CN206976394U - A kind of graphene film and semiconductor devices - Google Patents

Abstract

The utility model provides a graphene film and a semiconductor device. The graphene film has a plurality of micro-cavity structures with openings on one side, and the micro-cavity structure is composed of a convex structure and/or a concave structure on the surface of the graphene film. ; The opening of the micro-cavity structure is formed at the bottom of the protruding structure and/or the top of the concave structure. The utility model utilizes the graphene film with a microcavity structure to increase the deformation and specific surface area of the graphene film, and when the graphene film is used in fields such as piezoelectricity, photovoltaics, photocatalysis, and pressure detection, the power generation of the device is improved. efficiency, detection sensitivity, and accuracy.

Description

A kind of graphene film and semiconductor device

technical field

The utility model relates to the technical field of semiconductors, in particular to a graphene film and a semiconductor device with the graphene film.

Background technique

With the development of semiconductor technology and the continuous reduction of technology nodes, traditional silicon materials have shown many limitations and defects. Since graphene is a new type of nanomaterial with the thinnest, highest strength, and strongest electrical and thermal conductivity in the world, So graphene becomes an ideal substitute for silicon.

However, traditional graphene films use flat surfaces both macroscopically and microscopically, including monoatomic layer graphene, which is a flat surface in the microscopic sense. For example, when applied in the field of piezoelectricity, the deformation of flat graphene film is very small when it is subjected to external forces, and when it is prepared, it is necessary to additionally prepare a cavity of sufficient size in the substrate. Seriously restricting the convenience and extensiveness of the application of graphene films. At the same time, the specific surface area of the flat graphene film is not very ideal, especially as a battery electrode, sensor, and photocatalytic device, it is more desirable to have a larger specific surface area and carrier capture capacity.

Utility model content

In order to overcome the above problems, the utility model aims to provide a graphene film, which can produce more deformation and has better specific surface area.

In order to achieve the above object, the utility model provides a graphene film, the graphene film has a plurality of micro-cavity structures with openings on one side, the micro-cavity structure is formed by a raised structure on the surface of the graphene film and/or The concave structure is formed; the opening of the micro-cavity structure is formed at the bottom of the protruding structure and/or the top of the concave structure.

Preferably, the graphene film has a main plane, the plane where the opening of the raised structure and/or the plane where the opening of the concave structure is located is located at the plane where the main plane of the graphene film is located; or the graphene film It has a main plane, and the plane where the opening of the raised structure and/or the plane where the opening of the concave structure is located is different from the plane where the main plane of the graphene film is located.

Preferably, the micro-cavity structures are arranged in an array, and the micro-cavity structures in adjacent rows are arranged alternately.

Preferably, the convex structures and the concave structures in each row are arranged alternately, and the convex structures of adjacent rows are arranged alternately, and the concave structures of adjacent rows are arranged alternately.

Preferably, in each row, the projection profile of the protruding structure on the main plane is tangent to the projection profile of the concave structure on the main plane.

Preferably, the convex structure and the concave structure are in a congruent figure relationship.

Preferably, the projected contour of the opening of the micro-cavity structure on the main plane is surrounded by the largest contour of the projected contours of other regions of the micro-cavity structure on the main plane.

Preferably, the size of the projected profile of the opening on the main plane and the size of the largest profile are nanoscale, and the size of the projected profile of the opening is 1/5-1 of the size of the largest profile.

Preferably, the height of the micro-cavity structure is nanoscale, and the height of the micro-cavity structure is 1/4˜1 of the size of the opening.

Preferably, the projection outline of the opening of the micro-cavity structure on the main plane surrounds the projection outline of other regions of the micro-cavity structure on the main plane.

Preferably, the size of the opening is on the order of nanometers, the height of the micro-cavity structure is on the order of nanometers, and the height of the micro-cavity structure is 1/4˜1 of the size of the opening.

Preferably, the projected outline of the protruding structure and/or the recessed structure on the main plane is circular or rectangular, and the projected outline of the opening on the main plane is circular or rectangular.

Preferably, the micro-cavity structure is a sphere intercepted by an opening.

Preferably, the protruding structure includes an upper structure and a lower structure connected thereto, the upper structure has a flat surface or an arc-shaped surface, the lower structure is an inclined side wall, and the inclined side wall gradually outwards or upwards from bottom to top. Inclined inwardly; the concave structure is the inverse of the convex structure.

Preferably, the metal compound semiconductor nano-film is only formed on the inner wall of the micro-cavity structure and/or the entire surface of the graphene film.

Preferably, the semiconductor nano-film is titanium alloy nano-film and/or zinc alloy nano-film.

Preferably, the material of the titanium alloy nano film is TiOx, x is a positive number; the zinc alloy nano film is ZnO nano film.

Preferably, the semiconductor nanofilm is composed of nanowire arrays of metal compounds.

Preferably, the ratio of the thickness of the semiconductor nano film to the outline size of the opening is no greater than 1:3.

Preferably, the graphene film is a graphene film with a monoatomic layer thickness.

In order to achieve the above object, the utility model also provides a detector, which has the graphene film described in any one of the above as a detection component.

In order to achieve the above object, the utility model also provides a piezoelectric power generation device, which has the graphene film described in any one of the above as a piezoelectric conversion component; When force is applied, the multiple micro-cavity structures are deformed, thereby generating electric energy.

