WO2022141179A1 - 基于弱耦合增强的石墨烯结构、石墨烯膜及光电器件 - Google Patents

基于弱耦合增强的石墨烯结构、石墨烯膜及光电器件 Download PDF

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WO2022141179A1
WO2022141179A1 PCT/CN2020/141339 CN2020141339W WO2022141179A1 WO 2022141179 A1 WO2022141179 A1 WO 2022141179A1 CN 2020141339 W CN2020141339 W CN 2020141339W WO 2022141179 A1 WO2022141179 A1 WO 2022141179A1
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graphene
graphene film
film
layer
weak coupling
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French (fr)
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高超
彭蠡
李泠菲
方文章
刘英军
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浙江大学
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Priority to PCT/CN2020/141339 priority Critical patent/WO2022141179A1/zh
Priority to KR1020227018649A priority patent/KR20220098367A/ko
Priority to JP2022537093A priority patent/JP2023511653A/ja
Priority to EP20960193.9A priority patent/EP4049970A4/en
Priority to US17/696,899 priority patent/US20220204348A1/en
Publication of WO2022141179A1 publication Critical patent/WO2022141179A1/zh

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Definitions

  • the invention relates to graphene functional materials, in particular to a graphene structure based on weak coupling enhancement, a graphene film and a device and a method for preparing the material.
  • Macroscopically assembled graphene oxide or graphene nanosheets are the main application forms of nanoscale graphene, and the commonly used preparation methods are suction filtration, scraping, spin coating, spray coating, and dip coating. Through further high temperature treatment, the defects of graphene can be repaired, and the electrical conductivity and thermal conductivity of the graphene film can be effectively improved.
  • portable electronic devices such as laptops.
  • single-layer graphene absorbs very low light, it cannot absorb light of sufficient intensity, and has no response to electromagnetic waves in infrared, terahertz and other lower energy bands. To this end, researchers have done a lot of work on graphene device modification to improve the light absorption of the device. In addition, it is generally believed that single-layer graphene cannot effectively accumulate hot electrons and cannot cross the potential barriers of graphene and semiconductors, so graphene does not respond significantly at low energy bands.
  • the traditional Schottky junction is a metal/semiconductor structure, but the metal material itself has a very low photo-excited hot electron lifetime (about 0.1 ps), and the noise is large, so it cannot be applied in the field of room temperature optoelectronic devices.
  • the hot electron lifetime of single-layer graphene is increased by about an order of magnitude (1ps), and the noise at room temperature is greatly suppressed.
  • the excellent transparency of graphene makes it unable to carry out effective hot electron accumulation. Crossing the barrier between graphene and semiconductors, graphene does not respond significantly at low energy bands.
  • defect structure of graphene tends to increase the graphene hot electron-phonon scattering. Therefore, in order to improve the graphene hot electron relaxation time, high temperature treatment must be performed to repair the defect structure as much as possible, which increases the difficulty of fabrication of optoelectronic detection devices.
  • the existence of defect states increases the temperature of the device, which not only damages the response speed, but also contributes to the hot electron transition and improves the responsivity.
  • the present invention provides a graphene structure based on weak coupling enhancement.
  • This graphene structure increases the electron joint state density through the weak coupling effect of the non-AB structure and promotes light absorption; meanwhile, the non-AB structure is introduced into the graphene structure.
  • the graphene line performance band promotes the transition of hot electrons and increases the occupancy probability of hot electrons in high energy states.
  • the present invention provides a weak-coupling-enhanced graphene film, which increases electron combined state density, increases light absorption, and promotes thermal electron transition through weak coupling. This structure also reduces the requirements and costs of the membrane preparation process, and increases the success rate of membrane preparation.
  • the present invention provides a graphene optoelectronic device based on weak coupling enhancement, such as based on a graphene/silicon Schottky junction. Since the graphene film has a zero band gap, it can realize long-wavelength and low-energy photoelectric devices. Therefore, on the one hand, the responsivity of graphene/silicon optoelectronic devices can be improved, and on the other hand, the detection range can be extended from the visible and near-infrared to the mid- and far-infrared bands, enabling wide-spectrum detection.
  • graphene/semiconductor Schottky photodetectors such as graphene/germanium detectors, etc.
  • the graphene film can also be introduced into other photodetector systems (such as photoconductive detectors, PIN detectors, avalanche detectors) to enhance its absorption in the infrared band, and realize wide-spectrum detection and infrared detection.
  • Photodetectors are currently widely used in many fields such as military, national defense, medical, biological, and consumer electronics.
  • infrared photodetectors are needed in the military for reconnaissance and remote sensing; various spectral analysis instruments used in medical detection and material analysis also require high-precision photodetectors to collect and extract absorption, transmission, and emission spectra; In the field of smart home that is currently developing, wireless infrared detectors also play an important role in realizing the connection and interaction of devices.
  • High-speed and high-sensitivity photodetectors are also one of the core components of LiDAR, the core technology in the current popular unmanned field.
  • LiDAR the core technology in the current popular unmanned field.
  • the photodetector based on this graphene film can achieve wide-spectrum detection, it is expected to combine the multi-spectral fusion technology to fuse the visible image and the infrared image to realize the image.
  • photoelectric detection also has a wide range of applications.
  • blood oxygen detection is to extract the reflection of hemoglobin on infrared light through an infrared detector on a wearable device.
  • miniature photodetectors will also play an important role.
  • One object of the present invention is to provide a graphene structure enhanced by weak coupling, which is formed by stacking a plurality of graphene units up and down; the graphene unit is a single-layer graphene sheet, or is composed of more than two layers of graphene The sheets are stacked, and the stacking method is AB stacking; the upper and lower two adjacent graphene units are non-AB stacking structure regions, so that the two graphene units are weakly coupled.
  • the electron clouds are integrated into one, and the electronic structure of the graphene film is more inclined to the graphite structure.
  • the graphene electron phonon scattering is weakened, and the hot electron relaxation time is prolonged; while in the non-AB stacking structure area, the electron cloud layer Layer separation, the electronic structure of the graphene film is more inclined to the graphene structure, so that the electron combined state density increases, the light absorption increases, and the hot electron transition becomes easier.
  • Another object of the present invention is to provide a graphene structure based on weak coupling enhancement, which is formed by stacking a plurality of graphene units up and down; the graphene units are single-layer graphene sheets, or composed of 2-9 layers
  • the graphene sheets are stacked, and the stacking method is AB stacking; the upper and lower adjacent graphene units are weakly coupled, the combined state density is high, and the light absorption is enhanced.
  • the overlapped gap (vertical direction) of the sheets caused by the structural unit composed of graphene sheets within 9 layers can be controlled to be about 3 nm, and the hot electrons with higher combined state density can tunnel through without being affected.
  • Another object of the present invention is to provide a graphene structure based on weak coupling enhancement, which is formed by stacking a plurality of graphene units up and down; the graphene units are single-layer graphene sheets; Weak coupling between alkene units.
  • the electronic structure of single-layer graphene can effectively assist in increasing the combined state density, promote light absorption, promote hot electron transition, and increase the occupancy probability of high-energy hot electrons.
  • the present invention provides a graphene photoelectric film with enhanced weak coupling, which realizes the superposition of the light absorption of multilayer graphene through weak coupling, improves the light absorption rate and the thermal electron lifetime of the graphene film, thereby At low-energy wavelengths, hot electrons can still accumulate.
  • Another object of the present invention is to provide a graphene photoelectric film with enhanced weak coupling, which contains a graphene structure.
  • the graphene structure is formed by stacking a plurality of graphene units up and down; the graphene unit is a single-layer graphene sheet, or is formed by stacking more than two layers of graphene sheets, and the stacking method is AB stacking; Weak coupling between adjacent graphene units.
  • the stacking direction of the graphene units in the graphene structure is along the thickness direction of the graphene film. Light irradiates the surface of the graphene film, and photoelectrons pass through the AB stacking region and the non-AB stacking region from the surface.
  • the electron cloud merges into one, the electronic structure of the graphene film is more inclined to the graphite structure, and the thermal electron and phonon scattering are weakened. , increasing the hot electron relaxation time; while in the non-AB stacking structure region, the electron cloud layers are separated, and the electronic structure of the graphene film is more inclined to the graphene structure, the joint state density increases, and the light absorption increases, which promotes the hot electron transition.
  • the present invention also provides a weak coupling-enhanced graphene photoelectric film, which contains the above graphene structure.
  • the stacking direction of the graphene units in the graphene structure is along the thickness direction of the graphene film.
  • the non-AB structure content of the whole film is more than 5%, even more than 90%.
  • a large amount of non-AB structure content makes the graphene film have a large number of weakly coupled regions, which makes the overall electronic structure of the graphene film approach that of single-layer graphene, which greatly increases the combined density of states, enhances absorption and promotes hot electron transitions. , thereby increasing the number of high-energy hot electrons.
  • the ID/ IG of the graphene film is below 0.05.
  • defects in graphene will increase the scattering of graphene, thereby reducing the hot electron relaxation time of graphene, but the scattering of phonons by graphene defects is more reflected in the horizontal direction, and has little effect on the vertical direction;
  • the scattering effect of the uncoupled stacking of graphene units on hot electrons is mainly aimed at the vertical direction, so it has a greater impact on hot electron scattering and is the most useful.
  • the existence of weak coupling enhances the defect tolerance of the photoelectric effect of graphene films.
  • the graphene oxide film obtained by solution assembly is subjected to heat treatment (graphitization furnace annealing, laser heating annealing, microwave heating annealing, etc.) to repair defects Afterwards, the weak coupling-enhanced graphene film is obtained.
  • the graphene oxide film needs to be peeled off from the substrate and then heat treated.
  • the inventors of the present invention found in a large number of graphene exfoliation experiments that during the reduction process, the concentration of hydriodic acid vapor was insufficient, the relative vapor pressure was small, and the HI vapor was insufficient to completely penetrate into the contact interface between the graphene film and the substrate; in addition, the HI vapor was mixed with water Steam plays a role in wetting, which on the one hand hinders the rapid penetration of HI, and on the other hand infiltrates the interface and inhibits interface separation.
  • the asymmetric reduction and penetration of hydriodic acid greatly reduces the contact area and force of the interface agent, and the weak contact interface can be peeled off by solvents such as isopropanol; Cannot be separated from the base.
  • the graphene oxide film has a thickness of 20-120 nm, is deposited on a rigid substrate with a porosity greater than 60% by solution assembly, and is then peeled off from the rigid substrate by the following method: placing it on a reducing agent with HI vapor The chemical reduction is carried out in the chamber until the graphene oxide is automatically peeled off from the substrate; during the reduction process, at least the concentration of HI is above 0.3g/L and the concentration of water vapor is below 0.07g/L. Reduction for more than 10min.
  • HI steam with low water vapor content can be directly input, or an evaporation chamber communicated with the reduction chamber can be used to vaporize the hydroiodic acid, so as to input the HI steam into the reduction chamber.
  • the reduction chamber and the evaporation chamber are located in the same closed cavity, and the evaporation chamber is located below the reduction chamber, and the evaporation chamber is located in an oil bath or a water bath with a temperature of 80-120 degrees Celsius;
  • the top of the reduction chamber is a condensation zone, and the temperature of the condensation zone is controlled at 0-40°C (usually at room temperature).
  • the hydriodic acid solution evaporates into HI vapor and water vapor.
