CN118150271A - Detection method for metal substrate graphene film defects - Google Patents
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Abstract
The invention belongs to the technical field of graphene quality detection, and particularly relates to a method for detecting defects of a graphene film with a metal substrate. The detection method comprises the following steps: (1) Wetting the surface of the graphene film with a developing solution; (2) Cleaning and drying the metal substrate graphene film; (3) The color difference was observed by an optical microscope to determine whether or not a defect exists. The detection method omits a complex sample preparation process for observing the defects of the graphene by adopting high-end electronic equipment, and has low cost; the development of the defects can be completed within a few seconds (at least 2 seconds), and the large-area detection of the defects of the graphene film can be realized rapidly, accurately and efficiently; and the reaction of the developer only occurs at the defect position of the graphene, so that the defect development accuracy is high, and the influence on the non-defect position is avoided.
Description
Technical Field
The invention belongs to the technical field of graphene quality detection, and particularly relates to a method for detecting defects of a graphene film with a metal substrate.
Background
Graphene is a monoatomic layer two-dimensional atomic crystal with sp 2 hybridized carbon atoms arranged in a honeycomb shape, and the unique crystal structure endows the graphene with a plurality of excellent properties, so that the graphene has wide application prospects in various fields such as electronic devices, photoelectrons and the like. Chemical Vapor Deposition (CVD) as one of the graphene preparation techniques is the most commonly used method for large-scale preparation of graphene films, especially for preparing metal-based graphene films. Although researchers have made great progress in preparing high-quality graphene films by adopting a CVD method, defects are inevitably introduced in the growth process, and the graphene defects can obviously reduce the electrical, thermal, mechanical and other properties of graphene. Therefore, a method for overcoming the defects of graphene is needed to meet the requirements of quality inspection links in graphene industrialization.
At present, the graphene quality detection mainly comprises the following three methods: (1) The defects of the graphene are directly observed by using high-end electronic equipment such as a scanning tunnel microscope or a transmission electron microscope, but the method needs to transfer a graphene sample, has long time consumption, complex sample preparation, high cost, a detection area in a nanometer range and a small detection range, and cannot meet the requirements of high-efficiency, rapid and large-scale quality evaluation of the graphene product in the graphene industrialization process; (2) Detecting graphene defects through physical interaction, such as adsorption of liquid crystal molecules on graphene, and observing distribution orientation of the liquid crystal molecules by using a polarized light microscope to determine domain orientation and grain boundary defects of the graphene, wherein in the method, in order to avoid the influence of a graphene growth substrate, the graphene needs to be transferred to other substrates, so that the process is complicated; (3) The chemical reaction is also a method for detecting the defects of the graphene, for example, the graphene at the defect is destroyed by adopting oxygen plasma to treat a graphene sample, then the substrate at the defect is oxidized to display the defects of the graphene, but the method can destroy the graphene at the non-defect position, and new defects are additionally introduced, so that the defect detection precision is low; the method can oxidize metal which is not covered with graphene by heating and oxidizing the metal substrate graphene, and display large-area cracks or underspliced positions through the difference of color contrast, but the method can not display the grain boundary defects among graphene domain areas through optical microscope observation, and has the problems of low detection precision and the like.
Therefore, in order to make up for the defects in the prior art, a method for efficiently, rapidly, nondestructively, accurately and widely detecting defects of graphene (particularly graphene with a metal substrate) is urgently needed to meet the requirements of quality inspection links in graphene industrialization.
Disclosure of Invention
The invention provides a detection method for a graphene film defect of a metal substrate, which is characterized in that the defect position of the graphene is detected by developing the defect position of the graphene and observing color change, and the detection method is efficient, quick, nondestructive and accurate, and can detect the defect position of the graphene in a large area.
