CN110127667B - Controllable graphene quantum dot preparation method - Google Patents

Controllable graphene quantum dot preparation method Download PDF

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Publication number
CN110127667B
CN110127667B CN201910375510.XA CN201910375510A CN110127667B CN 110127667 B CN110127667 B CN 110127667B CN 201910375510 A CN201910375510 A CN 201910375510A CN 110127667 B CN110127667 B CN 110127667B
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quantum dots
substrate
graphene quantum
doping
injection
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CN110127667A (en
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王婷
王刚
陈达
李久荣
顾冰丽
高博
王梓豪
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ENZE New Material Technology (Jiangyin) Co.,Ltd.
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Ningbo University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon

Abstract

The invention discloses a controllable method for preparing graphene quantum dots, which comprises the following steps: preparing a substrate and forming photoresist on the substrate; forming an injection window on the photoresist by using a photoetching method or an ion exposure method; injecting a carbon source into the injection window by adopting an ion injection method; removing the photoresist; and annealing the substrate, and growing the graphene quantum dots on the surface of the substrate. According to the invention, on the basis of controlling the number of layers of the modified quantum dots by controlling the dose and the energy of the injection source, the size of the injection window is adjusted, so that the synthetic particle size of the quantum dots is changed, meanwhile, the doping concentration is adjusted by the dose of the doping source, and the shape and the position of the injection window are adjusted by photoetching, so that the arrangement mode of the later-stage synthesized quantum dots is controllable, the preparation process is simple, less waste is generated, and the method is relatively environment-friendly. If the doping is not carried out, the preparation of the intrinsic graphene quantum dots can be carried out, doping source ions are changed, and graphene quantum dots with different dopings can be prepared.