  • the water vapor condenses at the top, which reduces the water vapor content in the cavity, while the condensation temperature of HI is lower, and it remains gaseous.
  • a water-absorbing material is arranged in the condensation area to absorb water vapor and condensed water, so as to prevent the condensed water from re-evaporating after falling back.
  • the water-absorbing materials are: porous and strongly water-absorbing materials such as water-absorbing filter paper and superabsorbent resin, and strong water-absorbing chemicals such as calcium chloride and phosphorus pentoxide.
  • an HI-resistant rack is provided in the reduction chamber for loading the substrate, such as a PTFE mesh rack, a hollow glass rack, and the like.
  • the reduction chamber and the evaporation chamber are each located in a closed cavity. And the two closed cavities are communicated through a condenser pipe; the condenser pipe condenses the water vapor evaporated in the evaporation chamber, and returns to the evaporation chamber.
  • the iodic acid solution is evaporated into HI vapor and water vapor, and the water vapor is condensed in the condenser tube and refluxed to the evaporation chamber, while the condensation temperature of HI is lower, and it remains gaseous.
  • the condensation temperature of HI is lower, and it remains gaseous.
  • both the evaporation chamber and the reduction chamber are located in an oil bath or a water bath with a temperature of 80-120 degrees Celsius.
  • the temperature of the reduction chamber is lower than that of the evaporation chamber, which is beneficial to
  • the hydrogen iodide gas diffuses rapidly toward the reduction chamber.
  • the existence of the temperature difference will cause a pressure difference on both sides, and then the hydrogen iodide with higher mass density will be distributed in the reduction chamber in the low temperature region.
  • the substrate is anodized aluminum, tetrafluoroethylene filter membrane, glass fiber filter membrane, and the like.
  • the gas phase separation method is milder and hardly has any strong tearing effect on the film, while the solid phase transfer method is the opposite.
  • the specific performance is as follows: First, AAO is a brittle material. During the operation of the solid phase transfer agent, it will have a weight burden on AAO, which will damage the AAO film or fail to have good coverage continuity, resulting in discontinuous peeling of the solid phase transfer agent. Complete graphene nanofilms cannot be obtained (Fig. 9); however, gas-phase reduction does not have these problems, so perfect large-sized graphene films can be obtained.
  • the solid phase transfer method may cause strong adhesion between graphene oxide and AAO substrate due to insufficient reduction of graphene, and form hole-type tears in local areas under the action of cold shrinkage (Figure 10A1 ⁇ A2). ), while the mild gas-phase transfer method does not have this problem, and a perfect graphene film without any tearing can be obtained ( Figure 10B-D).
  • the solid-phase transfer method requires careful operation by the experimenter. If the operation is improper and the attention is not focused, it is very easy to damage the graphene nanofilm, especially in the process of cold grasping of the transfer agent. See Figures 10A1 to A2. In addition, the graphene and the substrate are still partially adhered.
  • a dense structure is formed through heat treatment (graphitization furnace annealing, laser heating annealing, microwave heating annealing, etc.) to obtain the weakly coupled enhanced graphene membrane.
  • the graphitizable material is assembled in solution, and graphitized by heat treatment (graphitization furnace annealing, laser heating annealing, microwave heating annealing, etc.) to obtain the weakly coupled enhanced graphene film.
  • the graphitizable materials include polyimide, polyacrylonitrile, and pitch.
  • the weak coupling enhanced graphene film is obtained by catalyzing small vitrifiable molecules (glucose, menthol, naphthalene, anthracene, etc.) under the catalysis of nickel-based catalysts.
  • mixtures of graphene oxide, polyimide, graphene oxide and non-graphitizable or low-graphitizable polymers eg, pitch, lignin, polyphenylene rings such as polyphenylene rings, polyphenylenes, polycyclic aromatic hydrocarbons, etc.
  • the mixing mass ratio is less than 1:6 (under normal circumstances, the carbon yield of graphene oxide is 66%, and the carbon yield of polymer graphitization is below 50%.)
  • the more the benzene ring structure the smaller the maximum mixing ratio).
  • the characteristics of the mixture are that graphene can be used as a template to induce low graphitization or non-graphitizable polymers to be graphitized in an orderly arrangement along the graphene plane; at the same time, the functional groups on the surface of graphene oxide can be polyimide, polyacrylonitrile, etc.
  • the polymer that needs to be pre-oxidized provides oxygen atoms, thereby avoiding the core-shell phenomenon in the pre-oxidation process of the material, ensuring the uniform pre-oxidation of the material, and then ensuring the uniformity of the material structure during the high temperature process; in addition, this method avoids polymerization.
  • the requirement of high orientation in the process of physical graphitization reduces the process conditions of polymer graphitization.
  • Graphene effectively catalyzes graphitization with 4 atomic layers, two upper and lower layers, and more than four layers. After high-temperature catalysis, there are many defects. As the matching of the conjugated structure of the polymer weakens, its catalytic effect also weakens.
  • the present invention also provides a graphene-based optoelectronic device, comprising a weak coupling-enhanced graphene film and a semiconductor substrate, wherein the graphene film realizes the superposition of light absorption through weak coupling, and improves the light absorption rate of the graphene film, so that the In the low-energy band, hot electrons can still accumulate, so that the hot electrons in the high-energy state region can cross the graphene/semiconductor barrier and finally obtain a collectable electrical signal.
  • the present invention also provides a graphene-based optoelectronic device, comprising a weak coupling-enhanced graphene film and a semiconductor substrate, wherein the graphene film includes a weak-coupling-enhancing graphene structure.
  • the weak coupling-enhanced graphene structure is formed by stacking a plurality of graphene units up and down; the graphene units are single-layer graphene sheets, or are formed by stacking more than two layers of graphene sheets, and the stacking method is AB Stacking; weak coupling between two adjacent graphene units above and below.
  • the stacking direction of the graphene units in the graphene structure is along the thickness direction of the graphene film.
  • the photoelectrons pass through the AB stacking region and the non-AB stacking region from the surface and then jump into the semiconductor layer.
  • the electron cloud is integrated into one, and the electronic structure of the graphene film is more inclined to the graphite structure.
  • the thermal electron relaxation time of graphene is In the non-AB stacking structure region, the electron cloud layers are separated, and the electronic structure of the graphene film is more inclined to the graphene structure, the joint density of states increases, and the light absorption in the infrared region increases, thereby promoting the thermal electron transition, and there are more and more Hot electrons in high-energy states transition from graphene to semiconductors.
  • the graphene film is spread on the semiconductor substrate by the following method: the graphene film is placed on the semiconductor substrate, and a solvent with high surface tension is dripped at the edge of the graphene film, so that the solvent moves from the edge of the graphene film to the surface of the semiconductor substrate.
  • the folds of the graphene membrane are unfolded during the internal penetration; then the solvent is volatilized.
  • the high surface tension solvent includes deionized water, dmf, dmac, ethylene glycol, propylene glycol, o-xylene, toluene, butyl acetate and mixtures thereof.
  • sintering temperature is 400-1000 degrees Celsius to build the graphene-semiconductor interface and further reduce the dark current.
  • the semiconductor substrate described in the present invention includes: elemental semiconductor, compound semiconductor, including but not limited to Si, Ge, C, Sn, GaAs, InP, AlGaAs, InGaP, InGaAs, AlInGaP, AlInGaAs, InGaAsP, AlInGaAsP, GaN, InGaN, One or more of AlGaN, AlInGaN, GaP, alloys thereof, or derivatives thereof.
  • Another object of the present invention is to provide a method for preparing a graphene-based optoelectronic device, comprising the steps of:
  • a working window is reserved on the semiconductor substrate, an insulating layer is plated outside the working window, and then an electrode layer is sputtered in the insulating layer;
  • the multi-layer graphene film is firstly spread on the working window, and is in contact with the electrode layer, and the organic solvent is dripped on the edge of the graphene film, and the organic solvent penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the present invention also provides a method for increasing the hot electron transition probability of hot electrons in the vertical transmission direction of the graphene film, the method at least comprising: increasing the number of non-AB structures in the vertical transmission direction of the graphene film, through weak coupling of the non-AB structures The action promotes the thermal electron transition.
  • the present invention also provides a method for enhancing the accumulation of hot electrons in the vertical transport direction of the graphene film, the method at least comprising: increasing the number of non-AB structures in the vertical transport direction of the graphene film, and increasing hot electrons through the weak coupling effect of the non-AB structures Transition probability; control the vertical AB stacking structure of graphene, prolong the hot electron relaxation time, and promote the generation and accumulation of hot electrons in the high-energy state region.
  • the method also includes: increasing the thickness of the film within the range of thickness ⁇ 60 nm; the greater the thickness, the greater the number of layers, the light absorption and the relaxation time of hot electrons will also be enhanced, and the more hot electrons are generated, further
  • the hot electron transition probability is increased through the weak coupling of the non-AB structure, and the joint state density of graphene is simultaneously increased, which promotes the generation and accumulation of hot electrons in the high-energy state region.
  • the thickness is greater than 60 nm, the excessive thickness will also increase the recombination of hot electrons and reduce the number of hot electrons that transition over the potential barrier.
  • Fig. 1 is the xps spectrogram of two graphene films prepared in Example 1;
  • Fig. 2 is the Raman map of two graphene films prepared in Example 1;
  • Fig. 3 is the TEM image of two graphene films prepared in Example 1;
  • Fig. 4 is the electron diffraction pattern of two graphene films prepared by embodiment 1;
  • Example 5 is a graph of the thermal electron relaxation time of the two graphene films prepared in Example 1.
  • Figure 6 shows the electron diffraction patterns and corresponding electron lifetimes after different temperature treatments
  • FIG. 7 is a schematic diagram of the superposition of light absorption of multilayer graphene through weak coupling.
  • Fig. 8 is a stepwise separation process diagram of graphene film and substrate
  • Figure 9 is a graphene oxide membrane (4 inches) obtained by suction filtration on a rigid anodized aluminum filter membrane.
  • Figure 10 is a graphene oxide membrane (4 inches) after separation.
  • Figure A1 is the graphene nanofilm transferred by the solid phase transfer agent.
  • B1-D1 are the non-damaged graphene nanofilms prepared by the transfer agent-free method in the present application (corresponding to Examples 2-4 in sequence);
  • A2-D2 are corresponding enlarged views.
  • FIG. 11 is a schematic plan view A and a schematic perspective view B of the separation device of Example 2;
  • Fig. 12 is the separation device diagram of embodiment 3.
  • FIG. 13 is a diagram of a separation device of Example 4.
  • the test method of ID/ IG is as follows: transfer the film to a silicon substrate, use a 532 laser as the light source to conduct a full-band Raman test at full power, and obtain a pull-up measurement including D peak, G peak and 2D peak. Mann Atlas. The areas of peak D and peak G are defined as the intensities ID and IG of peak D and peak G , respectively, and ID/ IG is obtained after division operation.
  • test method of AB structure content is as follows: Measuring the degree of stacking order in graphite by Raman spectroscopy, Carbon, 2008, 46(2), 272-275.
  • Single-layer graphene or multi-layer AB-stacked graphene will present a set of diffraction patterns composed of 6 diffraction spots (evenly distributed on the same circumference), and the higher the number of AB-stacked graphene layers, the higher the spot brightness;
  • the presence of the AB structure causes multiple sets of non-overlapping spots to appear in the diffraction pattern.
