TW201239948A - A method for making a substrate with micro-structure - Google Patents

Abstract

The present invention relates to a method for making a plate having micro-structures. The method includes following steps of: providing a substrate having an epitaxial growth surface; placing a carbon nanotube layer on the epitaxial growth surface, wherein the carbon nanotube layer has a plurality of openings; epitaxial growing a plurality of epitaxial grains on the epitaxial growth surface from the plurality of openings; and removing the carbon nanotube layer to obtain a plate having micro-structures. The method is simple and low cost.

Description

201239948 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a method of injuring a nano-structured substrate. [Prior Art] [0002] In the prior art, when various semiconductor devices are fabricated, it is often required to fabricate a nano-structure having a fine structure of several tens of nanometers to several hundreds of nanometers. U. A method of fabricating a nano pattern having the fine structure mainly includes a photolithography method of light or electron beam. 〇 [0003] In order to adapt to the rapid development of integrated circuit technology, while the previous optical lithography technology strives to break through the resolution limit, the next generation lithography technology has gained a lot of research in recent years. For example, deep ultraviolet lithography uses a light source with a wavelength of 13 to 14 nm and a highly accurate reflective optical system to effectively reduce the strong light absorption in the refractive system, but the lithography system, which is complicated in manufacturing methods and expensive, limits the technology. Applications. [0004] Since the 1990s, a new method of making and manufacturing nano-patterns has been developed (see Ch〇USY, Krauss p R, Ren_storm P. Imprint of sub 25 nin vias and trenches in polymers. Appl Phys. Lett., 1995, 67(21): 3114_3116). The new technique for making nanopatterns is known in the art as nanoimprint or nanoimprint lithography. Nano-printing refers to the use of a template with a nano-pattern to imprint a resist film on a substrate with a nano-pattern, and then process the nano-pattern on the substrate, such as etching, stripping, etc., and finally A pattern and a semiconductor device having a nanostructure are fabricated. A method of forming a nano pattern by nanoimprint technology 'by using a rigid template imprinted light having a nano pattern 100112869 Form No. A0101 Page 3 / 51 page 1002021432-0 201239948 Resisting layer forms a nano pattern without Rely on any radiation exposure. Therefore, nanoimprint technology can eliminate the limitations such as the wavelength of light required in conventional photolithography methods, as well as backscattering of particles in the photoresist and substrate, and optical interference constraints to achieve higher Resolution. Therefore, compared with lithography, nanoimprint technology has the advantages of low manufacturing cost, simplicity, and high efficiency, and has broad application prospects. [0005] [0007] Because nanoimprint technology mechanically aggregates The resistance of the photoresist is not achieved by changing the chemical properties of the photoresist of lithography. Therefore, 'nano imprint technology has high requirements for polymer photoresist, that is, the polymer photoresist should be thermoplastic or photocurable, and has good feeding ability, high modulus and maintaining deformation ability. And after curing, it is easy to demold, so that after the template is separated from the first resistance, the photoresist can still remain on the substrate. In the prior art, the photoresists of nanoimprinting mainly include bismuth rubber series, epoxy resin series, acrylate series, polystyrene series and the like. U.S. Patent No. 5,772, filed on Jun. 30, 1998, the disclosure of which is incorporated herein to The nano-pattern is formed on the substrate by spin-molding on the Shi Xi tablet. The disclosed method of nanoimprinting requires heating a nanoimprint resist (about causing a plastic 1±deformation) and then cooling the nano-house printing photoresist (below a glass transition temperature Tg of _eight). Mt:) After solidification molding, the template is removed to form a nano-scale pattern. However, since the glass transition temperature of polymethyl methacrylate is high, the heating temperature in the method is too high, so that the nano-imprinted light The mechanical stability of the resistance is reduced, and the adhesion to the template is 100112869. Form number A0101 Page 4 / 51 page 1002021432-0 201239948 Strong, difficult to demould, resulting in uneven graphics, resulting in lower resolution of the obtained nano graphics In the prior art, in order to improve the resolution of the nano-pattern, it is often necessary to pre-treat the template before imprinting, but the pre-processing of the template is complicated, thereby improving the complexity of the manufacturing method of the nanoimprint and the cost. The method is not conducive to practical application. SUMMARY OF THE INVENTION [0007] In summary, the invention provides a nanometer micro with a simple process, low cost, and no pollution to the surface of the substrate. A method for preparing a substrate is necessary. [0008] A method for fabricating a nano-microstructure substrate, comprising the steps of: providing a substrate having an epitaxial growth surface supporting epitaxial layer growth; Forming a carbon nanotube layer on the epitaxial growth surface; vertically growing an epitaxial layer on the epitaxial growth surface of the substrate, the epitaxial layer being a discontinuous epitaxial layer separated by a carbon nanotube in the carbon nanotube layer; and, removing The nano tube layer is obtained to obtain a substrate having a nano microstructure on the surface. [0009] A method for preparing a nano-micro structure substrate, comprising the steps of: providing a substrate having a supporting epitaxial layer growth An epitaxial growth surface; a first carbon nanotube layer disposed on the epitaxial growth surface of the substrate; a continuous first epitaxial layer on the epitaxial growth surface of the substrate and covering the first carbon nanotube layer; a second carbon nanotube layer is disposed on the surface of the first epitaxial layer; a second epitaxial layer is vertically grown on the surface of the continuous first epitaxial layer, and the second epitaxial layer is formed by a carbon nanotube layer a non-continuous epitaxial layer in which the carbon nanotubes are spaced apart; and removing the first carbon nanotube layer disposed on the surface of the continuous first epitaxial layer to obtain a form having a surface number of A1101 51 pages 1002021432-0 201239948 nano-microstructured substrate. [0010] A method for preparing a nano-microstructured substrate, comprising the steps of: providing a substrate having an epitaxial growth surface supporting epitaxial layer growth; The epitaxial growth surface of the substrate is provided with a carbon nanotube layer; a continuous epitaxial layer is grown on the epitaxial growth surface of the substrate and covers the carbon nanotube layer; and a nano carbon is disposed on the surface of the continuous epitaxial layer a tube layer; an epitaxial layer is vertically grown on a surface of the continuous epitaxial layer, the epitaxial layer being a discontinuous epitaxial layer separated by a carbon nanotube in the carbon nanotube layer; removing the continuous epitaxial layer surface setting a carbon nanotube layer; the carbon nanotube layer provided on the epitaxial growth surface of the substrate and the substrate is peeled off to obtain a nano-structured substrate. [0011] Compared with the prior art, the method for obtaining a patterned mask by providing a carbon nanotube layer on the epitaxial growth surface of the substrate is simple in process and low in cost, and the preparation cost of the epitaxial structure is greatly reduced, and at the same time Reduced pollution to the environment. Further, the epitaxial structure including the carbon nanotube layer makes the epitaxial structure have a wide range of uses. [Embodiment] A method for fabricating a nano-microstructure substrate provided by an embodiment of the present invention will be described in detail below with reference to the accompanying drawings. Referring to FIG. 1, an embodiment of the present invention provides a method for fabricating a nano-microstructure substrate 10, which specifically includes the following steps: [0014] S11: providing a substrate 100' and the substrate has a supporting epitaxial layer growth Epitaxial growth surface 101; [1215] S12: a carbon nanotube 100112869 is disposed on the epitaxial growth surface 101 of the substrate 100. Form No. A0101 Page 6 / 51 page 1002021432-0 201239948 Layer 102; [0016] S13: The epitaxial layer 1〇4 is vertically grown on the epitaxial growth surface 1〇1 of the substrate 100; _7] S14. The nano tube-breaking layer is removed to obtain a nano-structured substrate having a nano-microstructure 108. [0018] In step S11, the substrate 1 〇〇 provides an epitaxial growth surface 101 for growing the epitaxial layer 1〇4. The epitaxial growth surface 1〇1 of the substrate 1 is a molecularly smooth surface, and impurities such as oxygen or carbon are removed. The substrate 1〇〇 may be a single layer or a plurality of layers. When the substrate 1 is a single layer structure, the substrate 100 may be a single crystal structure having a crystal plane as the epitaxial growth surface 101 of the epitaxial layer 丨〇4. The material of the single-layer structure substrate 100 may be SOI (silicon on insulator),