Description

Controllable graphene quantum dot preparation method
[ technical field ] A method for producing a semiconductor device
The invention relates to a controllable method for preparing graphene quantum dots, and belongs to the field of graphene quantum dots.
[ background of the invention ]
Graphene Quantum Dots (GQDs) are quasi-zero-dimensional materials that exhibit unique properties such as photoluminescence and slow hot carrier relaxation due to quantum confinement and edge effects. Moreover, the shape and size of GQDs also determine their electrical, magnetic and chemical properties. At present, the GQDs are synthesized by two methods, namely top-down peeling and shearing and bottom-up synthesis. The top-down method refers to that carbon materials such as graphene, carbon nano tubes, fullerene and the like are subjected to shearing treatment by physical or chemical means to obtain GQDs, but the preparation method cannot effectively control the surface morphology and the particle size of products; the bottom-up principle is that the precursor with a certain number of conjugated carbon atom structures is chemically synthesized and converted into GQDs, and the synthesis principle of the method is complex and is not easy to purify. Thus, it is difficult to obtain GQDs of a specific edge shape and uniform size in large quantities.
The synthesis of GQDs is only the preparation stage, and the GQDs can be really put into the application stage by modification. Modifying the GQDs changes the fluorescence properties, biocompatibility and electrical characteristics to some extent, and reduces non-radiative excitation so as to enhance the optical properties and quantum yield. The modification means are generally divided into two methods: surface functionalization and hetero-atom doping. The surface functionalization mainly comprises the steps of purposefully converting certain groups on the surface of the GQDs by a chemical means or carrying out surface functionalization modification on the GQDs by utilizing molecules with strong electron withdrawing capability or electron donating capability; the doping of the hetero atoms on the GQDs can change the intrinsic electronic structure of the GQDs, the chemical activity of the GQDs can be obviously improved, the most common element of the doping elements used for the GQDs at present is nitrogen (N), and boron (B), chlorine (Cl), sulfur (S) and various elements are co-doped. The modification method which is easy to realize in the prior art and is more commonly used is hetero atom doping, but the doping solubility is uncontrollable and the purification is difficult.
Therefore, a preparation technology of modified GQDs which has controllable particle size and layer number, adjustable doping concentration, simple preparation process and high quality and can realize industrialized production is urgently needed.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provide a method for preparing graphene quantum dots with controllable layer number.
The technical scheme adopted by the invention is as follows:
a controllable method for preparing graphene quantum dots comprises the following steps:
the method comprises the following steps: preparing a substrate and forming photoresist on the substrate;
step two: forming an injection window on the photoresist by using a photoetching method or an ion exposure method;
step three: injecting a carbon source into the injection window by adopting an ion injection method;
step IV: removing the photoresist;
step five: and annealing the substrate, and growing the graphene quantum dots on the surface of the substrate.
In the first step of the invention, the substrate is a nickel substrate, a semiconductor substrate or a crystal substrate.
In the second step of the invention, the size of the injection window is 1 angstrom-100 nm.
In the second step of the invention, the size, shape, quantity and distribution of the implantation windows on the substrate are adjusted by a photoetching method or an ion exposure method.
In the third step of the invention, a doping source is injected while the carbon source is injected.
In the third step of the invention, the doping source is one or more doping atoms.
And in the third step, the doping concentration in the graphene quantum dots is adjusted by adjusting the concentration of the doping source.
In the third step of the invention, the number of layers of the graphene quantum dots is controlled by adjusting the injection energy and dosage of the carbon source.
In the step (iv) of the present invention, the photoresist is removed by acetone immersion.
In the fifth step of the invention, the annealing temperature is 200 ℃ and 800 ℃, and the annealing time is 5-120 minutes.
Compared with the prior art, the invention has the following beneficial effects:
on the basis of controlling the number of layers of the modified quantum dots by controlling the dose and the energy of the injection source, the size of the injection window is adjusted, so that the synthetic particle size of the quantum dots is changed, meanwhile, the doping concentration is adjusted by the dose of the doping source, and the shape and the position of the injection window are adjusted by photoetching, so that the arrangement mode of the later-stage synthesized quantum dots is controllable, the preparation process is simple, less waste is generated, and the method is relatively environment-friendly. If the doping is not carried out, the preparation of the intrinsic graphene quantum dots can be carried out, doping source ions are changed, different doped graphene quantum dots can be prepared, and the diatom or polyatomic co-doped graphene quantum dots can also be obtained by the preparation method.
Other features and advantages of the present invention will be disclosed in more detail in the following detailed description of the invention and the accompanying drawings.
[ description of the drawings ]
The invention is further described below with reference to the accompanying drawings:
fig. 1 is a flowchart of a controllable method for preparing graphene quantum dots according to embodiment 1 of the present invention.
[ detailed description ] embodiments
The technical solutions of the embodiments of the present invention are explained and illustrated below with reference to the drawings of the embodiments of the present invention, but the following embodiments are only preferred embodiments of the present invention, and not all embodiments. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative effort belong to the protection scope of the present invention.
In the following description, the appearances of the indicating orientation or positional relationship such as the terms "inner", "outer", "upper", "lower", "left", "right", etc. are only for convenience in describing the embodiments and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the present invention.
Example 1:
referring to fig. 1, the embodiment provides a controllable method for preparing graphene quantum dots, including the following steps:
the method comprises the following steps: preparing a substrate 1, and forming a photoresist 2 on the substrate 1;
the substrate 1 is a nickel substrate, a semiconductor substrate or a crystal substrate, and the nickel substrate is adopted in the embodiment to play a role in catalyzing the growth of the later-stage graphene quantum dots;
step two: forming an injection window 3 on the photoresist 2 by using a photoetching method or an ion exposure method;
the position, size, number and distribution of the implantation windows 3 can be adjusted by photolithography or ion exposure, for example, the implantation windows 3 in this embodiment are circular, all the implantation windows 3 are arranged in a rectangular array, and the diameter of the implantation windows 3 is 1 angstrom to 100 nm, preferably 10 nm;
step three: injecting a carbon source 4 into the injection window 3 by adopting an ion injection method, wherein the carbon source 4 is provided with energy by the ion injection method, and the carbon source 4 can enter the substrate 1 right below the injection window 3 regardless of the solubility of the substrate 1 to the carbon source 4;
step IV: removing the photoresist 2, wherein an acetone soaking method is adopted in the embodiment to remove the photoresist 2 as much as possible and simultaneously avoid chemical corrosion to the nickel substrate structure;
step five: and annealing the substrate 1 at the annealing temperature of 200-800 ℃ for 5-120 minutes, wherein the carbon source 4 in the substrate 1 is exuded from the surface of the substrate 1 to grow to form the intrinsic graphene quantum dots.
In the third step, the number of layers of the obtained intrinsic graphene quantum dots can be controlled by adjusting the injection energy and the dosage of the carbon source 4. For example, if the implantation energy is 60keV, the implantation dose is 4 x 105atoms/cm2Obtaining single-layer intrinsic graphene quantum dots, and if the injection amount is 8 x 105atoms/cm2And obtaining the double-layer intrinsic graphene quantum dots.
Therefore, a linear relation exists between the number of layers of the obtained intrinsic graphene quantum dots and the injection metering, the number of the layers of the obtained intrinsic graphene quantum dots can be clearly judged and controllably controlled through the improvement of the injection metering, the fact that the injected carbon source 4 completely forms the graphene quantum dots in the fifth step is shown that the utilization rate of the carbon source 4 is almost 100%, and accordingly, waste materials are hardly generated in the whole preparation process in the photoetching and photoresist removing 2 stages, and the environment protection effect is better. Meanwhile, the acetone solution for removing the photoresist 2 can be recycled, so that the cost can be further reduced.
In addition, the size, shape and distribution of the graphene quantum dots can be controlled by controlling the 3 stages of preparing the injection window in the second step. In the injection stage in the step (iv), the boundary of the carbon source entering the substrate 1 is limited by the boundary of the injection window 3 (i.e., the adjacent photoresist 2), so that the grown graphene quantum dots are located at the position of the injection window 3 prepared in the step (iv), the shape and distribution of the graphene quantum dots are also consistent with the shape and distribution of the injection window 3, and the shape and quantity distribution of the corresponding graphene quantum dots are also controllable due to the controllability of the preparation process of the injection window 3 by the photolithography method or the ion exposure method.
Accordingly, the size of the implantation window 3 should not be too small during the implantation process to avoid the carbon source 4 from being excessively hindered by the photoresist 2 during the process of entering the substrate 1, which results in the degradation of the implantation effect and the waste of the carbon source. Meanwhile, the size of the injection window 3 is not too large, so that too much carbon source is generated in the same injection window 3 area in the later period, the size of the graphene grown during annealing is too large, and quantum dots cannot be formed.
Example 2:
the difference between this embodiment and embodiment 1 is that, in the third step, a doping source, such as an N doping source, is also injected at the same time as the carbon source injection, and accordingly, the corresponding fifth step is to obtain the extrinsic doped graphene quantum dots. Meanwhile, the injection dosage of the N doping source and the carbon source dosage in the obtained doped graphene quantum dot are changed in the same ratio, namely the proportion between the doping element and the carbon source in the doped graphene quantum dot is the same as the proportion between the doping element dosage and the carbon source dosage in the injection process in the step III, so that the doping element in the embodiment can be injected with ions regardless of the type of the substrate and can fully enter the substrate, and in addition, the doping element can fully leave the inside of the substrate along with the carbon source in the annealing process and is mixed with the carbon source to form the doped graphene.
Meanwhile, through additional EDS representation, the N and C distribution in the prepared doped graphene can be verified to be very uniform, and the fact that the uniformity of the prepared doped graphene meets the actual requirement is fully demonstrated.
Example 3:
the difference between this embodiment and embodiment 2 is that, in the third step, an N doping source and a P doping source are also injected while injecting a carbon source, the ratio between N, P and C in the obtained doped graphene quantum dot is the same as the ratio between N, P and C injection dose in the third step, and by EDS representation, N, P and C can be uniformly distributed, which fully indicates that the doping element type number does not affect the doping uniformity, and the doping number and type are greatly expanded by the method of this embodiment.
Example 4:
the difference between this embodiment and embodiment 1 is that the substrate is selected as a Si substrate to be applied to a mature Si substrate process, which facilitates industrial production.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that the invention is not limited thereto, and may be embodied in many different forms without departing from the spirit and scope of the invention as set forth in the following claims. Any modification which does not depart from the functional and structural principles of the present invention is intended to be included within the scope of the claims.

