Method of manufacturing large area graphene and graphene-based photonics devices
10450650 ยท 2019-10-22
Assignee
Inventors
Cpc classification
C23C16/01
CHEMISTRY; METALLURGY
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
G02F1/011
PHYSICS
International classification
B32B9/00
PERFORMING OPERATIONS; TRANSPORTING
G02F1/01
PHYSICS
C23C16/01
CHEMISTRY; METALLURGY
Abstract
The present invention relates to a method of manufacturing large area graphene for graphene-based photonics devices such as bolometric graphene detectors, or for use as a saturable absorber in ultra-high bandwidth detectors for producing ultrafast laser pulses. The method includes: growing a first graphene layer on one side of a metal substrate, and a second graphene layer on another side of the metal substrate; coating the first graphene layer with a plurality of resist layers including a low molecular weight polymethylmethacrylate, and a high molecular weight polymethylmethacrylate; removing the second graphene layer and the metal substrate to reveal the first graphene layer; disposing the first graphene layer on an optical substrate; and removing the plurality of resist layers from the first graphene layer to reveal a final graphene layer, which can be used as the basis to manufacture a multilayer graphene structure for graphene detectors.
Claims
1. A method of preparing large area graphene for use in a tunable terahertz bandwidth range spectroscope capable of operating from mid infrared to long wave infrared, where mid infrared is 300 nanometers and long wave infrared is 6 micrometers in wavelength, plus or minus 10 percent in wavelength, for use in a space based vehicle, comprising: growing a first graphene layer on one side of a metal substrate without using metal pins, and a second graphene layer on another side of said metal substrate also without using metal pins, said first and second graphene layers with external photo responsivity of 6.1 mA/W at 1.55 micrometer wavelength; coating said first graphene layer with a plurality of resist layers; removing said second graphene layer and said metal substrate to reveal said first graphene layer; disposing said first graphene layer on an optical substrate; removing said plurality of resist layers from said first graphene layer to reveal a final graphene layer, and installing said tunable terahertz bandwidth range spectroscope integral to said space based vehicle; using said final graphene layer in a saturable absorber at the 1500 nm band by placing a single layer of graphene on the tip of a fiber optic cable in ultra-high bandwidth detectors for producing ultrafast laser pulses, each of said ultra-high bandwidth detectors integral to said spectroscope; wherein said saturable absorber is one of a single layer graphene and multiple layer graphene, and a saturable absorber performance of said multiple layer graphene detector is relatively less than that of a saturable absorber performance of said single layer graphene detector; patterning graphene films through photolithography to form microscale graphene ribbons of tunable plasmonic structures that support plasma oscillations by varying the width of graphene microstrips and electrostatic doping in said graphene microstrips; and further patterning a metal layer on graphene into strips to form a metal grating coupler to enable coupling to light at all wavelengths.
2. The method of claim 1, wherein said first graphene layer and said second graphene layer are prepared using a low pressure chemical vapor deposition (LPCVD) technique.
3. The method of claim 2, wherein said plurality of resist layers include a relatively low molecular weight polymethylmethacrylate, and a relatively high molecular weight polymethylmethacrylate.
4. The method of claim 3, wherein said second graphene layer and said metal substrate are removed by etching.
5. The method of claim 4, wherein ionic contaminants are removed after said metal substrate is etched away.
6. The method of claim 5, wherein said metal substrate is a copper substrate.
7. The method of claim 6, wherein said optical substrate is a lead free optical glass with a linear optical transmission in a visible range down to 350 nm.
8. The method of claim 7, further comprising: degasing to remove water molecules from between said first graphene layer and said optical substrate.
9. The method of claim 8, wherein said plurality of resist layers and any contaminants are removed by thermal or chemical processing.
10. The method of claim 1, further comprising: providing a third graphene layer with a plurality of resist layers thereon, and disposing said third graphene layer on said final graphene layer which is disposed on said optical substrate.
11. The method of claim 10, further comprising: removing said plurality of resist layers from said third graphene layer.
12. The method of claim 11, wherein said plurality of resist layers on said third graphene layer are removed by high temperature anneal.
13. The method of claim 10, further comprising: repeatedly adding additional graphene layers on said third graphene layer to form multiple graphene layers.
14. The method of claim 1, wherein said final graphene layer is used in a laser or mode locking application, or disposed on a tip of an optical fiber.
15. The method of claim 13, wherein dimensions of said multiple graphene layers are controlled by patterning graphene films through photolithography or electron beam lithography methods.