In order to achieve the above purpose, the utility model also provides a photocatalytic device, which has the graphene film described in any one of the above as a photocatalytic component.

In order to achieve the above purpose, the utility model also provides a solar cell, which has the graphene film described in any one of the above as an electrode or a photoelectric conversion component.

In order to achieve the above purpose, the utility model also provides an LED device, which has the graphene film described in any one of the above as an electroluminescent layer or an electrode layer.

In order to achieve the above object, the utility model also provides an energy storage battery, which has the graphene film described in any one of the above as an electrode layer.

The graphene thin film of the present utility model utilizes that the graphene thin film has a plurality of microcavity structures with openings on one side. First, since each microcavity structure can be deformed, the deformation output of a plurality of microcavity structures makes the graphene The total amount of deformation of the film increases. When the graphene film is applied to a pressure detector, the sensitivity and accuracy of the pressure detector can be improved; when the graphene film is applied to a pressure power generation device, the total amount of power generation can be increased, and the power generation Efficiency; And, the protruding structure that forms microcavity structure, concave structure can realize the pressure detection ability of the arbitrary orientation of graphene film, that is to say the force such as sideways, vertical or inclined force that is applied from any direction can all be detected Graphene film is detected, thereby further improving the sensitivity and accuracy of the pressure detection device, and improving the energy utilization rate, power generation capacity and power generation efficiency of the pressure power generation device; in addition, the setting of multiple micro-cavity structures can realize multi-point detection, And the pressure at each point can be accurately detected; secondly, both the convex structure and the concave structure can increase the specific surface area of the graphene film, which is beneficial to be used in devices that require a high specific surface area. Further, a metal compound semiconductor nano-film is formed on the surface of the graphene film, which further increases the specific surface area of the graphene film, and utilizes the outstanding properties of the metal compound semiconductor nano-film in photophysics, photochemistry, photocatalysis, etc., to endow graphite More semiconducting properties of graphene films can broaden the application fields of graphene films.

Moreover, due to the high hardness of the graphene film, it is difficult to micro-process the graphene film. The utility model utilizes sacrificial materials and chemical vapor deposition technology to realize the shaping of the graphene film, and realizes the removal of the sacrificial material through the release process; further, the utility model utilizes the deformation of the graphene film when it is subjected to external stimuli, so that Any shape and structure of the graphene film can be peeled off from the material layer to which it is attached. For example, the micro-cavity structure with narrower openings in one embodiment of the present invention, when the external stimulus is applied to the graphene film, the micro-cavity The cavity structure is deformed, so that the material layer on the inner wall or surface of the micro-cavity structure is separated from it. Therefore, the graphene method of the utility model has changed the processing and forming idea of the existing graphene film, which makes it possible for the graphene film to have various shapes and structures, and realizes the flexibility of forming the graphene film.

Description of drawings

Fig. 1 is the top view structural representation of the graphene thin film of embodiment one of the utility model

Fig. 2 is a schematic cross-sectional structure diagram of a micro-cavity structure in Embodiment 1 of the present utility model

Fig. 3 is a schematic cross-sectional structure diagram of another microcavity structure according to Embodiment 1 of the present utility model

Fig. 4 is a schematic cross-sectional structure diagram of yet another microcavity structure in Embodiment 1 of the present invention

Fig. 5 is a schematic cross-sectional structure diagram of a micro-cavity structure according to Embodiment 1 of the present utility model

Fig. 6 is a schematic cross-sectional structure diagram of another microcavity structure according to Embodiment 1 of the present utility model

Fig. 7 is a schematic cross-sectional structure diagram of yet another microcavity structure according to Embodiment 1 of the present utility model

Fig. 8 is a schematic cross-sectional structure diagram of a micro-cavity structure according to Embodiment 1 of the present utility model

Fig. 9 is a schematic cross-sectional structure diagram of another microcavity structure according to Embodiment 1 of the present utility model

Fig. 10 is a schematic cross-sectional structure diagram of yet another microcavity structure according to Embodiment 1 of the present utility model

Fig. 11 is the schematic flow sheet of the preparation method of the graphene thin film of embodiment one of the present utility model

Fig. 12～23 is the schematic diagram of each step of the preparation method of the graphene thin film of embodiment one of the present utility model

Fig. 24 is a top view structure schematic diagram of the graphene film of the second embodiment of the utility model

Fig. 25 is a schematic cross-sectional structure diagram of a micro-cavity structure in Embodiment 2 of the present utility model

Fig. 26 is a schematic cross-sectional structure diagram of another microcavity structure according to Embodiment 2 of the present utility model

Fig. 27 is a schematic cross-sectional structure diagram of yet another microcavity structure according to Embodiment 2 of the present utility model

Detailed ways

In order to make the content of the utility model clearer and easier to understand, the content of the utility model will be further described below in conjunction with the accompanying drawings of the description. Of course, the utility model is not limited to this specific embodiment, and general replacements known to those skilled in the art are also covered within the protection scope of the utility model.

The graphene film of the present utility model has a plurality of microcavity structures with openings on one side, and the microcavity structure is composed of a convex structure and/or a concave structure on the surface of the graphene film; the opening of the microcavity structure is formed on the protrusion the bottom of the structure and/or the top of the recessed structure.

Below in conjunction with accompanying drawing 1-27 and specific embodiment the utility model is described in further detail. It should be noted that the drawings are all in a very simplified form, using imprecise scales, and are only used to facilitate and clearly achieve the purpose of assisting in describing the present embodiment.

