技术领域technical field
本发明属于材料领域，涉及一种制备三维石墨烯的方法。The invention belongs to the field of materials and relates to a method for preparing three-dimensional graphene.
背景技术Background technique
石墨烯是一种单原子层厚度的碳材料，具有一系列独特的性质，比如超常的载流子迁移率(200,000cm2V-1s-1)，超高的热导率(5300Wm-1K-1)，极好的光透过率(97.7％)以及优异的机械性能。近年来，石墨烯已经被报道在光电子学、能量转化、电催化、生物检测等众多领域具有潜在应用。因而，为了实现这些应用，对石墨烯的尺寸、形貌、边缘结构、功能化等进行了大量的研究来调控石墨烯的性质。到目前为止，二维的本征石墨烯已经被扩展到零维的石墨烯量子点、一维的石墨烯纳米带以及三维的石墨烯网络结构。其中，三维石墨烯由于其独特的形貌结构特征，被证明具有许多不同于二维石墨烯本体的电学、化学以及机械性质。由于具有很高的比表面积和高密度的活性位点，三维石墨烯被广泛应用于生物与化学检测(ACSAppl.Mater.Inter.2012,4,3129.；Small2013,9,1703.；Nanoscale2015,7,2427.)。优异的电导率以及超高的表面积使三维石墨烯可以作为电极应用于高性能的柔性超级电容器(Small2011,7,3163.；ACSNano2012,6,3206.；ACSNano2013,7,4042.)。由于其独特的垂直形貌、高的边缘密度以及突出的电荷传输能力，三维石墨烯被证明具有优异的场发射性能(Appl.Phy.Lett.2011,98,263104.)。此外，作为由于具有低密度、可调节的电导率以及超高的可压缩性，三维石墨烯被用于超轻、可控的高性能宽带微波吸附(Adv.Mater.2015,27,2049.)。因而，实现温和、可控、高效率的三维石墨烯制备对于科学研究以及工业应用都具有重要的意义。Graphene is a monoatomic layer of carbon material with a series of unique properties, such as extraordinary carrier mobility (200,000cm2 V-1 s-1 ), ultrahigh thermal conductivity (5300Wm-1 K-1 ), excellent light transmittance (97.7%) and excellent mechanical properties. In recent years, graphene has been reported to have potential applications in many fields such as optoelectronics, energy conversion, electrocatalysis, and biodetection. Therefore, in order to achieve these applications, a lot of research has been done on the size, morphology, edge structure, and functionalization of graphene to regulate the properties of graphene. So far, two-dimensional intrinsic graphene has been extended to zero-dimensional graphene quantum dots, one-dimensional graphene nanoribbons, and three-dimensional graphene network structures. Among them, 3D graphene has been proved to have many electrical, chemical, and mechanical properties different from 2D graphene due to its unique morphology and structural characteristics. Due to its high specific surface area and high density of active sites, three-dimensional graphene is widely used in biological and chemical detection (ACS Appl. Mater. Inter. 2012, 4, 3129.; Small 2013, 9, 1703.; , 2427.). The excellent conductivity and ultra-high surface area make three-dimensional graphene can be used as an electrode for high-performance flexible supercapacitors (Small2011, 7, 3163.; ACSNano2012, 6, 3206.; ACSNano2013, 7, 4042.). Due to its unique vertical morphology, high edge density, and outstanding charge transport capability, three-dimensional graphene has been proven to have excellent field emission properties (Appl. Phy. Lett. 2011, 98, 263104.). In addition, as a result of its low density, tunable electrical conductivity, and ultrahigh compressibility, three-dimensional graphene is used for ultralight, controllable high-performance broadband microwave adsorption (Adv.Mater.2015, 27, 2049.) . Therefore, the realization of mild, controllable, and high-efficiency three-dimensional graphene preparation is of great significance for scientific research and industrial applications.