LiGa〇2, LiAl〇2, Al2〇3, Si, GaAs, GaN, GaSb,

InN, InP, InAs, InSb, A1P, AlAs, AlSb, AIN,

GaP, SiC, SiGe, GaMnAs, GaAlAs, GalnAs, GaAIN, GalnN, AlInN, GaAsP, InGaN, AlGalnN, Ah GalnP, GaP: Zn or GaP: N, and the like. When the substrate 100 is of a plurality of layers, it is required to include at least one of the single crystal structures, and the single crystal structure has a crystal plane as the epitaxial growth surface 101 of the epitaxial layer 104. The material of the substrate 100 may be selected according to the epitaxial layer 104 to be grown. Preferably, the substrate 100 and the epitaxial layer 104 have similar lattice constants and coefficients of thermal expansion. The thickness, size and shape of the substrate 1 are not limited and can be selected according to actual needs. The substrate 100 is not limited to the listed materials as long as the substrate 100 having the epitaxial growth surface 101 supporting the growth of the epitaxial layer 104 is within the scope of the present invention. 100112869 Form No. A0101 Page 7 of 51 1002021432-0 201239948 [0019] In step S12, the carbon nanotube layer 102 is a continuous overall structure including a plurality of carbon nanotubes. The carbon nanotube layer 102 is placed in contact with the epitaxial growth surface 101 of the substrate 1 . The plurality of carbon nanotubes in the carbon nanotube layer 102 extend in a direction substantially parallel to the surface of the carbon nanotube layer 102. When the carbon nanotube layer 102 is disposed on the epitaxial growth surface 101 of the substrate 1 , the extending direction of the plurality of carbon nanotubes in the carbon nanotube layer 102 is substantially parallel to the epitaxy of the substrate 100 Growth face 101. The carbon nanotube layer has a thickness of from 1 nm to 100 μm, or from 1 nm to 1 μm, or from 1 nm to 200 nm, preferably from 10 nm to 1 nm. The carbon nanotube layer 102 is a patterned carbon nanotube layer 1〇2. The "patterned" means that the carbon nanotube layer 10 2 has a plurality of openings 1 〇 5 penetrating the carbon nanotubes from the thickness direction of the carbon nanotube layer 1 〇 2 a layer 102. When the carbon nanotube layer 1〇2 covers the epitaxial growth surface 101 of the substrate 1〇0, the epitaxial growth surface 101 of the substrate 1〇〇 is exposed to a portion corresponding to the opening 105. In order to grow the epitaxial layer 1 〇 4. The opening 105 may be a micropore or a gap. The size of the opening 1 〇 5 is J 〇 nanometer ~ 500 micrometers, and the size refers to the pore size or the pore of the micro pore. The spacing of the gaps in the width direction. The size of the openings 1〇5 is 10 nm to 300 μm, or 1 nm to 120 μm, or 1 nm to 8 μm, or 10 nm to 10 μm. The smaller the size of the opening 1〇5, the smaller the generation of dislocation defects during the growth of the epitaxial layer is obtained to obtain a high-quality epitaxial layer 104. Preferably, the size of the opening 105 is 1 〇 nanometer~ 1 〇 micron. Further 'the duty cycle of the carbon nanotube layer 102 is 1:1 〇 0~100:1 ' or 1:10~10:1, or Or 1:4~4: 1. Preferably, the duty ratio is 丨: 4~4: 1. The so-called "duty ratio" means that the carbon nanotube layer 102 is disposed on the epitaxial growth surface 100112869 of the substrate 100. No. A0101 Page 8 of 51 1002021432-0 201239948 [0020] [0022] [0023] After 1 0 1 'the epitaxial growth surface 1 〇 1 is occupied by the carbon nanotube layer 1 〇 2 The ratio of the area to the portion exposed through the opening 105. Further, the term "patterning" means that the arrangement of the plurality of carbon nanotubes in the carbon nanotube layer 1〇2 is ordered and For example, the axial directions of the plurality of carbon nanotubes in the carbon nanotube layer 102 are substantially parallel to the epitaxial growth surface 1〇1 of the substrate 100 and extend substantially in the same direction. Alternatively, the nanometer The axial direction of the plurality of carbon nanotubes in the carbon tube layer 102 may regularly extend substantially in more than two directions. Alternatively, the axial direction of the plurality of carbon nanotubes in the carbon nanotube layer 102 may be along the substrate 1 〇 A crystal orientation of the crucible extends or extends at an angle to a crystal orientation of the substrate 100. The adjacent carbon nanotube layers 102 are adjacent in the same direction The carbon nanotubes are connected end to end by a van der Waals force. Under the premise that the carbon nanotube layer 102 has an opening 1〇5 as described above, the carbon nanotube layer 102 has a plurality of The carbon nanotubes may also be randomly arranged and randomly arranged. Preferably, the carbon nanotube layer 1〇2 is disposed on the entire epitaxial growth surface 101 of the substrate 1〇〇. The carbon nanotube layer 1 The carbon nanotubes in the crucible 2 may be one or a plurality of single-walled carbon nanotubes, double-walled nano-tubes or multi-walled carbon nanotubes, and the length and diameter thereof may be selected as needed. The carbon nanotube layer 1G2 is used as a mask for growing an epitaxial layer. The so-called "mask" means that the carbon nanotube (4) 2 is used to cover a portion of the epitaxial growth of the substrate 1 (H) And exposing a portion of the epitaxial growth surface iQ1 such that the epitaxial layer 104 grows only from the exposed portion of the epitaxial growth surface m. Since the nanoscale carbon nanotube layer 1G2 has a plurality of openings 1Q5, the nanotube 100112869 form number A0101 Page 9 of 51 1002021432-0 201239948 The layer 102 forms an epitaxial growth surface ln1 of the pattern bottom (10), and the layer 102 is disposed on the side of the base growth surface 1()1 to obtain a number of carbon nanotubes along the parallel The epitaxy of the substrate m is described as follows: since the carbon nanotubes (4) 2 form a plurality of D1G5 in the obtained G1, the external disaster of the substrate 1 is restored. It can be understood that there is a pattern mask on the opposite side. Λ ^ ; lithography and other microelectronic methods, through the i§ + broken layer (10) mask for epitaxial growth _ „. a ^, growth method early, low cost, not easy = substrate m epitaxial growth read and introduce pollution And the environmental protection 〇 greatly reduces the preparation cost of the epitaxial structure. [0024] [002 5] It can be understood that the substrate m and the carbon nanotube layer 1〇2 together constitute a substrate for growing an epitaxial structure. The substrate can be used to grow epitaxial layers 104 of different materials. The material of the epitaxial layer 104 can be The material is the same as or different from the material of the substrate 1. When the material of the epitaxial layer 104 is different from the material of the substrate 100, the growth method is called heteroepitaxial growth. When the material of the epitaxial layer 104 is the same as the material of the substrate 100. The growth method is called homoepitaxial growth. The carbon nanotube layer 102 can be directly formed and laid directly on the epitaxial growth surface 101 of the beauty substrate 100. The ratio of the carbon nanotube layer 1〇2 itself The surface area is very large' so that the carbon nanotube layer 102 itself has a strong viscosity. Therefore, the carbon nanotube layer 102 can be directly fixed to the epitaxial growth surface 101 of the substrate 100 by its own adhesiveness. The carbon nanotube layer is a macroscopic structure, and the nano-tube layer 102 is a self-supporting structure. "self-supporting" means that the carbon nanotube layer 102 does not require a large area of carrier support. As long as the support is provided on opposite sides That is, the whole can be suspended to maintain its state, that is, the carbon nanotube layer 102 is placed (or fixed) 100112869 Form No. A0101 Page 10 / Total 51 Page 1002021432-0 201239948 Two pushers arranged at a certain distance In the upper case, the nano-tube layer 102 located between the two rituals can be suspended to maintain its own state. Since the nano-tube layer 102 is a self-supporting structure, the carbon nanotube layer 1〇2 does not have to pass through the complex The chemical method is formed on the epitaxial growth surface of the substrate 1 〇. Preferably, the carbon nanotube layer 1〇2 is a pure carbon nanotube structure composed of a plurality of carbon nanotubes. The so-called "pure nanotube structure" means that the carbon nanotube layer is chemically treated in the entire preparation process, and does not contain any functional group modification such as a carboxyl group. Ο [The nanocarbon tube layer 102 can also be a composite structure comprising a plurality of carbon nanotubes and an additive material. The additive material includes one or a plurality of graphite, graphite thin, carbon carbide, I, nitridane, oxidized stone, amorphous carbon, and the like. The Wei addition material may also include one or a plurality of metal carbides, metal oxides, metal metal compounds, and the like. The additive material is coated on at least a portion of the surface of the nanotube in the nanotube layer 1〇2 or in the opening 1〇5 of the carbon nanotube 102. Preferably, the additive material is coated on the surface of the naphthalene tube. Since the additive material is coated on the surface of the carbon nanotube, the diameter of the carbon nanotube is made larger, thereby reducing the opening 105 between the carbon nanotubes. The additive material may be formed on the surface of the carbon nanotube by chemical vapor deposition (CVD), physical vapor deposition (PVD), magnetron extinction or the like. [0027] After the carbon nanotube layer 1〇2 is laid on the epitaxial growth surface 101 of the substrate 1 , an organic solvent treatment step may be further included to make the carbon nanotubes 102 and the epitaxial growth surface. 