Embodiment one

In this embodiment, please refer to FIGS. 1 to 10. The graphene film G has a plurality of microcavity structures with openings on one side. The microcavity structure is composed of a raised structure T and a concave structure A on the surface of the graphene film G. ; The opening of the micro-cavity structure is formed at the bottom of the protruding structure T and the top of the concave structure A.

In FIG. 1 , the opening AK of the recessed structure A is shown from the top view, while the opening of the raised structure T cannot be shown from the top view. The micro-cavity structures here are arranged in an array, and the micro-cavity structures in adjacent rows are arranged alternately. Preferably, a plurality of protruding structures T are congruent figures, and a plurality of recessed structures A are congruent figures; the micro-cavity structures of each row are alternately arranged with protruding structures T and recessed structures A, and the protruding structures A of adjacent rows The raised structures T are arranged alternately, and the recessed structures A in adjacent rows are arranged alternately; the raised structures T and the recessed structures A are in a congruent figure relationship.

In this embodiment, the graphene film G has a main plane, and the main plane is the plane where the large-area graphene film outside the convex structure and/or the concave structure area is located, or in other words, the plane where the edge region of the entire graphene film G is located. As indicated by the arrows in Figure 2-10. Here, the projections of the raised structures T and the depressed structures A on the main plane of the graphene film G are circular, as shown in FIG. 1 ; and the projections of the openings on the main plane of the graphene film G are also circular. Of course, in other embodiments of the present utility model, the projection of the convex structure and the concave structure on the main plane of the graphene film is a rectangle, and the projection of the opening on the main plane of the graphene film is also a rectangle, such as a rectangle or a square; or , in other embodiments of the present utility model, the shape of the projection of the opening on the main plane of the graphene film is different from the shape of the projection of the convex structure and the concave structure on the main plane of the graphene film, for example, the projected shape of the opening is circular, while the projected shapes of the concave structure and the convex structure are square, etc.

Referring to FIG. 1 again, in each row, the projected profile of the protruding structure T on the main plane is tangent to the projected profile of the recessed structure A on the main plane. Of course, in other embodiments of the present utility model, in each row, there may also be a certain interval between the projected contours of the protruding structures T on the main plane and the projected contours of the recessed structures A on the main plane, for example, in an equidistant row cloth.

The projected contour of the opening of the microcavity structure in this embodiment on the main plane is surrounded by the largest contours of other areas of the microcavity structure in the projected contours of the main plane. In short, the raised structure is "wide at the top and narrow at the bottom". "type, the concave structure is "wide at the bottom and narrow at the top".

In this embodiment, the microcavity structure can be a sphere cut by the opening, or the protruding structure forming the microcavity structure includes an upper structure and a lower structure connected thereto, and the upper structure has a flat surface (as shown in Figure 4 ) or a curved surface (as shown in Figure 3), the underlying structure is an inclined side wall, and the inclined side wall gradually slopes outward from bottom to top; and the concave structure is the inversion of the convex structure.

Please refer to FIG. 2 , the protruding structure T1 and the concave structure A1 are spheres cut by the openings T1K and A1K respectively; the protruding structure T1 forms the microcavity structure Q11 , and the concave structure A1 forms the microcavity structure Q12 . For example, the preparation of the convex structure and the concave structure of the truncated sphere in the graphene film may include but not limited to: first, transfer the prepared graphene film to a substrate, and then use mechanical manufacturing processes such as stamping Prepare a graphene film with a concave structure A1; at the same time, the substrate with a raised structure T1 can be prepared by using existing material molding processes such as inversion, pouring, and demoulding. The inverted groove of the convex structure, and then pouring material in the inverted groove, and then the substrate is turned upside down and bonded with the graphene film with the concave structure A1, so that the convex structure A1 is arranged at the corresponding position of the graphene film; The demoulding process removes the substrate, exposing the protruding structures T1 to be formed on the graphene film.

Please refer to Fig. 3, the protruding structure T2 forming the microcavity structure Q21 includes an upper structure and a lower structure connected thereto. The upper structure has a curved surface, and the lower structure is an inclined side wall, and the inclined side wall gradually outwards from bottom to top. Inclined; the bottom of the protruding structure T2 has an opening T2K; and the recessed structure A2 is the inversion of the protruding structure T2, the recessed structure A2 has a micro-cavity structure Q22, and the bottom of the recessed structure A2 has an opening A2K. For example, the preparation of the raised structure T2 and the depressed structure A2 in the graphene film may include, but is not limited to: first, transfer the prepared graphene film to a substrate, and then use a mechanical manufacturing process such as punching to prepare a structure with a concave structure. The graphene film of structure A2; At the same time, existing material molding processes such as pouring, pouring, and demoulding can be used to prepare a substrate with a raised structure T2. Invert the groove, then pour the material in the inverted groove, and then turn the substrate upside down and bond it with the graphene film with the concave structure A2, so that the raised structure A2 is set at the corresponding position of the graphene film; and then removed by the demoulding process The substrate exposes the raised structure T2, thereby forming on the graphene film.