三维石墨烯包括石墨烯泡沫和垂直直立石墨烯两种形式。其中石墨烯泡沫基本上采用模板法制备，比如利用化学气相沉积法在三维的金属泡沫、碳网络结构等模板上生长得到三维的石墨烯泡沫(Nat.Mater.2011,10,424.；ACSNano2012,6,4020.；Angew.Chem.Int.Ed.2014,53,1404.；Adv.Mater.2015,27,2049.)。但是此种方法需要复杂的模板设计以及后续的模板刻蚀来除去模板。而且模板以及刻蚀剂的残留通常是不可避免的，往往会影响甚至降低最终的三维石墨烯的性能。而垂直直立石墨烯一般都是通过等离子体辅助化学气相沉积或者微波辅助化学气相沉积来制备(Adv.Mater.2002,14,64.；Adv.EnergyMater.2013,3,1316.；Adv.Mater.2013,25,5799.；Adv.Mater.2013,25,5638.；ACSNano2014,8,5873.)。但是这些方法需要使用额外的设备以及严苛的生长环境如超低压等；而且所制备的三维石墨烯的形貌、密度、高度等难以实现可控。如果能够在多种基底上直接实现三维石墨烯的可控高效生长，对于三维石墨烯的大面积制备以及广泛工业应用将开辟新的道路。Three-dimensional graphene includes two forms of graphene foam and vertical vertical graphene. Wherein graphene foam basically adopts template method to prepare, for example utilizes chemical vapor deposition to grow on three-dimensional metal foam, carbon network structure and other templates to obtain three-dimensional graphene foam (Nat.Mater.2011,10,424.; ACSNano2012,6, 4020.; Angew. Chem. Int. Ed. 2014, 53, 1404.; Adv. Mater. 2015, 27, 2049.). However, this method requires complex template design and subsequent template etching to remove the template. Moreover, the residue of template and etchant is usually unavoidable, which often affects or even reduces the performance of the final three-dimensional graphene. Vertical vertical graphene is generally prepared by plasma-assisted chemical vapor deposition or microwave-assisted chemical vapor deposition (Adv.Mater.2002,14,64.; Adv.EnergyMater.2013,3,1316.; Adv.Mater. 2013, 25, 5799.; Adv. Mater. 2013, 25, 5638.; ACSNano 2014, 8, 5873.). However, these methods require the use of additional equipment and harsh growth environments such as ultra-low pressure; and the shape, density, and height of the prepared three-dimensional graphene are difficult to control. If the controllable and efficient growth of three-dimensional graphene can be directly realized on a variety of substrates, it will open up a new way for the large-scale preparation of three-dimensional graphene and its wide industrial application.
发明内容Contents of the invention
本发明的目的是提供一种制备三维石墨烯的方法。The purpose of the present invention is to provide a method for preparing three-dimensional graphene.
本发明提供的制备三维石墨烯的方法，包括如下步骤：The method for preparing three-dimensional graphene provided by the invention comprises the following steps:
在氢气和氩气气氛中，通入碳源气体于衬底上进行化学气相沉积，沉积完毕后于所述衬底上得到所述三维石墨烯。In the atmosphere of hydrogen and argon, the carbon source gas is fed on the substrate to carry out chemical vapor deposition, and the three-dimensional graphene is obtained on the substrate after the deposition is completed.
上述制备方法中，所述衬底为单晶硅、二氧化硅/硅、石英片或二氧化锆/硅；In the above preparation method, the substrate is single crystal silicon, silicon dioxide/silicon, quartz sheet or zirconium dioxide/silicon;
所述单晶硅的厚度为250-500微米，具体为400微米；The thickness of the single crystal silicon is 250-500 microns, specifically 400 microns;
所述二氧化硅/硅中，二氧化硅层的厚度为250-400纳米，具体为300纳米；硅层的厚度为250-500微米，具体为400微米；In the silicon dioxide/silicon, the silicon dioxide layer has a thickness of 250-400 nanometers, specifically 300 nanometers; the silicon layer has a thickness of 250-500 microns, specifically 400 microns;
所述石英片的厚度为1-3毫米，具体为1毫米；The thickness of the quartz sheet is 1-3 mm, specifically 1 mm;
所述二氧化锆/硅中，二氧化锆层的厚度为10-50纳米，具体为20纳米；硅层的厚度为250-500微米，具体为400微米。In the zirconium dioxide/silicon, the thickness of the zirconium dioxide layer is 10-50 nanometers, specifically 20 nanometers; the thickness of the silicon layer is 250-500 microns, specifically 400 microns.
所述碳源气体为甲烷、乙烯或乙烷，具体为甲烷；The carbon source gas is methane, ethylene or ethane, specifically methane;
所述碳源气体、氢气和氩气的流量比为7.0：50：50至14.0：50：50；The flow ratio of the carbon source gas, hydrogen and argon is 7.0:50:50 to 14.0:50:50;
具体的，所述碳源的流量为7.0-14.0sccm，具体可为7.0、7.5、8.0、8.5、9.0、9.5、10.0、10.5、11.0、11.5、12.0、12.5、13.0、13.5或14.0sccm；Specifically, the flow rate of the carbon source is 7.0-14.0 sccm, specifically 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5 or 14.0 sccm;
所述氢气的流量为50sccm；The flow rate of the hydrogen is 50 sccm;
所述氩气的流量为50sccm。The flow rate of the argon gas is 50 sccm.
