阅读说明：本技术 一种增强石墨烯与基材结合牢度的方法 (Method for enhancing bonding fastness of graphene and base material ) 是由 傅院霞 宫昊 李莉 徐丽 王莉 于 2020-05-22 设计创作，主要内容包括：本发明公开了一种增强石墨烯与基材结合牢度的方法,包括以下步骤：S1通过将石墨烯液相涂膜或熔覆在基材的表面,制备结合的样品；S2将S1制备的样品安装在真空室内的电动三维可移动平台上待用；S3打开激光,将激光的光路聚焦在S2中的样品上；S4激光通过聚焦在样品的规划点进行灼烧,快速形成等离子体,引入官能团,利用电子、粒子接枝和结合,本发明涉及石墨烯技术领域。该增强石墨烯与基材结合牢度的方法直接采用激光烧蚀方法快速形成等离子体,引入官能团,利用电子、离子接枝和结合,使增强石墨烯熔覆不同的基材的结合牢度。通过外部电磁场的改变使石墨烯与基材能够获得一种结合强度更高的束缚结构,从而实现两种表面均较稳定的材料的结合。(The invention discloses a method for enhancing the bonding fastness of graphene and a base material, which comprises the following steps: s1, preparing a combined sample by coating or cladding the graphene liquid phase on the surface of the base material; s2, mounting the sample prepared in the S1 on an electric three-dimensional movable platform in a vacuum chamber for standby; s3, turning on the laser, and focusing the light path of the laser on the sample in S2; the S4 laser is focused on a planned point of a sample to be burned, plasma is quickly formed, functional groups are introduced, and electrons and particles are used for grafting and combining. According to the method for enhancing the bonding fastness of the graphene and the base material, the plasma is rapidly formed by directly adopting a laser ablation method, functional groups are introduced, and the bonding fastness of different base materials cladded by the graphene is enhanced by utilizing electron and ion grafting and bonding. The graphene and the base material can obtain a bound structure with higher bonding strength through the change of an external electromagnetic field, so that the bonding of two materials with more stable surfaces is realized.)

1. A method for enhancing the bonding fastness of graphene and a substrate is characterized by comprising the following steps:

s1, preparing a combined sample by coating or cladding the graphene liquid phase on the surface of the rotating base material;

s2, mounting the sample prepared in the S1 on an electric three-dimensional movable platform in a vacuum chamber for standby;

s3, turning on the laser, and focusing the light path of the laser on the sample in S2;

s4 laser is focused on a planned point of a sample to be burned, plasma is rapidly formed, functional groups are introduced, and the bonding strength of graphene coated on a base material is enhanced by utilizing electron and particle grafting and bonding.

2. The method for enhancing the bonding fastness of graphene and a substrate according to claim 1, wherein: the substrate in S1 includes glass, silicone rubber, ceramic, lorentn, and metal, and the graphene is directly coated on the surface of the substrate by a coating method when the sample is prepared, so that the graphene forms a thin film.

3. The method for enhancing the bonding fastness of graphene and a substrate according to claim 2, wherein: and in the S2, the sample is fixed with the electric three-dimensional movable platform, the electric three-dimensional movable platform is positioned in the vacuum chamber, and the vacuum chamber is in a sealed state when in use.

4. The method for enhancing the bonding fastness of graphene and a substrate according to claim 3, wherein: the electric three-dimensional movable platform can be adjusted according to the requirement of an ablation point of the sample, so that the moving position and the moving speed of the sample are controlled.

5. The method for enhancing the bonding fastness of graphene and a substrate according to claim 4, wherein: when the laser in the S4 is focused on the surface of a product in the vacuum chamber, an emission spectrum and a Raman spectrum are generated, the emission spectrum and the Raman spectrum are transmitted to a spectrometer through a receiver and an optical fiber for light splitting, and the spectrum is taken through an ICCD and a spectrum signal is converted into an electric signal to be transmitted to a computer.