Please refer to FIG. 4, the protruding structure T3 forming the microcavity structure Q31 includes an upper structure and a lower structure connected thereto. The upper structure has a flat surface, and the lower structure is an inclined side wall, and the inclined side wall gradually slopes outward from bottom to top. The bottom of the protruding structure T3 has an opening T3K; and the recessed structure A3 is an inversion of the protruding structure T3, the recessed structure A3 has a micro-cavity structure Q32, and the bottom of the recessed structure A3 has an opening A3K. For example, the preparation of the convex structure T3 and the concave structure A3 in the graphene film, which are truncated by openings, may include, but is not limited to: first, transfer the prepared graphene film to a substrate, and then use machinery such as stamping to The manufacturing process prepares a graphene film with a concave structure A3; at the same time, existing material molding processes such as inversion, casting, and demoulding can be used to prepare a substrate with a convex structure T3. Prepare an inverted groove with a raised structure, pour materials into the inverted groove, and then turn the substrate upside down and bond it to the graphene film with the concave structure A3, so that the raised structure A3 is arranged at the corresponding position of the graphene film; Then, the substrate is removed through a demoulding process, exposing the raised structure T3 to be formed on the graphene film.

In addition, in this embodiment, the plane where the opening of the protruding structure T and/or the plane where the opening of the recessed structure A is located and the plane where the main plane of the graphene film G is located may or may not be the same.

The plane where the opening of the raised structure T and/or the plane where the opening of the recessed structure A is located can be the same as the plane where the main plane of the graphene film G is located. Please refer to Figures 2-4 again. The arrows in the figure refer to the graphene film G The plane where the main plane of the graphene film G is located; in Figure 2, the plane where the opening T1K of the raised structure T1 is located is the same as the plane where the opening A1K of the recessed structure A1 is located, and is also located on the plane where the main plane of the graphene film G is located. In FIG. 3 , the plane where the opening T2K of the protruding structure T2 is located is the same as the plane where the opening A2K of the concave structure A2 is located, and both are located on the plane where the main plane of the graphene film G is located. In FIG. 4 , the plane where the opening T3K of the raised structure T3 is located is the same as the plane where the opening A3K of the recessed structure A3 is located, and both are located on the plane where the main plane of the graphene film G is located.

The plane of the opening of the raised structure T and/or the plane of the opening of the recessed structure A and the plane of the main plane of the graphene film G may be different, please refer to Figures 5 to 10, where Figures 5 to 7 are graphene films The main plane of the graphene film G is higher than the opening of the convex structure and the example of the opening of the concave structure. At this time, the main plane of the graphene film G is flush with the top of the convex structure; An example of the opening of the structure and the opening of the recessed structure, at this time, the main plane of the graphene film G is flush with the bottom of the recessed structure.

In the present invention, the size of the projected profile of the opening on the main plane and the size of the above-mentioned maximum profile are both nanoscale. Preferably, the size of the profile of the opening is 1/5-1 of the size of the above-mentioned maximum profile. The size mentioned here includes dimensional data such as diameter, length, and width. In this embodiment, the projected contours of the convex structure and the concave structure on the main plane are both circular, and the diameters of the projected contours of the openings on the main plane and the diameter of the above-mentioned largest contour are both nanoscale. Preferably, the utility model The various sizes of the microcavity structure are nanoscale, the diameter of the contour of the opening can be 1-100nm, and the diameter of the largest contour can be greater than 1nm and less than 200nm; here, the diameter of the projected contour of the opening can be the diameter of the largest contour 4/5.

In the present invention, the height of the micro-cavity structure is nanoscale, and the height of the micro-cavity structure is 1/4 to 1 of the size of the opening. The size mentioned here includes dimensional data such as diameter, length, and width. In this way, the opening of the microcavity structure is narrow and other regions of the microcavity structure are wide. The flat micro-cavity structure can increase the lateral force contact area, and when the top of the micro-cavity structure is stressed, the side walls of the micro-cavity structure can provide better fixation and support; thirdly, the height of the entire graphene film can be reduced.

In this embodiment, a metal compound semiconductor nano film is formed on the inner wall of the micro-cavity structure. The semiconductor nanofilm can be composed of a nanowire array of a metal compound. The semiconductor nanofilm can be a titanium alloy nanofilm and/or a zinc alloy nanofilm. Preferably, the material of the titanium alloy nanofilm is TiOx, and x is a positive number; The nano film is a ZnO nano film. In this embodiment, the ratio of the thickness of the semiconductor nano-film to the outline size of the opening is not greater than 1:3, so that the semiconductor nano-film will not damage the microcavity structure. Preferably, the graphene film can be a graphene film with a single atomic layer thickness, and the single atomic layer graphene film has higher strength and transparency, and can be used more widely. It should be noted that, in other embodiments of the present invention, the metal compound semiconductor nano-film can be formed on the upper surface and/or the lower surface of the graphene film.

In this embodiment, the upper surface and/or the lower surface of the graphene film can also have a metal nanofilm; then the above-mentioned metal compound semiconductor nanofilm is only formed on the surface of the metal nanofilm on the inner wall of the microcavity structure; and/or A metal compound semiconductor nanofilm is formed on the metal nanofilm on the upper surface of the entire graphene film and/or on the metal nanofilm on the lower surface of the entire graphene film. The material of the metal nano film can be copper or nickel.