所述碳源、氢气与氩气的流量比为7.0-10.0：50：50时，所得三维石墨烯的密度与高度较小；所述碳源的流量具体为7.0或7.5或8.0或8.5或9.0或9.5或10.0sccm时，所述氢气的流量为50sccm，所述氩气的流量为50sccm；When the flow ratio of the carbon source, hydrogen and argon is 7.0-10.0:50:50, the density and height of the obtained three-dimensional graphene are small; the flow rate of the carbon source is specifically 7.0 or 7.5 or 8.0 or 8.5 or 9.0 Or when 9.5 or 10.0 sccm, the flow rate of the hydrogen gas is 50 sccm, and the flow rate of the argon gas is 50 sccm;
所述碳源、氢气与氩气的流量比为10.0-14.0：50：50时，所得三维石墨烯的密度与高度较大；其中，所述碳源的流量具体为10.5或11.0或11.5或12.0或12.5或13.0或13.5或14.0sccm时，所述氢气的流量为50sccm，所述氩气的流量为50sccm；When the flow ratio of the carbon source, hydrogen and argon is 10.0-14.0:50:50, the density and height of the obtained three-dimensional graphene are relatively large; wherein, the flow rate of the carbon source is specifically 10.5 or 11.0 or 11.5 or 12.0 or 12.5 or 13.0 or 13.5 or 14.0 sccm, the flow rate of the hydrogen is 50 sccm, and the flow rate of the argon is 50 sccm;
所述化学气相沉积步骤中，时间为2-8小时，具体为2、4或6小时；In the chemical vapor deposition step, the time is 2-8 hours, specifically 2, 4 or 6 hours;
压强为0-1.01×105Pa，但不为0，所述压强具体为1.01×105Pa。The pressure is 0-1.01×105 Pa, but not 0, and the pressure is specifically 1.01×105 Pa.
温度为1000-1250℃，具体为1130℃。The temperature is 1000-1250°C, specifically 1130°C.
所述方法还包括如下步骤：The method also includes the steps of:
在所述化学气相沉积步骤之前，将所述衬底进行退火。The substrate is annealed prior to the chemical vapor deposition step.
具体的，所述退火步骤中，退火的气氛为氢气和氩气气氛；Specifically, in the annealing step, the annealing atmosphere is a hydrogen and argon atmosphere;
氢气的流量为10-100sccm，具体为50sccm；The flow rate of hydrogen is 10-100 sccm, specifically 50 sccm;
氩气的流量为10-100sccm，具体为50sccm；The flow rate of argon is 10-100 sccm, specifically 50 sccm;
退火的时间为10-60分钟，具体为30分钟。The annealing time is 10-60 minutes, specifically 30 minutes.
另外，所述方法还包括如下步骤：In addition, the method also includes the following steps:
在所述化学气相沉积步骤之前，将所述衬底进行如下预处理：将所述衬底依次用去离子水、丙酮、乙醇超声清洗后，氮气吹干，再用由浓硫酸和双氧水组成的混合液浸泡，去离子水超声清洗，氮气吹干；Before the chemical vapor deposition step, the substrate is subjected to the following pretreatment: after the substrate is ultrasonically cleaned with deionized water, acetone, and ethanol in sequence, blown dry with nitrogen, and then sprayed with concentrated sulfuric acid and hydrogen peroxide Soak in the mixed solution, ultrasonically clean with deionized water, and blow dry with nitrogen;
其中，所述由浓硫酸和双氧水组成的混合液中，双氧水的质量百分浓度为70％；所述浓硫酸和双氧水的体积比为3：7；Wherein, in the mixed liquid composed of concentrated sulfuric acid and hydrogen peroxide, the mass percent concentration of hydrogen peroxide is 70%; the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:7;
所述浸泡步骤中，浸泡的时间具体可为30分钟；In the soaking step, the soaking time may be specifically 30 minutes;
所述超声清洗步骤中，时间具体可为3分钟。In the ultrasonic cleaning step, the time may be specifically 3 minutes.