  • the prepared thin films are placed under a high-resolution TEM to collect electron diffraction patterns, and the vertical stack structure can be tested according to the diffraction patterns.
  • the number of structural units in the film can be calculated by the number of sets of diffraction spots; on the other hand, the number of stacked layers of each structural unit can be inferred from the ratio of the brightness value of the diffraction spots to the diffraction brightness of single-layer graphene.
  • the weak coupling effect in the present invention refers to the electron cloud coupling effect caused by the disordered stacking between graphene sheets. At this time, the electron cloud between the sheets does not achieve a complete coupling effect, and the interlayer spacing is 0.334-0.36 nm; while AB Under the stacked structure, the coupling strength of electron cloud orbits between graphene sheets is the largest, and the interlayer spacing is 0.334 nm, which is called strong coupling.
  • the graphene unit is a single-layer graphene sheet, or is formed by stacking 2-9 layers of graphene sheets, and the number of graphene units in the vertical direction in the graphene film can be determined by measuring the total thickness of the graphene film, and by The thickness of the single-layer graphene can be calculated by dividing the thickness.
  • the number of layers of graphene sheets in a single graphene unit can be calculated by the Raman method to calculate the AB structure content and obtained by the average method.
  • Non-AB structure graphene film Graphene oxide is spin-coated to prepare a 24nm film, and the temperature is increased to 2000 degrees at a rate of 10 degrees per minute for 16 hours.
  • the non-AB structure content ⁇ 100%, the number of vertical graphene structural units is 30, and the number of graphene sheets in a single graphene structural unit is 1.
  • AB structure graphene film Graphene oxide is spin-coated to prepare a 24nm film, and the temperature is raised to 2800 degrees at a rate of 10 degrees Celsius per minute for 2 hours.
  • the TEM test results are in perfect agreement with the Raman results.
  • the electron diffraction surface of the AB-structured graphene film is composed of only two structural units stacked, and the spot brightness of one structural unit is significantly higher than that of the second structural unit, that is, two structural units
  • the structural unit has a very high thickness and a very few atomic layers, and the two are stacked on each other in a non-AB manner.
  • the graphene film with non-AB structure has more sets of diffraction spots (Fig. 4), and even forms an amorphous diffraction ring, indicating that the film is composed of a large number of structural units stacked on each other in the form of non-AB.
  • this patent tests the hot electron relaxation times of both. As shown in Figure 5, under the same excitation time of 200 fs, the hot electron relaxation time of the graphene film with the AB structure reaches 25 ps, while the hot electron relaxation time of the graphene film without the AB structure is maintained within 10 ps. It can be seen that the weak coupling between graphene units, and its structure is more inclined to the single-layer graphene unit, which can increase the joint state density, thereby increasing the number of high-energy hot electrons.
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V (silicon terminal is grounded) by using a keithley source meter; after connecting to the amplifier circuit and connecting to the oscilloscope, the test data can be obtained as shown in Table 1.
  • Step 1 The graphene oxide obtained by the hummer method is prepared into an aqueous solution of graphene oxide with a concentration of 0.5ug/mL, and a rigid tetrafluoroethylene filter membrane with a porosity of 60% is used as the base to form a membrane by suction filtration.
  • the thickness of the graphene oxide membrane is 100 nm, and the area is 80 ⁇ 5 cm 2 .
  • the device as shown in FIGS. 11A-B is used to peel the graphene oxide film.
  • the device includes a cylindrical cavity 3, and the cavity 3 contains a hydroiodic acid solution 2.
  • a polytetrafluoroethylene mesh frame 2 is fixed, and a water-absorbing filter paper 5 is arranged on the top cover 4 for sealing the cylindrical cavity.
  • the lower part of the cylindrical cavity is located in a water bath 1 at 80 degrees Celsius, and the sample to be peeled off is placed on a PTFE mesh frame 2 .
  • the hydroiodic acid solution evaporates into HI vapor and water vapor.
  • the water vapor condenses on the top and is absorbed by the water-absorbing filter paper to reduce the water vapor content in the cavity. Keep gaseous.
  • the volume of the cylindrical cavity 3 is 1 L and the bottom area is 120 cm 2 .
  • the mass concentration of the hydroiodic acid solution in the cavity 3 is 50%, the mass content of HI is 0.42g, and the rest is water (0.42g).
  • Water absorption filter paper (2g) has a water absorption limit of 60% of its mass.
  • the ambient temperature at the upper part of the cavity 3 is 0 degrees Celsius.
  • the hydroiodic acid solution 2 was completely evaporated, and the hydrogen iodide solution contained was reduced to invisible to the naked eye.
  • the condensation of some water droplets was seen on the top layer, and the absorbent paper was hygroscopic and swelled.
  • the water-absorbing filter paper gained 0.44g in weight.
  • the concentration of hydriodic acid remained at 0.33g/L. It is proved that the water vapor content in cavity 3 is below 0.07g/L.
  • the acid-base test was carried out through gas sampling, and the concentration of hydriodic acid remained at 0.32g/L.
  • the same device is set up in this embodiment, and the sampling of the water-absorbing filter paper (2g) and the gas in the cavity are not carried out, and the same graphene oxide film is directly peeled off, and the processing time is 4h, after 4h, the graphene is detached, as shown in Figures 10B1-B2. It can be seen from the figure that under the reduction of hydriodic acid, the graphene film is completely detached from the substrate under the action of stress, and there is no macroscopic damage or microscopic pores during the detachment process.
  • Step 2 The three sample films were annealed in a graphitization furnace at 1600°C, 1800°C, and 2000°C for 2 h.
  • the vertical stacking structure was tested by TEM electron diffraction, and the same analysis as in Example 1 confirmed that the three graphene films contained a large number of weakly coupled graphene structures;
  • the units are stacked on top of each other; the graphene unit is formed by stacking a single-layer graphene sheet in a turbostratic layer; there is a weak coupling between two adjacent graphene units up and down.
  • the thermal electron relaxation time of the graphene film is shown as B1 to B3 in FIG. 6 , all of which are not shorter than 5 ps.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V (silicon terminal is grounded) by using a keithley source meter; after connecting to the amplifier circuit and connecting to the oscilloscope, the test data can be obtained as shown in Table 2.
  • the graphene oxide obtained by the hummer method was prepared into an aqueous solution of graphene oxide with a concentration of 0.5ug/mL, and a rigid anodic aluminum oxide filter membrane with a porosity of 80% was used as the base to form a membrane by suction filtration, and the thickness of the graphene oxide membrane was 60nm, the area is 80 ⁇ 5cm 2 .
  • the device as shown in FIG. 12 is used to peel the graphene oxide film, and the device includes two cavities 11 and 12 on the left and right.
  • the cavities 11 and 12 are communicated through an inclined condenser pipe 13 .
  • Both chambers 11 and 12 are placed in a water bath 14 at 80 degrees Celsius.
  • the cavity 11 is filled with a hydroiodic acid solution, and the cavity 12 is used for placing the graphene oxide film to be peeled off.
  • the hydriodic acid solution in the cavity 11 is volatilized, and the water vapor in it is condensed and returned to the cavity 11 in the condenser tube, while the condensation temperature of HI is higher, which is input to the cavity 12 through the condenser tube 13 to construct the cavity 12 Environment with high HI concentration and low water vapor concentration.
  • the volume of the cavities 11 and 12 is 400 mL, and the bottom area is 50 cm 2 .
  • the content of the hydriodic acid solution in the cavity 11 is 0.5g (the mass concentration of HI is 55%), the ambient temperature of the condenser tube 13 is 40 degrees Celsius, the length of the condenser tube is 20cm, and the inclination angle is 30 degrees, which can effectively ensure the cavity Construction of an environment with high HI concentration and low water vapor concentration in body 12.
  • the evaporation chamber on the right kept the evaporation-condensation reflux, and there was still no condensed water at the rear of the condenser tube.
  • the concentration of hydriodic acid remained at 0.41g. /L.
  • the same device is set up in this embodiment, and the gas in the cavity is not sampled, and the same graphene oxide film is directly peeled off. After 1h of reduction, the graphene is separated. See Figures 10C1-C2. It can be seen from the figure that under the reduction of hydriodic acid, the graphene film is completely detached from the substrate under the action of stress, and there is no macroscopic damage or microscopic pores during the detachment process.
  • the vertical stacking structure is tested by TEM electron diffraction, and the graphene film contains a large number of weakly coupled graphene structures; it is formed by stacking multiple graphene units up and down; the graphene units are stacked by a single-layer graphene sheet turbostratic formed; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1 ⁇ m and a power of 5 mW, and a photocurrent signal of 1.1 mA was measured within 20 ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 97uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 8.3uA was measured within 80ns.
  • the graphene oxide obtained by the hummer method is prepared into an aqueous solution of graphene oxide with a concentration of 0.5ug/mL, and a rigid anodic aluminum oxide filter membrane with a porosity of 80% is used as the base to form a membrane by suction filtration.
  • the thickness of the graphene oxide membrane is is 60nm, and the area is 80 ⁇ 5cm 2 .
  • the device as shown in FIG. 13 is used to peel the graphene oxide film, and the device includes two cavities 11 and 12 on the left and right.
  • the cavities 11 and 12 are communicated through an inclined condenser pipe 13 .
  • the cavity 11 is placed in an oil bath 14 of 120 degrees Celsius, and the cavity 12 is placed in a water bath 14 of 80 degrees Celsius.
  • the cavity 11 is filled with a hydroiodic acid solution, and the cavity 12 is used for placing the graphene oxide film to be peeled off.
  • the hydriodic acid solution in the cavity 11 is volatilized, and the water vapor in it is condensed and returned to the cavity 11 in the condenser tube, while the condensation temperature of HI is higher, which is input to the cavity 12 through the condenser tube 13 to construct the cavity 12 Environment with high HI concentration and low water vapor concentration.
  • the volume of the chambers 11 and 12 is 400 mL, and the bottom area is 50 cm 2 .
  • the content of the hydroiodic acid solution in the cavity 11 is 0.3g (the mass concentration of HI is 55%), the ambient temperature where the condenser tube 13 is located is 20 degrees Celsius, the length of the condenser tube is 20cm, and the inclination is 30 degrees, which can effectively ensure the cavity Construction of an environment with high HI concentration and low water vapor concentration in body 12.
  • the evaporation chamber on the right kept the evaporation-condensation reflux, and there was still no condensed water at the rear of the condenser tube.
  • the concentration of hydriodic acid remained at 0.30g. /L.
  • the same device is set up in this embodiment, and the gas in the cavity is not sampled, and the same graphene oxide film is directly peeled off. After reduction for 2h, the graphene is separated. See Figures 10D1-D2. It can be seen from the figure that under the reduction of hydriodic acid, the graphene film is completely detached from the substrate under the action of stress, and there is no macroscopic damage or microscopic pores during the detachment process.
  • the vertical stacking structure is tested by TEM electron diffraction, and the graphene film contains a large number of weakly coupled graphene structures; it is formed by stacking multiple graphene units up and down; the graphene units are stacked by a single-layer graphene sheet turbostratic formed; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped on the edge of the graphene film.
  • the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1um and a power of 5mW, and a photocurrent signal of 1.13mA was measured within 20ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 99uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 8.1uA was measured within 80ns.