Please refer to FIG. 11 , the preparation method of the graphene film of the present embodiment is illustrated by preparing the graphene film with a raised structure and a concave structure in the above-mentioned FIG. 4 as an example, which includes:

Step 01: Referring to FIG. 12 , a sacrificial layer substrate 101 having a raised structure T and/or a recessed structure A is prepared by photolithography and etching processes;

Specifically, in this embodiment, the process of forming the protruding structure T and the recessed structure A on the sacrificial layer substrate 101 may specifically include:

Step 011: preparing a photolithography layout;

Here, in the layout graphics in this embodiment, the graphics of the microcavity structures are arranged in an array, the graphics of the microcavity structures in adjacent rows are arranged alternately, and one edge of the microcavity structure graphics of one row is arranged alternately with the One edge of another row of micro-cavity structure graphics is located on the same straight line; in the present utility model, the layout graphics include a raised structure graphics layer and/or a concave structure graphics layer, and in this embodiment, the layout graphics include a raised structure graphics layer and the concave structure graphics layer; when the convex structure graphics layer and the concave structure graphics layer are stacked, the multiple convex structure graphics are congruent graphics, and the multiple concave structure graphics are congruent graphics; the convex structure graphics and the depressions in each row The structural graphics are arranged alternately, and the convex structural graphics of adjacent rows are arranged alternately, and the concave structural graphics of adjacent rows are arranged alternately.

Step 012: Using the photolithography layout of step 011, through photolithography and dry etching process, etch the convex structure and/or the concave structure in the sacrificial layer.

Here, since this embodiment has both a raised structure and a recessed structure, here, firstly, a photoresist is coated on the surface of the sacrificial layer, and the pattern layer of the raised structure pattern is used to form in the photoresist after exposure and development. The pattern of the raised structure; then, the sacrificial layer is etched using but not limited to a plasma etching process, thereby forming a raised structure in the sacrificial layer; then, the photoresist is coated again, and the layout of the patterned layer of the recessed structure is used, After exposure and development, a recessed structure pattern is formed in the photoresist; the sacrificial layer can be etched by but not limited to a plasma etching process, thereby forming a recessed structure in the sacrificial layer; the final positional relationship between the raised structure and the recessed structure It is the same as the positional relationship of the graphics in the above photolithography layout.

Specifically, take the sacrificial layer substrate used to prepare the graphene thin film in FIG. 4 as an example. Please refer to Figures 13-16. First, referring to FIG. 13 , a sacrificial layer substrate 101 is provided, and a sacrificial material layer 102 different from the material of the sacrificial layer substrate 101 is deposited on the upper surface of the sacrificial layer substrate 101, and photolithography and etching processes are used to The shape between the convex structure and the concave structure is etched in the sacrificial material layer 102. Since the rate of the plasma dry etching process can be adjusted, usually the etched lines are trenches with a large top and a small bottom, so conventional The slanted sidewall can be etched by the process. As seen from FIG. 13, the slanted sidewall has two layers. Therefore, "depositing a sacrificial material layer-photolithography and etching the sacrificial material layer" can be used at least twice Cycle to obtain the structure in FIG. 13; then, please refer to FIG. 14, fill again the same sacrificial material 103 with the material of the sacrificial layer substrate 101 in the gap of the structure obtained in FIG. 13; then, please refer to FIG. The material of the material layer 102 adopts a corresponding release process to remove the sacrificial material layer 102, and the release process will not corrode the sacrificial layer substrate 101 and the sacrificial material 103; then, please refer to FIG. 16, apply photoresist, and The sacrificial material 103 at the rightmost edge of the sacrificial layer substrate in FIG. The photolithography process exposes the left edge of the sacrificial material 103 on the leftmost side of the sacrificial layer substrate 101 in FIG. The same sacrificial material 104 of the material of the substrate 101, the thickness of the sacrificial material 104 is less than the thickness of the sacrificial material 103, in order to make the opening of the raised structure and the recessed structure be on the same plane as the main plane of the graphene film, the top of the sacrificial material 104 and The tops of the lower layers of the sacrificial material 103 sloped sidewalls are flush. Then, deposit a layer of photoresist and cover the sacrificial material 104 through a photolithography process and expose the front layer of photoresist above the sacrificial material 103, and then use a release process or an etching process for the material of the sacrificial material 104 to remove The sacrificial material 104 on the front photoresist layer, and finally, all the photoresist is removed to obtain the structure shown in FIG. 12 . Certainly, in order to make the opening of the raised structure and the recessed structure higher than the main plane of the graphene film, the top of the sacrificial material 104 can also be made higher than the top of the lower layer of the sacrificial material 103 inclined sidewall; The opening of the recessed structure is lower than the main plane of the graphene film, and the top of the sacrificial material 104 may be lower than the top of the lower layer of the sacrificial material 103 with inclined sidewalls, or the step of depositing the sacrificial material 104 may not be performed. However, the structure in FIG. 12 can also be realized by combining other conventional means, which should be understood as being within the scope of the present invention.

Step 02: growing a metal catalyst nano film on the surface of the sacrificial layer substrate;

Specifically, the material of the metal catalyst nano film can be copper or nickel; here, but not limited to, a vacuum evaporation process can be used to deposit a layer of metal catalyst nano film on the surface of the sacrificial layer substrate formed with a raised structure and a recessed structure; consider To be used as a catalyst, and the metal catalyst film cannot be too thick, preferably, the thickness of the metal catalyst nano film is 1-5 nm. The metal catalyst nano-film here can also be used as the metal nano-film on the lower surface of the above-mentioned graphene film. If the metal catalyst nano-film is needed, step 05 is not required.