所述方法还可包括如下步骤：在所述化学气相沉积步骤之后，将体系在氩气和氢气的混合气氛中冷却；所述冷却步骤中，氩气的流量具体为50sccm；氢气的流量具体为50sccm；The method may also include the following steps: after the chemical vapor deposition step, the system is cooled in a mixed atmosphere of argon and hydrogen; in the cooling step, the flow of argon is specifically 50 sccm; the flow of hydrogen is specifically 50 sccm;
此外，按照上述方法制备得到的三维石墨烯，也属于本发明的保护范围。其中，所述三维石墨烯的密度与高度可以精确调控。In addition, the three-dimensional graphene prepared according to the above method also belongs to the protection scope of the present invention. Wherein, the density and height of the three-dimensional graphene can be precisely regulated.
本发明提供的制备三维石墨烯的方法，是在化学气相沉积的过程中，利用无模板无催化剂的方法直接通过控制碳源流量在多种衬底上生长三维石墨烯。通过改变碳源的流量来控制碳源浓度从而达到密度与高度可控的效果。该方法具有特征和优点：The method for preparing three-dimensional graphene provided by the present invention is to grow three-dimensional graphene on various substrates directly by controlling the carbon source flow rate in the process of chemical vapor deposition using a template-free and catalyst-free method. Control the concentration of carbon source by changing the flow of carbon source to achieve the controllable effect of density and height. This method has features and advantages:
1.本发明第一次公开了在热化学气相沉积系统中生长出三维石墨烯的方法。1. The present invention discloses a method for growing three-dimensional graphene in a thermal chemical vapor deposition system for the first time.
2.本发明第一次公开了碳源流量是影响生长的石墨烯维度的决定性因素。2. The present invention discloses for the first time that the flow rate of the carbon source is the decisive factor affecting the dimensionality of the grown graphene.
3.本发明第一次公开了热化学气相沉积系统中三维石墨烯生长的机理。3. The present invention discloses for the first time the mechanism of three-dimensional graphene growth in a thermal chemical vapor deposition system.
4.本发明第一次公开了对三维石墨烯密度与高度有效调控的方法。4. The present invention discloses for the first time a method for effectively controlling the density and height of three-dimensional graphene.
5.本发明第一次公开了三维石墨烯在多种衬底上的生长。5. The present invention discloses the growth of three-dimensional graphene on various substrates for the first time.
6.本发明公开的方法，与传统的方法相比，既不需要复杂的模板也不需要额外的等离子体设备，提供了一种可以实现更高效更温和地生长三维结构石墨烯的方法。6. Compared with the traditional method, the method disclosed in the present invention does not require complex templates or additional plasma equipment, and provides a method for growing three-dimensional graphene more efficiently and mildly.
附图说明Description of drawings
图1为实施例1制备的低密度的三维石墨烯的低倍和高倍扫描电子显微镜照片；Fig. 1 is the low-magnification and high-magnification scanning electron micrographs of the low-density three-dimensional graphene prepared by embodiment 1;
图2为实施例1制备的低密度的三维石墨烯的45度倾角扫描电子显微镜照片；Fig. 2 is the 45 degree inclination scanning electron micrographs of the low-density three-dimensional graphene prepared by embodiment 1;
图3为实施例1制备的低密度的三维石墨烯的低倍和高倍透射电子显微镜图；Fig. 3 is the low-magnification and high-magnification transmission electron micrographs of the low-density three-dimensional graphene prepared in embodiment 1;
图4为实施例2制备的高密度的三维石墨烯的低倍和高倍扫描电子显微镜照片；Fig. 4 is the low-magnification and high-magnification scanning electron micrographs of the high-density three-dimensional graphene prepared in embodiment 2;
图5为实施例2制备的高密度的三维石墨烯的低倍和高倍透射电子显微镜图；Fig. 5 is the low-magnification and high-magnification transmission electron micrographs of the high-density three-dimensional graphene prepared in embodiment 2;
图6为实施例2制备的高密度的三维石墨烯具有典型代表性的石墨烯拉曼光谱图；Fig. 6 is that the high-density three-dimensional graphene prepared by embodiment 2 has a typical representative graphene Raman spectrum;
图7为控制生长条件制备的不同高度的三维石墨烯的原子力显微镜三维图；Fig. 7 is the atomic force microscope three-dimensional diagram of the three-dimensional graphene of different heights prepared by controlling the growth conditions;
图8为三维石墨烯随时间的生长变化过程的扫描电子显微镜图。Fig. 8 is a scanning electron microscope image of the growth process of three-dimensional graphene over time.