1〇1 is more closely integrated. The organic solvent may be selected from one or more of ethanol, methanol, hydrazine, di-ethane and gas. The organic solvent in this embodiment employs ethanol. The organic solvent 100112869 form nickname 1010101 page 11 / 51 page 1002021432-0 201239948 [0028] [0030] 100112869 The step of the agent treatment can drop the organic solvent on the surface of the carbon nanotube layer 102 through the test tube The entire carbon nanotube layer 102 is wetted or the substrate 100 and the entire carbon nanotube layer 102 are immersed in a container containing an organic solvent to be infiltrated. The carbon nanotube layer 102 may also be directly grown on the epitaxial growth surface 101 of the substrate 100 by a chemical vapor deposition (CVD) method or the epitaxial growth of the substrate 100 and then transferred to the substrate 100. The face 101 〇 specifically 'the carbon nanotube layer 102 may include a carbon nanotube film or a nano carbon line. The carbon nanotube layer 102 can be a single layer of carbon nanotube film or a plurality of laminated carbon nanotube films. The carbon nanotube layer 1〇2 may comprise a plurality of carbon nanotube lines arranged in parallel or a plurality of nano carbon lines arranged in a cross. When the carbon nanotube layer 102 is a carbon nanotube film provided in a plurality of layers, the number of layers of the carbon nanotube film is not too high, and preferably, it is a layer of 2 to 1 layer. When the carbon nanotube layer 102 is a plurality of carbon nanotubes arranged in parallel, the distance between the adjacent two nanocarbon lines is from 1 μm to 200 μm, preferably from 10 μm to 100 μm. The space between the adjacent two nanocarbon lines constitutes the opening 105 of the nanocarbon layer 102. The length of the gap between the adjacent two carbon nanotube lines may be equal to the length of the nano broken line. The carbon nanotube film or the nanocarbon line may be directly laid on the epitaxial growth surface 101 of the substrate to constitute the carbon nanotube layer 1〇2. The size of the opening 105 in the carbon nanotube layer 102 can be controlled by controlling the number of layers of the carbon nanotube film or the distance between the carbon nanotubes. The carbon nanotube membrane is a self-supporting structure composed of a number of carbon nanotubes. The plurality of carbon nanotubes extend in a preferred orientation along the same direction. The preferred orientation refers to the overall extension of most of the carbon nanotubes in the carbon nanotube film. Form No. A0101 Page 12 of 51 1002021432-0 201239948 The direction is substantially the same direction. Moreover, the overall direction of extension of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube film. Most of the carbon nanotubes in the nanotube membrane are connected by van der Waals 3 . Specifically, the carbon nanotube film has a basic __ square (four) extension = each of the carbon nanotubes in each of the carbon nanotubes is adjacent to the nano tube in the extending direction, and is connected end to end by van der Waals force . Of course, there are a small number of randomly arranged carbon nanotubes in the carbon nanotube membrane, which do not significantly affect the overall orientation of most of the carbon nanotubes in the carbon nanotube membrane. The self-supporting building is a carbon nanotube film that does not require a large-area carrier ' support', and as long as the supporting force is provided on both sides, it can be suspended as a whole to maintain its own membranous state, that is, the carbon nanotube film is placed ( Or when it is fixed on two supports arranged at a certain distance, the carbon nanotube film located between the two supports can be suspended to maintain its own film state. The self-supporting is mainly achieved by the presence of a continuous carbon nanotube in the nano carbon film which is continuously extended by van der Waals. [0031] Specifically, most of the Q carbon nanotubes extending substantially in the same direction in the carbon nanotube film are absolutely straight and can be appropriately bent; or are not arranged in the extending direction, and may be appropriately The deviation extends in the direction. Therefore, it cannot be excluded that there may be partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes extending substantially in the same direction. [0032] Please refer to FIG. 2 and FIG. 3, specifically, The carbon nanotube membrane comprises a plurality of continuous and oriented elongated carbon nanotube segments 143. The plurality of carbon nanotube segments 143 are connected end to end by van der Waals force. Each nano carbon tube segment includes a plurality of mutually parallel nano carbon camps 145, the plurality of mutually parallel nano carbon 100112869 Form No. A0101 No. 13 Buy/Total 51 Pages 1_21432_〇201239948 Tube 145 is tightly coupled by Van der Waals . The carbon nanotube segments 143 have any length, thickness, uniformity, and shape. The carbon nanotube film can be obtained by directly drawing a part of a carbon nanotube from an array of carbon nanotubes. The carbon nanotube film has a thickness of from 1 nm to 100 μm, and the width is related to the size of the carbon nanotube array in which the carbon nanotube film is taken out, and the length is not limited. There are micropores or gaps between adjacent carbon nanotubes in the carbon nanotube film to form an opening 105, and the pore size or gap of the micropore is less than 10 microns. Preferably, the carbon nanotube film has a thickness of from 100 nm to 10 μm. The carbon nanotubes 145 in the carbon nanotube film extend in a preferred orientation in the same direction. For details of the carbon nanotube film and the preparation method thereof, please refer to the patent No. 1 3271 77 of the Republic of China patent "Nano carbon nanotube film structure" filed on February 12, 2010 by the applicant. And its preparation method". In order to save space, only the above is cited, but all the technical disclosures of the above application should also be considered as part of the technical disclosure of the present application. [0033] Referring to FIG. 4, when the carbon nanotube layer includes a plurality of laminated carbon nanotube films stacked in a stack, the extending direction of the carbon nanotubes in the adjacent two carbon nanotube films forms a cross. The angle α, and α is greater than or equal to 0 degrees and less than or equal to 90 degrees (0°S α $90° ). [0034] In order to reduce the thickness of the carbon nanotube film, the carbon nanotube film may be further subjected to heat treatment. In order to prevent the carbon nanotube film from being destroyed upon heating, the method of heating the carbon nanotube film adopts a local heating method. Specifically, the method comprises the steps of: locally heating the carbon nanotube film, so that a part of the carbon nanotube film is oxidized at a local position; and moving the carbon nanotube to be locally heated, from the local to the whole Heating of the carbon nanotube film. Specifically, the carbon nanotube film can be divided into a plurality of small regions, and the carbon nanotubes are heated region by region by means of the form 100112869 Form No. 1010101, page 14 / 51 pages 1002021432-0 201239948. membrane. The method of locally heating the carbon nanotube film may be plural, such as laser heating, microwave heating, or the like. In this embodiment, the carbon nanotube film is irradiated by a laser scan having a power density of more than 0.1 x 10 4 watts per square meter, and the carbon nanotube film is heated from a partial to a whole. The carbon nanotube film is irradiated by laser, and some of the carbon nanotubes are oxidized in the thickness direction, and at the same time, the larger diameter carbon nanotube bundle in the carbon nanotube film is removed, so that the carbon nanotube film becomes thin. ο _5] It is understood that the above method of scanning the carbon nanotube film is not limited as long as the carbon nanotube film can be uniformly irradiated. The laser scan can be performed row by row along the arrangement direction of the carbon nanotubes in the parallel carbon nanotube film, or column by column along the direction perpendicular to the arrangement of the carbon nanotubes in the carbon nanotube film. The smaller the speed of the laser-scanned carbon nanotube film with fixed power and fixed wavelength, the more heat absorbed by the carbon nanotube bundle in the carbon nanotube film, the more the corresponding carbon nanotube bundle is destroyed, after laser treatment The thickness of the carbon nanotube film becomes small. However, if the laser scanning speed is too small, the carbon nanotube film ❹ will absorb too much heat and be burned. 