Claims (6)

1. A controllable method for preparing graphene quantum dots is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: preparing a substrate and forming photoresist on the substrate;
step two: forming an injection window on the photoresist by using a photoetching method or an ion exposure method;
step three: injecting a carbon source into the injection window by adopting an ion injection method;
step IV: removing the photoresist;
step five: annealing the substrate, and growing graphene quantum dots on the surface of the substrate;
and step three, injecting a doping source while injecting the carbon source, wherein the doping source is one or more doping atoms, adjusting the doping concentration in the graphene quantum dots by adjusting the concentration of the doping source, and controlling the layer number of the graphene quantum dots by adjusting the injection energy and dosage of the carbon source.
2. The controllable method for preparing the graphene quantum dots according to claim 1, wherein the controllable method comprises the following steps: in the first step, the substrate is a nickel substrate, a semiconductor substrate or a crystal substrate.
3. The controllable method for preparing the graphene quantum dots according to claim 1, wherein the controllable method comprises the following steps: in the second step, the size of the injection window is 1 angstrom-100 nanometers.
4. The controllable method for preparing the graphene quantum dots according to claim 1, wherein the controllable method comprises the following steps: and step two, adjusting the size, shape, quantity and distribution of the implantation windows on the substrate by a photoetching method or an ion exposure method.
5. The controllable method for preparing the graphene quantum dots according to claim 1, wherein the controllable method comprises the following steps: and step IV, removing the photoresist by soaking in acetone.
6. The controllable method for preparing the graphene quantum dots according to claim 1, wherein the controllable method comprises the following steps: in the fifth step, the annealing temperature is 200-800 ℃, and the annealing time is 5-120 minutes.
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