16. The method of claim 14, wherein said laser application is used in a laser ranging and altimeter system, including a laser imaging detection and ranging (LIDAR) sensor.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF THE INVENTION
(11) The present invention relates to a method of manufacturing large area graphene, for use in graphene-based photonics devices, and which are used in a variety of applications. The present invention includes the fabrication of large area monolayer and multi-layer graphene samples of optical quality for a mode locking process. The present invention includes production of an ultrafast laser ranging instrument and an ultrawide bandwidth detector based on graphene as a saturable absorber, to demonstrate mode locking locked laser pulses in a laser application.
(12) In addition, the present invention takes advantage of the unique optical and electrical properties of graphene, as well as enhances the responsivity with plasmonic effects of graphene-grating metamaterials, to enable spectral imaging in the THz range important for applications in astrophysics, gas analysis for planetary bodies, thermal imaging for homeland security, and remote sensing.
(13) Graphene is a flat single layer carbon atoms packed in a honeycomb lattice (see
(14) Graphene differs from typical semiconductors in that the valence and conduction bands are smooth cones and meet at a point called the Dirac point. One of the more interesting properties of graphene is that there is no energy bandgap and as such it can absorb photons at all wavelengths (see
(15) Based upon the above attributes, a graphene-based saturable absorber is an ideal passive mode-locker for many types of lasers. This unique property of full band mode locking by a graphene-based saturable absorber, has relevance for the passive mode locking of fiber lasers, to generate ultrafast pulses in the picosecond to femtosecond regimes, as well as for use as a photosensitive medium for photodetection. Further, due to this full band mode locking property, graphene has application in ultrafast photonics, and the optical response of graphene/graphene oxide layers can be tuned electrically.
(16) A single atomic layer graphene has an external photo responsivity of 6.1 mA.Math.W.sup.1 at 1.55 m wavelength. In order to improve the overall absorption of incident light and to increase the photo-responsivity, the present invention includes increasing the thickness of graphene by stacking multiple layers, as well as increasing the interaction length between the incident photons and the graphene. The present invention has a novel detector architecture that balances the interaction lengths and thus, increases the absorption and the overall bandwidth of the detector.
(17) Current methods to produce graphene include mechanical cleavage (i.e., taking layers from multi-layered graphite using adhesive tape), or by depositing one layer of carbon onto another material. Graphene platelets are also created by chemically cutting open carbon nanotubes, using potassium permanganate and sulfuric acid, for example, or by solvent or sonic exfoliation (separation) of graphite, as well as by plasma deposition, the reduction of graphene oxides (RGO), or other technologies.
(18) In current device fabrication processes, graphene is grown using methods including exfoliation or chemical vapor deposition (CVD) process.
(19) In the exfoliation-based approach, graphene films are produced in a process including exfoliating graphene flakes (10-20 microns) from Highly Oriented Pyrolitic Graphite (HOPG) crystals. Since many small flakes of exfoliated graphene make it challenging for laser applications, the small flakes of exfoliated graphene, which show superior electrical properties, are mixed with polyvinyl alcohol (PVA) or other polymers in an ultrasonic mixer, to make a graphene composite.
(20) In one embodiment, the composite uniform suspension of graphene flakes is applied on a silicon dioxide wafer through spincoating to make a thin and uniform film, evaporating the solvent, and removing the film from the silicon dioxide substrate upon desiccation, to obtain a free-standing graphene composite that is patterned to make the laser. This technique generates ultrafast laser pulses.
(21) In another method, a low pressure chemical vapor deposition (LPCVD) system is used to make a large area of LPCVD graphene as the solution for ultrawide bandwidth detectors. In this method, a graphene film is grown on a substrate, such as a metal (i.e., copper) substrate, through an LPCVD process, where H.sub.2, CH.sub.4, and Ar gases are utilized to grow graphene at 1000 C. Although LPCVD graphene can be produced in large pieces (a few inches), it shows relatively weaker electrical properties compared to the exfoliating graphene approach. However, the CVD approach provides control of the graphene size and thickness. Single layer and multi-layer graphene can be produced by selecting the right substrate and process conditions.
(22) Specifically, in one current transfer method to produce large area graphene, graphene 101 (see
(23) In another current transfer method, graphene 101 (see
(24) In the manufacturing process of the present invention, a low pressure chemical vapor deposition (LPCVD) technique is used to grow large area graphene. A transition metal substrate such as copper is heated in a CVD reactor to a temperature of about 850 C. to about 1000 C. under an ambient pressure of hydrogen (H2), or argon (Ar), or a mixture thereof, introducing reactions gas mixtures to the CVD reactor, and growing graphene on the copper substrate. In some embodiments, the reaction gas mixtures include flowing methane (CH.sub.4) of about 1 to about 20 standard cubic centimeters per minute (sccm), flowing H.sub.2 of about 5 to about 50 sccm, and flowing Ar of about 200 to about 1000 sccm.