6. The method for enhancing the bonding fastness of graphene and a substrate according to claim 5, wherein: the input end of the laser is provided with a pulse digital delayer which can adjust the triggering delay of the laser and the ICCD.

7. The method for enhancing the bonding fastness of graphene and a substrate according to claim 6, wherein: and a scanning tunnel microscope is arranged on one side of the vacuum chamber, and the output end of the scanning tunnel microscope is matched with the vacuum chamber, so that the interface can be observed in real time and the graphene can be represented.

8. A microscope position adjusting platform for adjusting and fixing the scanning tunneling microscope in the method for enhancing the bonding fastness of graphene and a substrate according to claim 7, wherein the microscope position adjusting platform comprises:

the bottom of the inner wall of the fixed box is fixedly connected with a lifting motor, the output end of the lifting motor is fixedly connected with a lifting screw rod, the surface of the lifting screw is in threaded connection with a linkage plate, the top of the linkage plate is fixedly connected with at least two lifting shafts, the top ends of the at least two lifting shafts are fixedly connected with a supporting plate, the top of the supporting plate is provided with a sliding groove, the inside of the supporting plate is fixedly connected with two fixed shafts, the surfaces of the two fixed shafts are both connected with moving slide blocks in a sliding way, the tops of the two moving slide blocks are fixedly connected with a mounting plate, the bottom of the mounting plate is fixedly connected with a movable plate, the inside of the sliding groove is fixedly connected with a movable telescopic rod, the output end of the movable telescopic rod is fixedly connected with one side of the movable plate, and the bottom of the supporting plate is fixedly connected with a height detection ruler.

9. A microscope position adjustment stage according to claim 8, wherein: the top ends of at least two lifting shafts penetrate through the fixed box and extend to the upper side of the fixed box, the lifting shafts are vertically distributed with the surface of the linkage plate, and the lifting shafts are parallel to each other.

10. A microscope position adjustment stage according to claim 9, wherein: the two fixed shafts are parallel to each other, and the bottom end of the height detection ruler penetrates through the fixed box and extends to the inside of the fixed box.

Technical Field

The invention relates to the technical field of graphene, in particular to a method for enhancing the bonding fastness of graphene and a base material.

Background

Graphene has excellent physical properties, and each excellent physical property lays a foundation for the development of the graphene in the application field, but the ultra-thin two-dimensional structure of the graphene determines that the graphene is difficult to be used independently, and the properties can be expressed only by depending on a certain substrate to form a graphene composite material, at present, the preparation methods of the graphene composite material mainly comprise two methods: one method comprises the steps of coating a graphene film on the surface of a base material by a liquid-phase coating method by using liquid-phase exfoliated graphene or reduced graphene oxide as a raw material; the other is that graphene growing on the surface of a metal substrate by a chemical vapor deposition method is used as a raw material, a graphene film is transferred to the surface of a substrate by a transfer method, and in a liquid-phase coating method, due to the small size, many defects and uneven layer number of graphene sheets, the uniformity of the graphene film obtained by spin coating is poor and has a large difference from the theoretical performance, and the film and the substrate do not have the effect of chemical bonds, so that the bonding fastness is low.

However, in the process of transferring graphene growing on the surface of a metal substrate to the surface of another substrate, due to the use of a liquid phase chemical reagent, the problem of graphene pollution is caused, the transfer process is complicated, defects, wrinkles and the like of graphene are easily caused, and these factors greatly restrict the performance of the obtained graphene.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a method for enhancing the bonding fastness of graphene and a base material, and solves the problem of low bonding fastness between a film and a substrate in common methods such as liquid-phase coating and the like.

