devices are constantly seeking new materials to further scale integrated circuits applications. Potential candidates for new materials must eventually achieve the highest possible density integration in combination with high ballistic conductance, high thermal conductivity, and high current density. These new materials will be able to outperform silicon, the material currently used to fabricate semiconductors. For example, the charge carrier density in a sub-10 nm Field Effect Transistor (FET) is four times higher in Carbon Nanotubes (CNTs) than for silicon-based devices after normalizing for diameter. The current market barrier for these materials is in part due to the difficulty in producing and purifying exclusively semi-conducting or metallic states. Metallic CNTs and graphenes are potential candidates for the on-chip interconnect materials in future integrated circuits because they have potential advantages for achieving the highest possible density integration in combination with ballistic conductance, high thermal conductivity, and high current density.
The inventors have discovered a high performance, low-cost, solution processed, metallic, self-assembled columnar molecular wire for use as low resistance contacts in CNT or graphene based devices. Embodiments of the current invention provide a solution to the difficulties associated with producing metallic CNTs and graphenes. In particular, the inventors have developed an inexpensive ohmic nanocarbon material (ohmic materials are those materials for which Ohm's law (V=IR) holds true), which will enable smaller devices with less carrier scattering and thus higher energy efficiency. This novel nanocarbon material can be deposited from solution and is an attractive alternative for top down deposition of metallic nanowires and interconnects with low-temperature ballistic transport with higher thermal/oxidative stability than currently used metals (i.e., copper).
The present disclosure is related to a method of fabricating a stacked nanographene structure which is assembled into quantum wires or ribbons. While it has been demonstrated that nanowires can be fabricated from various raw carbon materials including PAHs, research and industry has not produced a self-assembled nanowire produced from asphaltene materials that exhibits a metallic character and electronic structure. Asphaltenes are molecular substances that are found in crude oil, along with resins, aromatic hydrocarbons, and saturates. Asphaltenes consist primarily of carbon, hydrogen, nitrogen, oxygen, and sulfur, as well as trace amounts of vanadium and nickel. The C:H ratio is approximately 1:1.2, depending on the asphaltene source. Asphaltenes are defined operationally as the n-heptane insoluble, toluene-soluble component of a carbonaceous material such as crude oil, bitumen, or coal. Asphaltenes have been shown to have a distribution of molecular masses in the range of 400 to 1500, but the average and maximum values are difficult to determine due to aggregation of the molecules in solution. The methods and materials described herein can be used to produce a new class of materials consisting of a self-assembled quantum wire out of asphaltene.
Asphaltene mesophase that is thermally treated in the absence of air is capable of self-assembling into one dimensional columnar nanowires due to the alignment of stacked aromatic cores. The inventors show that this thermal treatment contributes to a large increase in conductivity in the sample due to the loss of insulating hydrogen groups, the increase in sp2 hybridization and the stacking of aromatic cores. Density Functional Theory (DTF) simulations of the structure predict this behavior and explain the materials conductivity with increasing a continuous density of states at the Fermi energy. This material shows potential for use in nanowires and molecular electronics as the inventors were also able to predict that the structure has a larger number of states available at the Fermi level near conduction states than single layer graphene. It represents a class of carbon conductors that rivals current state of the art nanocarbon materials in part because of advantageous metallic properties but also its low cost self-assembly and cheap carbon precursor feedstock, asphaltene.
Certain embodiments are directed to methods of producing a one-dimensional self-assembled molecular wire. The method comprises thermally activating asphaltene. Depositing a dilute thermally activated asphaltene solution on a target location of a substrate under conditions for molecular wire self-assembly. In certain aspects, the molecular wire is formed by drop-casting. The thermally activated asphaltene solution can include an aromatic based solvent, such as chlorobenzene or the like. In certain aspects, the dilute thermally activated asphaltene solution includes 0.001, 0.005, 0.01, 0.05 to 0.5 mg/ml thermally activated asphaltene, including all values and ranges there between. In particular aspects, the dilute thermally activated asphaltene solution is or is about 0.005 mg/ml thermally activated asphaltene. The thermally activation method of asphaltene can include heating asphaltene, such as precursor discotic liquid crystals in an inert environment, such as in the absence of air. In certain aspects, the asphaltene, precursor discotic liquid crystals are heated to 350, 400, 450, 500, 550, to 600° C. In particular aspects, the asphaltene, precursor discotic liquid crystals are heated to about 500° C. The asphaltene, precursor discotic liquid crystals can be heated for 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, to 60 minutes. In particular aspects, the asphaltene, precursor discotic liquid crystals are heated for about 10 minutes. In certain aspects the asphaltene, precursor discotic liquid crystals are produced from mesophase pitch by (a) extracting crude oil with n-alkane; (b) filtering the n-alkane; (c) dissolving the retentate in toluene forming a toluene solution; (d) filtering the toluene solution; (e) evaporating the toluene; and (f) collecting the residual asphaltene precursor discotic liquid crystals. In some aspects, the thermally activated asphaltene can contain multi-layer nanographene (MLNG). The asphaltene can be dissolved in an aromatic solvent, such as chlorobenzene or the like.