(25) The novel fabrication method of the present invention includes transferring graphene, in multiple layers, to suitable optical substrates, as well as the tips of optical fibers. The novel process of the present invention produces clean (i.e., no contaminants such as tape residue, which is produced in previous methods), large area graphene, suitable for use in laser or mode locking applications.
(26) Specifically, in one embodiment in the novel large area graphene manufacturing process of the present invention, as illustrated in
(27) As shown in
(28) As illustrated in
(29) N-BK7 is an arsenic- and lead-free optical glass used for high quality optical components, and is activated by dry or wet processing techniques. It has good scratch resistance, low inclusions, almost bubble-free, and high linear optical transmission in the visible range down to 350 nm.
(30) As shown in
(31) The transmission of the monolayer graphene samples produced by this novel method, were measured using a spectrometer, and the absorption of the single layer graphene was found to have excellent results of approximately 2% over a range of nearly all wavelengths (i.e., 200 nm to 1060 nm)which is about 60 times better than gallium arsenide (GaAs) with the same thickness.
(32) In addition, a novel process was also developed for depositing multiple graphene layers on the same substrate. This second process provides control over the exact number of graphene layers used and minimizes the folding or voids that could develop when depositing multiple graphene layers on top of one another.
(33) Specifically, in one embodiment, as illustrated in
(34) As shown in step
(35) In one embodiment, in preparation of the graphene-based laser, the graphene and graphene composite films produced are tailored and transferred to an optical substrate as noted above. An electron beam (E-beam) writing tool may be utilized to define metal contacts on the graphene films. The contacts allow electrical characterization of the devices. Produced graphene and graphene composites may be characterized using a Scanning Electron Microscope (SEM), Scanning Tunneling Microscope (STM), Atomic Force Microscope (AFM), and Raman Spectroscope.
(36) In one embodiment, using the graphene layer(s) transferred on the optical substrate (i.e., BK7 substrate) as the saturable absorber at the 1500 nm band, a passive solid-state mode-locked laser can be built. The laser cavity optical parameters contribute to the optimal design of a mode locked laser.
(37) In one embodiment, as noted above, a graphene saturable absorber is produced by placing a single layer of graphene on the tip of a fiber optic cable. The fiber optic cable offers ease of measurement and integration to other optical elements. Normally, an optical fiber is immersed in solution with dispersed graphene flakes or floating graphene pieces, and a light source was used to shine through the fiber. The graphene piece or flake is collected at the fiber tip due to multiple causes, including convection induced by the light and thermophoresis.
(38) In the present invention, mode locking is achieved with the single layer graphene on the polarization maintaining (PM) fiber tip. The PM fiber tip was placed inside of a fiber ring cavity. Results of the mode locked pulses and optical spectrum are shown in
(39) The layer-dependency of graphene on pulse energy, losses in cavity, pulse width, etc., were analyzed, whereas a known number of graphene layers were deposited on dielectric coated substrates (i.e., fused silica substrate with SiO.sub.2 coating) that could be used for intra-cavity mode-locking. The saturable absorber may be single layer graphene, multi-layer graphene, or graphene-polymer composites. The graphene samples of the present invention were tested and characterized with a laser transmitter and high energy (10 s nJ), and femtosecond pulses with repetition rate on order of 100's MHz have been demonstrated using graphene as saturable absorber.
(40) The saturable absorber performance is strongly dependent on the number of layers of graphene. Monolayer graphene has one of the largest modulation depths of all known saturable absorbers, a value of >60%, whereas the modulation depth of multilayer graphene is greatly reduced due to nonsaturable absorption and scattering loss. Defects such as wrinkles will also increase the nonsaturable absorption and lower the performance of the mode-locker in the laser. Femtosecond ultrafast laser pulses can be generated using monolayer graphene as a saturable absorber. Due to the ultrafast relaxation time, larger modulation depth and lower scattering loss of monolayer graphene, it has advantages over multilayer graphene in terms of pulse shaping ability, pulse stability and output energy. Thus, the graphene produced by the present invention is useful as an absorber as it is wavelength independent and can be used in many different laser systems.
(41) In one embodiment, the graphene device dimensions can be controlled by patterning graphene films through photolithography and electron beam lithography methods to form microscale graphene ribbons or strips that form a tunable plasmonic structure and that can support plasma oscillations (see
(42) In one embodiment, a tunable plasmonic structure is formed by coupling light into graphene transistors using grating couplers. Specifically, in one embodiment, as illustrated in
(43) Furthermore, an external bias voltage can be applied between the coupler and graphene to electrostatically gate graphene. By varying the bias voltage or doping in silicon, the carrier density can be tuned, as shown in
(44) In another embodiment, when graphene is doped either chemically or by applying a gate voltage, it produces a two-dimensional sea of electrons that can absorb radiation, producing a population of energized hot electrons. The unique nature of graphene offers a much weaker electron-phonon coupling than in competing materials or detectors. As a result, it is possible to directly sense the hot electrons in graphene before they have a chance to dissipate to the lattice, allowing for fast thermal measurement.