5秒。 In this embodiment, the laser power is greater than 0. 053x1 012 watts / square meter, the diameter of the laser spot is in the range of 1 mm to 5 mm, the laser scanning exposure time is less than 1.8 seconds. Preferably, the laser is a carbon dioxide laser having a power of 30 watts, a wavelength of 10.6 micrometers, a spot diameter of 3 mm, and a relative movement speed of the laser device and the carbon nanotube film of less than 10 mm. /second. [0036] The nanocarbon line may be a non-twisted nanocarbon line or a twisted nanocarbon line. The non-twisted nanocarbon line and the twisted nanocarbon line are both self-supporting structures. Specifically, referring to FIG. 5, the non-twisted nanometer 100112869 Form No. A0101 Page 15 of 51 1002021432-0 201239948 The carbon pipeline includes a plurality of carbon nanotubes extending along the length of the non-twisted nanocarbon pipeline. . Specifically, the non-twisted nanocarbon pipeline includes a plurality of carbon nanotube segments, and the plurality of carbon nanotube segments are connected end to end by a van der Waals force, and each of the carbon nanotube segments includes a plurality of parallel and pass through a van der Waals force. Tightly bonded carbon nanotubes. The carbon nanotube segments have any length, thickness, uniformity, and shape. The non-twisted nano carbon line is not limited in length, and has a diameter of 0.5 nm to 100 μm. The non-twisted nano carbon line is obtained by treating the carbon nanotube membrane with an organic solvent. Specifically, the organic solvent is used to impregnate the entire surface of the carbon nanotube film, and the mutually parallel complex carbon nanotubes in the carbon nanotube film pass through the surface tension generated by the volatilization of the volatile organic solvent. The wattage is tightly combined to shrink the carbon nanotube membrane into a non-twisted nanocarbon pipeline. The organic solvent is a volatile organic solvent such as ethanol, methanol, acetone, dioxane or chloroform, and ethanol is used in this embodiment. The non-twisted nanocarbon line treated by the organic solvent has a smaller specific surface area and a lower viscosity than the carbon nanotube film which is not treated with the organic solvent. [0037] The twisted nanocarbon line is obtained by twisting both ends of the carbon nanotube film in opposite directions by a mechanical force. Referring to Figure 6, the twisted nanocarbon line includes a plurality of carbon nanotubes extending axially around the twisted nanocarbon line. Specifically, the twisted nanocarbon pipeline includes a plurality of carbon nanotube segments, and the plurality of carbon nanotube segments are connected end to end by van der Waals, and each of the carbon nanotube segments includes a plurality of parallel and through van der Waals Tightly bonded carbon nanotubes. The carbon nanotube segments have any length, thickness, uniformity, and shape. 5纳米〜100微米。 The twisted nano carbon line length is not limited, the diameter is 0. 5 nanometers ~ 100 microns. Further, the twisted nanocarbon line can be treated with an organic solvent using a volatile 100112869 Form No. A0101 Page 16 of 51 1002021432-0. Under the action of surface tension generated by the volatilization of volatile organic solvents, the adjacent carbon nanotubes in the treated reversed carbon nanotubes are tightly bonded by van der Waals to make the specific surface area of the twisted nanocarbon pipeline. Reduce 'density and strength increase. For the nano carbon pipeline and its preparation method, please refer to the Republic of China patent No. 1303239, filed on November 5, 2008, filed by the applicant on November 5, 2002. Applicant: Hon Hai Precision Industry Co., Ltd. And the application for the Republic of China patent No. 1 312337, which was filed on December 16, 2005, was filed on July 21, 2009. Applicant: Hon Hai Precision Industry Co., Ltd. In step S13, the growth method of the epitaxial layer 104 can be performed by molecular beam epitaxy (MBE), chemical beam epitaxy (CBE), vacuum deuteration, low temperature epitaxy, selective epitaxy, liquid deposition epitaxy (LPE). , one or more of metal organic vapor phase epitaxy (MOVPE), ultra-vacuum chemical vapor deposition (UHVCVD), hydride vapor phase epitaxy (HVPE), and metal organic chemical vapor deposition (MOCVD) Implementation. The epitaxial layer 104 refers to a single crystal structure grown by epitaxial growth on the epitaxial growth surface 101 of the substrate 1 . The epitaxial layer 1 〇 4 may be a semiconductor epitaxial layer ' and the material of the semiconductor epitaxial layer is GaMnAs , GaA1As,

GalnAs, GaAs, SiGe, InP, si, AIN, GaN, GalnN,

AlInN 'GaAIN or AlGalnN. The epitaxial layer i 〇 4 may be a metal epitaxial layer, and the metal epitaxial layer is made of aluminum, platinum, copper or silver. The epitaxial layer 104 may be an alloy epitaxial layer, and the material of the epitaxial layer of the alloy is MnGa, CoMnGa or C〇2MnGa. The material of the epitaxial layer 1〇4 may be the same as the material of the substrate 100. Growing homoepitaxial layer form number A0101 page / 51 buy 1002 201239948 104, the material of the epitaxial layer 104 may also be different from the material of the substrate 100, in which case a heteroepitaxial layer may be grown. [0041] In step S13, a plurality of epitaxial grains 1042 are formed by nucleation and epitaxial growth along a direction substantially perpendicular to the epitaxial growth surface 101 of the substrate 100. The plurality of epitaxial grains 1042 are grown on a portion of the epitaxial growth surface 101 of the substrate 100 exposed through the opening 105 of the nanotube layer 102 and grow in a direction substantially perpendicular to an epitaxial growth surface of the substrate 100. 101, that is, in the step, the plurality of epitaxial grains 1042 are longitudinally epitaxially grown, and a trench 103 is formed between the adjacent epitaxial grains 104. A carbon nanotube layer 102 is disposed in the trench 103. Specifically, the carbon nanotubes in the carbon nanotube layer 102 are respectively distributed in the trench 103. The discontinuous complex epitaxial grains 1042 are entirely the epitaxial layer 104. The thickness of the epitaxial layer 104 can be controlled by controlling the time during which the epitaxial grains 1042 grow, thereby forming the epitaxial layer 104 into a configuration having a plurality of trenches 103. [0042] In the first embodiment of the present invention, the substrate 100 is a gallium nitride (GaN) substrate sheet, and the carbon nanotube layer 102 is a single-layer carbon nanotube film, and the carbon nanotube film Each of the carbon nanotubes in the majority of the carbon nanotubes extending in the same direction and the carbon nanotubes adjacent in the extending direction are connected end to end by the van der Waals force. In this embodiment, the gallium nitride epitaxial layer 104 is epitaxially grown by the MOCVD method. Among them, high-purity ammonia (NH3) is used as the source gas of nitrogen, hydrogen (H2) is used as the carrier gas, and trimethylgallium (TMGa) or triethylgallium (TEGa) or trimethylindium (TMIn) is used. Trimethylaluminum (TMA1) acts as a Ga source, an In source, and an A1 source. Specifically, the following steps include:

[0043] First, the gallium nitride substrate 100 is placed in a reaction chamber, heated to 1100 ° C ~ 1 200 ° C, and passed H2, \ or its mixed gas as a carrier gas, high temperature drying 100112869 Form No. A0101 Page 18 / Total 51 pages 1002021432-0 201239948 Copy 2 seconds to 1000 seconds, the substrate 100 is subjected to high temperature purification treatment. Secondly, continue to carry the carrier gas, keep the temperature of the reaction chamber at 1 000 °c ~ ll00 °c, keep the pressure of the reaction chamber at 100 Torr ~ 300 Torr, and pass into the top three; ^ marry or diethyl marriage and ammonia The plurality of GaN epitaxial grains 1042 are grown and have a height of 10 nm to 50 nm. Thereby, an epitaxial layer 104 composed of the complex GaN epitaxial grains 1042 is formed. Here, the entire structure in which the epitaxial layer 104 is grown on the gallium nitride (GaN) substrate 100 on which the carbon nanotube layer 1 2 is laid is defined as a mother substrate having a microstructure. [〇〇45] The method of removing the carbon nanotube layer 102 in the small step S14 may be an ion etching method, an ultrasonic method, a recording heating method, or a heating furnace heating method. The carbon nanotubes in the carbon nanotube layer 102 can be physically etched by the method or the carbon nanotubes can be oxidized to form a gas to be removed. [0046] The method for removing a carbon nanotube layer by plasma etching comprises the following steps: [〇〇47] a small step S141; placing a mother substrate having a microstructure in a vacuum chamber; [0048] #STEP5142; A reaction gas is introduced into the vacuum chamber to form a plasma of the reaction gas, and the plasma is reacted with the carbon nanotube layer 102. [0049] Step S142 specifically includes the following steps: step (1), vacuuming the vacuum chamber of the reactive ion etching machine; and step (2), introducing a reaction into the vacuum chamber of the reactive ion etching machine a gas, the reaction gas may be selected from oxygen, hydrogen or carbon tetrafluoride; in step (3), a plasma of the reaction gas is generated by a glow discharge reaction in the vacuum chamber, and is performed with the carbon nanotube layer 102. reaction. 100112869 Form No. A0101 Page 19 of 51 1〇〇2〇21432~〇201239948 [0050] In the step (3), the reaction gas forms a plasma by glow discharge, and the plasma includes charged ions and electronic. Depending on the reaction gas, the plasma includes conventional plasma such as oxygen plasma, hydrogen plasma or carbon tetrafluoride plasma. Preferably, the reaction gas is oxygen, and the plasma is an oxygen plasma. Since the plasma has good fluidity, the plasma can penetrate into the grooves 103 by appropriately controlling the gas pressure and reaction time in the vacuum chamber. Therefore, the plasma enters the trench 103 of the epitaxial layer 104 and strikes the surface of the carbon nanotube to physically mark the carbon nanotube, or generates carbon dioxide by reacting with a carbon atom in the carbon nanotube layer 102. The volatile reaction product chemically etches the carbon nanotube layer 102. The reaction time is not too short, otherwise the carbon nanotube layer 102 is not sufficiently reacted with the plasma to achieve the purpose of removing the carbon nanotube layer 102. The glow discharge reaction may have a power of 20 to 300 watts, preferably 150 watts. The reaction gas flow rate is 10 to 100 standard conditions of milliliters per minute (seem), preferably 50 seem. The gas pressure in the vacuum chamber is from 1 to 100 Pa, preferably 10 Pa. The reaction time of the plasma with the carbon nanotubes is from 10 seconds to 1 hour, preferably from 15 seconds to 15 minutes. [0051] The method for removing the carbon nanotube layer 102 by laser heating in an oxygen environment specifically includes the following steps: [0052] Step S422; providing a laser device, and emitting a laser beam from the laser device to the The surface of the carbon nanotube layer 102 in the microstructured mother substrate. [0053] Step S424; in the environment containing oxygen, the laser beam is caused to move relative to the carbon nanotube layer 102 in the micro-structured mother substrate to scan the carbon nanotube layer 1 〇 2 and epitaxial layer 104. 100112869 Form No. A0101 Page 20 of 51 1002021432-0 201239948 [0054] In step S422, the laser device includes a solid laser, a liquid laser, a gas laser, and a semiconductor laser. 8秒。 The laser power density is greater than 0.053xl012 watts / square meter, the spot diameter is in the range of 1 mm to 5 mm, the laser irradiation time is less than 1.8 seconds. In this embodiment, the laser device 140 is a carbon dioxide laser having a power of 30 watts, a wavelength of 10.6 micrometers, and a spot diameter of 3 millimeters. Preferably, the laser beam is incident perpendicularly to the surface of the carbon nanotube layer 102 in the mother substrate. [0055] The laser device comprises at least one laser, and when the laser device comprises _ a laser, the laser device is illuminated to form a spot having a diameter of 1 mm to 5 mm. When the laser device comprises a plurality of lasers, the laser device is illuminated to form a continuous laser scanning zone, which is a strip-shaped spot composed of a plurality of consecutive laser spots, the strip-shaped spot having a width of 1 The mm is 5 mm and the length is greater than or equal to the width of the carbon nanotube layer 102. [0056] Step S424 can be implemented by the following two methods: [0057] Method 1: Fixing a mother substrate having a microstructure, and then moving the laser device C) ^ illuminating the mother substrate having the microstructure, which specifically includes the following steps: fixing a mother substrate having a microstructure; providing a movable laser device; and moving the laser device to scan a surface of the carbon nanotube layer 102 and the epitaxial layer 104 in the microstructured mother substrate. [0058] Method 2: Fixing the laser device, moving the mother substrate having the microstructure to irradiate the surface of the carbon nanotube layer 102 and the surface of the epitaxial layer 104 in the micro-structured mother substrate by laser, which specifically includes the following steps: providing a laser device a fixed laser device that forms a laser scanning area in a fixed area; drawing 100112869 Form No. A0101 No. 21 Buying/Total 51 Page 1002021432-0 201239948 Providing a mother substrate with a micro-structure to make the mother substrate with micro-structure The surface of the carbon nanotube layer 102 and the epitaxial layer in the middle passes through the mis-scanning scanning zone at a certain speed. [0059] Step S424 t the laser beam is directly irradiated on the carbon nanotube layer 1〇2. Since the carbon nanotube has good absorption characteristics for the laser, and the carbon nanotube in the carbon nanotube layer 102 will Absorbing heat to be ablated, and controlling the time of laser irradiation of the carbon nanotube layer 102 by controlling the moving speed of the micro-structured mother substrate or the moving speed of the laser scanning region, thereby controlling the carbon nanotube layer 102 The energy absorbed by the carbon nanotubes causes the carbon nanotubes in the carbon nanotube layer 102 to be oxidized to carbon dioxide gas. It can be understood that for a laser device with a fixed power density and a fixed wavelength, the smaller the speed of the carbon nanotube layer 102 passing through the laser scanning region, the longer the carbon nanotube layer 1〇2 is irradiated, and the carbon nanotube layer. The more energy absorbed by the carbon nanotube bundle in 1〇2, the more easily the carbon nanotube layer 1〇2 is ablated. In this embodiment, the relative movement speed of the laser and the carbon nanotube layer 1〇2 is mm/sec. It can be understood that the method of laser-scanning the carbon nanotube layer 102 is not limited as long as the carbon nanotube layer 102 can be irradiated uniformly. The laser scanning may be performed row by row along the arrangement direction of the carbon nanotubes in the parallel carbon nanotube layer 102, or may be performed column by column in the direction perpendicular to the arrangement of the carbon nanotubes in the carbon nanotube layer 102. The method for removing the carbon nanotube layer 102 by heating under the oxygen gas specifically includes the following steps: [0061] Step S432, a heating furnace is provided. Just 4 can be added to the structure of the secret as long as it can provide heating from the mosquito net

100112869 Form No. A0101 Page 22 of 51 1002021432-0 201239948 Temperature is OK. Preferably, the heating furnace is a resistance furnace which may be a resistance furnace of the prior art. The electric resistance furnace [0063] step S432', placing the micro-structured mother substrate inside the heating furnace, heating the micro-structured mother board in an oxygen environment [0064] The carbon nanotube layer 102 in the mother substrate absorbs heat from the furnace and reacts with oxygen to be ablated. The heating furnace of the resistance furnace is above SC 600SC' to ensure that the carbon nanotubes get enough heat to react with oxygen. Preferably, the mother substrate having the microstructure is heated above the crucible by an electric resistance furnace to remove the carbon nanotube layer 102. [0065] In the first embodiment of the present invention, the surface of the carbon nanotube layer in the micro-structured mother substrate is irradiated by a carbon dioxide laser in an oxygen-containing environment. The surface of the carbon nanotube layer is such that the carbon nanotube layer is burned and then removed, and the nanostructured substrate 10 is obtained. The CO2 laser has a power of 30 watts, a wavelength of 1 〇.6 μm, and a spot diameter of 3 mm. The relative movement speed of the carbon dioxide laser device and the micro-structured mother substrate is less than 10 mm/sec. [0067] 100112869 In this embodiment, the substrate 100 and the epitaxial layer 104 are of a homogenous structure, that is, when the epitaxial layer 104 is homogenously grown, the interface between the substrate 1 and the epitaxial layer 1〇4 is almost indistinguishable. The structure having the nano-microstructure substrate 1 is actually a layer of homostructure. Referring to FIG. 7, a second embodiment of the present invention provides a method for fabricating a nano-microstructure substrate 20, which specifically includes the following steps: S10: providing a base substrate 200, and the base substrate has a form number Α0101 Page 23 / Total 51 page 1002021432-0 [0068] [0073] [0073] [0073] Epitaxial growth surface 2〇1; S20. a first carbon nanotube layer 2〇2 is disposed on the epitaxial growth surface of the substrate 2〇〇; S30. a first epitaxial layer 204 is grown on the epitaxial growth surface 2〇1 of the base substrate 2〇〇; S40. A second carbon nanotube layer 2〇7 is disposed on the surface 206 of the epitaxial layer 2〇4 away from the base substrate 2〇〇; S50. The first epitaxial layer 2〇4 is away from the base substrate 2〇 The surface 206 of the crucible is vertically grown with the second epitaxial layer 209; S60. The second carbon nanotube layer 2〇7 is removed to obtain a nano-structured substrate 20. [1124] 100112869

