CN110922068A - Graphene optical fiber and preparation method thereof - Google Patents

Graphene optical fiber and preparation method thereof Download PDF

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Publication number
CN110922068A
CN110922068A CN201911024425.5A CN201911024425A CN110922068A CN 110922068 A CN110922068 A CN 110922068A CN 201911024425 A CN201911024425 A CN 201911024425A CN 110922068 A CN110922068 A CN 110922068A
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Prior art keywords
optical fiber
graphene
preparing
graphene optical
preparation
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CN201911024425.5A
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付磊
熊良明
曾梦琪
李琳怡
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Wuhan University WHU
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Wuhan University WHU
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/106—Single coatings
    • C03C25/1061—Inorganic coatings
    • C03C25/1062—Carbon
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/12—General methods of coating; Devices therefor
    • C03C25/22—Deposition from the vapour phase
    • C03C25/223—Deposition from the vapour phase by chemical vapour deposition or pyrolysis

Abstract

The invention provides a graphene optical fiber and a preparation method thereof, and the preparation method provided by the invention is characterized by comprising the following steps: step 1, taking an optical fiber as a growth substrate, and placing liquid metal on the upstream of the optical fiber; step 2, in inert atmosphere and H2Heating to a growth temperature, introducing a carbon source, keeping the temperature constant for a period of time, and growing a graphene film on the optical fiber; and 3, after the growth is finished, cooling to room temperature to obtain the graphene optical fiber. According to the method, the metal steam is used as the catalyst, the graphitized carbon is allowed to be directly deposited on the surface of the optical fiber to form the low-defect graphene film, the method does not need etching after growth and evaporation of the metal catalyst, no possible damage risk exists, and the graphene film with higher quality can be obtained.