  • the graphene oxide obtained by the hummer method was prepared into an aqueous solution of graphene oxide with a concentration of 0.5 ug/mL, and a film was formed by suction filtration with anodized aluminum oxide as the base, and the number of graphene atomic layers was 120.
  • the existing solid transfer agent is used to finely transfer the graphene oxide film deposited on the anodic aluminum oxide, and a completed independent self-supporting film is obtained after several attempts.
  • the non-AB structure content is 50%; the number of graphene structural units in the vertical direction is 60, and the graphene in a single graphene structural unit The number of slices is 2.
  • the vertical stacking structure is tested by TEM electron diffraction, the graphene film contains a large number of weakly coupled graphene structures; it is formed by stacking multiple graphene units up and down; the graphene units are stacked by a single-layer graphene sheet turbostratic formed; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1um and a power of 5mW, and a photocurrent signal of 1.3mA was measured within 20ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 122mA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 10uA was measured within 80ns.
  • the graphene oxide obtained by the hummer method was prepared into an aqueous solution of graphene oxide with a concentration of 0.5ug/mL, and a film was formed by suction filtration with anodized aluminum oxide as the base, and the number of graphene oxide atomic layers was 120.
  • the existing solid transfer agent is used to finely transfer the graphene oxide film deposited on the anodic aluminum oxide, and a completed independent self-supporting film is obtained after several attempts.
  • the vertical stacking structure is tested by TEM electron diffraction.
  • the graphene film contains a large number of strongly coupled graphene structures; it is formed by stacking a small number of graphene units up and down; the graphene units are composed of single-layer graphene sheets in an AB structure. Stacked; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1 ⁇ m and a power of 5 mW, and a photocurrent signal of 1.1 mA was measured within 20 ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 113uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 9uA was measured within 80ns.
  • the single-layer graphene prepared by the copper-based CVD method was removed from the substrate by the hydrogen evolution method, and stacked layer by layer until the number of graphene atomic layers was 150.
  • the vertical stacking structure is tested by TEM electron diffraction, and the graphene film contains a large number of weakly coupled graphene structures; it is formed by stacking multiple graphene units up and down; the graphene units are stacked by a single-layer graphene sheet turbostratic formed; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1 ⁇ m and a power of 5 mW, and a photocurrent signal of 4 mA was measured within 20 ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 160uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 15uA was measured within 80ns.
  • the single-layer graphene prepared by the copper-based CVD method was removed from the substrate by the hydrogen evolution method, and stacked layer by layer until the number of graphene atomic layers was 150.
  • the vertical stacking structure is tested by TEM electron diffraction.
  • the graphene film contains a large number of strongly coupled graphene structures; it is formed by stacking a small number of graphene units up and down; the graphene units are composed of single-layer graphene sheets in an AB structure. Stacked; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1 ⁇ m and a power of 5 mW, and a photocurrent signal of 3.3 mA was measured within 20 ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 130uA was measured within 18ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 14uA was measured within 20ns.
  • the multi-layer graphene prepared by nickel-based CVD method removes the substrate with the method of hydrochloric acid and hydrogen peroxide etching, and superimposes layer by layer, until the graphene atomic layer number is 180.
  • the vertical stacking structure is tested by TEM electron diffraction, and the graphene film contains a large number of weakly coupled graphene structures; it is formed by stacking multiple graphene units up and down; the graphene units are stacked by a single-layer graphene sheet turbostratic formed; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1um and a power of 5mW, and a photocurrent signal of 5.0mA was measured within 20ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 190uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 17uA was measured within 80ns.
  • the multilayer graphene prepared by the nickel-based CVD method was etched with hydrochloric acid and hydrogen peroxide to remove the substrate, and stacked layer by layer until the number of graphene atomic layers was 180.
  • the vertical stacking structure is tested by TEM electron diffraction.
  • the graphene film contains a large number of strongly coupled graphene structures; it is formed by stacking a small number of graphene units up and down; the graphene units are composed of single-layer graphene sheets in an AB structure. Stacked; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1 ⁇ m and a power of 5 mW, and a photocurrent signal of 4.1 mA was measured within 20 ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 120uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 11uA was measured within 80ns.
  • the multi-layer graphene prepared by the nickel-based CVD method is etched with hydrochloric acid and hydrogen peroxide to remove the substrate and the single-layer graphene prepared by the copper-based single-layer graphite, and mix and stack layer by layer until the number of graphene atomic layers is 180 .
  • the AB structure content is 75%; the number of vertical graphene structural units is 60, and the number of graphene sheets in a single graphene structural unit is 3.
  • the vertical stacking structure is tested by TEM electron diffraction.