图9为对照例1制备的平面二维石墨烯的扫描电子显微镜照片；Fig. 9 is the scanning electron micrograph of the planar two-dimensional graphene that comparative example 1 prepares;
图10为对照例1制备的平面二维石墨烯的拉曼光谱图；Fig. 10 is the Raman spectrogram of the plane two-dimensional graphene prepared by comparative example 1;
图11为对照例2制备的无定形碳的扫描电子显微镜照片；Fig. 11 is the scanning electron micrograph of the amorphous carbon prepared in comparative example 2;
图12为对照例2制备的无定形碳的拉曼光谱图；Fig. 12 is the Raman spectrogram of the amorphous carbon prepared in comparative example 2;
具体实施方式detailed description
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径获得。The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The raw materials can be obtained from open commercial channels unless otherwise specified.
实施例1、热化学气相沉积法直接生长低密度的三维石墨烯Embodiment 1, thermal chemical vapor deposition method directly grows low-density three-dimensional graphene
1)清洗硅生长基底：1) Clean the silicon growth substrate:
将硅依次用去离子水、丙酮、乙醇各超声清洗3分钟，氮气吹干，用3:7的浓硫酸/70％双氧水浸泡30分钟，再用去离子水超声清洗3分钟，氮气吹干；The silicon was ultrasonically cleaned with deionized water, acetone, and ethanol for 3 minutes each, blown dry with nitrogen, soaked in 3:7 concentrated sulfuric acid/70% hydrogen peroxide for 30 minutes, then ultrasonically cleaned with deionized water for 3 minutes, and blown dry with nitrogen;
2)将洁净的衬底(400微米厚的硅)放置于石英管中。再将石英管放入管式炉中，硅衬底对准管式炉的热电偶区，通入50sccm氢气与50sccm氩气20分钟后，开始加热，当管式炉中心区域的温度达到1130℃时，保持稳定退火30分钟；2) Place a clean substrate (400 micron thick silicon) in a quartz tube. Then put the quartz tube into the tube furnace, align the silicon substrate with the thermocouple area of the tube furnace, feed 50sccm hydrogen and 50sccm argon for 20 minutes, then start heating, when the temperature in the central area of the tube furnace reaches 1130°C , maintain stable annealing for 30 minutes;
3)生长石墨烯：3) Growing graphene:
维持步骤2)中管式炉石英管中的温度为1130℃，通入流量为8sccm的甲烷和50sccm的氢气以及50sccm的氩气，在1.01×105Pa压强下生长4小时后，关闭甲烷，在流量为50sccm的氢气和50sccm氩气混合气流下随管式炉冷却到室温，得到本发明提供的低密度三维石墨烯，如图1与图2扫描电子显微镜照片所示，并且制备样品经透射电子显微镜表征，如图3所示。Maintain the temperature in the quartz tube of the tube furnace in step 2) at 1130° C., feed in methane with a flow rate of 8 sccm, hydrogen with 50 sccm and argon with 50 sccm, grow at a pressure of 1.01×105 Pa for 4 hours, and then close the methane. Under the flow of 50sccm of hydrogen and 50sccm of argon gas mixture, the tube furnace is cooled to room temperature to obtain the low-density three-dimensional graphene provided by the present invention, as shown in Fig. 1 and Fig. 2 scanning electron micrographs, and the prepared sample is transmitted through Electron microscopy characterization, as shown in Figure 3.
由图可知，该实施例所制备的石墨烯具有垂直于基底的三维形貌，而且垂直直立的石墨烯片密度比较低。It can be seen from the figure that the graphene prepared in this embodiment has a three-dimensional morphology perpendicular to the substrate, and the density of vertically erect graphene sheets is relatively low.
实施例2、热化学气相沉积法直接生长高密度的三维石墨烯Embodiment 2, thermal chemical vapor deposition method directly grows high-density three-dimensional graphene
按照与实施例1完全相同的方法，仅将步骤3)中通入甲烷流量增加到12sccm。通过增加甲烷的流量从而改变碳原子的浓度，进而影响所得三维石墨烯的密度，图4为获得的高密度的三维石墨烯低倍和高倍扫描电子显微镜图。并且制备样品经透射电子显微镜表征，如图5所示。并且对高密度的三维石墨烯进行了拉曼表征，如图6所示。According to the same method as in Example 1, only step 3) is passed into the methane flow to increase to 12sccm. By increasing the flow rate of methane, the concentration of carbon atoms is changed, thereby affecting the density of the obtained three-dimensional graphene. Figure 4 is a low-power and high-power scanning electron microscope image of the obtained high-density three-dimensional graphene. And the prepared samples were characterized by transmission electron microscopy, as shown in FIG. 5 . And the Raman characterization of the high-density three-dimensional graphene was carried out, as shown in Figure 6.