Certain embodiments are directed to a self-assembled molecular wire produced by the method(s) described herein, wherein the self-assembled molecular wires have a length of 2 to 100 microns. In certain aspects the self-assembled molecular wire has an average height of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 nm, but does not exceed 100 nm. In particular aspects the self-assembled molecular wire has an average height of 5, 10, 15, to 20 nm, in certain alternative 10 nm. The self-assembled molecular wire exhibits quantum confinement.
Other embodiments of the invention are discussed throughout this application. Any embodiment discussed with respect to one aspect of the invention applies to other aspects of the invention as well and vice versa. Each embodiment described herein is understood to be embodiments of the invention that are applicable to all aspects of the invention. It is contemplated that any embodiment discussed herein can be implemented with respect to any method or composition of the invention, and vice versa.
The term “quantum wire” refers to an electrically conducting wire in which quantum effects influence transport properties and is a one-dimensional nanowire limited to be nanosized in two directions of three spatial dimensions.
The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”
The term “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.
The terms “wt. %,” “vol. %,” or “mol. %” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol. % of component.
The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.”
As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
The compositions and methods of making and using the same of the present invention can “comprise,” “consist essentially of,” or “consist of” particular ingredients, components, blends, method steps, etc., disclosed throughout the specification.
Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of the specification embodiments presented herein.
The realization of functioning high performance electronic and optoelectronic devices based on nanomaterials, in general, is impacted significantly by the electrical connections, wires and interconnects that link nanomaterials with external circuitry. One dimensional molecular wires described here in can be produced and used to provide electrical connections and interconnects between nanomaterials and other circuitry components.
Thermal treatment of asphaltene, precursor discotic liquid crystals (DLC) results in self assembles into a one dimensional columnar multi-layer nanographene due to the alignment of stacked aromatic cores and when deposited from dilute solutions further self-assemble into molecular nanowire. Without being bound of theory, it is believed that due to the loss of insulating hydrogen groups, the increase in sp2 hybridization and the stacking of aromatic cores, the thermal treatment contributes to a large increase in conductivity. Discotic liquid crystals precursors are mesophases formed from disc-shaped molecules known as “discotic mesogens”. These phases are also referred to as columnar phases. Discotic mesogens are typically composed of an aromatic core surrounded by flexible alkyl chains. The aromatic cores allow charge transfer in the stacking direction through the π conjugate systems. The charge transfer allows the discotic liquid crystals or molecular wires produce from DLCs to be electrically semi-conductive along the stacking direction. Self-assembled nanowires microns in length (1 to 100 μm) may be fabricated from a dilute thermally activated asphaltene solution where the solvent is aromatic. These nanowires exhibit quantum confinement and range in height between 3 nm to 20 nm, and in certain aspects on average about 10 nm in height. These quantum confinements result in a conductive electronic state and ohmic properties are observed from these structures. In certain aspects the nanowires have a resistance on the same order or lower than that of copper.
The following examples as well as the figures are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples or figures represent techniques discovered by the inventors to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.
Synthesis:
Asphaltene mesophase pitch was used as the precursor discotic liquid crystal (DLC) and was extracted from Crude oil (Mayan) by n-alkane (1:40 v/v). The solution was mixed for 24 hours and filtered (Whatman 40). The retentate was dissolved in toluene and filtered again and the solution was collected and evaporated. 100 mg of sample was heated to 500° C. in the absence of air for 10 minutes in a flask using Schlenk technique and kept under vacuum.
Nanowire Fabrication:
After thermal treatment, dilute solutions of samples in chlorobenzene (5 μg/ml) were drop coated onto various substrates (Cu, Highly Ordered Pyrolytic Graphite, SiO2/Si) and nanowires self-assemble on the surface of substrates. Drop coating is the deposition of a volume of material in solution, after which the solvent is evaporated depositing the material at the location of deposition.