Step 03: Please refer to Figure 17, using a chemical vapor deposition process, a graphene film G is grown on the surface of the metal catalyst nano-film including the surface of the raised structure and/or the inner wall surface of the recessed structure; the graphene film G is attached to the raised structure and / or the growth of the recessed structure, so that the graphene film G is formed on the same sacrificial layer substrate 101 with a plurality of raised structures and/or recessed structures;

Specifically, specific parameters of the chemical vapor deposition process can be adjusted according to actual needs, and are not limited here. Since the graphene film grows attached to the surface of the sacrificial layer substrate, using the principle of shape retention, a convex structure and a concave structure are formed in the graphene film, and the convex structure and the concave structure form a plurality of micro cavities with openings on one side structure.

In addition, the surface of the above-mentioned graphene film of the present embodiment also has a metal compound semiconductor nano-film, therefore, after step 03 and before step 04, it also includes: but not limited to using chemical vapor deposition or aqueous solution method on the graphene film Surface preparation of metal compound semiconductor nano film;

Moreover, after step 03 and before step 04, it may also include: firstly, preparing a metal nano-film on the upper surface of the graphene film; then preparing a metal compound semiconductor nano-film on the metal nano-film.

Step 04: Referring to Figure 18, remove the sacrificial layer substrate using a release process;

Here, the material of the sacrificial layer can be an organic material, such as photoresist, polyimide, etc., or an inorganic material, such as amorphous silicon material, silicon oxide, etc.; the material of the sacrificial layer and the corresponding release process can be conventional The process is known to those skilled in the art and will not be repeated here.

What needs to be explained here is that considering the difficulties in finding the graphene film after the release and removal of the sacrificial layer substrate, it can be realized that before performing the release process, as shown in Figure 18, a support can be formed on the bottom and side walls of the sacrificial layer substrate Layer Z, the support layer Z will not be released in any release process, for example, silicon nitride material is used as the material of the support layer. The formation of the support layer Z can be in step 04, and before the release process, but this may cause some damage such as abrasion to the graphene film, so, preferably, it should be in step 01, after photolithography and etching Before, a sacrificial layer substrate is formed whose bottom and sidewalls are surrounded by the supporting layer Z. In this way, when the releasing process in this step 04 ends and the sacrificial layer substrate is removed, the support layer is supported under the graphene film G, which not only facilitates the positioning of the graphene film G, but also forms a large space under the graphene film G simultaneously. cavity, and this structure can be further used in related processes for preparing semiconductor devices.

In addition, steps 01 to 04 can also be used to prepare the above-mentioned graphene film having a metal nano film on the upper surface and/or the lower surface.

Step 05: Please refer to Fig. 19, using separation technology to separate the metal catalyst nano film from the graphene film to obtain the graphene film G.

Here, when the support layer Z in FIG. 18 is used, the support layer Z may be removed. Then, the metal catalyst nanofilm (not shown) and the graphene film can be separated directly by mechanical exfoliation or electrostatic adsorption technology. However, considering that the opening of the micro-cavity structure in the first embodiment is narrow, which will lead to incomplete separation or difficulty in separation, the following separation technology can be further adopted in this embodiment: first, please refer to FIG. 20 , by applying light, Humidity, temperature and/or pH make the graphene film G stretch and deform to obtain the graphene film G'. Of course, the tensile deformation of the graphene film G may not be as uniform as in Figure 20, and here is only a schematic deformation trend. The film G is separated, and the above-mentioned deformation makes this splitting operation easier; then, please refer to Figure 21, stop applying light, humidity, temperature and/or pH to make the graphene film G shrink back to its original shape, of course, the actual graphite The size of graphene film G restored to its original shape may be slightly changed from the size before deformation, but the basic shape and position relationship of the convex structure and concave structure of graphene film G are consistent with those before deformation, which can be approximated as the graphene film before deformation g. Here, the illumination can be infrared laser irradiation; the specific parameters of illumination, humidity, temperature and/or pH can be determined according to the actual process, and there is no limitation here.

In this embodiment, after step 05, it may also include: preparing a metal compound semiconductor nano-film on the lower surface of the graphene film or only on the inner wall of the microcavity structure; for example, first placing the graphene film on another substrate, Then prepare the metal compound semiconductor nano film, and the process of preparing the metal compound semiconductor nano film on the lower surface of the graphene film can adopt the existing technology and will not repeat them here.

The preparation of metal compound semiconductor nanofilms only on the inner wall of the microcavity structure may include:

First, prepare a photoresist plate; the photoresist pattern includes a raised structure photoresist and a concave structure photoresist of the graphene film;

Then, the metal compound semiconductor nano film is prepared on the inner wall of the microcavity structure of the raised structure, including: referring to FIG. 22, transferring the graphene film to a substrate upside down; Resist R1; using a raised structure photolithography plate to etch the photoresist, forming a raised structure pattern in the photoresist R1, thereby exposing the inverted raised structure TT; then, using a solution method to invert the raised structure A metal compound semiconductor nanofilm (not shown) grows on the inner wall of the microcavity structure of the structure TT;

The metal compound semiconductor nano film is prepared on the inner wall of the microcavity structure of the concave structure, including: referring to FIG. 23, transferring the graphene film to a substrate 301; forming a layer of photoresist R2 on the graphene film; The photoresist is etched by the structural lithography plate to form a recessed structure pattern in the photoresist R2, thereby exposing the recessed structure A; then, a metal compound semiconductor nanometer is grown on the inner wall of the microcavity structure of the recessed structure A by a solution method. film.