由图可知，随着甲烷流量的增大，衬底上所制备得到的三维垂直直立石墨烯片的密度增大。It can be seen from the figure that with the increase of methane flux, the density of three-dimensional vertical upright graphene sheets prepared on the substrate increases.
实施例3、热化学气相沉积法直接生长不同高度的三维石墨烯Embodiment 3, thermal chemical vapor deposition method directly grows three-dimensional graphene of different heights
按照与实施例1完全相同的方法，仅将步骤3)中通入甲烷流量分别取值9、11、13sccm。通过观察所得三维石墨烯密度的演变，发现所得三维石墨烯的高度由低到高变化，如原子力显微镜图7所示。According to the same method as in Example 1, only the methane flow rate of feeding in step 3) is respectively 9, 11, and 13 sccm. By observing the evolution of the density of the obtained 3D graphene, it is found that the height of the obtained 3D graphene varies from low to high, as shown in Figure 7 of the atomic force microscope.
由图可知，随着甲烷流量的增大，衬底上所制备得到的三维垂直直立石墨烯片的高度逐渐增大。It can be seen from the figure that with the increase of the methane flow rate, the height of the three-dimensional vertical upright graphene sheets prepared on the substrate gradually increases.
实施例4、热化学气相沉积法直接生长三维石墨烯的变化过程Embodiment 4, the changing process of directly growing three-dimensional graphene by thermal chemical vapor deposition
按照与实施例1完全相同的方法，仅将步骤3)中生长时间分别取值2、4、6小时，观察所得石墨烯形貌的变化过程，发现所得三维石墨烯先经石墨烯片生长连接成膜后才得到三维结构的石墨烯，如图8所示为生长时间的3个取值所得3个阶段的不同石墨烯对应的扫描电子显微镜图。According to the same method as in Example 1, only the growth time in step 3) is taken as 2, 4, and 6 hours respectively, and the change process of the obtained graphene morphology is observed, and it is found that the obtained three-dimensional graphene is first connected by graphene sheet growth. The graphene with a three-dimensional structure is obtained after the film is formed. As shown in FIG. 8 , the scanning electron microscope images corresponding to different graphenes in three stages obtained by three values of the growth time.
由图可知，石墨烯首先延衬底平面二维生长，连接成膜后再生长才得到垂直于基底的三维石墨烯。It can be seen from the figure that graphene first grows two-dimensionally along the plane of the substrate, and then grows after connecting to form a film to obtain three-dimensional graphene perpendicular to the substrate.
对照例1、热化学气相沉积法生长二维石墨烯按照与实施例1完全相同的方法，仅将步骤3)中通入甲烷流量降低到6sccm。通过减少甲烷的流量从而改变碳原子的浓度，进而影响所制备材料的结构与形貌，图9为在低于7sccm甲烷的条件下得到的平面二维石墨烯的扫描电子显微镜图。并且对制备样品进行了拉曼表征，如图10所示。由图可知，在其他参数不变的情况下，当甲烷流量低于7sccm时只能得到二维的平面石墨烯。Comparative example 1, growth of two-dimensional graphene by thermal chemical vapor deposition In the same way as in Example 1, only the methane flow rate in step 3) was reduced to 6 sccm. By reducing the flow of methane, the concentration of carbon atoms is changed, thereby affecting the structure and morphology of the prepared material. Figure 9 is a scanning electron microscope image of planar two-dimensional graphene obtained under the condition of less than 7 sccm methane. And Raman characterization was performed on the prepared samples, as shown in FIG. 10 . It can be seen from the figure that when other parameters remain unchanged, only two-dimensional planar graphene can be obtained when the methane flow rate is lower than 7 sccm.