In step S10, the base substrate 2 is provided with an epitaxial growth surface 201 of the first epitaxial layer 204. The epitaxial growth surface 201 of the base substrate 2 is a molecularly smooth surface, and impurities such as oxygen or carbon are removed. The base substrate 200 can be a single layer or a plurality of layers. When the base substrate 200 has a single layer structure, the base substrate 200 may be a single crystal structure and have a crystal plane as the epitaxial growth surface 201 of the first epitaxial layer 204. The material of the base substrate 200 of the single-layer structure may be GaAs, GaN, Si, SOI (silicon on insulator ' on the insulating substrate), AIN, SiC, Mg 〇, ZnO, LiGa 〇 2, LiAl 〇 24 Al 2 〇 3 and so on. When the base substrate 200 is of a plurality of layers, it is required to include at least one layer of the single crystal structure, and the single crystal structure has a crystal plane as the epitaxial growth surface 201 of the first epitaxial layer 204. The material of the base substrate 200 may be selected according to the first epitaxial layer 204 to be grown, preferably, the base form number A_1 page 24 / 51 S 1〇〇: 201239948 [0075] 0 [0076] [ 0077] Ο 100112869 The base substrate 200 has a similar lattice constant and a coefficient of thermal expansion as the first epitaxial layer 204. The thickness, size and shape of the base substrate 200 are not limited and may be selected according to actual needs. The base substrate 2 is not limited to the listed materials, as long as the base substrate 200 having the epitaxial growth surface 201 supporting the growth of the first epitaxial layer 204 is within the scope of the present invention. The structure, arrangement, formation method, material, and the like of the first carbon nanotube layer 202 in S20 are the same as those of the carbon nanotube layer of the first embodiment, and thus will not be described herein. In step S30, the growth method of the first epitaxial layer 204 may be performed by molecular beam epitaxy (ΜΒΕ), chemical beam epitaxy (CBE), vacuum deuteration, low temperature epitaxy, selective epitaxy, liquid deposition epitaxy (LpE), metal organic vapor phase epitaxy (M0VPE), ultra-vacuum chemical vapor deposition (UHVCVD), hydride vapor phase epitaxy (HVpE), and metal organic chemical vapor deposition (MOCVD) Or a plurality of implementations. The first epitaxial layer 204 refers to a single crystal structure grown by epitaxial growth on the epitaxial growth surface 201 of the base substrate 2, which material is different from the base substrate 200, and thus may also be referred to as a heteroepitaxial layer. The thickness of the growth of the first epitaxial layer can be prepared as needed. Specifically, the growth thickness of the first epitaxial layer 204 may be 0.5 nm to 丨 mm. For example, the thickness of the first epitaxial layer 204 may be from 1 nanometer to 5 nanometers or from 2 nanometers to 200 micrometers, or from 500 nanometers to 1 micrometer. The first epitaxial layer 204 may be a semiconductor epitaxial layer, and the material of the semiconductor epitaxial layer is __nAs, GaAlAs, GalnAs, GaAs, SiGe, InP, Si, A1N, GaN, GaInN, A1InN, GaAIN or AlGalnN » The first epitaxial layer 2G4 may be a metal epitaxial layer, and the material of the metal epitaxial layer is No. A0101, page 25/51, 1002021432-0 201239948 [0078] [0080] [0081] 0082] [0083] 100112869 Ming, platinum, copper or silver. The first epitaxial layer 2〇4 may be an alloy epitaxial layer' and the material of the epitaxial layer of the alloy is Ga, (10). Give. 'refer to FIG. 8 'specifically' the growth process of the epitaxial layer 204 specifically includes the following steps: 531: nucleation and epitaxial growth along a direction substantially perpendicular to the epitaxial growth surface 201 of the base substrate _ to form a complex epitaxy a crystal grain 2〇42; 532: the plurality of epitaxial grains 2_ are epitaxially grown along a direction substantially parallel to the epitaxial growth surface 2G1 of the base substrate 200 to form a continuous epitaxial film 2044; 533. The epitaxial film 2〇 44 is epitaxially grown in a direction substantially perpendicular to the epitaxial growth surface 2〇1 of the base substrate 200 to form a continuous first epitaxial layer 204. In step S31, the complex epitaxial grains 2〇42 are grown on the exposed surface 201 of the base substrate 2 through the exposed portion 2〇5 of the first carbon nanotube layer 2〇2, And the growth direction thereof is substantially perpendicular to the epitaxial growth surface 2〇1 of the base substrate 200, that is, the plurality of epitaxial grains 2042 are longitudinally epitaxially grown in this step. In step S32, the first carbon nanotube layer 202 is covered by controlling the growth conditions such that the plurality of epitaxial grains 2〇42 are uniformly grown in the direction of the epitaxial growth surface 201 of the base substrate 200. That is, in the step, the plurality of epitaxial grains 2042 are laterally epitaxially grown to directly merge and finally form a plurality of holes 203 around the carbon nanotubes. Preferably, the carbon nanotubes are spaced apart from the first epitaxial layer 2〇4 surrounding the carbon nanotubes. The shape of the hole and the first nanometer form number A0101 page 26/51 page 1002021432-0 201239948 [0084] 008 [0086] [0087] The arrangement of the carbon nanotubes in the carbon tube layer 202 Direction related. When the first carbon nanotube layer 202 is a single-layer carbon nanotube film or a plurality of parallel-lined nano-barrier lines, the plurality of holes 203 are substantially parallel grooves. When the first carbon nanotube layer 202 is a plurality of layers of a carbon nanotube film or a plurality of interdigitated carbon nanotubes, the plurality of holes 2 〇 3 are intersecting groove networks. In step S33, due to the presence of the first carbon nanotube layer 202, lattice dislocations between the epitaxial grains 2042 and the base substrate 200 stop growing during the formation of the continuous epitaxial film 2044. Therefore, the first epitaxial layer 204 of this step corresponds to homoepitaxial growth on the surface of the epitaxial film 2044 having no defects. The first epitaxial layer 204 has fewer defects. In the first embodiment of the present invention, the base substrate 200 is a sapphire (Al2〇3) substrate sheet. The first carbon nanotube layer 202 is a single-layer carbon nanotube film, and the carbon nanotube tube. Each of the carbon nanotubes in the majority of the carbon nanotubes extending substantially in the same direction in the film and the carbon nanotubes adjacent in the extending direction are connected end to end by van der Waals force. This embodiment uses the MOCVD method for epitaxial growth. Among them, high purity ammonia (NHQ) is used as the source gas of nitrogen, and 0 hydrogen (H2) is used as the carrier gas, and trimethyl gallium (TMGa) or triethyl gallium (TEGa) and tris-decyl indium (TMIn) are used. ), triammonium aluminum (TMA1) as a Ga source, an In source, and an A1 source. Specifically, the following steps are included: First, the sapphire base substrate 200 is placed in a reaction chamber, heated to ll 〇〇 ° C to 1200 ° C, and H2, \ or a mixed gas thereof is introduced as a carrier gas, and baked at a high temperature for 200 sec-1 000 seconds. Secondly, continue to carry the same carrier gas, and cool down to 500 ° C ~ 650 ° C, access to the top three 100112869 Form No. A0101 Page 27 / Total 51 page 1002021432-0 201239948 Based gallium or triethyl gallium and ammonia, grow GaN The low temperature buffer layer 2045 (see FIGS. 7 and 8) has a thickness of 10 nm to 50 nm. [0088] Then, the passage of trimethylgallium or triethylgallium is stopped, the ammonia gas and the carrier gas are continuously introduced, and the temperature is raised to 1100 ° C to 1 200 ° C, and the temperature is maintained for 30 seconds to 300 seconds. , annealing. [0089] Finally, the temperature of the base