In order to achieve the above purpose, the present invention may adopt the following technical scheme:
The invention provides a method for detecting defects of a graphene film with a metal substrate, which comprises the following steps: (1) Wetting the surface of the graphene film of the metal substrate by using a developing solution, wherein the developing solution is a metal salt solution, cations of the metal salt can diffuse through the graphene defect, and electrode potential values of oxidation/reduction pairs consisting of cations and corresponding reduction products of the cations are larger than electrode potential values of oxidation/reduction pairs consisting of the metal substrate and corresponding oxidation products of the cations, so that the cations react with the metal substrate at the defect; (2) Cleaning and drying the metal substrate graphene film; (3) The color difference was observed by an optical microscope to determine whether or not a defect exists.
Preferably, the metal substrate is a copper substrate, a nickel substrate, a cobalt substrate, a copper-nickel alloy substrate, or a copper-cobalt alloy substrate.
Preferably, in the step (1), the metal salt solution is AgNO 3 solution or FeCl 3 solution.
Preferably, in the step (1), the solvent in the metal salt solution is water or alcohol.
Preferably, in the step (1), the method of wetting the surface of the graphene film with the developing solution includes spraying or soaking.
Preferably, in the step (1), the method of wetting the surface of the graphene film with the developing solution is soaking, and the soaking time is more than or equal to 2s.
Preferably, in the step (1), the concentration of the metal salt solution in the step (1) is selected according to the following conditions: (a) The metal salt solution is AgNO 3 solution, and the concentration of the solution is 1 mu M-10M; (b) The metal salt solution is FeCl 3 solution, and the concentration of the metal salt solution is less than 0.1M.
Preferably, the metal salt solution is AgNO 3 solution or FeCl 3 solution, and the region where black spots are observed by an optical microscope after development is the defect of the graphene film.
The beneficial effects of the invention at least comprise:
(1) The method for detecting the defects of the graphene film with the metal substrate provided by the invention omits a complex sample preparation process of observing the defects of the graphene by adopting high-end electronic equipment (such as a scanning tunnel microscope or a transmission electron microscope), can complete development of the defects within a few seconds (at least 2 seconds), and can rapidly, accurately and efficiently realize large-area detection of the defects of the graphene film.
(2) The method for detecting the defects of the graphene film with the metal substrate adopts the developer as a common reagent, adopts a common optical microscope as observation equipment, and has low quality evaluation cost; and the reaction of the developer only occurs at the defect position of the graphene, so that the defect development accuracy is high, and the influence on the non-defect position is avoided.
Drawings
FIG. 1 is an optical microscope image of a graphene defect developed using a 5mMAgNO 3 solution as a developer in accordance with the present invention;
FIG. 2 is an optical microscope image of a graphene defect developed using a 5mMFeCl 3 solution as a developer in accordance with the present invention;
FIG. 3 is an optical microscope image of a graphene defect developed using a 10mM FeCl 3 solution as a developer in accordance with the present invention;
FIG. 4 is an optical microscope image of a graphene defect developed using a 0.1M FeCl 3 solution as a developer in accordance with the present invention;
FIG. 5 is a Raman spectrum of graphene defect sites and non-defect sites after development according to the present invention;
FIG. 6 is an optical microscope image of domains of graphene grown in accordance with the present invention;
FIG. 7 is an optical microscope image of the development of graphene defects using developers of different ionic species in accordance with the present invention;
Fig. 8 is an optical microscope image of the invention after development using different substrates.
Detailed Description
The examples are presented for better illustration of the invention, but the invention is not limited to the examples. Those skilled in the art will appreciate that various modifications and adaptations of the embodiments described above are possible in light of the above teachings and are intended to be within the scope of the invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. Unless the context clearly differs, singular forms of expression include plural forms of expression. As used herein, it is understood that terms such as "comprising," "having," "including," and the like are intended to indicate the presence of a feature, number, operation, component, part, element, material, or combination. The terms of the present invention are disclosed in the specification and are not intended to exclude the possibility that one or more other features, numbers, operations, components, elements, materials or combinations thereof may be present or added. As used herein, "/" may be interpreted as "and" or "as appropriate.