In order to achieve the purpose, the invention is realized by the following technical scheme: a method for enhancing the bonding fastness of graphene and a substrate comprises the following steps:

s1, preparing a combined sample by coating or cladding the graphene liquid phase on the surface of the base material;

s2, mounting the sample prepared in the S1 on an electric three-dimensional movable platform in a vacuum chamber for standby;

s3, turning on the laser, and focusing the light path of the laser on the sample in S2;

s4 laser is focused on a planned point of a sample to be burned, plasma is rapidly formed, functional groups are introduced, and the bonding strength of graphene coated on a base material is enhanced by utilizing electron and particle grafting and bonding.

Further, the substrate in S1 includes glass, silicone rubber, ceramic, lorentz and metal, and the graphene is directly film-coated on the surface of the substrate by a film coating method when the sample is prepared, so that the graphene forms a thin film. Effectively prevents the sample from being damaged due to air oxidation in laser ablation

Further, in the step S2, the sample is fixed to a motorized three-dimensional movable platform, the motorized three-dimensional movable platform is located inside the vacuum chamber, and the vacuum chamber is in a sealed state during use.

Further, the electric three-dimensional movable platform can be adjusted according to the requirement of an ablation point of the sample, so that the moving position and speed of the sample can be controlled.

Further, the laser in the S4 generates an emission spectrum and a Raman spectrum when being focused on the surface of the product in the vacuum chamber, the emission spectrum and the Raman spectrum are transmitted to the spectrometer through the receiver and the optical fiber for light splitting, and the spectrum is taken through the ICCD and the spectrum signal is converted into an electric signal to be transmitted to the computer.

Furthermore, a pulse digital delayer is arranged at the input end of the laser, and the triggering delay of the laser and the ICCD can be adjusted.

Furthermore, a scanning tunnel microscope is arranged on one side of the vacuum chamber, and the output end of the scanning tunnel microscope is matched with the vacuum chamber, so that the interface can be observed in real time and the graphene can be represented.

A microscope position adjustment platform for adjusting and fixing a scanning tunneling microscope in the method for enhancing the bonding fastness of graphene and a substrate, the microscope position adjustment platform comprising:

the bottom of the inner wall of the fixed box is fixedly connected with a lifting motor, the output end of the lifting motor is fixedly connected with a lifting screw rod, the surface of the lifting screw is in threaded connection with a linkage plate, the top of the linkage plate is fixedly connected with at least two lifting shafts, the top ends of the at least two lifting shafts are fixedly connected with a supporting plate, the top of the supporting plate is provided with a sliding groove, the inside of the supporting plate is fixedly connected with two fixed shafts, the surfaces of the two fixed shafts are both connected with moving slide blocks in a sliding way, the tops of the two moving slide blocks are fixedly connected with a mounting plate, the bottom of the mounting plate is fixedly connected with a movable plate, the inside of the sliding groove is fixedly connected with a movable telescopic rod, the output end of the movable telescopic rod is fixedly connected with one side of the movable plate, and the bottom of the supporting plate is fixedly connected with a height detection ruler.

Furthermore, the top ends of at least two lifting shafts penetrate through the fixed box and extend to the upper side of the fixed box, the at least two lifting shafts are vertically distributed with the surface of the linkage plate, and the at least two lifting shafts are parallel to each other.

Furthermore, the two fixing shafts are parallel to each other, and the bottom end of the height detection ruler penetrates through the fixing box and extends to the inside of the fixing box.

Compared with the prior art, the invention has the beneficial effects that:

according to the method for enhancing the bonding fastness of the graphene and the base material, the plasma is rapidly formed by directly adopting a laser ablation method, functional groups are introduced, and the bonding fastness of different base materials cladded by the graphene is enhanced by utilizing electron and ion grafting and bonding. The graphene and the base material can obtain a bound structure with higher bonding strength through the change of an external electromagnetic field, so that the bonding of two materials with more stable surfaces is realized.

Drawings

Fig. 1 is a system diagram of a method for enhancing the bonding fastness of graphene and a substrate according to the present invention;

FIG. 2 is a schematic structural diagram of a microscope position adjustment stage according to the present invention;

fig. 3 is a schematic structural view of the support plate portion shown in fig. 2 according to the present invention.