Description

Graphene optical fiber and preparation method thereof
Technical Field
The invention belongs to the technical field of graphene films, and particularly relates to a graphene optical fiber and a preparation method thereof.
Technical Field
Graphene is a single atomic layer two-dimensional carbon elemental material in a honeycomb lattice arrangement, and has unique electrical and optical characteristics, such as high carrier mobility 100 times higher than that of silicon, broadband optical response and the like. Meanwhile, the composite material also has excellent performances such as high thermal conductivity, high strength, high transparency, ultra-large specific surface area and the like, so that the composite material has wide application prospect in the field of photoelectric devices. However, although the optical species interactions in graphene are theoretically quite strong, the interactions actually measured are quite weak. To enhance the interaction of graphene with light, efforts have been made to build applications by combining graphene sheets with well-designed optical structures such as gratings, waveguides and pores.
The transparent, soft and tough characteristics of graphene provide a natural opportunity for bonding with a waveguide. Graphene is attached or wrapped along the waveguide, which can affect the optical signal by evanescent wave effects. In this process, the graphene exhibits its optical characteristics, and the light also completes the conduction. The combination of graphene and waveguide greatly increases the optical efficiency of graphene, while enriching the function of the waveguide structure. Therefore, a method for finding a more appropriate combination with an optical structure for the graphene film is a fundamental scientific problem in graphene photonics design, a preparation basis of various graphene optical devices, and a necessary way for various novel graphene optical applications.
Optical fibers, which are one of the most important optical transmission devices, provide the highest quality optical waveguides for information communication and photonic manipulation, and are also one of the most fundamental dielectric waveguides, have been produced on a large scale. The integration of the optical fiber and various functional materials greatly expands the application field of the optical fiber. The advent of two-dimensional graphene stimulated a strong interest in combining optical fibers with graphene.
In recent years, researchers have studied graphene as part of the structure of an optical fiber, such as growing graphene on the inner core or outer layer of the optical fiber, or wrapping or coating graphene on the outer core of the optical fiber. Graphene fiber composites have several unique advantages:
(1) graphene is easily and tightly attached to the optical fiber;
(2) graphene of atomic thickness can maintain the integrity of the optical fiber structure and the main optical functions;
(3) the unique properties of graphene bring unique functions that cannot be achieved by any other conventional material. The advent of graphene has brought new opportunities for incorporation into optical fibers, making them electrically tunable, broadband optical response, and all-fiber integration capability.
To date, various chemical vapor deposition methods (CVD) have been developed to produce graphene thin films on different substrates, such as epitaxial growth with the aid of copper vapor or growth without a metal catalyst. Unfortunately, the graphene thin films obtained tend to be discontinuous or non-uniform over large areas, which is an impediment to high performance optical applications. At present, how to controllably prepare high-quality graphene optical fibers becomes a problem which is of common concern to researchers.
Disclosure of Invention
The present invention is made to solve the above problems, and an object of the present invention is to provide a graphene optical fiber and a method for manufacturing the same, which can grow a high-quality graphene thin film on an optical fiber. In order to achieve the purpose, the invention adopts the following scheme:
< preparation method >
The invention provides a preparation method of a graphene optical fiber, which is characterized by comprising the following steps: step 1, taking an optical fiber as a growth substrate, and placing liquid metal on the upstream of the optical fiber; step 2, in inert atmosphere and H2Heating to a growth temperature, introducing a carbon source, keeping the temperature constant for a period of time, and growing a graphene film on the optical fiber; and 3, after the growth is finished, cooling to room temperature to obtain the graphene optical fiber. The substrate carrying the optical fiber and the liquid metal should be a solid material, such as quartz boat, with a smooth and clean surface, a melting point higher than 1100 ℃, and a low probability of reacting with Ga atoms.
Preferably, the preparation method of the graphene optical fiber provided by the invention can further have the following characteristics: in step 1, the liquid metal is at least one of Ga, In, and Sn.
Preferably, the preparation method of the graphene optical fiber provided by the invention can further have the following characteristics: in the step 1, acetone, ethanol and ultrapure water are sequentially put into the reactor for ultrasonic cleaning for 20min, and the cleaned optical fiber is blown dry by high-purity nitrogen.
Preferably, the preparation method of the graphene optical fiber provided by the invention can further have the following characteristics: in step 2, the temperature is raised to 1100 ℃, and then the temperature is kept constant for 2 hours.
Preferably, the preparation method of the graphene optical fiber provided by the invention can further have the following characteristics: in the step 2, the heating rate is 30-40 ℃/min, and the most preferable is 40 ℃/min.
Preferably, the preparation method of the graphene optical fiber provided by the invention can further have the following characteristics: in step 2, the flow rate of the inert gas is 100-300 sccm, more preferably 100 sccm; h2The flow rate of (b) is 20sccm to 50sccm, more preferably 50 sccm. The inert gas can be Ar or N2And the like, preferably Ar.
Preferably, the preparation method of the graphene optical fiber provided by the invention can further have the following characteristics: in step 2, the carbon source is at least one of methane, ethane, propane, carbon monoxide, butadiene, pentadiene, acetylene, methanol, and ethanol, preferably methane.
Preferably, the preparation method of the graphene optical fiber provided by the invention can further have the following characteristics: in step 3, the cooling rate is 15 ℃/min.
< graphene film >
The invention also provides a graphene optical fiber, which is characterized in that: was obtained by the method described in < preparation method > above.
Action and Effect of the invention
1. According to the method, the graphene optical fiber is prepared by using a liquid metal vapor-assisted CVD method, and the liquid metal vapor-assisted CVD method is used for catalyzing the reaction process of graphene deposition, so that the purpose of growing a high-quality graphene film with uniform thickness on the surface of the optical fiber is achieved, and the high-quality graphene film is controllably prepared. According to the method, liquid metal is heated in an inert atmosphere to volatilize the liquid metal into a gas state, and in the process, liquid metal steam is utilized to catalyze and decompose carbon source methane to deposit a more uniform high-quality graphene film, so that the aim of preparing a high-quality graphene optical fiber is fulfilled. The method achieves the aim of controlling the concentration of the liquid metal by strictly controlling the use amount and the existence form of the liquid metal in the system, thereby realizing the controllable preparation of the high-quality graphene optical fiber.
2. Compared with the traditional CVD method, the method uses metal vapor as a catalyst, allows graphitized carbon to be directly deposited on the surface of the optical fiber, and forms the graphene film with low defects. The method does not need etching after growth and evaporation of a metal catalyst, does not have any possible damage risk, and can obtain the graphene film with higher quality.