The embodiment of the invention provides a method for detecting defects of a graphene film with a metal substrate, which comprises the following steps: (1) Wetting the surface of the graphene film of the metal substrate by using a developing solution, wherein the developing solution is a metal salt solution, cations of the metal salt can diffuse through the graphene defect, and electrode potential values of oxidation/reduction pairs consisting of cations and corresponding reduction products of the cations are larger than electrode potential values of oxidation/reduction pairs consisting of the metal substrate and corresponding oxidation products of the cations, so that the cations react with the metal substrate at the defect; (2) Cleaning and drying the metal substrate graphene film; (3) The color difference was observed by an optical microscope to determine whether or not a defect exists.
It should be noted that, for graphene with a metal substrate, the graphene completely covers the metal substrate, point defects, line defects and the like of the graphene are defects with atomic scale, cations of a developing solution need to overcome diffusion energy barriers at the defects of the graphene, the positions of the defects of the graphene can be detected after the cations and oxidation/reduction pairs corresponding to the cations are diffused through the defects of the graphene, electrode potential values of the oxidation/reduction pairs formed by the metal substrate and the corresponding reduction products are larger than electrode potential values of the oxidation/reduction pairs formed by the metal substrate and the corresponding oxidation products, so that the cations can react with the metal substrate at the defects, if the reaction products of the cations are simple substances, simple substance particles can be deposited at the defects of the graphene, if the reaction products of the cations are ions, corrosion points of the metal substrate appear at the defects of the graphene, and the color differences of the cations can be detected by an optical microscope. Different metal cations have different diffusion energy barriers through the graphene defects, so that the capability of the cations to penetrate the graphene defects is different; the difference in electrode potential of the oxidation/reduction pair of cations and their corresponding reduction products results in a difference in reaction rates of the cations, and thus, a difference in development rates when different cations are used as the developer. The defect distribution and defect density of the graphene can be judged through an optical microscope, so that the quality of the graphene product can be rapidly evaluated.
It should be understood that the AgNO 3 or FeCl 3 solution in the present invention is obtained by a conventional preparation method in the art, for example, when the developer is AgNO 3, a proper amount of AgNO 3 is taken and placed in a beaker, a small amount of solvent is added to stir and dissolve, the volume is fixed in a volumetric flask, the prepared concentrated solution is stored in a brown reagent bottle, and the prepared concentrated solution is diluted to the low concentration used in the experiment.
In some embodiments, the metal substrate may be a copper substrate, a nickel substrate, a cobalt substrate, a copper-nickel alloy substrate, or a copper-cobalt alloy substrate.
In some embodiments, in step (1) above, the metal salt solution is an AgNO 3 solution or a FeCl 3 solution. It should be noted that, the cations in the metal salt solution in the present invention can diffuse through the graphene defect and react with the metal substrate at the defect, so not all metal salt solutions can play a role in developing, such as Cu (NO 3)2 solution, which has NO obvious defect developing effect in the same time as other metal salt solutions, and NO defect developing is observed after the development time is prolonged, which indicates that Cu (NO 3)2 solution cannot be used as the developing solution in the present invention).
In some embodiments, in the step (1), the solvent in the metal salt solution is water or alcohol. The solvent of the metal salt solution in the present invention may be known in the art, and water or alcohol is preferable as the solvent, and water and alcohol as the solvent may allow the metal salt solution to be well developed.
In some specific embodiments, in the step (1), the method of wetting the surface of the graphene film with the developing solution includes spraying or soaking. In the above detection method, the purpose of wetting the surface of the graphene film with the developing solution is to develop the defect, so that the method can be performed by soaking or spraying; alternatively, the spraying may be performed by means of an associated spraying device. It should be noted that, the spraying process needs to uniformly spread the developing solution over the area to be detected, and the soaking process needs to completely immerse the area to be detected in the developing solution.
In some embodiments, in the step (1), the method of wetting the surface of the graphene film with the developing solution is soaking, and the soaking time is not less than 2s. In the detection method of the present invention, wetting can be completed in a short time by immersing.