In the figure: 1-laser, 2-vacuum chamber, 3-ground tunneling microscope, 4-receiver, 5-spectrometer, 6-ICCD, 7-computer, 8-pulse digital delayer, 9-fixed box, 91-lifting motor, 92-lifting screw, 93-linkage plate, 94-lifting shaft, 95-support plate, 951-sliding groove, 96-fixed shaft, 97-moving slide block, 98-mounting plate, 981-moving plate, 99-moving telescopic rod and 10-height detection ruler.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Referring to fig. 1-3, the present invention provides a technical solution: a method for enhancing the bonding fastness of graphene and a substrate comprises the following steps:

s1, preparing a combined sample by coating or cladding the graphene liquid phase on the surface of the base material;

s2 mounting the sample prepared at S1 on an electric three-dimensional movable platform in the vacuum chamber 2 for use;

s3, turning on the laser 1, and focusing the optical path of the laser 1 on the sample in S2;

s4 laser 1 is focused on a planned point of a sample to be burned, plasma is rapidly formed, functional groups are introduced, and the bonding strength of graphene coated on a base material is enhanced by utilizing electron and particle grafting and bonding.

The planning point is determined by setting the moving mode of the mobile platform through software.

The method directly adopts a laser ablation method to quickly form plasma, introduces functional groups, and utilizes electron and ion grafting and combination to enhance the combination fastness of different substrates cladded by graphene. The graphene and the base material can obtain a bound structure with higher bonding strength through the change of an external electromagnetic field, so that the bonding of two materials with more stable surfaces is realized.

The laser 1 has the characteristics of monochromaticity, high directivity, concentrated energy distribution and the like, is widely applied in the field of material processing, commercializes ultraviolet, infrared, visible light and tunable lasers and simplifies the structure thereof, greatly expands the selection range of the laser processing method, reduces the cost of the laser processing method, improves the efficiency, and leads the laser processing method to show high application value in the field of material processing, the band gap-free graphene hinders the wide application of the magic material, the artificial dynamic band gap can be manufactured by irradiating the graphene with laser, along with the development of laser technology and electronic science technology, the research on the physical chemistry and mechanical property stability of the graphene material under the action of laser is crucial to the development and development of optoelectronic devices and the like, and meanwhile, the research on the defect characteristics of the graphene material under the action of laser plays a decisive role in understanding and predicting certain characteristics of the graphene material, experiments prove that the carbon material can be mutually transformed in different phase structures by irradiating the carbon material with laser, the carbon material can be transformed into carbon plasma by the laser, the planar deposition of carbon atoms is realized by changing the surrounding environment of the carbon plasma during cooling during the laser action so as to prepare graphene, the laser processing technology becomes an effective means for synthesizing and processing the graphene by utilizing the interaction mechanism and physical effect of the laser and the graphene to be different from those of the traditional manufacturing technology, the patterning, in-situ reduction, controllable graphene thinning, graphene growth, functional modification and the like of the graphene oxide can be realized by utilizing the laser micromachining technology, and the functionalized graphene material can be realized.

The laser burns only a very small local area of the surface of the candle sample, and the mass of the candle-stripping sample is as small as tens to hundreds of nanograms, which is also often regarded as a non-destructive ablation means.

The substrate in S1 includes glass, silicone rubber, ceramic, lorentn, and metal, and the graphene is directly coated on the surface of the substrate by a coating method when the sample is prepared, so that the graphene forms a thin film.

Different materials such as glass, silicon rubber, ceramic, Lorentz, metal and the like are used as base materials, graphene covers the surface of the base materials to form a layer of film, the two materials are combined through a common film coating method, in order to prevent air oxidation during laser ablation and increase sample damage, a sample is placed in a vacuum chamber and is fixed on an electric three-dimensional movable platform.

Effectively prevents the sample from being damaged due to air oxidation in laser ablation.