对照例2、热化学气相沉积法生长无定形碳Comparative Example 2, Growth of Amorphous Carbon by Thermal Chemical Vapor Deposition
按照与实施例1完全相同的方法，仅将步骤3)中通入甲烷流量提高到15sccm。通过增加甲烷的流量从而改变碳原子的浓度，进而影响所制备材料的结构与形貌，图11为该条件下得到的无定形碳的扫描电子显微镜图。并且对制备样品进行了拉曼表征，如图12所示。According to the exact same method as in Example 1, only step 3) is passed into the methane flow to improve to 15sccm. By increasing the flow rate of methane, the concentration of carbon atoms is changed, thereby affecting the structure and morphology of the prepared material. Figure 11 is a scanning electron microscope image of amorphous carbon obtained under this condition. And Raman characterization was performed on the prepared sample, as shown in FIG. 12 .
由图可知，在其他参数不变的情况下，当甲烷流量高于14sccm时只能得到无定形碳。It can be seen from the figure that when other parameters remain unchanged, only amorphous carbon can be obtained when the methane flow rate is higher than 14 sccm.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610008722.0ACN105668555B (en) | 2016-01-07 | 2016-01-07 | A kind of method for preparing three-dimensional grapheme |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610008722.0ACN105668555B (en) | 2016-01-07 | 2016-01-07 | A kind of method for preparing three-dimensional grapheme |
| Publication Number | Publication Date |
|---|---|
| CN105668555Atrue CN105668555A (en) | 2016-06-15 |
| CN105668555B CN105668555B (en) | 2018-04-06 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610008722.0AActiveCN105668555B (en) | 2016-01-07 | 2016-01-07 | A kind of method for preparing three-dimensional grapheme |
| Country | Link |
|---|---|
| CN (1) | CN105668555B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106324291A (en)* | 2016-08-15 | 2017-01-11 | 清华大学 | Graphene film ball probe for atomic force microscopes and method of acquiring friction coefficient |
| CN106323867A (en)* | 2016-08-15 | 2017-01-11 | 清华大学 | Preparation method of graphene membrane spheres |
| CN107452841A (en)* | 2017-09-04 | 2017-12-08 | 湘能华磊光电股份有限公司 | LED epitaxial growth methods based on graphene |
| CN109502575A (en)* | 2018-12-25 | 2019-03-22 | 江苏鲁汶仪器有限公司 | A kind of method of chemical vapor deposition preparation large-area graphene |
| CN109850908A (en)* | 2019-04-12 | 2019-06-07 | 中国科学院重庆绿色智能技术研究院 | A kind of preparation method and product of silica/graphene complex |
| CN110342502A (en)* | 2019-06-26 | 2019-10-18 | 上海交通大学 | A kind of preparation method of graphite flake growth in situ graphene complex carbon material |
| CN110354700A (en)* | 2018-04-11 | 2019-10-22 | 广州墨羲科技有限公司 | A kind of polymer graphite alkene composite filtering film |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12217958B2 (en) | 2019-03-04 | 2025-02-04 | Samsung Electronics Co., Ltd. | Method of pre-treating substrate and method of directly forming graphene using the same |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161482A (en)* | 2011-01-25 | 2011-08-24 | 中国科学院化学研究所 | Method for preparing graphene |
| CN102874801A (en)* | 2012-10-15 | 2013-01-16 | 中国科学院上海微系统与信息技术研究所 | Preparation method for graphene |
| CN104018136A (en)* | 2014-04-30 | 2014-09-03 | 中国科学院重庆绿色智能技术研究院 | Method for directly and conformally covering graphene film on full surface of substrate with three-dimensional structure |
| CN104211054A (en)* | 2014-09-09 | 2014-12-17 | 中国科学院化学研究所 | Method for controllably preparing graphene |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161482A (en)* | 2011-01-25 | 2011-08-24 | 中国科学院化学研究所 | Method for preparing graphene |
| CN102874801A (en)* | 2012-10-15 | 2013-01-16 | 中国科学院上海微系统与信息技术研究所 | Preparation method for graphene |
| CN104018136A (en)* | 2014-04-30 | 2014-09-03 | 中国科学院重庆绿色智能技术研究院 | Method for directly and conformally covering graphene film on full surface of substrate with three-dimensional structure |
| CN104211054A (en)* | 2014-09-09 | 2014-12-17 | 中国科学院化学研究所 | Method for controllably preparing graphene |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106324291A (en)* | 2016-08-15 | 2017-01-11 | 清华大学 | Graphene film ball probe for atomic force microscopes and method of acquiring friction coefficient |