In some embodiments, in the step (1), the concentration of the metal salt solution is selected according to the following conditions: (a) The metal salt solution is AgNO 3 solution, and the concentration of the solution is 1 mu M-10M; (b) The metal salt solution is FeCl 3 solution, and the concentration of the metal salt solution is less than 0.1M. In the detection method of the present invention, the concentration of the developing solution (metal salt solution) may be selected according to the specific conditions of the graphene product. For example, for FeCl 3 solution, the concentration is too high, the reaction is too fast, excessive corrosion of the substrate is easy to cause, the formed corrosion point is very large, the defect site detection precision is reduced, and meanwhile, the graphene film is easy to be damaged, so the concentration is less than 0.1M; for example, in the AgNO 3 solution, ag particles generated at defects can prevent subsequent Ag + from diffusing through graphene defects, and excessive reaction is not easy to occur even at relatively high concentration, so that the AgNO 3 solution has good reaction in the range of 1 mu M-10M, such as 1 mu M-5 mM, 5mM-10mM or 1M-10M.
In some embodiments, the metal salt solution is AgNO 3 solution or FeCl 3 solution, and the region where black spots are observed by an optical microscope after development is the graphene film defect. The development rates of different metal salt solutions are different, the development rates are different, and the development depths are different, namely, the development rates are different in substantial reaction. AgNO 3 solution or FeCl 3 solution is preferable in the invention, and the developing rate is relatively high; the solution may be an aqueous solution or an alcoholic solution.
For a better understanding of the present invention, the content of the present invention is further elucidated below in connection with the specific examples, but the content of the present invention is not limited to the examples below.
In the following examples, the preparation method of the CVD-grown Cu-based graphene film includes: and respectively ultrasonically cleaning the copper foil for 10min by dilute acetic acid, acetone and isopropanol in sequence, then washing the copper foil by ultrapure water, drying the copper foil by nitrogen, putting the cleaned copper foil into a tube furnace, annealing for 1H at 1050 ℃ under Ar and H 2 atmosphere, introducing a carbon source CH 4, growing for 10min at 1050 ℃, and cooling the sample to room temperature to obtain the copper-based graphene film.
Example 1 Effect of AgNO 3 solution as developer on graphene Defect development
(1) The copper-based graphene film grown by CVD is immersed in 5mMAgNO 3 aqueous solution for development, the development time is set to be different for 2s, 10s and 20s, then the sample is washed by ultrapure water and dried.
(2) The developed samples were observed under an optical microscope to obtain the corresponding optical microscope pictures in fig. 1.
The optical microscope image is provided with black Ag particles on a sample, a region surrounded by the black Ag particles is a graphene domain region, and a graphene grain boundary or defect is located at an Ag point; along with the development time prolonged to 10s, edges surrounded by the Ag points are more obvious, so that the crystal boundary defects of the graphene are clearer; the development time is continuously increased to 20s, and Ag points are more continuous.
The above results demonstrate that graphene defects can be clearly visualized in a few seconds using AgNO 3 as a defect developer.
Example 2 effect of FeCl 3 solution as developer on graphene Defect development
(1) The Cu substrate graphene film grown by CVD is respectively immersed into 5mMFeCl 3 aqueous solution for development, the development time is set to be different, the time is 2s, 10s and 50s, then the sample is washed by ultrapure water, and the sample is dried.
(2) The developed samples were observed under an optical microscope to obtain the corresponding optical microscope pictures in fig. 2. When the optical microscope image shows that the development time is 2s, black points can be observed, the points are corrosion points of Cu at the defect, the enclosed area is a graphene domain area, and the area where the corrosion points are located is a graphene grain boundary or the defect; along with the development time prolonged to 10s, the edges surrounded by the black points are more obvious, so that the graphene grain boundary is clearer; the development time was continued to increase to 50s and the black dots were more continuous.
(3) The CVD-grown Cu-based graphene films were immersed in 10mMFeCl 3 aqueous solutions, respectively, for 2s development, followed by washing the samples with ultrapure water, and drying.
(4) The developed samples were observed under an optical microscope to obtain the corresponding optical microscope pictures in fig. 3.
Comparing the development effects of fig. 2 (a) and fig. 3, it was found that the defect points developed at low concentration of FeCl 3 were dispersed and the color was light, and the development points developed at proper concentration of FeCl 3 were darker, so that the development effect was more remarkable.
(5) The CVD grown Cu-based graphene films were each immersed in 0.1M FeCl 3 aqueous solution for 10s development, followed by washing the samples with ultrapure water and drying.
(6) The developed samples were observed under an optical microscope to obtain the corresponding optical microscope pictures in fig. 4.
Comparing the development effects of fig. 2 (b) and fig. 4, it is found that when the concentration of FeCl 3 is too high, the reaction rate is too high, excessive corrosion of the substrate is caused, and the formed corrosion point is very large, so that the defect site detection accuracy is reduced, and meanwhile, the graphene film is easily damaged.
The above results demonstrate that the graphene defects can be clearly visualized in a few seconds using FeCl 3 as a defect developer.
In addition, the raman spectra of the developed graphene defect and non-defect are shown in fig. 5, and the graphene at the black point has a distinct D peak, while the graphene at the non-black point has no D peak, which proves that the black point is the graphene defect or the grain boundary.
Meanwhile, the comparison of fig. 2 and fig. 1 shows that the AgNO 3 is more obvious than the FeCl 3 in the same concentration, because, although the ionic radius (0.126 nm) of Ag + is larger than that of Fe 3+ (0.064 nm), that is, the resistance of Ag + diffusing through graphene is larger than that of Fe 3+, and the Ag + penetrating through graphene defects is less than that of Fe 3+, the oxidizing property of Ag + is stronger than that of Fe 3+, resulting in that the developing speed of AgNO 3 is faster than that of FeCl 3 when used as a developer.
Example 3 comparing graphene Domain and graphene actual Domain displayed by defect development
The Cu substrate graphene film grown by CVD is formed by AgNO 3 and FeCl 3, the black points are the displayed graphene crystal boundaries or defects, the areas surrounded by the black points are the domains of the graphene, and the domains of the graphene are about 15-30 μm in the figures 1,2 and 3.
In addition, according to the preparation method of the Cu-based graphene film grown by CVD, the time for CVD growth of the metal-based graphene film is shortened to 3min, so that all domains of the graphene are sufficiently grown but are not completely connected with each other, namely, growth is stopped immediately before all domains of the graphene are spliced, so that the domain size of the graphene is observed, an obtained sample is heated in air, cu which is not covered with the graphene is oxidized, and therefore, the domain size distribution of the graphene can be determined, and the distribution is consistent with the result obtained by defect development, as shown in FIG. 6.
Example 4 comparison of the Effect of ionic species on graphene film developer Effect
(1) The CVD grown Cu-based graphene films were developed with 5mM AgNO 3、Cu(NO3)2, respectively, followed by washing the samples with ultrapure water and drying.
(2) Observing the developed sample under an optical microscope to obtain an optical microscope picture corresponding to fig. 7, wherein (a) is the condition that AgNO 3 solution is used as a developer to develop for 15 s; (b) (c) and (d) are the results of developing Cu (NO 3)2 as developer for 15s, 40s and 50s, respectively.
The optical microscope image shows that when AgNO 3 is used as a developer, the graphene defect can be developed, but when Cu (NO 3)2 is used as the developer, NO obvious defect developing effect exists in the same time, and defect developing is not observed after the development time is prolonged to 40s and 50s, the optical microscope image shows that although the ionic radius (0.070 nm) of Cu 2+ is smaller than Ag + (0.126 nm), the diffusion resistance of the graphene at the graphene defect through the graphene is smaller than Ag +, cu 2+ does not react with Cu, so that NO color change exists at the graphene defect, and NO developing effect exists.