3. The method has universality, and for most of liquid metals (Ga, In, Sn and the like), the graphene film can be prepared by utilizing a metal steam assisted chemical vapor deposition method by adjusting experimental parameters.
4. According to the method disclosed by the invention, low-melting-point metal is introduced as the catalyst, so that the metal catalyst residue in the traditional preparation method is avoided, and the high-quality graphene optical fiber with uniform film thickness is prepared.
5. The method for preparing the graphene optical fiber provided by the invention has simple conditions, does not need to rigorously control conditions such as heating speed, growth temperature, system pressure, cooling speed and the like, and further does not need to consider the directionality of the substrate. The experimental preparation parameters (such as temperature rise speed, growth temperature, system pressure, temperature drop speed and the like) are high in control fault tolerance, the prepared graphene optical fiber is strict and uniform, the product repeatability is good, the substrate is low in price and easy to obtain, and the method is particularly suitable for industrial production and especially suitable for controllable preparation of the graphene optical fiber.
Drawings
Fig. 1 is a schematic diagram of a graphene optical fiber manufacturing process according to a first embodiment of the present invention;
fig. 2 is an OM diagram of a graphene optical fiber prepared in the first embodiment of the present invention;
FIG. 3 is a graph comparing an optical fiber after growth (a) and before growth (b) of a graphene thin film according to a first embodiment of the present invention;
fig. 4 is a Raman chart of a graphene optical fiber prepared in the first embodiment of the present invention;
fig. 5 is an SEM image of a graphene optical fiber prepared in the first embodiment of the present invention.
Detailed Description
Specific embodiments of the graphene optical fiber and the method for manufacturing the same according to the present invention will be described in detail below with reference to the accompanying drawings.
< example one >
The method for preparing the graphene optical fiber provided by the first embodiment specifically includes the following steps:
(1) removing the organic layer coated on the surface of the optical fiber by using a blade, sequentially putting the optical fiber into acetone, ethanol and ultrapure water for ultrasonic cleaning for 20min, and drying the cleaned optical fiber by using high-purity nitrogen;
(2) cutting the cleaned optical fiber to 5-6 cm by using a blade, and putting the optical fiber into a clean quartz boat; dripping a drop of liquid metal Ga (30mg) into a new quartz boat, wherein the purity of the liquid metal Ga is more than or equal to 99.9999 percent;
(3) as shown in FIG. 1, the sample obtained in step (2) was directly placed in a chemical vapor deposition apparatus at an Ar gas flow rate of 100sccm and H2Under the protection of gas flow of 50sccm, temperature is programmed, and when the temperature is raised and is kept at 1100 ℃, a carbon source CH is introduced4(gas flow 10sccm) and held for 2 h;
(4) stopping introducing CH4Cooling by a program of 30min, cooling at a speed of 15 ℃/min, cooling to room temperature, and closing Ar and H2And taking out the sample to obtain the optical fiber with the graphene film, namely the graphene optical fiber.
Respectively characterizing the prepared graphene optical fiber by adopting an optical microscope, a Raman spectrum and a scanning electron microscope: as shown in fig. 2, it can be seen from an optical microscope that the obtained graphene optical fiber is very uniform in a wide range; as shown in fig. 3, as can be seen from comparison between the before and after deposition of the graphene optical fiber, the graphene optical fiber after deposition (a) has a visually distinct difference in appearance from the graphene optical fiber before deposition (b), indicating that the graphene optical fiber is successfully prepared. As shown in fig. 4, which is a single-point Raman diagram of the graphene optical fiber, the stronger 2D peak and G peak in the diagram show that the obtained graphene has better quality. As shown in fig. 5, it can be seen from the scanning electron microscope that the graphene optical fiber prepared in this embodiment has a smooth surface, and the graphene is very continuous and uniform.
< example two >
The method for preparing the graphene optical fiber provided by the second embodiment specifically includes the following steps:
(1) removing the organic layer coated on the surface of the optical fiber by using a blade, sequentially putting the optical fiber into acetone, ethanol and ultrapure water for ultrasonic cleaning for 20min, and drying the cleaned optical fiber by using high-purity nitrogen;
(2) cutting the cleaned optical fiber to 5-6 cm by using a blade, and putting the optical fiber into a clean quartz boat; adding 30mg indium (In) into a new quartz boat;
(3) directly putting the sample in the step (2) into a chemical vapor deposition device, and controlling the Ar gas flow to be 100sccm and H2Under the protection of gas flow of 50sccm, temperature is programmed, and when the temperature is raised and is kept at 1100 ℃, a carbon source CH is introduced4(gas flow 10sccm) and held for 2 h;
(4) stopping introducing CH4Cooling by a program of 30min, cooling at a speed of 15 ℃/min, cooling to room temperature, and closing Ar and H2And taking out the sample to obtain the optical fiber with the graphene film growing, namely the graphene optical fiber.
< example three >
The method for preparing the graphene optical fiber provided by the third embodiment specifically includes the following steps:
(1) removing the organic layer coated on the surface of the optical fiber by using a blade, sequentially putting the optical fiber into acetone, ethanol and ultrapure water for ultrasonic cleaning for 20min, and drying the cleaned optical fiber by using high-purity nitrogen;
(2) cutting the cleaned optical fiber to 5-6 cm by using a blade, and putting the optical fiber into a clean quartz boat; adding 30mg of tin (Sn) into a new quartz boat;
(3) directly putting the sample in the step (2) into a chemical vapor deposition device, wherein the Ar gas flow is 100sccm、H2Under the protection of gas flow of 50sccm, temperature is programmed, and when the temperature is raised and is kept at 1100 ℃, a carbon source CH is introduced4(gas flow 10sccm) and held for 2 h;
(4) stopping introducing CH4Cooling for 30min, naturally cooling, cooling to room temperature, and closing Ar and H2And taking out the sample to obtain the optical fiber with the graphene film, namely the graphene optical fiber.
< example four >
The method for preparing the graphene optical fiber provided by the fourth embodiment specifically includes the following steps:
(1) removing the organic layer coated on the surface of the optical fiber by using a blade, sequentially putting the optical fiber into acetone, ethanol and ultrapure water for ultrasonic cleaning for 20min, and drying the cleaned optical fiber by using high-purity nitrogen;
(2) cutting the cleaned optical fiber to 5-6 cm by using a blade, and putting the optical fiber into a clean quartz boat; dropping a drop of Ga (30mg) in a new quartz boat;
(3) directly putting the sample in the step (2) into a chemical vapor deposition device, and controlling the Ar gas flow to be 300sccm and H2Under the protection of the gas flow of 20sccm, temperature is programmed, and when the temperature is raised and is kept at 1050 ℃, a carbon source CH is introduced4(gas flow 5sccm) and held for 2 h;
(4) stopping introducing CH4Cooling for 30min, naturally cooling, cooling to room temperature, and closing Ar and H2And taking out the sample to obtain the optical fiber with the graphene film, namely the graphene optical fiber.
The above embodiments are merely illustrative of the technical solutions of the present invention. The graphene optical fiber and the method for manufacturing the same according to the present invention are not limited to the description in the above embodiments, but are subject to the scope defined by the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.