In the step S2, the sample is fixed to an electric three-dimensional movable platform, the electric three-dimensional movable platform is located inside the vacuum chamber 2, and the vacuum chamber 2 is in a sealed state when in use.

Plasma is generated through pulsed laser ablation, so that different substrates such as graphene cladding glass, silicon rubber, ceramic, Lorentz and metal materials are made; the experimental parameters such as laser power, laser pulse frequency, lens focal length, laser ablation time, acquisition orientation, acquisition delay and the like need to be optimized for different base materials.

The electric three-dimensional movable platform can be adjusted according to the requirement of an ablation point of the sample, so that the moving position and the moving speed of the sample are controlled.

The laser 1 in the S4 generates an emission spectrum and a Raman spectrum when being focused on the surface of a product in the vacuum chamber 2, the emission spectrum and the Raman spectrum are transmitted to the spectrometer 5 through the receiver 4 and the optical fiber for light splitting, the spectrum is captured through the ICCD6, and a spectrum signal is converted into an electric signal to be transmitted to the computer 7.

The input end of the laser 1 is provided with a pulse digital delayer 8 which can adjust the triggering delay of the laser and the ICCD.

One side of the vacuum chamber 2 is provided with a scanning tunnel microscope 3, and the output end of the scanning tunnel microscope 3 is matched with the vacuum chamber 2, so that the interface can be observed in real time and the graphene can be represented.

Focusing laser 1 on the surface of a sample to generate an emission spectrum and a Raman spectrum, transmitting the emission spectrum and the Raman spectrum to a spectrometer 5 through a receiver 4 and an optical fiber for light splitting, carrying out ICCD6 spectrum shooting, converting spectrum information into telecommunication signals and transmitting the telecommunication signals to a computer, changing the changes of laser parameters, sample temperature, current and the like, analyzing the spectrum information by collecting the plasma emission spectrum on the surface of the material before and after ablation, and analyzing the performance change of the material before and after ablation by combining the evolution characteristic of the plasma; and (4) observing the influence of the laser ablation on the graphene substrate structure by combining Raman spectrum characterization and a tunneling microscope.

For the spectrum result obtained by researching the binding fastness and the performance stability of the material by laser ablation, the related binding fastness and performance stability results are obtained by comparing the difference of the two acquisition results.

When the graphene cladding material is in work, plasma is directly and rapidly formed by a laser ablation method, functional groups are introduced, the bonding fastness of different graphene cladding base materials is enhanced by utilizing electron and ion grafting and bonding, a binding structure with higher bonding strength can be obtained by the graphene and the base materials through the change of an external electromagnetic field, and therefore the bonding of two materials with more stable surfaces is realized.

A microscope position adjustment stage for adjusting and fixing a scanning tunnel microscope 3, the microscope position adjustment stage comprising:

the lifting device comprises a fixed box 9, wherein a lifting motor 91 is fixedly connected to the bottom of the inner wall of the fixed box 9, an output end of the lifting motor 91 is fixedly connected with a lifting screw 92, a linkage plate 93 is in threaded connection with the surface of the lifting screw 92, at least two lifting shafts 94 are fixedly connected to the top of the linkage plate 93, a support plate 95 is fixedly connected to the top ends of the at least two lifting shafts 94, a sliding groove 951 is formed in the top of the support plate 95, two fixed shafts 96 are fixedly connected to the inside of the support plate 95, moving sliders 97 are slidably connected to the surfaces of the two fixed shafts 96, a mounting plate 98 is fixedly connected to the tops of the two moving sliders 97, a moving plate 981 is fixedly connected to the bottom of the mounting plate 98, a moving telescopic rod 99 is fixedly connected to the inside of the sliding groove 951, and an output end of, the bottom of the supporting plate 95 is fixedly connected with a height detection ruler 10.