substrate 200 is maintained at 1 000 ° C to 1100 ° C, and the ammonia gas and the carrier gas are continuously introduced, and at the same time, trimethylgallium or triethylgallium is re-introduced, and GaN is completed at a high temperature. The lateral epitaxial growth process and the growth of a high quality GaN epitaxial layer. [0090] After the samples were grown, the samples were observed and tested by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. Referring to FIG. 9 and FIG. 10, in the epitaxial structure prepared in this embodiment, the first epitaxial layer is grown only from the position where the epitaxial growth surface of the substrate has no carbon nanotube layer, and then integrated. The surface of the first epitaxial layer in contact with the substrate forms a plurality of holes, and the carbon nanotube layer is disposed in the hole and spaced apart from the first epitaxial layer. Specifically, it can be clearly seen from FIG. 9 that the interface between the GaN epitaxial layer and the sapphire substrate is seen, wherein the dark portion is a GaN epitaxial layer and the light portion is a sapphire substrate. The surface of the GaN epitaxial layer in contact with the sapphire substrate has a row of holes. As can be seen from Fig. 10, a carbon nanotube is disposed in each of the holes. The carbon nanotubes in the holes are disposed on the surface of the sapphire substrate and are spaced apart from the GaN epitaxial layer forming the holes. [0091] In S40, the second carbon nanotube layer 207 is disposed on a surface 206 of the first epitaxial layer 204 away from the base substrate 200. In S40, the 100112869 Form No. A0101 Page 28/51 Page 1002021432-0 201239948 The structure, arrangement, formation method and materials of the second carbon nanotube layer 207 are the same as those of the first embodiment. The carbon tube layers are the same, so they are not described here. In this embodiment, the second carbon nanotube layer 207 is a plurality of parallel and spaced nanocarbon pipelines, and micropores are formed between adjacent nanocarbon pipelines. [0093] The nanocarbon line may be a non-twisted nanocarbon line or a twisted carbon carbon line. Specifically, the non-twisted nanocarbon line includes a plurality of carbon nanotubes extending along the length of the non-twisted nanocarbon line. The twisted nanocarbon pipeline includes a plurality of carbon nanotubes extending axially around the twisted nanocarbon pipeline. [0094] The method of vertically growing the second epitaxial layer 209 on the surface 206 of the first epitaxial layer 2〇4 away from the base substrate 200 is exactly the same as the step S13 of the first embodiment, where No more details are given. The material construction configuration of the second epitaxial layer 209 is the same as that of the gallium nitride first epitaxial layer 204 grown in the step of S13 of the first embodiment. [0095] The second epitaxial layer 209 is composed of a plurality of discrete GaN epitaxial grains 1042. [0096] The method of removing the second carbon nanotube layer 2〇7 in S60 is exactly the same as the step of S14 of the first embodiment, and details are not described herein again. [0097] Referring to FIG. 11, a third embodiment of the present invention provides a method for fabricating a nano-microstructure substrate 30, which includes the following steps: [0098] S100: providing a base substrate 2, and the base substrate 200 has an epitaxial growth surface 201 supporting the growth of the first epitaxial layer 2〇4; 100112869 Form No. A0101 Page 29/51 Page 1002021432-0 201239948 [0099] S2〇〇: Extension of the base substrate 2〇〇 The growth surface 2〇1 is provided with a first carbon nanotube layer 202; [0100] S300′ grows a first epitaxial layer 204 on the epitaxial growth surface of the base substrate 20Q; [0101] S400. The first epitaxial layer 2〇 a second carbon nanotube layer 207 is disposed on the surface 206 away from the base substrate; _2] S5GG. The second epitaxial layer 209 is vertically grown on the surface 206 of the first epitaxial layer 2Q4 away from the base substrate;闺湖G: remove the second nai (four) tube layer 2 () 7; _] S7 () (). Peel off the base substrate 200 and the first - Nai carbon tube layer 202, to obtain the opposite two surfaces have nano Microstructure 208 having a nano-microstructure substrate 30[0105] This embodiment provides a substrate having a nano-microstructure The preparation method is basically the same as the preparation method of the nano-structured substrate of the second embodiment, except that the removal of the second carbon nanotube layer 2〇7 further includes a removal of the base substrate 200 and the first nanocarbon. The step of the tube layer 2〇2. Therefore, the same steps as those of the second embodiment will not be described herein, and only the specific steps of the S700 will be described. [0106] In step S700, the peeling method of the base substrate 200 may be a laser irradiation method, an etching method, or a temperature difference self-peeling method. The stripping method can be selected depending on the base substrate 200 and the material of the first epitaxial layer 2〇4. In the present embodiment, the peeling method of the base substrate 200 is a laser irradiation method. The specific method of the radiant irradiation peeling comprises the following steps: 100112869 Form No. A0101 Page 30/51 Page 1002021432-0 201239948 [0107] [0109] 〇[0110] [0111] ο S701, Polishing and cleaning the surface of the base substrate 2 without growing the first epitaxial layer 2〇4; S702, placing the surface-cleaned base substrate 2〇〇 on a platform (not shown), and using a laser pair The base substrate 2〇〇 and the first epitaxial layer 204 are scanned and irradiated; S703, the base substrate 2〇〇 and the first epitaxial layer 2〇4 after laser irradiation are immersed in the solution to remove the base substrate 2〇 The tantalum and the first carbon nanotube layer 2〇2' form the nanostructured substrate 3〇. In step S701, the polishing method may be a mechanical polishing method or a chemical polishing method to smooth the surface of the base substrate 200 where the first epitaxial layer 204 is not grown to reduce the scattering of laser light in subsequent laser irradiation. The cleaning may wash the surface of the base substrate 200 where the first epitaxial layer 204 is not grown by hydrochloric acid, sulfuric acid, or the like, thereby removing metal impurities, oil stains, and the like on the surface of the base substrate 200. In step S702, the laser is incident from the polished surface of the base substrate 200, and the incident direction is substantially perpendicular to the polished surface of the base substrate 200, that is, substantially perpendicular to the base substrate 2 and the first epitaxial layer. 204 interface. The wavelength of the laser is not limited and may be selected according to the material of the buffer layer 2045 and the base substrate 200. Specifically, the energy of the laser is smaller than the band gap energy of the base substrate 200 and larger than the band gap energy of the buffer layer 2045, so that the laser can pass through the base substrate 200 to reach the buffer layer 2045' at the buffer layer 2045 and the base substrate 200. Laser stripping at the interface. The buffer layer 2045 at the interface strongly absorbs the laser light, so that the temperature of the buffer layer 2045 at the interface is rapidly increased to decompose. In the present embodiment, 100112869 Form No. 1010101 Page 31/51 Page 1002021432-0 201239948 Epitaxial layer Π) 4 is (10), its band gap energy is 3.3 ev; the base is just sapphire, and its band gap energy is 9.9 ev; The laser is a KrF laser, and the emitted laser has a wavelength of 248, the energy is 5 ev, the width is 2 〇 to 40 ns, the energy density is 400 〇〇 6 〇〇 mj/cm 2 , and the spot shape is square. The focus size is 0·5m_. 5_; the scanning position starts from the edge position of the base substrate 200, and the scanning step size is 〇5 mm/s. During the scanning process, the (four) low buffer layer 2045 grown in step S33 of step S30 starts to be decomposed into (ja and N2. It can be understood that the pulse width, energy density, spot shape, focus size, and scanning The step size can be adjusted according to actual needs; the laser having a corresponding wavelength can be selected according to the buffer layer 2〇45 to have a strong absorption effect on the laser of a specific wavelength [0112] [0114] Since the low temperature buffer layer 2045 is opposite to the above The laser of the wavelength has a strong absorption effect, and therefore, the temperature of the low temperature buffer layer 2〇45 is rapidly increased to be decomposed; and the first epitaxial layer 2〇4 has weak or no absorption of the laser light of the above wavelength, Therefore, the first epitaxial layer 2〇4 is not destroyed by the laser. It can be understood that lasers of different wavelengths can be selected for different buffer layers 2〇45, so that the low temperature buffer layer 2 〇45 5 has a misalignment. Strong absorption. The laser irradiation process is carried out in a vacuum environment or a protective gas atmosphere to prevent the carbon nanotubes from being destroyed by oxidation during laser irradiation. It is an inert gas such as nitrogen, helium or argon. In step S703, the base substrate 2〇〇 after the laser irradiation, the first epitaxial layer 204, and the first carbon nanotube layer 2〇2 disposed therebetween may be immersed. 