  • the graphene film contains a large number of strongly coupled graphene structures; it is formed by stacking a small number of graphene units up and down; the graphene units are composed of single-layer graphene sheets in an AB structure. Stacked; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped at the edge of the graphene film, and the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1 ⁇ m and a power of 5 mW, and a photocurrent signal of 4.4 mA was measured within 20 ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 130uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 14uA was measured within 80ns.
  • the vertical stacking structure is tested by TEM electron diffraction.
  • the graphene film contains a large number of strongly coupled graphene structures; it is formed by stacking a small number of graphene units up and down; the graphene units are composed of single-layer graphene sheets in an AB structure. Stacked; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped on the edge of the graphene film.
  • the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1um and a power of 5mW, and a photocurrent signal of 0.91mA was measured within 20ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 97uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 7.3uA was measured within 80ns.
  • the substrate is removed by the hydrogen evolution method.
  • the vertical stacking structure is tested by TEM electron diffraction.
  • the graphene film contains a large number of strongly coupled graphene structures; it is formed by stacking a small number of graphene units up and down; the graphene units are composed of single-layer graphene sheets in an AB structure. Stacked; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped on the edge of the graphene film.
  • the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1um and a power of 5mW, and a photocurrent signal of 1.21mA was measured within 20ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 109uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 9.2uA was measured within 80ns.
  • the vertical stacking structure is tested by TEM electron diffraction.
  • the graphene film contains a large number of strongly coupled graphene structures; it is formed by stacking a small number of graphene units up and down; the graphene units are composed of single-layer graphene sheets in an AB structure. Stacked; weak coupling between the upper and lower adjacent graphene units.
  • the graphene film prepared above is made into an optoelectronic device according to the following steps:
  • the graphene film is firstly spread on the working window, and is in contact with the electrode layer, and ethylene glycol is dripped on the edge of the graphene film.
  • the ethylene glycol penetrates from the edge of the graphene film to the inside, volatilizes the solvent, and utilizes the The surface tension realizes the close combination of the film and the semiconductor, and an independent optoelectronic device is obtained;
  • the electrodes and semiconductors of the device are tested by applying a reverse bias voltage of -2V to -1V with a keithley source meter; after connecting with the amplifying circuit and connecting with the oscilloscope, the test data can be obtained.
  • the graphene layer was irradiated with infrared light with a wavelength of 1um and a power of 5mW, and a photocurrent signal of 3.1mA was measured within 20ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 4um and a power of 20mW, and a photocurrent signal of 112uA was measured within 25ns.
  • the graphene layer was irradiated with infrared light with a wavelength of 10.6um and a power of 50mW, and a photocurrent signal of 12.5uA was measured within 80ns.

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Abstract

本发明提供一种基于弱耦合增强的石墨烯结构，这种石墨烯结构通过弱耦合作用使得本体材料具有线性能带特征，促进热电子的跃迁，增加联合态密度；AB结构的存在和厚度的增加配合延长热电子弛豫时间，从而提升高能态热电子数量，同时降低了膜制备工艺的要求和成本，增加了膜制备的成功率。另外，基于石墨烯/半导体肖特基结，可以探测低能量的光，将石墨烯/硅光电器件的探测范围从可见和近红外拓展到中远红外。本发明还提供一种弱耦合增强的石墨烯光电膜，通过弱耦合实现多层石墨烯的光吸收的叠加，提高石墨烯膜的光吸收率，从而在低能量波段，热电子仍然可以积累。

Description

基于弱耦合增强的石墨烯结构、石墨烯膜及光电器件 技术领域
本发明涉及石墨烯功能材料，尤其涉及一种基于弱耦合增强的石墨烯结构、石墨烯膜和器件及其材料制备方法。
背景技术
2010年，英国曼彻斯特大学的两位教授Andre Geim和Konstantin Novoselov因为首次成功分离出稳定的石墨烯获得诺贝尔物理学奖，掀起了全世界对石墨烯研究的热潮。石墨烯有优异的电学性能(室温下电子迁移率可达2×10 5cm 2/Vs)，突出的性能(5000W/(mK)，超常的比表面积(2630m 2/g)，其杨氏模量(1100GPa)和断裂强度(125GPa)。石墨烯优异的导电导热性能完全超过金属，同时石墨烯具有耐高温耐腐蚀的优点，而其良好的机械性能和较低的密度更让其具备了在电热材料领域取代金属的潜力。
宏观组装氧化石墨烯或者石墨烯纳米片的石墨烯膜是纳米级石墨烯的主要应用形式，常用的制备方法是抽滤法、刮膜法、旋涂法、喷涂法和浸涂法等。通过进一步的高温处理，能够修补石墨烯的缺陷，能够有效的提高石墨烯膜的导电性和热导性，可以广泛应用于发声、声波探测、光电探测、智能手机、智能随身硬件、平板电脑、笔记本电脑等随身电子设备中去。
但是，因为单层石墨烯吸光度很低，不能吸收足够强度的光，在红外、太赫兹以及其他更低能量波段对电磁波没有任何的响应。为此，科研工作者在石墨烯器件改性方面做了大量的工作，以提高器件对光的吸收。另外通常认为，单层石墨烯不能进行有效的热电子积累，不能跨越石墨烯和半导体的势垒，因而在低能量波段，石墨烯并没有明显响应。
传统肖特基结为金属/半导体结构，但是金属材料本身光激发热电子寿命极 低(0.1ps左右)，噪声大，因而不能在常温光电子器件领域得到应用。相比于金属材料，单层石墨烯热电子寿命提高了一个量级左右(1ps)，常温噪声得到了极大的抑制，然而石墨烯极好的透明度使得其不能进行有效的热电子积累，不能跨越石墨烯和半导体的势垒，因而在低能量波段，石墨烯并没有明显响应。另外单层石墨烯膜的转移困难，还不能完全去除金属以及聚合物的污染；有效热电子积累的石墨烯膜(AB结构堆积的多层石墨烯膜)已经被初步报道，但是其热电子积累效率很低，究其原因在于AB结构的石墨烯膜电子结构偏重于石墨结构，其电子态密度相对较低，高能态轨道占据能力相对较弱，因此探测能力相对较低。
另外，石墨烯的缺陷结构往往会增加石墨烯热电子-声子散射，因此为了提高石墨烯热电子弛豫时间，必须高温处理尽可能的修复缺陷结构，增加了光电子探测器件的制备难度。但是，缺陷态的存在增加了器件温度，在损伤响应速度的同时，有助于热电子跃迁，提高响应度。
发明内容
作为本发明的一方面，本发明提供一种基于弱耦合增强的石墨烯结构，这种石墨烯结构通过非AB结构的弱耦合作用增加电子联合态密度，促进光吸收；同时引入非AB结构的石墨烯线性能带，促进热电子跃迁，提升高能态热电子占据概率。
作为本发明的另一方面，本发明提供一种基于弱耦合增强的石墨烯膜，其通过弱耦合作用增加电子联合态密度，增加光吸收，促进热电子跃迁。这种结构也降低了膜制备工艺的要求和成本，增加了膜制备的成功率。
作为本发明的另一方面，本发明提供一种基于弱耦合增强的石墨烯光电器件，比如基于石墨烯/硅肖特基结，由于石墨烯膜具有零带隙，可以实现长波长低能量的光的吸收，从而一方面可提高石墨烯/硅光电器件的响应度，另一方面 探测范围从可见和近红外拓展到中远红外波段，实现宽光谱的探测。这一思路也同样可以拓展到其他石墨烯/半导体肖特基型光电探测器中(比如石墨烯/锗探测器等)。该石墨烯膜也可以引入其他的光电探测器体系(比如光电导型探测器，PIN型探测器，雪崩型探测器)，增强其红外波段的吸收，实现宽光谱探测和红外探测。光电探测器目前在军工、国防、医疗、生物、和消费电子等诸多领域都有广泛的应用。比如在军事上需要用到红外光电探测器进行侦察和遥感；医疗检测和物质分析所用的各个光谱分析仪器中也需要高精度的光电探测器对吸收、透射、发射谱等进行采集和提取；在目前正发展的智能家居领域，无线红外探测器在实现设备的连接和交互中也扮演着重要的作用。在目前热门的无人驾驶领域的核心技术激光雷达中，高速高灵敏度的光电探测器也是其核心部件之一。就消费电子而言，在成像中，由于基于这一石墨烯膜的光电探测器可以实现宽光谱的探测，因此有望结合多光谱融合技术将可见的图像和红外的图像进行融合处理，实现图像的细节的增强，清晰度的提高。在医疗领域，光电探测也有广泛的应用，比如，血氧检测就是通过可穿戴设备上的红外探测器提取血红蛋白对红外光的反射，在未来的可穿戴式乃至可植入式的生物传感领域，微型光电探测也将扮演重要作用。
本发明的一个目的在于提供一种基于弱耦合增强的石墨烯结构，其由多个石墨烯单元上下堆叠而成；所述石墨烯单元为单层石墨烯片，或由两层以上的石墨烯片堆叠而成，且所述堆叠方式为AB堆叠；上下两个相邻的石墨烯单元为非AB堆叠结构区域，使得两个石墨烯单元之间弱耦合。在AB堆叠区域，电子云融合成一体，石墨烯膜电子结构偏重于石墨结构，这种结构下石墨烯电子声子散射减弱，热电子弛豫时间延长；而在非AB堆叠结构区域，电子云层层分离，石墨烯膜电子结构更倾向于石墨烯结构，从而电子联合态密度增加、光吸收增加、热电子跃迁变得容易。