Characterization:
Fourier Transform Infrared (FTIR) was taken of samples in KBr pellets (Nicolet, Thermo Scientific). X-Ray Diffraction was taken from 10-60° using Cu Kαλ=0.154 nm at a 0.01 scan step (Bruker). Scanning Electron Microscopy was taken of solutions on SiO2/Si (S-4800, Hitachi). Transmission Electron Microscopy (H-7650, Hitachi, Japan) was performed after drop casting samples on lacy carbon grids. Scanning Probe Microscopy/Scanning Tunneling Spectroscopy (NT-MDT) was performed with Pt/Ir tips (DPT-10, Bruker) on Highly Ordered Pyrolytic Graphite substrates by drop coating solutions (0.05 mg/ml) from chlorobenzene (Sigma). Each sample was applied three times independently and measurements were taken of across a line one micron in length with 10 points and cycled for 5 five minutes to ensure a stable scan. Two point probe measurements were taken using an Omnicron instrument with Tungsten STM probes which were annealed prior to experimentation to remove native oxide.
Molecular modeling: Simulations were carried out using modules available in Materials Studio v. 7.0, distributed by BIOVIA. The proposed structure was built imbedded within an otherwise empty simple cubic cell of lattice parameter 30 Å (in order to approximate a molecular model when using periodic DFT algorithms). The structure geometry was as an initial approximation optimized using a Forcite force field minimization with a universal force field. The structure's geometry was further optimized via a DFT method (CASTEP), using a Generalized Gradient Approximation (GGA) with a WC functional (Wu and Cohen, 2006). The electronic Hamiltonian used an energy cutoff of 240.0 eV, a Self-Consistent Field (SCF) tolerance of 2.0×10-6 eV/atom, a 1×1×1 Monkhorst-Pack grid for Brillouin zone k-point sampling, and an ultrasoft pseudopotential. After optimizing the geometry of the structure, electronic Density of States (DOS) and band structure were calculated using an energy band tolerance of 1.0×10-5 eV, as well as the same electronic parameters as were used for the geometry optimization of the structure
During the heat treatment of the asphaltene, precursor DLC, cyclodehydrogenation occurs and as a result sp3 hybridized carbon atom is converted to sp2 carbon. As evidenced by Fourier Transform Infrared (FTIR) spectroscopy and X-Ray Diffraction (XRD), that the structure of the asphaltene is significantly changed by the thermal treatment and can be realized as a stacked sp2 hybridized carbon structure after the removal of alkyl side chain from the precursor and the rearrangement or stacking of polycyclic asphaltene molecules.
In the asphaltene, DLC precursor (
After heat treatment (
Raman spectroscopy was performed shows that both asphaltene (
A nanographene tri-layer single stack was used as the simulated structure (
Images taken using Transmission Electron Microscope (TEM) indicate the asphaltene comprise of molecules that are spherical with sizes ranging from 10-100 nanometers which lack any formal organization. After thermal processing, the dilute solutions of MLNG remarkably self-assemble into highly ordered nanowires that appear similar to nanoribbons or nanotubes can be seen in TEM images. Scanning Electron Microscope (SEM) images of the precursor and heat treated asphaltene prepared on SiO2/Si wafers reveal the structure of the asphaltene to appear spherical with large dendritic structures which exemplifies the discotic PAH properties associated with having aromatic cores attached to alkyl chains (J. Chem. Phys. 53, 1126-1130, 1970; Phys. Rev. B. 81, 115315 2010). However, images after thermal treatment show that the MLNG sample formed nanowires consistent with TEM analysis (Fuel, 87, 3481-3482, 2008). They show a remarkable linear organization microns in length and demonstrate an ability to form nanowires from self-assembled 1-D stacks fabricated from asphaltene.
To characterize the electronic structure of the MLNG compared to that of the asphaltene at a nanoscale molecular domain, Scanning Tunneling spectroscopy (STS) was performed for both samples on highly ordered pyrolytic graphite (HOPG) in air. Scans were taken using multiple HOPG substrates with up to 5000 scans per sample over areas 1 micron in length.
Further analysis on the conductive nature of thermally treated asphaltene was done using a nano-scale two-point-probe (
Surface scattering is an influential occurrence after the miniaturization of devices and interconnects (Solid State Physics, Elsevier Science, 1985; Phys. Rev. B., 74, 085109, 2006) whereby electrons undergo either elastic or inelastic scattering depending on the local surface states. Furthermore, the surface electron density located near the nanowire surface makes a large contribution to the total conduction electron density. In
Electron Dispersion X-ray (EDX) Elemental analysis shows both the starting material and the novel product to be made up of only carbon and no other elements in
This application claims priority to U.S. Provisional Application 62/730,729 filed Sep. 13, 2018, which is incorporated by reference in its entirety.
Number | Date | Country | |
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62730729 | Sep 2018 | US |