Example 5 comparison of Effect of different substrates on graphene film developer Effect
(1) Transferring a graphene film to a silicon wafer by adopting a wet transfer method, specifically performing spin coating of PMMA on copper-based graphene (PMMA/G/Cu), heating at 150 ℃ for 5min, putting PMMA/G/Cu into a 1M FeCl 3 solution, obtaining PMMA/G after copper foil etching is finished, soaking and cleaning the PMMA/G in ultrapure water for two times, taking out the PMMA/G by using the cleaned silicon wafer, heating at 150 ℃ for 10min, and then removing the PMMA by using acetone to obtain the silicon wafer-based graphene film (G/SiO 2/Si).
(2) Developing the copper-based graphene film and the graphene film on the silicon wafer by using 5mMAgNO 3, cleaning a sample by using ultrapure water, and drying.
(3) And observing the developed sample under an optical microscope to obtain an optical microscope picture corresponding to the image in fig. 7, wherein (a) is the development condition of the copper substrate, and (b) is the development condition of the graphene film on the silicon wafer.
The optical microscope image shows that after the substrate is replaced by a silicon wafer, although the developer can diffuse through graphene at the defect of the graphene, the developer does not react with the substrate, so that the color change at the defect is avoided, and the defect development process cannot be realized.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (10)
1. The method for detecting the defects of the graphene film on the metal substrate is characterized by comprising the following steps of: (1) Wetting the surface of the graphene film of the metal substrate by using a developing solution, wherein the developing solution is a metal salt solution, cations of the metal salt can diffuse through the graphene defect, and electrode potential values of oxidation/reduction pairs consisting of cations and corresponding reduction products of the cations are larger than electrode potential values of oxidation/reduction pairs consisting of the metal substrate and corresponding oxidation products of the cations, so that the cations react with the metal substrate at the defect; (2) Cleaning and drying the metal substrate graphene film; (3) The color difference was observed by an optical microscope to determine whether or not a defect exists.
2. The method for detecting a graphene film defect on a metal substrate according to claim 1, wherein the metal substrate is a copper substrate, a nickel substrate, a cobalt substrate, a copper-nickel alloy substrate or a copper-cobalt alloy substrate.
3. The method for detecting defects of a graphene film on a metal substrate according to claim 1 or 2, wherein in the step (1), the metal salt solution is AgNO 3 solution or FeCl 3 solution.
4. The method for detecting defects of a graphene film on a metal substrate according to claim 3, wherein in the step (1), the solvent in the metal salt solution is water or alcohol.
5. The method for detecting defects of a metal-based graphene film according to claim 1, 2 or 4, wherein in the step (1), the method for wetting the surface of the metal-based graphene film with the developer solution comprises spraying or immersing.
6. The method for detecting defects of a metal-based graphene film according to claim 1, 2 or 4, wherein in the step (1), the method for wetting the surface of the metal-based graphene film by using the developing solution is soaking, and the soaking time is not less than 2s.
7. The method for detecting defects of a graphene film on a metal substrate according to claim 1,2 or 4, wherein in the step (1), the concentration of the metal salt solution is selected according to the following conditions: (a) The metal salt solution is AgNO 3 solution, and the concentration of the solution is 1 mu M-10M; (b) The metal salt solution is FeCl 3 solution, and the concentration of the metal salt solution is less than 0.1M.
8. The method for detecting defects of a graphene film on a metal substrate according to claim 6, wherein the concentration of the metal salt solution is selected according to the following conditions: (a) The metal salt solution is AgNO 3 solution, and the concentration of the solution is 1 mu M-10M; (b) The metal salt solution is FeCl 3 solution, and the concentration of the metal salt solution is less than 0.1M.
9. The method for detecting defects of graphene film on metal substrate according to claim 1,2,4 or 8, wherein the metal salt solution is AgNO 3 solution or FeCl 3 solution, and the region where black spots are observed by an optical microscope after development is the defect of graphene film.
10. The method for detecting the defects of the graphene film on the metal substrate according to claim 7, wherein the metal salt solution is AgNO 3 solution or FeCl 3 solution, and the region where black spots are observed by an optical microscope after development is the defects of the graphene film.
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