本发明的另一个目的在于提供一种基于弱耦合增强的石墨烯结构，其由多个石墨烯单元上下堆叠而成；所述石墨烯单元为单层石墨烯片，或由2～9层的石墨烯片堆叠而成，且所述堆叠方式为AB堆叠；上下两个相邻的石墨烯单元之间弱耦合，联合态密度较高，光吸收增强。9层以内的石墨烯片构成的结构单元所造成的片层搭接空隙(垂直方向)可以控制在3nm左右，具有较高联合态密度的热电子可以隧穿而过不受影响。
本发明的另一个目的在于提供一种基于弱耦合增强的石墨烯结构，其由多个石墨烯单元上下堆叠而成；所述石墨烯单元为单层石墨烯片；上下两个相邻的石墨烯单元之间弱耦合。单层石墨烯电子结构可以有效辅助增加联合态密度，促进光吸收，促进热电子跃迁，增加高能态热电子占据概率。
作为本发明的另一个方面，本发明提供一种弱耦合增强的石墨烯光电膜，通过弱耦合实现多层石墨烯的光吸收的叠加，提高石墨烯膜的光吸收率和热电子寿命，从而在低能量波段，热电子仍然可以积累。
本发明的另一个目的在于提供一种弱耦合增强的石墨烯光电膜，其中包含有石墨烯结构。石墨烯结构由多个石墨烯单元上下堆叠而成；所述石墨烯单元为单层石墨烯片，或由两层以上的石墨烯片堆叠而成，且所述堆叠方式为AB堆叠；上下两个相邻的石墨烯单元之间弱耦合。所述石墨烯结构中的石墨烯单元的堆叠方向沿所述石墨烯膜厚度方向。光照射到石墨烯膜的表面，光电子从表面经过AB堆叠区域和非AB堆叠区域，其中AB堆叠区域，电子云融合成一体，石墨烯膜电子结构偏重于石墨结构，热电子和声子散射减弱，增加热电子弛豫时间；而在非AB堆叠结构区域，电子云层层分离，石墨烯膜电子结构更倾向于石墨烯结构，联合态密度增加、光吸收增加，促进热电子跃迁。
本发明还提供一种弱耦合增强的石墨烯光电膜，其中包含有上述石墨烯结构。所述石墨烯结构中的石墨烯单元的堆叠方向沿所述石墨烯膜厚度方向。整 个膜的非AB结构含量为5％以上，甚至在90％以上。大量的非AB结构含量使得石墨烯膜内存在大量的弱耦合作用区域，使得石墨烯膜整体电子结构和单层石墨烯趋近，极大的增加了联合态密度，增强吸收并促进热电子跃迁，进而提升了高能态热电子数量。
在某些实施例中，石墨烯膜的I D/I G在0.05以下。通常情况下，石墨烯中缺陷会增加石墨烯的散射，从而降低石墨烯热电子弛豫时间，但是石墨烯缺陷对声子的散射更多的体现在水平方向，对垂直方向影响较小；而石墨烯单元的非耦合堆叠对热电子的散射作用主要针对垂直方向，因而对热电子散射的影响更大，起到决定最用。简而言之，弱耦合作用的存在，增强了石墨烯膜光电效应对缺陷的容忍性。
在某些实施例中，将由溶液组装(抽滤、旋涂、喷涂以及铺膜法等)得到的氧化石墨烯膜，经热处理(石墨化炉退火、激光加热退火、微波加热退火等)修复缺陷后，得到所述弱耦合增强的石墨烯膜。
由于基底不适用高温热处理，因此，一般情况下，需要将氧化石墨烯膜从基底剥离后进行热处理。本发明发明人在大量石墨烯剥离实验中发现，还原过程中氢碘酸蒸汽浓度不够，相对蒸汽压小，HI蒸汽不足以完全渗透入石墨烯膜和基底接触界面；另外HI蒸汽中夹杂着水蒸汽，起到浸润作用，一方面阻碍HI的快速渗透，另一方面浸润界面，抑制界面分离。氢碘酸的不对称还原和渗透作用极大减少了界面剂接触面积以及作用力，此微弱接触界面可以被异丙醇等溶剂作用剥离；但是水蒸气的浸润以及HI蒸汽压力的不足，薄膜并不能和基底分离。本申请中，我们针对具有孔隙的刚性基底，提出一种石墨烯膜的剥离方法，通过调控HI以及控制水份的蒸汽压，使得HI的不对称还原以及界面渗透作用增强，石墨烯膜和基底逐步分离(图8)。具体为：所述氧化石墨烯膜厚度为20-120nm，通过溶液组装沉积在一孔隙率大于60％的刚性基底上，然后通 过以下方法从所述刚性基底剥离：置于一具有HI蒸汽的还原室中进行化学还原至氧化石墨烯从基底自动剥离；还原过程中，至少在HI的浓度在0.3g/L以上，且水蒸气的浓度在0.07g/L以下的环境下还原10min以上。
本申请中，可以直接输入低水蒸气含量的HI蒸汽，也可以采用一与所述还原室相连通的蒸发室对氢碘酸进行蒸发，以向所述还原室输入HI蒸汽。
在某些实施例中，所述还原室和蒸发室位于同一密闭腔体中，且所述蒸发室位于所述还原室下方，蒸发室位于温度为80-120摄氏度的油浴或水浴中；所述还原室顶部为冷凝区，冷凝区的温度控制在0-40℃(通常在室温下即可进行)。氢碘酸溶液蒸发成HI蒸汽和水蒸气，水蒸气一方面在顶部凝结，降低了腔体内的水蒸气含量，而HI的冷凝温度较低，其仍旧保持气态。作为较为优选的方案，冷凝区中设置吸水材料，以吸收水蒸气和冷凝水，避免冷凝水回落后重新蒸发。作为本领用的常用技术手段，所述吸水材料为：吸水滤纸、高吸水性树脂等多孔强亲吸水材料以及氯化钙、五氧化二磷等强吸水性化学品。
为方便制备，还原室内设有耐HI载物架，用于装载所述基底，例如聚四氟乙烯网架、镂空玻璃架等。
在某些实施例中，所述还原室和蒸发室分别位于一密闭腔体中。且两个密闭腔体通过一冷凝管连通；所述冷凝管对所述蒸发室蒸发的水蒸气进行冷凝，回流至所述蒸发室。碘酸溶液蒸发成HI蒸汽和水蒸气，水蒸气在冷凝管内冷凝，回流至蒸发室，而HI的冷凝温度较低，其仍旧保持气态。作为本领域的公知常识，通过设置冷凝管的长度、倾斜度、所处冷凝环境等参数，可以有效控制进入还原室的水蒸气含量。
优选的，所述蒸发室和还原室均位于温度为80-120摄氏度的油浴或水浴中，在某些较为优选的方案中，所述还原室所处温度低于所述蒸发室，有利于碘化氢气体向还原室快速扩散。同时，在碘化氢全部蒸发后，温差的存在会使的两侧存在压差，进而在低温区的还原室分布更高质量密度的碘化氢。
本申请中，基底为阳极氧化铝、四氟乙烯滤膜、玻璃纤维滤膜等。
相对于固相转移的制备方法，该气相分离法更为温和，对薄膜几乎没有任 何强烈撕裂效应，而固相转移法则相反。具体表现如下：其一，AAO为脆性材料，固相转移剂操作过程中会对AAO有重量负担，会损伤AAO膜或者不能有完好的覆盖连续性，导致固相转移剂剥离的不连续，最终不能得到完整的石墨烯纳米膜(图9)；而气相还原不存在这些问题，因而可以得到完美的大尺寸石墨烯膜。而在微观结构上，固相转移法的中有可能会因为石墨烯还原程度不够从而造成氧化石墨烯和AAO基底的强粘连，冷缩作用下对局部地方形成孔洞型撕裂(图10A1～A2)，而温和的气相转移法所则不存在这方面问题，可以得到无任何撕裂的完美的石墨烯膜(图10B～D)。总的来讲,固相转移法分离时，需要实验人员精细操作，若操作不当、注意力不集中则十分容易破损石墨烯纳米膜，尤其是转移剂冷抓过程中有机会出现局部孔洞破损，见图10A1～A2。另外，石墨烯和基底仍有部分粘连。宏观上，由于温度或者转移剂沉积不均匀，导致局部应力分布不均，固相转移剂收缩抓取不均匀，不能得到完整的大尺寸石墨烯膜(10A1)；微观上，由于一些极小的粘连或者还原不均匀，抓取过程中未能对此部分石墨烯有效剥离，进而会形成微小孔洞，导致材料的不均匀，影响其应用场景下性能稳定性。
在某些实施例中，将由CVD法生长的石墨烯薄膜层层堆叠后，经热处理(石墨化炉退火、激光加热退火、微波加热退火等)形成致密结构，得到所述弱耦合增强的石墨烯膜。
在某些实施例中，将可石墨化材料经溶液组装，经热处理(石墨化炉退火、激光加热退火、微波加热退火等)使其石墨化，得到所述弱耦合增强的石墨烯膜。所述可石墨化材料包括聚酰亚胺、聚丙烯腈、沥青。
在某些实施例中，将可玻璃化小分子(葡萄糖、薄荷醇、萘、蒽等)在镍基催化剂的催化下得到所述弱耦合增强的石墨烯膜。
在某些实施例中，将氧化石墨烯、聚酰亚胺、氧化石墨烯和不可石墨化或者低石墨化高分子的混合物(例如沥青、木质素、在聚合以及天然稠环芳烃等 多苯环结构以及聚丙烯腈等线性共轭结构体系；混合质量比小于1：6(常规情况下，氧化石墨烯的碳收率为66％，聚合物石墨化后的碳收率在50％以下。)以内，苯环结构越多，其最大混合比越小)。混合物特点在于，石墨烯可以作为模板，诱导低石墨化或者不可石墨化高分子沿着石墨烯平面进行有序排列石墨化；同时氧化石墨烯表面的官能团可以为聚酰亚胺、聚丙烯腈等需要预氧化的高分子提供氧原子，从而避免了材料预氧化过程中存在的核壳现象，保证材料的均匀预氧化，进而保证高温过程中材料结构的均匀性；再有，此方法避免了聚合物石墨化过程对高取向的要求，降低了聚合物石墨化工艺条件。石墨烯有效催化石墨化原子层数为4层，上下各两层，超过四层，高温催化之后其缺陷较多。随着聚合物共轭结构的匹配性减弱，其催化效果也会随之减弱。
本发明还提供一种石墨烯基光电器件，包括弱耦合增强的石墨烯膜和半导体衬底，所述石墨烯膜通过弱耦合实现光吸收的叠加，提高石墨烯膜的光吸收率，从而在低能量波段，热电子仍然可以积累，使得高能态区域热电子可以跨过石墨烯/半导体势垒并最终得到可收集的电信号。
本发明还提供一种石墨烯基光电器件，包括弱耦合增强的石墨烯膜和半导体衬底，所述石墨烯膜中包含有弱耦合增强的石墨烯结构。弱耦合增强的石墨烯结构由多个石墨烯单元上下堆叠而成；所述石墨烯单元为单层石墨烯片，或由两层以上的石墨烯片堆叠而成，且所述堆叠方式为AB堆叠；上下两个相邻的石墨烯单元之间弱耦合。所述石墨烯结构中的石墨烯单元的堆叠方向沿所述石墨烯膜厚度方向。光电子从表面经过AB堆叠区域和非AB堆叠区域然后跃迁进入半导体层，其中AB堆叠区域，电子云融合成一体，石墨烯膜电子结构偏重于石墨结构，这种结构下石墨烯热电子弛豫时间得到延长；而在非AB堆叠结构区域，电子云层层分离，石墨烯膜电子结构更倾向于石墨烯结构，联合态密度增加、红外区光吸收增加，从而促进热电子跃迁，有更多以及更高能态的热电子 从石墨烯向半导体跃迁。
所述石墨烯膜是通过以下方法平铺于半导体衬底上：将石墨烯膜置于半导体衬底上，在石墨烯膜边缘滴加高表面张力的溶剂，以使得溶剂从石墨烯膜边缘向内部渗透的过程中展开石墨烯膜的褶皱；然后挥发溶剂。
本发明中，所述的高表面张力的溶剂包括去离子水、dmf、dmac、乙二醇、丙二醇、邻二甲苯、甲苯、醋酸丁酯及其混合。
优选地，在挥发溶剂后，进一步烧结处理。烧结温度在400-1000摄氏度，以构建石墨烯－半导体界面，进一步降低暗电流。
本发明所述的半导体衬底包括：元素半导体、化合物半导体，包括但不限于Si、Ge、C、Sn、GaAs、InP、AlGaAs、InGaP、InGaAs、AlInGaP、AlInGaAs、InGaAsP、AlInGaAsP、GaN、InGaN、AlGaN、AlInGaN、GaP、其合金或其衍生物中的一种或多种。
本发明的另一个目的在于提供石墨烯基光电器件的制备方法，包括如下步骤：
(1)首先在半导体衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射电极层；
(2)将多层石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加有机溶剂，有机溶剂从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
本发明还提供一种增加热电子在石墨烯膜垂直传输方向的热电子跃迁概率的方法，该方法至少包括：增加上述石墨烯膜垂直传输方向的非AB结构数量，通过非AB结构的弱耦合作用促进热电子跃迁。
本发明还提供一种增强热电子在石墨烯膜垂直传输方向的累积的方法，该方法至少包括：增加石墨烯膜垂直传输方向的非AB结构数量，通过非AB结构的弱耦合作用增加热电子跃迁概率；调控石墨烯垂直方向AB堆叠结构，延长热电子弛豫时间，促进高能态区域的热电子的生成和累积。
进一步地，该方法还包括：在厚度≤60nm范围内，增加膜的厚度；厚度越大，层数越大，光吸收以及热电子弛豫时间也会增强，产生的热电子越多，进一步的通过非AB结构的弱耦合增加热电子跃迁概率，同时增加石墨烯联合态密度，促进高能态区域的热电子的生成和累积。当厚度大于60nm后，过高的厚度也会增加热电子的复合，减少跃迁过势垒热电子的数量。
附图说明
图1为实施例1制备的两个石墨烯膜的xps光谱图；
图2为实施例1制备的两个石墨烯膜的拉曼图；
图3为实施例1制备的两个石墨烯膜的TEM图；
图4为实施例1制备的两个石墨烯膜的电子衍射图；
图5为实施例1制备的两个石墨烯膜的热电子弛豫时间图。
图6为不同温度处理后的电子衍射图及对应电子寿命
图7为通过弱耦合实现多层石墨烯的光吸收的叠加的原理图。
图8为石墨烯膜和基底逐步分离过程图；
图9为在刚性阳极氧化铝滤膜上通过抽滤得到的氧化石墨烯膜(4英寸)。
图10为分离后的氧化石墨烯膜(4英寸)。其中，A1图为固相转移剂辅助转移的石墨烯纳米膜。B1～D1为本申请无转移剂法制备无破损石墨烯纳米膜(依次对应实施例2-4)；A2～D2为对应的放大图。
图11为实施例2的分离装置的平面示意图A和立体示意图B；
图12为实施例3的分离装置图；
图13为实施例4的分离装置图。
具体实施方式
以下描述用于揭示本发明，以使得本领域技术人员能够实现本发明。以下描述中的优选实施例只是作为举例，本领域技术人员可以想到其他显而易见的变形。以下描述中界定的本发明的基本原理可以应用于其他实施方案、变形方案、改进方案、等同方案以及没有背离本发明的精神和范围的其他技术方案。
以下实施例中，I D/I G的测试方法如下：将薄膜转移到硅基底上，用532激光作为光源全功率下进行拉曼全波段测试，得到包含D峰，G峰以及2D峰的拉曼图谱。界定D峰和G峰的面积分别为D峰和G峰的强度I D、I G，进行除法运算后得到I D/I G。
以下实施例中，AB结构含量的测试方法如下文所载：Measuring the degree of stacking order in graphite by Raman spectroscopy,Carbon,2008,46(2),272–275.
单层石墨烯或者多层AB堆叠的石墨烯会呈现一套由6个衍射斑点构成的衍射图样(均匀分布于同一圆周上)，同时AB堆积石墨烯层数越高，斑点亮度越高；非AB结构的存在会使得衍射图样中出现多套不重叠斑点。基于此，以下实施例中，将制备好的薄膜置于高分辨TEM下进行采集电子衍射图样，根据衍射图样即可测试垂直堆叠结构。一方面，可以通过衍射斑点的套数来计算薄膜中结构单元的数量；另一方面，可以通过衍射斑点的亮度值与单层石墨烯衍射亮度之比来推测各个结构单元的堆积层数。
本发明所述弱耦合作用是指石墨烯片层间的无序堆叠带来的电子云耦合作用，此时片层间电子云没有达到完全的耦合效果，层间距为0.334-0.36nm；而AB堆叠结构下石墨烯片层间电子云轨道耦合强度最大，层间距为0.334nm，被 称为强耦合作用。
本发明中，石墨烯单元为单层石墨烯片，或由2～9层的石墨烯片堆叠而成，石墨烯膜中垂直方向石墨烯单元的数量可以通过测定石墨烯膜总厚度，并通过单层石墨烯厚度相除计算得到，同时，单个石墨烯单元中石墨烯片的层数可以通过拉曼方法测算AB结构含量并通过平均法方法得到。
实施例1：弱耦合增强计算
本实施例制备了具有同样厚度的薄膜，在缺陷都≈0的前提下验证了石墨烯膜结构转变对热电子弛豫时间以及光电探测的影响。制备方法如下：