Claims (10)

1. A preparation method of a graphene optical fiber is characterized by comprising the following steps:
step 1, taking an optical fiber as a growth substrate, and placing liquid metal on the upstream of the optical fiber;
step 2, in inert atmosphere and H2Heating to a growth temperature, introducing a carbon source, keeping the temperature constant for a period of time, and growing a graphene film on the optical fiber;
and 3, after the growth is finished, cooling to room temperature to obtain the graphene optical fiber.
2. The method for preparing the graphene optical fiber according to claim 1, wherein:
in step 1, the liquid metal is at least one of Ga, In, and Sn.
3. The method for preparing the graphene optical fiber according to claim 1, wherein:
in the step 1, acetone, ethanol and ultrapure water are sequentially put into the reactor for ultrasonic cleaning for 20min, and the cleaned optical fiber is dried by high-purity nitrogen.
4. The method for preparing the graphene optical fiber according to claim 1, wherein:
wherein, in the step 2, the temperature is raised to 1100 ℃, and then the temperature is kept for 2 hours.
5. The method for preparing the graphene optical fiber according to claim 1, wherein:
wherein in the step 2, the heating rate is 30-40 ℃/min.
6. The method for preparing the graphene optical fiber according to claim 1, wherein:
wherein, in step 2, the flow rate of the inert gas is 100-300 sccm, H2The flow rate of (2) is 20sccm to 50 sccm.
7. The method for preparing the graphene optical fiber according to claim 5, wherein:
wherein, in step 2, the flow rate of the inert gas is 100sccm, H2The flow rate was 50 sccm.
8. The method for preparing the graphene optical fiber according to claim 1, wherein:
in the step 2, the carbon source is at least one of methane, ethane, propane, carbon monoxide, butadiene, pentene, acetylene, methanol and ethanol.
9. The method for preparing the graphene optical fiber according to claim 1, wherein:
wherein, in the step 3, the cooling rate is 15 ℃/min.
10. A graphene optical fiber, characterized in that:
prepared by the preparation method of any one of claims 1 to 9.
CN201911024425.5A 2019-10-25 2019-10-25 Graphene optical fiber and preparation method thereof Withdrawn CN110922068A (en)

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Publication number Priority date Publication date Assignee Title
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US20150205040A1 (en) * 2013-11-03 2015-07-23 Tyson York Winarski Graphene coated optic fibers
CN107540245A (en) * 2016-06-24 2018-01-05 北京大学 A kind of direct preparation method in situ of graphene optical fiber
CN108545966A (en) * 2018-07-16 2018-09-18 北京石墨烯研究院 A kind of Graphene glass fiber and preparation method thereof
CN105645778B (en) * 2014-12-03 2018-10-23 北京大学 Superior graphite alkene glass and the preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110244210A1 (en) * 2007-10-29 2011-10-06 Samsung Electronics Co., Ltd. Graphene sheet and method of preparing the same
US20150205040A1 (en) * 2013-11-03 2015-07-23 Tyson York Winarski Graphene coated optic fibers
US20160207829A1 (en) * 2013-11-03 2016-07-21 Tyson York Winarski Graphene coated optic fibers
CN105645778B (en) * 2014-12-03 2018-10-23 北京大学 Superior graphite alkene glass and the preparation method and application thereof
CN107540245A (en) * 2016-06-24 2018-01-05 北京大学 A kind of direct preparation method in situ of graphene optical fiber
CN108545966A (en) * 2018-07-16 2018-09-18 北京石墨烯研究院 A kind of Graphene glass fiber and preparation method thereof

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