(45) In fact, the present invention includes a scalable graphene-based bolometer technology, which measures the power of incident electromagnetic radiation using the hot electron phenomenon. Multilayer turbostratic and (Bernal) AB-stacked graphene, which can be reliably synthesized from the CVD processes, were used to determine the impact of the layer thickness and stacking structure on the bolometric performance. Devices fabricated using single layer graphene were used as the benchmark for the performance of a defect-free graphene-based sensor and as the starting point for exploring how the bolometric response can be optimized.
(46) In one embodiment, a novel ultra-high bandwidth detector is derived from graphene-based photodetectors operating in several different novel detection modes, and is used in an apparatus to measure the bolometric response is shown in
(47) The device 706 is connected to current/voltage preamplifier 707, and grounded. The chopper 702 is connected to a lock-in amplifier 708 which measures the modulation frequency input, and the lock-in amplifier 708 is connected to preamplifier 707.
(48) The bolometric response of these devices 706 was determined by optical absorptivity and temperature dependent resistivity. The bolometric response to broad wavelengths was measured as a function of type of substrates used, incoming wavelengths, and applied gate voltage. For example, the ultimate performance limitations of the graphene detector were measured, and the responsivity was characterized, along with the noise equivalent power (NEP), the normalized detectivity and spectral resolution of the spectrometers.
(49) As a result, it was determined that the performance of these detectors may be optimized by using more than one layer of graphene, thus, increasing the total radiation absorption and by tuning the temperature dependent resistivity using different substrates. Further, optimization may be achieved using bilayer graphene and doped graphene in graphene-based photodetectors.
(50) In another novel property of the photonic device of the present invention, the optical absorption band of graphene can be tuned to create a passband filter by controlling the size of the graphene devices or by controlling the chemical potential of graphene. Second, bandgaps of bilayer graphene can be used to yield a continuously tunable photodetection bandwidth from mid-infrared (MIR) to LWIR radiation and beyond. Therefore, the performance of bilayer-graphene-based photodetectors can be tuned on demand. Finally, it was found that programmable band gaps of graphene nanoribbons can be utilized to fabricate detectors for wavelengths above 6 m.
(51) In another novel property of the photonic device of the present invention, high Kerr nonlinearity effects of graphene under intense illumination can be used to make various nonlinear functional devices, including but not limited to, optical switches, wavelength converters, and signal regenerators. The present invention of graphene photonic device is advantageous over other Kerr-nonlinearity mediums because of wavelength independence and non-resonant nature.
(52) A laser ranging and altimeter system of the present invention, with an ultrashort pulse duration in picosecond-femtosecond regime, would be able to provide sub-millimeter range information for applications in proximity sensing, terrain relative navigation, landing, docking, etc. Similar short pulsed laser systems can be used in a frequency up-conversion scheme to generate entangled photon pairs for quantum communications and quantum key distribution applications. A frequency comb with femtosecond pulses can be used to generate precision clocks for laser time transfer and clock synchronization. The present invention can achieve LIDAR missions which require high bandwidth and low-noise photodetectors operating in the 1-1.6 m wavelength regions.
(53) In summary, the graphene-based saturable absorber photonic device of the present invention is used to generate high repetition rate mode locked lasers, with applications in a variety of fields, including, but not limited to, laser ranging and altimeter systems with high precision (in sub-millimeter accuracy); ultra-fast detectors for high speed optical communications and navigation; time distributions with laser time transfer technique using frequency comb, quantum communications, imaging LIDAR, remote sensing and in-situ optical sensors, optical signal processing, two-photon microscopy, Q-switches, wavelength converters, signal regenerators, tunable terahertz spectrometers, and laser surgery. The ultrafast laser and ultrawide bandwidth detector demonstrates a laser ranging instrument that provides unprecedented precision, and that is useful for space applications. Further, spectral imaging in the THz range makes the tunable THz detector useful for astrophysics, earth science, gas analysis for planetary bodies, thermal imaging for homeland security, as well as remote sensing.
(54) It should be emphasized that the above-described embodiments of the invention are merely possible examples of implementations set forth for a clear understanding of the principles of the invention. Variations and modifications may be made to the above-described embodiments of the invention without departing from the spirit and principles of the invention. All such modifications and variations are intended to be included herein within the scope of the invention and protected by the following claims.