| CN106323867A (en)* | 2016-08-15 | 2017-01-11 | 清华大学 | Preparation method of graphene membrane spheres |
| CN106324291B (en)* | 2016-08-15 | 2018-10-30 | 清华大学 | For the graphene film talent scout needle of atomic force microscope and the acquisition methods of friction coefficient |
| CN106323867B (en)* | 2016-08-15 | 2019-04-05 | 清华大学 | The preparation method of graphene film ball |
| CN107452841A (en)* | 2017-09-04 | 2017-12-08 | 湘能华磊光电股份有限公司 | LED epitaxial growth methods based on graphene |
| CN107452841B (en)* | 2017-09-04 | 2019-07-09 | 湘能华磊光电股份有限公司 | Graphene-based LED epitaxial growth method |
| CN110354700A (en)* | 2018-04-11 | 2019-10-22 | 广州墨羲科技有限公司 | A kind of polymer graphite alkene composite filtering film |
| CN109502575A (en)* | 2018-12-25 | 2019-03-22 | 江苏鲁汶仪器有限公司 | A kind of method of chemical vapor deposition preparation large-area graphene |
| CN109502575B (en)* | 2018-12-25 | 2021-09-21 | 江苏鲁汶仪器有限公司 | Method for preparing large-area graphene through chemical vapor deposition |
| CN109850908A (en)* | 2019-04-12 | 2019-06-07 | 中国科学院重庆绿色智能技术研究院 | A kind of preparation method and product of silica/graphene complex |
| CN109850908B (en)* | 2019-04-12 | 2020-01-14 | 中国科学院重庆绿色智能技术研究院 | Preparation method and product of silicon dioxide/graphene compound |
| CN110342502A (en)* | 2019-06-26 | 2019-10-18 | 上海交通大学 | A kind of preparation method of graphite flake growth in situ graphene complex carbon material |
| Publication number | Publication date |
|---|---|
| CN105668555B (en) | 2018-04-06 |
| Publication | Publication Date | Title |
|---|---|---|
| CN105668555B (en) | A kind of method for preparing three-dimensional grapheme | |
| CN109809372B (en) | A method for preparing monolayer tungsten diselenide nanoribbons based on spatial confinement strategy | |
| Xia et al. | CVD synthesis of large-area, highly crystalline MoSe 2 atomic layers on diverse substrates and application to photodetectors | |
| CN112853290B (en) | A kind of preparation method of large-area molybdenum disulfide thin film | |
| CN104377114B (en) | A kind of growing method of germanium quantum point, germanium quantum point composite and its application | |
| CN105839072B (en) | A kind of method that chemical vapor deposition prepares rhenium disulfide film | |
| CN104389016A (en) | Method for quickly preparing large-size single-crystal graphene | |
| CN113278948B (en) | A kind of tin sulfide/tin disulfide heterojunction material and preparation method thereof | |
| CN111620325B (en) | A kind of method for preparing graphene nanoribbon array | |
| CN110416065A (en) | Preparation method of molybdenum disulfide/tungsten diselenide vertical heterojunction | |
| CN103172061A (en) | Method for growing large-area graphene on insulating substrate | |
| Wei et al. | Monolayer MoS2 epitaxy | |
| CN105271800A (en) | Preparation method of large-area molybdenum disulfide film material | |
| CN103935996B (en) | One CO 2the method of direct synthesizing graphite alkene | |
| CN105970296A (en) | Molybdenum disulfide film and preparation method thereof | |
| CN104211054B (en) | A kind of controlled method of preparing Graphene | |
| CN110055589A (en) | Large-size single-layer hexagonal boron nitride single crystal or film and preparation method thereof | |
| CN106098533A (en) | The method preparing molybdenum disulfide film for substrate with GaN | |
| CN112456452B (en) | A kind of preparation method of germanium diselenide nanomaterial | |
| CN107032331A (en) | A kind of graphene preparation method based on dielectric base | |
| CN108423659A (en) | A kind of preparation method of the grade single layer single crystal graphene based on polycrystalline copper foil | |
| CN104233454A (en) | Method for effectively synthesizing monocrystal hexagonal boron nitride structure by substitution reaction | |
| CN115341273B (en) | Preparation of a large-size two-dimensional thermoelectric material bismuth telluride single crystal | |
| CN114381806B (en) | Preparation method of two-dimensional aluminum nitride crystal | |
| CN110453280B (en) | A kind of preparation method of high-quality wafer-level graphene single crystal |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |