Ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture

Abstract

The invention discloses an ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture which is characterized in that phosphorus and magnesium are injected into the bottom plane of a pure silicon wafer of which the length is less than 1 mu m and the height is less than 160nm by adopting ions, and the weight percentage of the phosphorus and the magnesium is not more than 3.5%; carrying out ion implantation on the upper surface of the pure silicon wafer by using not more than 3.5% (wt%) of indium and bismuth; an approximately circular through hole or a circular pit with the maximum length smaller than 160 nm and the depth larger than 3 nm is formed in the middle of the upper surface of the pure silicon wafer, and a meso-porous silicon unit is formed; cleaning and drying the meso-porous silicon unit and the graphene with the flat surface; the bottom planes of the meso-porous silicon units are orderly and flatly placed on the flat surface of the graphene, and the meso-porous silicon units and the graphene are integrated through a'pressure + silane grafting 'composite process and are conductive; a plurality of indium-bismuth-tin-yttrium oxides with the maximum size smaller than 30 nm are arranged on the outer surface of the meso-porous silicon unit, and the indium-bismuth-tin-yttrium oxides and the meso-porous silicon unit form a whole and are conductive.

Description

Technical Field

[0001] The invention relates to an ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture. Background Art

[0002] Resistive gas sensors detect gas by using the change in the resistance of materials caused by gas. They are one of the most widely used gas sensors and can be divided into surface conductivity type and bulk conductivity type. The sensing principle of surface conductivity type gas sensors is that gas is adsorbed on the surface of the element, and after the reaction occurs, its surface resistance changes; the principle of bulk conductivity type sensitive elements is that the gas-sensitive material reacts with gas molecules, the material undergoes a reversible change, and its conductivity changes accordingly. The resistance change of the test element can be used to obtain the gas concentration according to the proportional relationship. Resistive gas sensors can be divided into sintering type, thick film type, thin film type, silicon-based microstructure type, multilayer film type and new resistive sensor devices according to the device structure. Thick film devices are made by mixing gas-sensitive materials with appropriate amounts of adhesives and dispersants to form a paste, and then the slurry is printed on a ceramic substrate with test electrodes and heating elements by screen printing, and then calcined at high temperature. The structure of thin film devices is similar to that of thick films. The sensitive material is formed into a thin film on the substrate by evaporation, sputtering, spray pyrolysis or chemical vapor deposition. Its manufacturing process equipment is complex, expensive, and has high cost.

[0003] Gas sensors with a height of less than 700nm have small size and great application prospects in the fields of wearable fabrics and flexible automation.

[0004] The ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture of the invention is a novel micro-nano flexible gas sensor with a height less than 700nm.

[0005] According to the results of literature and patent searches, there are currently no relevant patent literature reports in China regarding mesoporous silicon / aluminum magnesium / indium bismuth oxide-graphene composite textures with a height of less than 700 nm. Summary of the invention

[0006] The task of the present invention is to provide an ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture, and the task of the present invention is achieved through the following technical solutions: Each pure silicon wafer used in the present invention contains more than 99.99% (wt%) silicon, is in the shape of a spherical cap or an ellipsoidal spherical cap, has a flat bottom plane, a maximum length of less than 1 μm, and a height of less than 160 nm; on the bottom plane of the pure silicon wafer, ion implantation of phosphorus and magnesium is performed, the total content of phosphorus and magnesium does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the ion implantation of phosphorus and magnesium is performed is located in an area below 1 / 4 of the height of the pure silicon wafer; on the upper surface of the pure silicon wafer, ion implantation of indium and bismuth is performed, the total content of indium and bismuth does not exceed 3.5% (wt%) of the pure silicon wafer, the area where the ion implantation of indium and bismuth is performed is located in an area above 2 / 3 of the height of the pure silicon wafer, and no phosphorus, magnesium, indium or bismuth is implanted in the area between 1 / 4 and 2 / 3 of the height of the pure silicon wafer, and the pure silicon wafer forms a composite semiconductor heterojunction containing phosphorus, magnesium, indium and bismuth; in the middle position of the upper surface of the pure silicon wafer, a substantially circular through hole or circular pit with a maximum length of less than 160 nm and a depth of more than 3 nm is formed, and the diameter of the circular through hole or circular pit is greater than 1 / 4 of the height of the pure silicon wafer. The maximum length of the circular through hole or circular pit is less than 3 / 4 of the maximum length of the ion implantation area on the upper surface of the pure silicon wafer, forming a mesoporous silicon unit; the mesoporous silicon unit is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120°C; the graphene with a thickness of less than 300nm and a flat surface is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120°C; the bottom plane of the clean mesoporous silicon unit is orderly placed on the flat surface of the clean graphene, and the mesoporous silicon unit is integrated with the graphene and conductive by applying a matching pressure of less than 0.05N on the mesoporous silicon unit and connecting the edge of the mesoporous silicon unit with silane grafted polyethylene, etc.; a plurality of mesoporous silicon units orderly arranged on the surface of the graphene and integrated with the graphene form a mesoporous silicon unit layer; a plurality of maximum size less than 30 is set on the outer surface of the mesoporous silicon unit forming a semiconductor heterojunction nm indium bismuth tin yttrium oxide, indium bismuth tin yttrium oxide and mesoporous silicon units forming semiconductor heterojunctions are integrated and conductive, forming an ordered mesoporous silicon / magnesium phosphorus / indium bismuth oxide-graphene composite texture.

[0007] The task of the ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture is achieved through the following technical solutions: Each pure silicon wafer used in the present invention contains more than 99.99% (wt%) silicon, is in the shape of a spherical cap or an ellipsoidal cap with a flat bottom plane, a maximum length of less than 1 μm, and a height of less than 160 nm; on the bottom plane of the pure silicon wafer, ions are implanted with phosphorus and magnesium, and the total content of phosphorus and magnesium does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the phosphorus and magnesium are ion-implanted is located below 1 / 4 of the height of the pure silicon wafer; on the upper surface of the pure silicon wafer, ions are implanted with indium and bismuth, and the total content of indium and bismuth does not exceed 1.5% (wt%) of the pure silicon wafer. 3.5% (wt%) of the silicon wafer, the area where indium and bismuth are ion-implanted is located above 2 / 3 of the height of the pure silicon wafer, and the area between 1 / 4 and 2 / 3 of the height of the pure silicon wafer is not injected with phosphorus, magnesium, indium or bismuth, and the pure silicon wafer forms a composite semiconductor heterojunction containing phosphorus, magnesium, indium and bismuth; by using a focused ion beam with a power of less than 500W, a nearly circular through hole or circular pit with a maximum length of less than 160nm and a depth of more than 3nm is formed in the middle position of the upper surface of the pure silicon wafer, and the diameter of the circular through hole or circular pit is from the top to the bottom The maximum length of the circular through hole or circular pit is less than 3 / 4 of the maximum length of the ion implantation area on the surface of the pure silicon wafer, forming a mesoporous silicon unit; the mesoporous silicon unit is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120℃; the graphene with a flat surface less than 300nm in thickness is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120℃; the bottom plane of the clean mesoporous silicon unit is placed flat in an orderly manner On the flat surface of clean graphene, the mesoporous silicon unit is integrated with the graphene and conductive by applying a fitting pressure of less than 0.05N on the mesoporous silicon unit and connecting the edge of the mesoporous silicon unit with silane-grafted polyethylene. A mesoporous silicon unit layer is composed of many mesoporous silicon units that are orderly arranged on the graphene surface and integrated with the graphene. By adjusting and controlling parameters such as enthalpy and entropy of the self-assembly process, many indium bismuth tin yttrium oxides with a maximum size of less than 30 nm are self-assembled on the outer surface of the mesoporous silicon unit that forms a semiconductor heterojunction. The indium bismuth tin yttrium oxide is integrated with the mesoporous silicon unit that forms a semiconductor heterojunction and conductive, forming an ordered mesoporous silicon / magnesium phosphorus / indium bismuth oxide-graphene composite texture.

[0008] The ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture is achieved by the following technical scheme: the pure silicon wafer of the present invention contains more than 99.99% (wt%) silicon, and is in the shape of a spherical cap or an ellipsoidal cap with a flat bottom plane, a maximum length of less than 1 μm, and a height of less than 160 nm; on the bottom plane of the pure silicon wafer, ions are implanted with phosphorus and magnesium, the total content of phosphorus and magnesium does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the ions are implanted with phosphorus and magnesium is located below 1 / 4 of the height of the pure silicon wafer; on the upper surface of the pure silicon wafer, ions are implanted with indium and bismuth, the total content of indium and bismuth does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the ions are implanted with indium and bismuth is located above the height of the pure silicon wafer. The area between 1 / 4 and 2 / 3 of the height of the pure silicon wafer is not implanted with phosphorus, magnesium, indium or bismuth, and the pure silicon wafer forms a composite semiconductor heterojunction containing phosphorus, magnesium, indium and bismuth; by using a focused ion beam with a power of less than 500W, an approximately circular through hole or circular pit with a maximum length of less than 160nm and a depth of more than 3nm is formed in the middle position of the upper surface of the pure silicon wafer, and the diameter of the circular through hole or circular pit gradually decreases from the top to the bottom, and the maximum length of the circular through hole or circular pit is less than the ion implantation area on the upper surface of the pure silicon wafer. The maximum length of the domain is 3 / 4, forming a mesoporous silicon unit; the mesoporous silicon unit is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120℃; the graphene with a thickness of less than 300nm and a flat surface is cleaned and dried by "ultrasonic wave + detergent + deionized water cleaning + argon drying below 120℃"; the bottom plane of the clean mesoporous silicon unit is orderly placed on the flat surface of the clean graphene, and a pressure of less than 0.05N is applied on the mesoporous silicon unit. The method comprises the following steps: pressure reduction, connection of the edges of the mesoporous silicon unit with silane-grafted polyethylene, etc., so that the mesoporous silicon unit is integrated with the graphene and is conductive; a plurality of mesoporous silicon units orderly arranged on the graphene surface and integrated with the graphene form a mesoporous silicon unit layer; a layer of indium-bismuth composite material layer containing more than 40.0% (wt%) indium, more than 40.0% (wt%) bismuth, more than 4.0% (wt%) tin, more than 5.1% (wt%) yttrium, and a thickness of less than 150 nm is provided on the outer surface of the mesoporous silicon unit forming the semiconductor heterojunction; the indium-bismuth composite material layer is integrated with the mesoporous silicon unit, oxygen is introduced, and a laser beam is irradiated for less than 1 second to form a plurality of indium-bismuth-tin-yttrium oxides with a maximum size of less than 30 nm; the indium-bismuth-tin-yttrium oxides are integrated with the mesoporous silicon unit forming the semiconductor heterojunction and are conductive, thereby forming an ordered mesoporous silicon / magnesium phosphorus / indium-bismuth oxide-graphene composite texture.

[0009] The shape and size of the mesoporous silicon unit of the ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture can be varied.

[0010] The shape and size of the nano-pits or through-holes of the mesoporous silicon unit of the ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture can be varied.

[0011] After years of in-depth research, the inventors found that the microcrystalline unit structure and large specific surface area characteristics of ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide with micro-nano pits can effectively promote the transmission and diffusion of gas molecules in the micro-region around the microcrystalline unit, and provide more reactive sites for chemical interactions between gas molecules and the material surface; the thickness of its pore wall is in the nanoscale range, which improves the density of carriers in the sensitive layer, and indium bismuth tin yttrium oxide shows high sensitivity to specific gas molecules, significantly enhancing its gas-sensitive response sensitivity; the mesoporous silicon unit forms a composite semiconductor heterojunction containing phosphorus and magnesium and indium and bismuth, which has good signal unidirectionality, anti-interference and low noise; the height of a single sensing unit is less than 700nm and the width is less than 1μm, and multiple sensing units can be arranged to be applied in the micro-nano field and the field of flexible ultra-small sensors. Therefore, the invention has important application value and practical significance.

[0012] Compared with the prior art, the related technologies of the ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture of the present invention have significant improvements: (1) Patented technology: A graphene / hydrogenated indium oxide composite photocatalyst and its preparation method, CN202110093326.3, provides a graphene / hydrogenated indium oxide composite photocatalyst and its preparation method, which are significantly different from the composition and structure of the present invention, and the present invention does not involve hydrogenated indium oxide. (2) Patented technology: An indium selenide / nitrogen-doped reduced graphene oxide composite material and its preparation method and application, CN202010829785.9, provides an indium selenide / nitrogen-doped reduced graphene oxide composite material and its preparation method and application, the composite material includes reduced graphene oxide, and the surface of the reduced graphene oxide is loaded with indium selenide nanodots; the composite material is doped with nitrogen. The composition and structure are significantly different from the present invention. (3) Patented technology: An indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and its preparation method and application, CN201911311852.1, the composite photocatalytic material comprises a three-dimensional nitrogen doped graphene foam and a two-dimensional indium zinc sulfide sheet arranged vertically on the surface of the nitrogen doped graphene foam. The preparation method is as follows: after the polyurethane sponge is hydrophilic treated, it is immersed in a graphene oxide suspension, dried and calcined, and ion cleaning is performed to obtain a three-dimensional nitrogen doped graphene foam; then it is mixed with an inorganic zinc salt, an inorganic indium salt and a sulfur-containing organic matter, and then hydrothermally reacted, and post-treated to obtain an indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material. It is significantly different from the composition and structure of the present invention. (4) Patented technology: An indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and its preparation method and application, CN201911311852.1, relates to an indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and its preparation method and application. The composition and structure of the present invention are obviously different. (5) Patented technology: Preparation of an indium sulfide sheet array / three-dimensional foam graphene supercapacitor electrode, CN201910633823.0, discloses the preparation of an indium sulfide sheet array / three-dimensional foam graphene supercapacitor electrode. The composition and structure of the present invention are obviously different. (6) Patented technology: An indium-based MOFs / graphene oxide composite material and its preparation method and application, CN201811092761.9, belongs to the technical field of metal organic framework materials, discloses an indium-based MOFs / graphene oxide composite material and its preparation method and application, which are obviously different from the composition and structure of the present invention. The present invention does not contain organic framework materials. (7) Patented technology: An indium sulfide / graphene composite film and its preparation method and application, CN201811524841.7, discloses an indium sulfide (In2S3) / graphene composite film and its preparation method and application, which are obviously different from the composition and structure of the present invention.(8) Patented technology: An indium tin oxide / vertical graphene photodetector composite structure and its preparation method, CN201910372272.7, characterized in that its structure from bottom to top is: glass as the substrate of the device; vertical graphene on the substrate as the light absorption layer and electron transport layer of the device; indium tin oxide film on the vertical graphene as the transparent current auxiliary diffusion layer; titanium / gold electrodes on both sides of the vertical graphene are connected to the external power supply, which is significantly different from the composition and structure of the present invention. (9) Patented technology: Preparation method of graphene-like structure copper indium sulfur sheet array film, CN201410098261.1, discloses a preparation method of graphene-like structure copper indium sulfur sheet array film in the field of nanomaterial preparation technology, the copper source used is monovalent copper salt, the indium source is indium chloride, the sulfur source is sulfur powder and thiourea, and the regular nanofilm is prepared by in-situ solvent thermal method. It is significantly different from the composition and structure of the present invention. (10) The paper "Study on Nitrogen Dioxide Gas Sensor Based on Reduced Graphene Oxide-Indium Oxide Composite Materials" prepared two different hierarchical structure In2O3 and graphene composite materials and graphene aerogel-supported In2O3 composite materials, respectively, and improved the sensing performance through the synergistic effect of the composite materials, realizing the development of high-performance, low-power NO2 sensors; the composition and structure are significantly different from those of the present invention. (11) The paper "Microwave-assisted carbon-induced preparation and performance regulation of metal oxide gas-sensitive materials" uses a normal pressure microwave-assisted method to uniformly load metal oxides on carbon nanomaterials, induce the preparation of metal oxides or metal oxide structured materials, and study the sensitive properties of metal oxide gas-sensitive materials; the composition and structure are significantly different from those of the present invention. (12) The paper "Preparation and anti-bovine serum albumin performance of graphene oxide / indium oxide / zwitterionic acrylic fluorinated polymer composite film", using GO / In2O3 composite material as filler and PAZFP resin emulsion as matrix, prepared a new organic / inorganic composite coating with micro / nano surface structure and low surface energy - graphene oxide / indium oxide / zwitterionic acrylic fluorinated polymer (GO / In2O3 / PAZFP) composite film, and studied its anti-protein performance; it is significantly different from the composition and structure of the present invention. (13) The paper "Research and Regulation of Optical Properties of InSe / Graphene Heterojunction", prepared a heterostructure of graphene and InSe by dry transfer, and then regulated the interaction between the two by staged annealing treatment; it is significantly different from the composition and structure of the present invention. (14) The paper “Identification of the number of graphene and indium selenide layers by optical contrast” uses a multi-beam parallel plate interference model to calculate the theoretical reflectivity contrast values ​​of samples with 1 to 4 layers on a single-polished silicon wafer; and uses a mechanical peeling method to prepare samples with 1 to 4 layers; the composition and structure are significantly different from those of the present invention.(15) The paper "Controllable Synthesis and Gas Sensing Properties of Ordered Mesoporous Indium Oxide / Reduced Graphene Oxide Nanocomposites" uses an ultrasound-assisted hybrid assembly strategy to achieve ordered mesoporous indium oxide / reduced graphene oxide nanocomposites; the matrix material used is reduced graphene oxide, which is different from the graphene of the present invention and does not contain mesoporous aluminum oxide and magnesium oxide. Therefore, the morphology of the indium oxide / reduced graphene oxide nanocomposites reported in this article is significantly different from the appearance and structure of the present invention. (16) The paper "Preparation of Mesoporous Indium Oxide Nanoparticles and Their Gas Sensing Properties" uses mesoporous silicon oxide KIT-6 as a hard template to prepare mesoporous indium oxide nanoparticles, which do not contain mesoporous aluminum oxide and magnesium oxide. The shape and structure of the mesoporous indium oxide nanoparticles are significantly different from the microcrystals of the ordered mesoporous silicon / magnesium phosphate / indium bismuth oxide of the present invention, and they do not form an integral body with graphene. Therefore, the relevant technology of the present invention has significant improvements.

[0013] The beneficial effects of the present invention are that it has high sensitivity to specific gas molecules, significantly enhances its gas-sensitive response sensitivity, has low noise, can be widely used in the micro-nano field with a height of less than 700nm and the field of flexible ultra-small sensors, is easy to use, has a simple structure, strong applicability, and has appropriate application costs, and is suitable for mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is a schematic diagram of the structure of the ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture of Example 1 of the present invention.

[0015] Figure 2 This is a scanning electron microscope photograph magnified 500,000 times of a sample in which orderly arranged mesoporous silicon units and graphene are integrated in the production process of Example 1 of the present invention.

[0016] Figure 3 This is a scanning electron microscope photograph of the ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture sample of Example 1 of the present invention, magnified 350,000 times.

[0017] In the accompanying drawings, 1-graphene, 2-mesoporous silicon unit layer. DETAILED DESCRIPTION

[0018] The present invention will be further described below in conjunction with the accompanying drawings. Example

[0019] Figure 1 This is a simplified structural diagram of the ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture of Example 1 of the present invention. In the figure, 1 is graphene and 2 is a mesoporous silicon unit layer.

[0020] Each pure silicon wafer used in the present invention contains more than 99.99% (wt%) silicon, is in the shape of a spherical cap or an ellipsoidal spherical cap, has a flat bottom plane, a maximum length of less than 1 μm, and a height of less than 160 nm; on the bottom plane of the pure silicon wafer, ion implantation of phosphorus and magnesium is performed, the total content of phosphorus and magnesium does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the ion implantation of phosphorus and magnesium is performed is located in an area below 1 / 4 of the height of the pure silicon wafer; on the upper surface of the pure silicon wafer, ion implantation of indium and bismuth is performed, the total content of indium and bismuth does not exceed 3.5% (wt%) of the pure silicon wafer, the area where the ion implantation of indium and bismuth is performed is located in an area above 2 / 3 of the height of the pure silicon wafer, and no phosphorus, magnesium, indium or bismuth is implanted in the area between 1 / 4 and 2 / 3 of the height of the pure silicon wafer, and the pure silicon wafer forms a composite semiconductor heterojunction containing phosphorus, magnesium, indium and bismuth; in the middle position of the upper surface of the pure silicon wafer, a substantially circular through hole or circular pit with a maximum length of less than 160 nm and a depth of more than 3 nm is formed, and the diameter of the circular through hole or circular pit is greater than 1 / 4 of the height of the pure silicon wafer. The maximum length of the circular through hole or circular pit is less than 3 / 4 of the maximum length of the ion implantation area on the upper surface of the pure silicon wafer, forming a mesoporous silicon unit; the mesoporous silicon unit is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120°C; the graphene with a thickness of less than 300nm and a flat surface is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120°C; the bottom plane of the clean mesoporous silicon unit is orderly placed on the flat surface of the clean graphene, and the mesoporous silicon unit is integrated with the graphene and conductive by applying a matching pressure of less than 0.05N on the mesoporous silicon unit and connecting the edge of the mesoporous silicon unit with silane grafted polyethylene, etc.; a plurality of mesoporous silicon units orderly arranged on the surface of the graphene and integrated with the graphene form a mesoporous silicon unit layer; a plurality of maximum size less than 30 is set on the outer surface of the mesoporous silicon unit forming a semiconductor heterojunction nm indium bismuth tin yttrium oxide, indium bismuth tin yttrium oxide and mesoporous silicon units forming semiconductor heterojunctions are integrated and conductive, forming an ordered mesoporous silicon / magnesium phosphorus / indium bismuth oxide-graphene composite texture. Example

[0021] Each pure silicon wafer used in the present invention contains more than 99.99% (wt%) silicon, is in the shape of a spherical cap or an ellipsoidal cap, has a flat bottom plane, a maximum length of less than 1 μm, and a height of less than 160 nm; on the bottom plane of the pure silicon wafer, phosphorus and magnesium are ion-implanted, and the total content of phosphorus and magnesium does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the phosphorus and magnesium are ion-implanted is located below 1 / 4 of the height of the pure silicon wafer; on the upper surface of the pure silicon wafer, indium and bismuth are ion-implanted, and the total content of indium and bismuth does not exceed 1.5% (wt%) of the pure silicon wafer. 3.5% (wt%) of the silicon wafer, the area where indium and bismuth are ion-implanted is located above 2 / 3 of the height of the pure silicon wafer, and the area between 1 / 4 and 2 / 3 of the height of the pure silicon wafer is not injected with phosphorus, magnesium, indium or bismuth, and the pure silicon wafer forms a composite semiconductor heterojunction containing phosphorus, magnesium, indium and bismuth; by using a focused ion beam with a power of less than 500W, a nearly circular through hole or circular pit with a maximum length of less than 160nm and a depth of more than 3nm is formed in the middle position of the upper surface of the pure silicon wafer, and the diameter of the circular through hole or circular pit is from the top to the bottom The maximum length of the circular through hole or circular pit is less than 3 / 4 of the maximum length of the ion implantation area on the surface of the pure silicon wafer, forming a mesoporous silicon unit; the mesoporous silicon unit is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120℃; the graphene with a flat surface less than 300nm in thickness is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120℃; the bottom plane of the clean mesoporous silicon unit is placed flat in an orderly manner On the flat surface of clean graphene, the mesoporous silicon unit is integrated with the graphene and conductive by applying a fitting pressure of less than 0.05N on the mesoporous silicon unit and connecting the edge of the mesoporous silicon unit with silane-grafted polyethylene. A mesoporous silicon unit layer is composed of many mesoporous silicon units that are orderly arranged on the graphene surface and integrated with the graphene. By adjusting and controlling parameters such as enthalpy and entropy of the self-assembly process, many indium bismuth tin yttrium oxides with a maximum size of less than 30 nm are self-assembled on the outer surface of the mesoporous silicon unit that forms a semiconductor heterojunction. The indium bismuth tin yttrium oxide is integrated with the mesoporous silicon unit that forms a semiconductor heterojunction and conductive, forming an ordered mesoporous silicon / magnesium phosphorus / indium bismuth oxide-graphene composite texture. Example

[0022] Figure 1 A simplified structural diagram of an ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture according to an embodiment of the present invention; Figure 2 This is a scanning electron microscope photograph magnified 500,000 times of a sample of ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture in Example 3 of the present invention, in which ordered arranged mesoporous silicon units and graphene form an integral whole; Figure 3This is a 350,000-fold magnified scanning electron microscope photograph of the ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture sample of Example 3 of the present invention. In the figure, 1 is graphene, and 2 is a mesoporous silicon unit layer.

[0023] The pure silicon wafer of the present invention contains more than 99.99% (wt%) of silicon, is in the shape of a spherical cap or an ellipsoidal spherical cap, has a flat bottom plane, a maximum length of less than 1 μm, and a height of less than 160 nm; on the bottom plane of the pure silicon wafer, phosphorus and magnesium are ion-implanted, the total content of phosphorus and magnesium does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the phosphorus and magnesium are ion-implanted is located below 1 / 4 of the height of the pure silicon wafer; on the upper surface of the pure silicon wafer, indium and bismuth are ion-implanted, the total content of indium and bismuth does not exceed 3.5% (wt%) of the pure silicon wafer, the area where the indium and bismuth are ion-implanted is located above 2 / 3 of the height of the pure silicon wafer, and phosphorus, magnesium, indium, or bismuth is not injected into the area between 1 / 4 and 2 / 3 of the height of the pure silicon wafer, and the pure silicon wafer forms a composite semiconductor heterojunction containing phosphorus, magnesium, indium, and bismuth; by using a focused ion beam with a power of less than 500 W, a maximum length of less than 160 nm and a depth of more than 3 nm is formed in the middle position of the upper surface of the pure silicon wafer. The diameter of the approximately circular through hole or circular pit gradually decreases from the top to the bottom, and the maximum length of the circular through hole or circular pit is less than 3 / 4 of the maximum length of the ion implantation area on the upper surface of the pure silicon wafer, so as to form a mesoporous silicon unit; the mesoporous silicon unit is cleaned and dried by "ultrasonic wave + cleaning liquid" + deionized water cleaning + argon drying below 120°C; the graphene with a thickness of less than 300nm and a flat surface is cleaned and dried by "ultrasonic wave + cleaning liquid" + deionized water cleaning + argon drying below 120°C; the bottom plane of the clean mesoporous silicon unit is orderly placed on the flat surface of the clean graphene, and the mesoporous silicon unit is integrated with the graphene and is conductive by applying a matching pressure of less than 0.05N on the mesoporous silicon unit and connecting the edge of the mesoporous silicon unit with silane grafted polyethylene; a plurality of mesoporous silicon units orderly arranged on the graphene surface and integrated with the graphene form a mesoporous silicon unit layer, such as Figure 2 As shown; a layer of indium-bismuth composite material layer containing more than 40.0% (wt%) indium, more than 40.0% (wt%) bismuth, more than 4.0% (wt%) tin, and more than 5.1% (wt%) yttrium, and having a thickness of less than 150 nm is provided on the outer surface of the mesoporous silicon unit forming a semiconductor heterojunction, the indium-bismuth composite material layer is integrated with the mesoporous silicon unit, oxygen is introduced, and a laser beam is used for irradiation time of less than 1 second to form a plurality of indium-bismuth-tin-yttrium oxides with a maximum size of less than 30 nm, and the indium-bismuth-tin-yttrium oxide is integrated with the mesoporous silicon unit forming a semiconductor heterojunction and is conductive, as shown Figure 3 As shown, an ordered mesoporous silicon / magnesium phosphorus / indium bismuth oxide-graphene composite texture was formed.

Claims

1. Ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture, characterized by : Each pure silicon wafer used in the present invention contains more than 99.99% (wt%) silicon, is in the shape of a spherical cap or an ellipsoidal cap, has a flat bottom plane, a maximum length of less than 1 μm, and a height of less than 160 nm; on the bottom plane of the pure silicon wafer, ions are implanted with phosphorus and magnesium, the total content of phosphorus and magnesium does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the ions are implanted with phosphorus and magnesium is located below 1 / 4 of the height of the pure silicon wafer; on the upper surface of the pure silicon wafer, ions are implanted with indium and bismuth, the total content of indium and bismuth does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the ions are implanted with indium and bismuth is located above 2 / 3 of the height of the pure silicon wafer, and the pure silicon wafer forms a composite semiconductor heterojunction containing phosphorus and magnesium and indium and bismuth; in the middle position of the upper surface of the pure silicon wafer, a nearly circular through hole or circular pit with a maximum length of less than 160 nm and a depth of more than 3 nm is formed, the diameter of the circular through hole or circular pit gradually decreases from the top to the bottom, and the circular through hole or circular pit The maximum length of the pit is less than 3 / 4 of the maximum length of the ion implantation area on the surface of the pure silicon wafer, forming a mesoporous silicon unit; the mesoporous silicon unit is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120°C; the graphene with a thickness of less than 300nm and a flat surface is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120°C; the bottom plane of the clean mesoporous silicon unit is orderly placed on the flat surface of the clean graphene, and the mesoporous silicon unit is integrated with the graphene and conductive by applying a matching pressure of less than 0.05N on the mesoporous silicon unit and connecting the edge of the mesoporous silicon unit with silane grafted polyethylene, etc.; a plurality of mesoporous silicon units orderly arranged on the graphene surface and integrated with the graphene form a mesoporous silicon unit layer; a plurality of maximum sizes less than 30 are set on the outer surface of the mesoporous silicon unit forming a semiconductor heterojunction. nm indium bismuth tin yttrium oxide, indium bismuth tin yttrium oxide and mesoporous silicon units forming semiconductor heterojunctions are integrated and conductive, forming an ordered mesoporous silicon / magnesium phosphorus / indium bismuth oxide-graphene composite texture.

2. Ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture, characterized by : Each pure silicon wafer used in the present invention contains more than 99.99% (wt%) silicon, is in the shape of a spherical cap or an ellipsoidal cap with a flat bottom plane, a maximum length of less than 1 μm, and a height of less than 160 nm; on the bottom plane of the pure silicon wafer, phosphorus and magnesium are ion-implanted, the total content of phosphorus and magnesium does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the phosphorus and magnesium are ion-implanted is located below 1 / 4 of the height of the pure silicon wafer; on the upper surface of the pure silicon wafer, indium and bismuth are ion-implanted, and the content of indium and bismuth is less than 1 / 4 of the height of the pure silicon wafer. The total content does not exceed 3.5% (wt%) of the pure silicon wafer, the area where indium and bismuth are ion-implanted is located in an area above 2 / 3 of the height of the pure silicon wafer, and the pure silicon wafer forms a composite semiconductor heterojunction containing phosphorus and magnesium and indium and bismuth; by using a focused ion beam with a power of less than 500W, a nearly circular through hole or circular pit with a maximum length of less than 160nm and a depth of more than 3nm is formed in the middle position of the upper surface of the pure silicon wafer, and the diameter of the circular through hole or circular pit gradually decreases from the top to the bottom, and the maximum length of the circular through hole or circular pit is less than 160nm and the depth is greater than 3nm. The maximum length is less than 3 / 4 of the maximum length of the ion implantation area on the surface of the pure silicon wafer to form a mesoporous silicon unit; the mesoporous silicon unit is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120°C; the graphene with a thickness of less than 300nm and a flat surface is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120°C; the bottom plane of the clean mesoporous silicon unit is orderly placed on the flat surface of the clean graphene, and the mesoporous silicon unit is integrated with the graphene and conductive by applying a matching pressure of less than 0.05N on the mesoporous silicon unit and connecting the edge of the mesoporous silicon unit with silane grafted polyethylene, etc.; many mesoporous silicon units orderly arranged on the graphene surface and integrated with the graphene form a mesoporous silicon unit layer; by adjusting and controlling the parameters such as enthalpy and entropy of the self-assembly process, many mesoporous silicon units with a maximum size of less than 30 are self-assembled on the outer surface of the mesoporous silicon unit forming the semiconductor heterojunction. nm indium bismuth tin yttrium oxide, which is integrated with the mesoporous silicon unit that forms a semiconductor heterojunction and is conductive, forming an ordered mesoporous silicon / magnesium phosphate / indium bismuth oxide-graphene composite texture.

3. Ordered mesoporous silicon / phosphorus magnesium / indium bismuth oxide-graphene composite texture, characterized by: The pure silicon wafer of the present invention contains more than 99.99% (wt%) silicon, is in the shape of a spherical cap or an ellipsoidal cap, has a flat bottom plane, a maximum length of less than 1 μm, and a height of less than 160 nm; on the bottom plane of the pure silicon wafer, phosphorus and magnesium are ion-implanted, the total content of phosphorus and magnesium does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the phosphorus and magnesium are ion-implanted is located below 1 / 4 of the height of the pure silicon wafer; on the upper surface of the pure silicon wafer, indium and bismuth are ion-implanted, the total content of indium and bismuth does not exceed 3.5% (wt%) of the pure silicon wafer, and the area where the indium and bismuth are ion-implanted is located below 1 / 4 of the height of the pure silicon wafer. The domain is located in an area above 2 / 3 of the height of the pure silicon wafer, and the pure silicon wafer forms a composite semiconductor heterojunction containing phosphorus and magnesium and indium and bismuth; by using a focused ion beam with a power of less than 500W, an approximately circular through hole or circular pit with a maximum length of less than 160nm and a depth of more than 3nm is formed in the middle position of the upper surface of the pure silicon wafer, and the diameter of the circular through hole or circular pit gradually decreases from the top to the bottom, and the maximum length of the circular through hole or circular pit is less than 3 / 4 of the maximum length of the ion implantation area on the upper surface of the pure silicon wafer, forming a mesoporous silicon. Unit; the mesoporous silicon unit is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120℃; the graphene with a thickness of less than 300nm and a flat surface is cleaned and dried by "ultrasonic wave + detergent" + deionized water cleaning + argon drying below 120℃; the bottom plane of the clean mesoporous silicon unit is orderly placed on the flat surface of the clean graphene, and the mesoporous silicon unit is pressed by applying a matching pressure of less than 0.05N on the mesoporous silicon unit. The edges of the mesoporous silicon unit are connected by silane grafted polyethylene, etc., so that the mesoporous silicon unit is integrated with the graphene and is conductive; a number of mesoporous silicon units that are orderly arranged on the graphene surface and integrated with the graphene constitute a mesoporous silicon unit layer; a layer of indium-bismuth composite material layer containing more than 40.0% (wt%) indium, more than 40.0% (wt%) bismuth, more than 4.0% (wt%) tin, and more than 5.1% (wt%) yttrium with a thickness of less than 150 nm is provided on the outer surface of the mesoporous silicon unit forming a semiconductor heterojunction, the indium-bismuth composite material layer is integrated with the mesoporous silicon unit, oxygen is introduced, and a laser beam is irradiated for less than 1 second to form many indium-bismuth-tin-yttrium oxides with a maximum size of less than 30 nm, the indium-bismuth-tin-yttrium oxides are integrated with the mesoporous silicon unit forming a semiconductor heterojunction and are conductive, forming an ordered mesoporous silicon / magnesium-phosphorus / indium-bismuth oxide-graphene composite texture.

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