During actual use, the scanning tunnel microscope 3 is fixedly arranged above the mounting plate 98, the movable plate 981 is driven to synchronously move by the movable telescopic rod 99, the movable plate 981 synchronously drives the mounting plate 98 to move, and the mounting plate 98 synchronously drives the scanning tunnel microscope 3 to move, so that the horizontal distance of the scanning tunnel microscope 3 can be conveniently adjusted, independent inflation or pushing of the scanning tunnel microscope 3 to move is not needed, the stability during moving is guaranteed, and the increase of adjusting time caused by the change of the angle and the observation position of the scanning tunnel microscope 3 due to the fact that the scanning tunnel microscope 3 is touched by mistake is avoided;

the lifting motor 91 at the bottom drives the lifting screw 92 to synchronously rotate, the lifting screw 92 synchronously drives the linkage plate 93 to move up and down for adjustment through a threaded connection structure, the two lifting shafts 94 at the top synchronously drive the supporting plate 95 to move up and down for adjustment when the linkage plate 93 moves up and down, the supporting plate 95 synchronously drives the mounting plate 98 at the top to move up, and the mounting plate 98 synchronously drives the scanning tunnel microscope 3 above to carry out height adjustment so as to adapt to the use requirements of the scanning tunnel microscope 3 on different heights and conveniently adjust the position of the scanning tunnel microscope;

the backup pad 95 drives the height detection chi 10 in step and reciprocates when reciprocating the regulation and reciprocates, and when the bottom of backup pad 95 and the top contact of fixed case 9, the top of fixed case 9 corresponds the zero scale department of height detection chi 10, and when the backup pad 95 upwards moved gradually, the scale that height detection chi 10 and fixed case 9's top correspond increased gradually to the distance that risees to backup pad 95 carries out quick accurate measuring.

The top ends of at least two lifting shafts 94 penetrate through the fixed box 9 and extend to the upper part of the fixed box 9, the at least two lifting shafts 94 are vertically distributed with the surface of the linkage plate 93, and the at least two lifting shafts 94 are parallel to each other.

The two fixing shafts 96 are parallel to each other, and the bottom end of the height detection ruler 10 penetrates through the fixing box 9 and extends into the fixing box 9.

When the lifting motor 91 is used, an external power supply and a control switch are connected, and the starting and stopping of the lifting motor 91 are controlled through the control switch.

When in use:

the movable rod 99 is moved to drive the movable plate 981 to move synchronously, the movable plate 981 is moved to drive the mounting plate 98 to move synchronously, and the mounting plate 98 is moved synchronously to drive the scanning tunnel microscope 3 to move, so that the horizontal distance of the scanning tunnel microscope 3 can be adjusted conveniently, independent inflation or pushing of the scanning tunnel microscope 3 to move is not needed, the stability during moving is guaranteed, and the increase of adjusting time caused by the change of the angle and the observation position of the scanning tunnel microscope 3 due to the fact that the scanning tunnel microscope 3 is touched by mistake is avoided;

the lifting motor 91 at the bottom drives the lifting screw 92 to synchronously rotate, the lifting screw 92 synchronously drives the linkage plate 93 to move up and down for adjustment through a threaded connection structure, the two lifting shafts 94 at the top synchronously drive the supporting plate 95 to move up and down for adjustment when the linkage plate 93 moves up and down, the supporting plate 95 synchronously drives the mounting plate 98 at the top to move up, and the mounting plate 98 synchronously drives the scanning tunnel microscope 3 above to carry out height adjustment so as to adapt to the use requirements of the scanning tunnel microscope 3 on different heights and conveniently adjust the position of the scanning tunnel microscope;

the backup pad 95 drives the height detection chi 10 in step and reciprocates when reciprocating the regulation and reciprocates, and when the bottom of backup pad 95 and the top contact of fixed case 9, the top of fixed case 9 corresponds the zero scale department of height detection chi 10, and when the backup pad 95 upwards moved gradually, the scale that height detection chi 10 and fixed case 9's top correspond increased gradually to the distance that risees to backup pad 95 carries out quick accurate measuring.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.