非AB结构石墨烯膜：将氧化石墨烯用旋涂的方法制备24nm的薄膜，并以10摄氏度每分钟的速度升温到2000度维持16个小时。非AB结构含量≈100％，垂直方向石墨烯结构单元的数量为30，单个石墨烯结构单元中的石墨烯片数量为1。
AB结构石墨烯膜：将氧化石墨烯用旋涂的方法制备24nm的薄膜，并以10摄氏度每分钟的速度升温到2800度维持2个小时。
如图1所示，经过高温烧结后，两种材料的氧都已经完全消失，xps光谱没有探测到任何O的信号峰。在此基础上，本专利用拉曼手段表征了薄膜的sp3结构含量和堆叠方式。由图2所示，两者D峰都不可见，说明两者sp3结构都不再存在；而2D峰具有明显的差别，AB结构含量高的薄膜2D峰具有更强的不对称性。
TEM的测试结果和拉曼的结果完全吻合。如图3所示，AB结构的石墨烯膜的电子衍射表面，此石墨烯膜只有两个结构单元堆叠而成，其中一个结构单元斑点亮度明显高于第二个结构单元，也就是说两个结构单元一个厚度极高，一个原子层数极少，两者以非AB的方式相互堆叠。而非AB结构的石墨烯膜具有更多套数的衍射斑点(图4)，甚至形成了非晶衍射环，说明此薄膜由大量的结 构单元以非AB的形式相互堆叠而成。
基于以上结构，本专利测试了两者的热电子弛豫时间。如图5所示，在相同的200fs的激发时间下，具有AB结构的石墨烯膜热电子弛豫时间达到了25ps，而非AB结构的石墨烯膜的热电子弛豫时间维持在10ps以内。由此可见，石墨烯单元之间弱耦合，其结构更偏向于单层石墨烯单元，可以增加联合态密度，进而增加高能态热电子数目。
将上述制备得到的两种石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压(硅端接地)进行测试；与放大电路连接后，与示波器相连，即可获得检测数据如下表1。
表1
Figure PCTCN2020141339-appb-000001
实施例2
步骤1：将hummer法获得的氧化石墨烯配制成浓度为0.5ug/mL氧化石墨烯水溶液，以孔隙率为60％的刚性四氟乙烯滤膜为基底抽滤成膜，该氧化石墨烯膜厚度为100nm，面积为80±5cm 2。
本实施例采用如图11A～B所述的装置进行氧化石墨烯膜的剥离，该装置包括筒状腔体3，腔体3内盛氢碘酸溶液2，在氢碘酸溶液液面上方，固定有聚四氟乙烯网架2，用于密封该筒状腔体的顶盖4上设置有吸水滤纸5。
该筒状腔体下部位于80摄氏度水浴1中，聚四氟乙烯网架2上放置待剥离样品。
氢碘酸溶液在加热下，蒸发成HI蒸汽和水蒸气，水蒸气一方面在顶部凝结，并给吸水滤纸吸收，达到降低了腔体内的水蒸气含量，而HI的冷凝温度较低，其仍旧保持气态。
本实施例中，筒状腔体3容积为1L、底面积为120cm 2。腔体3内氢碘酸溶液的质量浓度为50％，HI质量含量为0.42g，其余部分为水(0.42g)。吸水滤纸(2g)吸水极限为其质量的60％。腔体3上部所处的环境温度为0摄氏度。
在加热5分钟后，氢碘酸溶液2完全蒸发，盛有的碘化氢溶液肉眼减少至不可见。在顶层看到部分水液滴的凝结，吸水纸吸湿膨胀。经过取样测试，吸水滤纸便增重0.44g，而此时经过气体取样进行酸碱测试，氢碘酸的浓度仍保持在0.33g/L。证明腔体3中水蒸气含量在0.07g/L以下。持续1h后，再经过气体取样进行酸碱测试，氢碘酸的浓度仍保持在0.32g/L。
为避免上述取样测量对于石墨烯膜的影响，本实施例另设相同的装置，不进行吸水滤纸(2g)取样和腔体内气体的取样，直接对相同的氧化石墨烯膜进行剥离，处理时间为4h，4h后，石墨烯脱离，见图10B1～B2。从图中可以看出在氢碘酸的还原作用下，石墨烯膜在应力作用下和基底完全脱离，且脱离过程中没有任何宏观破损和微观孔洞出现。
按照步骤1来制备3个石墨烯膜。
步骤2：将3个样品膜分别经1600℃、1800℃、2000℃石墨化炉退火处理2h。
经拉曼测试，其I D/I G和非AB结构含量如表2；
如图6的A1～A3所示，经TEM电子衍射对垂直堆积结构测试，及同实施例1的分析确定：三个石墨烯膜包含大量的弱耦合作用的石墨烯结构；由多个石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片乱层堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
在200fs的激发时间下，该石墨烯膜热电子弛豫时间如图6的B1～B3所示，均不短于5ps。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压(硅端接地)进行测试；与放大电路连接后，与示波器相连，即可获得检测数据如下表2。
表2
Figure PCTCN2020141339-appb-000002
Figure PCTCN2020141339-appb-000003
实施例3
(1)将hummer法获得的氧化石墨烯配制成浓度为0.5ug/mL氧化石墨烯水溶液，以孔隙率为80％的刚性阳极氧化铝滤膜为基底抽滤成膜，氧化石墨烯膜厚度为60nm，面积为80±5cm 2。
本实施例采用如图12所述的装置进行氧化石墨烯膜的剥离，该装置包括左右两个腔体11和12。腔体11和12通过一倾斜的冷凝管13相连通。腔体11和12均置于80摄氏度水浴14中。
腔体11内盛有氢碘酸溶液，腔体12用于放置待剥离的氧化石墨烯膜。腔体11内的氢碘酸溶液挥发，其中的水蒸气在冷凝管中冷凝回流至腔体11，而HI的冷凝温度较高，其通过冷凝管13输入至腔体12，以构建腔体12高HI浓度、低水蒸气浓度的环境。
本实施例中，腔体11和12的容积为400mL、底面积为50cm 2。腔体11中的氢碘酸溶液含量为0.5g(HI质量浓度为55％)，冷凝管13所处的环境温度为40摄氏度，冷凝管长度为20cm，倾斜角度为30度，能有效保证腔体12高HI浓度、低水蒸气浓度的环境的构建。
经实验证明，在加热5分钟后，氢碘酸溶液完全蒸发，水蒸气在冷凝管前部冷凝回流至腔体11，在冷凝管的后部没有产生任何冷凝水，说明几乎没有水蒸 气进入右侧的还原室。经过对还原室的气体取样进行酸碱测试，氢碘酸的浓度仍保持为0.43g/L。
30分钟后，右侧的蒸发室保持蒸发-冷凝回流，在冷凝管的后部依旧没有产生任何冷凝水，经过对还原室的气体取样进行酸碱测试，氢碘酸的浓度仍保持为0.41g/L。
为避免上述取样测量对于石墨烯膜的影响，本实施例另设相同的装置，不进行腔体内气体的取样，直接对相同的氧化石墨烯膜进行剥离，在还原1h后，石墨烯脱离，见图10C1～C2。从图中可以看出在氢碘酸的还原作用下，石墨烯膜在应力作用下和基底完全脱离，且脱离过程中没有任何宏观破损和微观孔洞出现。
(2)经2000摄氏度石墨化炉退火处理0.5h。
经拉曼测试，其I D/I G为0.05，非AB结构含量≈100％；非AB结构含量≈100％，垂直方向石墨烯结构单元的数量为60，单个石墨烯结构单元中的石墨烯片数量为1。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的弱耦合作用的石墨烯结构；由多个石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片乱层堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得1.1mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得97uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得8.3uA的光电流信号。
实施例4
(1)将hummer法获得的氧化石墨烯配制成浓度为0.5ug/mL氧化石墨烯水溶液，以孔隙率为80％的刚性阳极氧化铝滤膜为基底抽滤成膜，该氧化石墨烯膜厚度为60nm，面积为80±5cm 2，。
本实施例采用如图13所述的装置进行氧化石墨烯膜的剥离，该装置包括左右两个腔体11和12。腔体11和12通过一倾斜的冷凝管13相连通。腔体11置于120摄氏度油浴14中，腔体12均置于80摄氏度水浴14中。
腔体11内盛有氢碘酸溶液，腔体12用于放置待剥离的氧化石墨烯膜。腔体11内的氢碘酸溶液挥发，其中的水蒸气在冷凝管中冷凝回流至腔体11，而HI的冷凝温度较高，其通过冷凝管13输入至腔体12，以构建腔体12高HI浓度、低水蒸气浓度的环境。
同实施例2，本实施例中，腔体11和12的容积为400mL、底面积为50cm 2。腔体11中的氢碘酸溶液含量为0.3g(HI质量浓度为55％)，冷凝管13所处的环境温度为20摄氏度，冷凝管长度为20cm，倾斜度为30度，能有效保证腔体12高HI浓度、低水蒸气浓度的环境的构建。
经实验证明，在加热5分钟后，氢碘酸溶液完全蒸发，水蒸气在冷凝管前部 冷凝回流至腔体11，在冷凝管的后部没有产生任何冷凝水，说明几乎没有水蒸气进入右侧的还原室。经过对还原室的气体取样进行酸碱测试，氢碘酸的浓度仍保持为0.33g/L。
10分钟后，右侧的蒸发室保持蒸发-冷凝回流，在冷凝管的后部依旧没有产生任何冷凝水，经过对还原室的气体取样进行酸碱测试，氢碘酸的浓度仍保持为0.30g/L。
为避免上述取样测量对于石墨烯膜的影响，本实施例另设相同的装置，不进行腔体内气体的取样，直接对相同的氧化石墨烯膜进行剥离，在还原2h后，石墨烯脱离，见图10D1～D2。从图中可以看出在氢碘酸的还原作用下，石墨烯膜在应力作用下和基底完全脱离，且脱离过程中没有任何宏观破损和微观孔洞出现。
(2)经2000摄氏度石墨化炉退火处理12h。
经拉曼测试，其I D/I G为0.003，非AB结构含量≈100％；垂直方向石墨烯结构单元的数量为60，单个石墨烯结构单元中的石墨烯片数量为1。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的弱耦合作用的石墨烯结构；由多个石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片乱层堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得1.13mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得99uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得8.1uA的光电流信号。
实施例5
(1)将hummer法获得的氧化石墨烯配制成浓度为0.5ug/mL氧化石墨烯水溶液，以阳极氧化铝为基底抽滤成膜，石墨烯原子层数为120。
本实施例采用现有的固体转移剂对沉积在阳极氧化铝上的氧化石墨烯膜景下精细转移，尝试多次后得到完成的独立自支撑膜。
(2)经2300摄氏度石墨化炉退火处理4h。
经拉曼测试，其I D/I G≈0(在拉曼检测线以下)，非AB结构含量为50％；垂直方向石墨烯结构单元的数量为60，单个石墨烯结构单元中的石墨烯片数量为2。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的弱耦合作用的石墨烯结构；由多个石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片乱层堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得1.3mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得122mA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得10uA的光电流信号。
实施例6
(1)将hummer法获得的氧化石墨烯配制成浓度为0.5ug/mL氧化石墨烯水溶液，以阳极氧化铝为基底抽滤成膜，氧化石墨烯原子层数为120。
本实施例采用现有的固体转移剂对沉积在阳极氧化铝上的氧化石墨烯膜景下精细转移，尝试多次后得到完成的独立自支撑膜。
(2)经2800摄氏度石墨化炉退火处理2h。
经拉曼测试，其I D/I G≈0，AB结构含量为90％；垂直方向石墨烯结构单元的数量为13，单个石墨烯结构单元中的石墨烯片数量为9。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的强耦合作用的石墨烯结构；由少量石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨 烯片以AB结构方式堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得1.1mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得113uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得9uA的光电流信号。
实施例7
(1)将铜基CVD法制备的单层石墨烯用析氢法去掉基底，并逐层叠加，直到石墨烯原子层数为150。
(2)经2000摄氏度石墨化炉退火处理12h。
经拉曼测试，其I D/I G为0.003，非AB结构含量≈100％；垂直方向石墨烯结构单元的数量为150，单个石墨烯结构单元中的石墨烯片数量为1。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的弱耦合作用的石墨烯结构；由多个石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片乱层堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得4mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得160uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得15uA的光电流信号。
实施例8
(1)将铜基CVD法制备的单层石墨烯用析氢法去掉基底，并逐层叠加，直到石墨烯原子层数为150。
(2)经2800摄氏度石墨化炉退火处理2h。
经拉曼测试，其I D/I G≈0，AB结构含量≈50％；垂直方向石墨烯结构单元的数量为75，单个石墨烯结构单元中的石墨烯片数量为2。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的强耦合作用的石墨烯结构；由少量石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片以AB结构方式堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得3.3mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在18ns内测得130uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在20ns内测得14uA的光电流信号。