It should be noted here that, in this embodiment, step 03 and step 04 can be canceled to prepare a metal compound semiconductor nano-film on the upper surface of the graphene film; but after step 05, the graphene film surface includes the upper surface and the lower surface To prepare the metal compound semiconductor nano film or only prepare the metal compound semiconductor nano film on the inner wall of the micro cavity structure.

It should also be noted that, in this embodiment, the graphene film has a convex structure and a concave structure. In other embodiments of the present utility model, the graphene film only has a convex structure, or only has a concave structure. Regarding only having The preparation method of the graphene film with the raised structure can be similarly referred to the preparation method of this embodiment, and the preparation method of the graphene film with only the concave structure can be referred to the preparation method of the present embodiment in the same way, and will not be repeated here.

Embodiment two

The difference between the graphene film of the second embodiment and the graphene film of the above-mentioned embodiment 1 is that, as shown in FIG. The projected profile of the main plane is rectangular. A rectangle can be a rectangle or a square. In addition, the protruding structure T' and the concave structure A' are alternately arranged at equal intervals, and the opening of the protruding structure T' and the opening of the concave structure A' can also be arranged to contact at the interface, and the opening of the protruding structure T' The edge of and the edge of the opening of the recessed structure A' are coincident or tangent.

The difference between this second embodiment and the above-mentioned first embodiment is that the projection contour of the opening of the micro-cavity structure on the main plane surrounds the projection contours of other regions of the micro-cavity structure on the main plane, that is, the micro-cavity structure of the raised structure is "narrow at the top and wide at the bottom", and the micro-cavity structure of the concave structure is "wide at the top and narrow at the bottom". Please refer to FIGS. 25 to 27 , taking the arrangement of the protruding structures T' and the concave structures A' at equal intervals as an example.

Please refer to Fig. 25, the protruding structure T1' and the concave structure A1' are hemispheres cut by the openings T1K' and A1K' respectively; the protruding structure T1' forms the microcavity structure Q11', and the concave structure A1' forms A micro-cavity structure Q12' is obtained.

Please refer to FIG. 26, the protruding structure T2' forming the microcavity structure Q21' includes an upper structure and a lower structure connected thereto. The upper structure has a curved surface, and the lower structure is an inclined side wall, and the inclined side wall gradually Inclined inward; the bottom of the raised structure T2' has an opening T2K'; and the depressed structure A2' is the inversion of the raised structure T2', the depressed structure A2' has a microcavity structure Q22', and the bottom of the depressed structure A2' has an opening A2K'.

Please refer to Fig. 27, the protruding structure T3' forming the microcavity structure Q31' includes an upper structure and a lower structure connected thereto. The upper structure has a flat surface, and the lower structure has inclined side walls, and the inclined side walls gradually Outward slope; the bottom of the raised structure T3' has an opening T3K'; and the recessed structure A3' is the inversion of the raised structure T3', the recessed structure A3' has a microcavity structure Q32', and the bottom of the recessed structure A3' has an opening A3K '.

Here, the size of the opening is nanoscale, the height of the micro-cavity structure is nanoscale, and the height of the micro-cavity structure may be 1/4-1 of the size of the opening.

It should be noted that, except for the above differences, other specific dimensions and relationship descriptions of the second embodiment are the same as those of the first embodiment, and reference may be made to the relevant descriptions of the first embodiment above, which will not be repeated here.

The preparation of the graphene thin film of this embodiment 2 can refer to the preparation method of the above-mentioned embodiment 1, which will not be repeated here.

It should be noted that the above-mentioned Embodiment 1 and Embodiment 2 of the present invention respectively describe that the opening is surrounded by the maximum contour of the projected contours of other areas of the micro-cavity structure on the main plane, and that the opening surrounds other areas of the micro-cavity structure on the main plane. In the case of the projected profile of the plane, then, in other embodiments of the present utility model, the raised structure and/or the recessed structure can also be a cuboid or a cube, so, the profile of the opening and other regions of the microcavity structure projected on the graphene film coincide.

In a preferred embodiment of the present utility model, a pressure power generation device is also provided, using the graphene film of the above-mentioned embodiment one and/or two as the piezoelectric conversion component; And/or when the concave structure exerts force, the multiple micro-cavity structures are deformed, thereby generating more electric energy. Moreover, the arrangement of the convex structure and the concave structure in the above embodiment enables forces from all directions to act on the graphene film, thereby improving the utilization rate.

In a preferred embodiment of the present utility model, a detector is also provided, and the graphene film of the above-mentioned embodiment 1 and/or 2 is used as the detection component, which realizes multi-point detection and multi-directional detection, and improves the detection efficiency. precision and sensitivity.

In a preferred embodiment of the present invention, a photocatalytic device is also provided, using the graphene thin film of the above-mentioned embodiment 1 and/or 2 as the photocatalytic component.

In a preferred embodiment of the present invention, a solar cell is also provided, using the graphene film of the above-mentioned embodiment 1 and/or 2 as an electrode or a photoelectric conversion component.

In a preferred embodiment of the present invention, an LED device is also provided, using the graphene thin film of the above-mentioned embodiment 1 and/or 2 as the electroluminescent layer or the electrode layer.

In a preferred embodiment of the present invention, an energy storage battery is also provided, using the graphene film of the above-mentioned embodiment 1 and/or 2 as the electrode layer.

Although the utility model has been disclosed above with preferred embodiments, the embodiments are only examples for convenience of description, and are not intended to limit the utility model. Those skilled in the art will not depart from the spirit and scope of the utility model. Some changes and modifications can be made below, and the scope of protection claimed by the utility model should be based on the claims.

Claims (26)

1. a kind of graphene film, it is characterised in that the graphene film is with microdischarge cavities knot of multiple one sides with opening Structure, microdischarge cavities structure are made up of the bulge-structure and/or sunk structure on graphene film surface；The opening shape of microdischarge cavities structure Into in the top of the bottom of bulge-structure and/or sunk structure.

2. graphene film according to claim 1, it is characterised in that the graphene film has principal plane, described The master that plane where plane where the opening of bulge-structure and/or the opening of the sunk structure is located at the graphene film puts down Plane where face；Or the graphene film has a principal plane, plane where the opening of the bulge-structure and/or described recessed Plane where falling into the opening of structure differs with plane where the principal plane of the graphene film.

3. graphene film according to claim 2, it is characterised in that the microdischarge cavities structure is arranged in array, adjacent The capable alternate setting of microdischarge cavities structure.

4. graphene film according to claim 3, it is characterised in that often row relief structure and sunk structure is alternate sets Put, and alternate setting between the bulge-structure of adjacent lines, alternate setting between the sunk structure of adjacent lines.

5. graphene film according to claim 4, it is characterised in that in often going, bulge-structure is in the principal plane Projected outline is tangent in the projected outline of the principal plane with the sunk structure.

6. graphene film according to claim 4, it is characterised in that the bulge-structure and the sunk structure are complete Deng graphics relationship.

7. graphene film according to claim 2, it is characterised in that the opening of the microdischarge cavities structure is put down in the master The projected outline in face is wrapped by largest contours of the other regions of the microdischarge cavities structure in the projected outline of the principal plane Enclose.

8. graphene film according to claim 7, it is characterised in that the chi of projected outline of the opening in principal plane The size of very little and described largest contours is nanoscale, and the size of the projected outline of the opening is the size of the largest contours 1/5~1.

9. graphene film according to claim 8, it is characterised in that the height of the microdischarge cavities structure is nanoscale, The height of the microdischarge cavities structure is the 1/4~1 of the size of the opening.

10. graphene film according to claim 2, it is characterised in that the opening of the microdischarge cavities structure is in the master The projected outline of plane surrounds projected outline of other regions in the principal plane of the microdischarge cavities structure.

11. graphene film according to claim 10, it is characterised in that the size of the opening is nanoscale, described The height of microdischarge cavities structure is nanoscale, and the height of the microdischarge cavities structure is the 1/4~1 of the size of the opening.

12. the graphene film according to claim 7 or 10, it is characterised in that the bulge-structure and/or the depression Structure is circular or rectangle in the projected outline of the principal plane, the opening the projected outline of the principal plane to be circular or Rectangle.

13. the graphene film according to claim 7 or 10, it is characterised in that the microdischarge cavities structure is by opening institute The spheroid cut.

14. the graphene film according to claim 7 or 10, it is characterised in that the bulge-structure includes superstructure With the understructure being attached thereto, the superstructure has flat surfaces or curved surfaces, and the understructure is inclined side Wall, sloped sidewall gradually inwardly or outwardly tilt from bottom to top；Sunk structure is the inversion of the bulge-structure.

15. graphene film according to claim 1, it is characterised in that only in the microdischarge cavities inner structural wall and/or whole Individual graphene film surface is formed with metal semiconductor compound nano thin-film.

16. graphene film according to claim 15, it is characterised in that the semiconductor nanomembrane is received for titanium alloy Rice film and/or kirsite nano thin-film.

17. graphene film according to claim 16, it is characterised in that the material of the titanium alloy nano film is TiOx, x are positive number；The kirsite nano thin-film is ZnO nano film.

18. graphene film according to claim 15, it is characterised in that the semiconductor nanomembrane is by metal compound The nano-wire array of thing is formed.

19. graphene film according to claim 15, it is characterised in that the thickness of the semiconductor nanomembrane and institute The ratio for stating the overall size of opening is not more than 1:3.

20. graphene film according to claim 1, it is characterised in that the graphene film is monoatomic layer thickness Graphene film.

21. a kind of detector, it is characterised in that there is the graphene film described in claim 1-20 any one as detection Part.

22. a kind of pressure electricity-generating device, it is characterised in that there is the graphene film described in claim 1-20 any one to make For piezoelectricity converting member；It is multiple described when the external world applies bulge-structure from active force to graphene film and/or sunk structure Microdischarge cavities structure deforms upon, so as to produce electric energy.

23. a kind of photocatalytic device, it is characterised in that there is the graphene film conduct described in claim 1-20 any one Photocatalysis part.

24. a kind of solar cell, it is characterised in that there is the graphene film conduct described in claim 1-20 any one Electrode or photoelectric conversion part.

25. a kind of LED component, it is characterised in that there is the graphene film described in claim 1-20 any one as electricity Electroluminescent layer or electrode layer.

26. a kind of energy-storage battery, it is characterised in that there is the graphene film described in claim 1-20 any one as electricity Pole layer.