实施例9
(1)将镍基CVD法制备的多层石墨烯用盐酸和双氧水刻蚀的方法去掉基 底，并逐层叠加，直到石墨烯原子层数为180。
(2)经2000摄氏度石墨化炉退火处理12h。
经拉曼测试，其I D/I G为0.003，非AB结构含量为50％；垂直方向石墨烯结构单元的数量为90，单个石墨烯结构单元中的石墨烯片数量为2。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的弱耦合作用的石墨烯结构；由多个石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片乱层堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得5.0mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得190uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得17uA 的光电流信号。
实施例10
(1)将镍基CVD法制备的多层石墨烯用盐酸和双氧水刻蚀的方法去掉基底，并逐层叠加，直到石墨烯原子层数为180。
(2)经2800摄氏度石墨化炉退火处理2h。
经拉曼测试，其I D/I G≈0，AB结构含量为89％；垂直方向石墨烯结构单元的数量为60，单个石墨烯结构单元中的石墨烯片数量为3。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的强耦合作用的石墨烯结构；由少量石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片以AB结构方式堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得4.1mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得120uA 的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得11uA的光电流信号。
实施例11
(1)将镍基CVD法制备的多层石墨烯用盐酸和双氧水刻蚀的方法去掉基底以及铜基单层石墨制备的单层石墨烯，混合逐层叠加，直到石墨烯原子层数为180。
(2)经2800摄氏度石墨化炉退火处理2h。
经拉曼测试，其I D/I G≈0，AB结构含量为75％；垂直方向石墨烯结构单元的数量为60，单个石墨烯结构单元中的石墨烯片数量为3。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的强耦合作用的石墨烯结构；由少量石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片以AB结构方式堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得4.4mA 的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得130uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得14uA的光电流信号。
实施例12
(1)将镍基CVD法制备的多层石墨烯上旋涂聚酰亚胺溶液，并得到总厚度100nm厚度的聚酰亚胺/石墨烯复合膜，用盐酸和双氧水刻蚀的方法去掉基底。
(2)经2800摄氏度石墨化炉退火处理2h。
经拉曼测试，其I D/I G≈0，AB结构含量为90％；垂直方向石墨烯结构单元的数量为14，单个石墨烯结构单元中的石墨烯片数量为9。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的强耦合作用的石墨烯结构；由少量石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片以AB结构方式堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试； 与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得0.91mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得97uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得7.3uA的光电流信号。
实施例13
(1)将铜基CVD法制备的单层石墨烯上旋涂100nm厚度的聚丙烯腈后，析氢法去掉基底。
(2)经2300摄氏度石墨化炉退火处理12h。
经拉曼测试，其I D/I G为0.04，非AB结构含量为50％；垂直方向石墨烯结构单元的数量为60，单个石墨烯结构单元中的石墨烯片数量为2。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的强耦合作用的石墨烯结构；由少量石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片以AB结构方式堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输 出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得1.21mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得109uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得9.2uA的光电流信号。
实施例14
(1)用抽滤法在阳极氧化铝表面抽滤单层石墨烯，然后抽滤200nm厚度的沥青和氧化石墨烯混合物后(混合质量比为1：1)，用樟脑转移法去掉基底。
(2)经2800摄氏度石墨化炉退火处理2h。
经拉曼测试，其I D/I G≈0，AB结构含量为95％；垂直方向石墨烯结构单元的数量为8，单个石墨烯结构单元中的石墨烯片数量为19。
经TEM电子衍射对垂直堆积结构测试，该石墨烯膜包含大量的强耦合作用的石墨烯结构；由少量石墨烯单元上下堆叠而成；所述石墨烯单元由单层石墨烯片以AB结构方式堆叠而成；上下两个相邻的石墨烯单元之间弱耦合。
将上述制备得到的石墨烯膜按照如下步骤制作光电器件：
(1)首先在Si衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射Pt电极层；
(2)将石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加乙二醇，乙二醇从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张 力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
(3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
在器件的电极和半导体利用keithley源表施加-2V～-1V的反向偏压进行测试；与放大电路连接后，与示波器相连，即可获得检测数据。
用波长为1um，功率为5mW的红外光照射石墨烯层，在20ns内测得3.1mA的光电流信号。
用波长为4um，功率为20mW的红外光照射石墨烯层，在25ns内测得112uA的光电流信号。
用波长为10.6um，功率为50mW的红外光照射石墨烯层，在80ns内测得12.5uA的光电流信号。

Claims (31)

  1. 基于弱耦合增强的石墨烯结构，其特征在于，由多个石墨烯单元上下堆叠而成；所述石墨烯单元为单层石墨烯片，或由两层以上的石墨烯片以AB堆叠的方式堆叠而成；上下两个相邻的石墨烯单元之间弱耦合，促进热电子跃迁、增加电子联合态密度，从而增加高能态热电子的数量。
  2. 根据权利要求1所述的石墨烯结构，其特征在于，单个石墨烯单元的石墨烯层数小于9层。
  3. 根据权利要求1所述的石墨烯结构，其特征在于，单个石墨烯单元的石墨烯层数为1层。
  4. 如权利要求1所述的石墨烯结构在增强热电子积累中的应用，其特征在于，所述应用为：通过所述的石墨烯AB堆叠结构增加热电子弛豫时间，弱耦合结构增加热电子跃迁概率，并最终促进高能态区域的热电子的生成和累积。
  5. 弱耦合增强的石墨烯膜，包含权利要求1所述的基于弱耦合增强的石墨烯结构，所述石墨烯结构中的石墨烯单元的堆叠方向沿所述石墨烯膜厚度方向；所述石墨烯膜通过所述基于弱耦合增强的石墨烯结构增强高能态区域的热电子积累。
  6. 根据权利要求5所述的石墨烯膜，其特征在于，所述石墨烯膜的I D/I G在0.05以下。
  7. 根据权利要求5所述的石墨烯膜，其特征在于，所述石墨烯膜的非AB结构含量为5％以上。
  8. 根据权利要求5所述的石墨烯膜，其特征在于，是通过将由溶液组装得到的氧化石墨烯膜，经过热处理修复缺陷后得到的。
  9. 根据权利要求8所述的石墨烯膜，其特征在于，所述氧化石墨烯膜厚度为20-120nm，通过溶液组装沉积在一孔隙率大于60％的刚性基底上，然后通过以下方法从所述刚性基底剥离：置于一具有HI蒸汽的还原室中进行化学还原至氧化石墨烯从基底自动剥离；还原过程中，至少在HI的浓度在0.3g/L以上，且水蒸气的浓度在0.07g/L以下的环境下还原10min以上。
  10. 根据权利要求9所述的石墨烯膜，其特征在于，该方法还采用一与所述还原室相连通的蒸发室对氢碘酸进行蒸发，以向所述还原室输入HI蒸汽。
  11. 根据权利要求10所述的石墨烯膜，其特征在于，所述还原室和蒸发室位于同一密闭腔体中，且所述蒸发室位于所述还原室下方，蒸发室位于温度为80-120摄氏度的油浴或水浴中；所述还原室顶部具有冷凝区，冷凝区的温度为0～40℃。
  12. 根据权利要求11所述的石墨烯膜，其特征在于，所述冷凝区设有吸水材料，所述吸水材料为：吸水滤纸、高吸水性树脂等多孔强亲吸水材料以及氯化钙、五氧化二磷等强吸水性化学品。
  13. 根据权利要求11所述的石墨烯膜，其特征在于，所述还原室内设有耐HI载物架，用于装载所述基底。
  14. 根据权利要求10所述的石墨烯膜，其特征在于，所述还原室和蒸发室分别位于一密闭腔体中；且两个密闭腔体通过一冷凝管连通；冷凝管所处温度为0～40℃；所述冷凝管对所述蒸发室蒸发的水蒸气进行冷凝，回流至所述蒸发室。
  15. 根据权利要求14所述的石墨烯膜，其特征在于，所述蒸发室和还原室均位于温度为80-120摄氏度的油浴或水浴中，且所述还原室所处温度低于所述蒸发室。
  16. 根据权利要求9所述的石墨烯膜，其特征在于，基底为阳极氧化铝、四氟乙烯滤膜、玻璃纤维滤膜。
  17. 根据权利要求5所述的石墨烯膜，其特征在于，是通过将由CVD法生长的石墨烯薄膜层层堆叠后，经热处理形成致密结构得到的。
  18. 根据权利要求5所述的石墨烯膜，其特征在于，是通过将可石墨化材料经溶液组装，经热处理使其石墨化得到的。
  19. 根据权利要求18所述的石墨烯膜，其特征在于，所述可石墨化材料包括氧化石墨烯、聚酰亚胺以及氧化石墨烯和不可石墨化或者低石墨化高分子的混合物。
  20. 根据权利要求5所述的石墨烯膜，其特征在于，是通过将可玻璃化小分子在镍基催化剂的催化下得到的。
  21. 如权利要求5所述的石墨烯膜在光电转换中的应用，其特征在于，所述石墨烯膜通过所述基于弱耦合增强的石墨烯结构促进热电子跃迁，促进高能态区域的热电子的生成和累积。
  22. 一种石墨烯光电器件，包括权利要求5所述的弱耦合增强的石墨烯膜和半导体衬底，所述弱耦合增强的石墨烯膜平铺于半导体衬底上。
  23. 根据权利要求22所述的光电器件，其特征在于，所述石墨烯膜是通过以下方法平铺于半导体衬底上：将石墨烯膜置于半导体衬底上，在石墨烯膜边缘滴加高表面张力的溶剂，以使得溶剂从石墨烯膜边缘向内部渗透的过程中展开石墨烯膜的褶皱；然后挥发溶剂。
  24. 根据权利要求22所述的光电器件，其特征在于，高表面张力的溶剂包括但不限于去离子水、dmf、dmac、乙二醇、丙二醇、邻二甲苯、甲苯、醋酸丁酯、液体石蜡、薄荷脑及其混合。
  25. 根据权利要求22所述的光电器件，其特征在于，在挥发溶剂后，进一步烧结处理；烧结温度在400-1000摄氏度。
  26. 根据权利要求22所述的光电器件，其特征在于，所述的半导体衬底包括：元素半导体、化合物半导体，包括但不限于Si、Ge、金刚石、Sn、InP、GaAs、AlGaAs、InGaP、InGaAs、AlInGaP、AlInGaAs、InGaAsP、AlInGaAsP、GaN、InGaN、AlGaN、AlInGaN、GaP、其合金或其衍生物中的一种或多种。
  27. 一种权利要求22中所述的石墨烯基光电器件的制备方法，其特征在于，包括如下步骤：
    (1)首先在半导体衬底预留一个工作窗口，在工作窗口以外镀绝缘层，随后在绝缘层内溅射电极层；
    (2)将多层石墨烯膜先平铺于工作窗口上，且与电极层接触，在石墨烯膜边缘滴加有机溶剂，有机溶剂从石墨烯膜边缘向内部渗透，挥发溶剂，利用溶剂的表面张力实现膜与半导体的紧密结合，便得到了一个独立的光电器件；
    (3)封装，并利用引线与光电器件的电极层、半导体衬底分别相连，用于输出检测信号。
  28. 通过石墨烯非AB结构的弱耦合作用促进热电子跃迁的方法。
  29. 一种增加热电子在石墨烯膜垂直传输方向的热电子跃迁概率的方法，其特征在于，该方法至少包括：增加石墨烯膜垂直传输方向的非AB结构数量，通过非AB结构的弱耦合作用促进热电子跃迁。
  30. 一种增强热电子在石墨烯膜垂直传输方向的累积的方法，其特征在于，该方法至少包括：增加石墨烯膜垂直传输方向的非AB结构数量，通过非AB结构的弱耦合作用增加热电子跃迁概率；调控石墨烯垂直方向AB堆叠结构，延长热电子弛豫时间，促进高能态区域的热电子的生成和累积。
  31. 根据权利要求30所述的方法，其特征在于，该方法还包括：在厚度≤60nm范围内，增加膜的厚度；厚度越大，层数越大，光吸收以及热电子弛豫时间也会增强产生的热电子越多，进一步的通过非AB结构的弱耦合增加热电子跃迁概率，同时增加石墨烯联合态密度，促进高能态区域的热电子的生成和累积。
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