'In an acidic solvent' to remove the decomposed Ga, thereby removing the peeling of the base substrate 2〇〇 from the first epitaxial layer 204, removing the base substrate 10042869 in the peeling. Form No. A0101 Page 32 of 51 page 1002021432 -0 201239948 [0115] 〇 [0117] [0118] [0119] [0120] 100112869 2〇〇¥ 'The first carbon nanotube layer 202 applied to the surface of the base substrate 2〇〇 will also be The nano-structured substrate 30 having the nano-structures shown in Fig. u having a nano-structure is obtained. The solvent may be a solvent such as hydrochloric acid, sulfuric acid or nitric acid. Due to the presence of the first carbon nanotube layer 202, the stress between the first epitaxial layer 204 and the base substrate 200 during the growth process is reduced, and the base substrate 2 is made during the laser irradiation to peel off the base substrate 200. The peeling of the cockroach is much easier 'also reduces the extension The present invention provides a method for epitaxially growing a nano-scale microstructured substrate by using the carbon nanotube layer as a mask on the epitaxial growth surface growth epitaxial layer. The method directly forms a hole-like microstructure on the surface of the substrate by setting the nanocarbon tube layer as a mask, and has a simple process and low cost. The method of the prior art (10) and nano imprinting is overcome, and the manufacturing method is complicated. The technical problem of the first method is as follows: The first epitaxial structure prepared by the method of the present invention is applied to the surface of the epitaxial layer when the epitaxial structure is applied to manufacture the light-emitting body, thereby effectively improving the light-emitting efficiency of the south-emitting diode without The substrate is advantageous for simplifying the manufacturing method. The carbon nanotube layer is a self-supporting structure and can be directly laid on the surface of the substrate. The method is simple and is advantageous for large-scale industrial manufacturing. - Fourth 'The method of the present invention can realize a structure in which a plurality of nano-scale microporous structures are distributed in a plane or in a plurality of planes parallel to each other and spaced apart, in the field of semiconductor technology, etc. Form No. A0101 Page 33 of 51 1002021432-0 201239948 The plural field has broad application prospects. [0128] [0128] [0130] [0130] 100112869 In summary, the present invention has indeed met the requirements of the invention patent, and patented according to law. Application. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a manufacturing method of a method for preparing a nano-micro structure substrate according to a first embodiment of the present invention. 2 is a scanning electron micrograph of a carbon nanotube film used in the present invention. Fig. 3 is a schematic view showing the configuration of a carbon nanotube segment in the carbon nanotube film of Fig. 2. Figure 4 is a scanning electron micrograph of a carbon nanotube film disposed at a plurality of layers in the present invention. Figure 5 is a scanning electron micrograph of a non-twisted nanocarbon line employed in the present invention. Figure 6 is a scanning electron micrograph of a twisted nanocarbon line used in an embodiment of the present invention. Fig. 7 is a flow chart showing a manufacturing method of a method for preparing a nano-micro structure substrate according to a second embodiment of the present invention. FIG. 8 is a schematic diagram of a growth process of an epitaxial layer according to a second embodiment of the present invention. Figure 9 is a scanning electron micrograph of a cross section of an epitaxial structure prepared in accordance with a second embodiment of the present invention. Form No. A0101 Page 34 of 51 1002021432-0 201239948 [0010] FIG. 10 is a transmission electron micrograph at an epitaxial construction interface prepared in accordance with a second embodiment of the present invention. Figure 11 is a flow chart showing a method of fabricating a method for fabricating a nano-microstructured substrate according to a third embodiment of the present invention. [Explanation of main component symbols] Nano-structured substrate: 10, 20, 30 [0134] Substrate: 100 [0136] Base substrate: 200 Epitaxial growth surface: 101, 201 [0137] Nano carbon Tube layer: 102 [0138] Trench: 103 [0139] Epitaxial layer: 1 0 4 [0140] Epitaxial grain: 1042 [0141] 〇 Microstructure: 108, 208 [0142] First carbon nanotube layer: 202 Second carbon nanotube layer: 207 [0144] Hole: 203 [0145] First epitaxial layer: 204 [0146] Second epitaxial layer: 209 [0147] Opening: 105, 205 100112869 Form No. A0101 No. 35 Page / Total 51 pages 1002021432-0 201239948 [0148] Surface: 206 [0149] Epitaxial grain: 2042 [0150] Epitaxial film: 2044 [0151] Buffer layer: 2045 [0152] Carbon nanotube segment: 143 [0153] Carbon nanotubes: 145 100112869 Form number A0101 Page 36 / Total 51 pages 1002021432-0

Claims (1)

201239948 VII. Patent application scope: A preparation method for a nano-micro structure substrate, comprising the steps of: providing a substrate having an epitaxial growth surface supporting epitaxial layer growth on the epitaxial growth surface of the substrate a carbon nanotube layer; an epitaxial layer vertically grown on the epitaxial growth surface of the substrate, the epitaxial layer being a discontinuous epitaxial layer separated by a carbon nanotube in the carbon nanotube layer; and removing the nanocarbon The tube layer is obtained as a substrate having a nano microstructure on its surface. The method for producing a nano-microstructure substrate according to the invention of claim 2, wherein the epitaxial layer is a homoepitaxial layer. 3. The method of claim 4, wherein the substrate is a single crystal structure, and the material of the substrate is SOI, LiGa〇2, LiAl〇2. , Al2〇3, Si, GaAs, GaN, GaSb, InN, InP, InAs, InSb, A1P, AlAs, AlSb, AIN, GaP, SiC, SiGe, GaMnAs, GaAlAs, GalnAs, GaAIN, GalnN, AlInN, GaAsP, InGaN , AlGalnN, ❹ AlGaInP, GaP: Zn or GaP: N. 4. The method for preparing a nano-microstructure substrate according to the invention of claim 1, wherein the method of providing a carbon nanotube layer on the epitaxial growth surface of the substrate is a carbon nanotube film or a naphthalene film. The carbon carbon pipeline is directly laid on the epitaxial growth surface of the substrate as a carbon nanotube layer. 5. The method of claim 4, wherein the carbon nanotube layer has a plurality of openings therein, the epitaxial layer passing through the epitaxial growth surface of the substrate The exposed portion of the opening grows vertically. 100112869 Form No. A0101 Page 37/51 Page 1002021432-0 201239948 8 10 11 As in the preparation of the nano-structured substrate according to Item 5 of the patent application, when the epitaxial layer is grown, it is substantially perpendicular to the The base is nucleated in the long face direction and epitaxially grown to form a plurality of epitaxial grains. The method for preparing a nano-micro-structure substrate, wherein the epitaxial growth surface of the substrate is a molecularly smooth surface, and the impurity is further removed before the epitaxial layer is grown, as described in claim i. step. The epitaxial growth surface of the substrate is washed, as in the patent application scope, item i, and has a preparation method of a nano-micro structure substrate, wherein the nano carbon camp includes an organic solvent treatment for epitaxial growth. After the surface, the step of further extending the carbon tube layer to make the carbon nanotube layer more long. The method of claim i, wherein the preparation of the epitaxial layer on the nano-microstructure substrate comprises a molecular beam epitaxy method, a chemical extraction epitaxy, a reduced-pressure epitaxial liquid deposition external material, Metal h, low temperature outside the county, selective epitaxy method, organic vapor phase epitaxy method, Zhao vacuum chemical vapor deposition method, hydride gas phase, U-realization, pore-phase method, or a plurality of species. ', M and metal organic chemical vapor deposition as claimed in the scope of the second paragraph &amp; square half, and by _ <the preparation of nano-microstructured substrate, the nano- 碜, 罄 罄, good ^ The addition method is an ion etching method, an ultrasonic method, a laser heating method or a connection with a gentleman, a cooked furnace heating method. Method for preparing micro-structure substrate - g-substrate, the substrate has an outer material (four) epitaxial growth surface f, a first carbon nanotube layer is disposed on the epitaxial growth surface of the substrate; and a continuous growth surface is grown on the epitaxial growth surface of the substrate - an epitaxial layer covering the first carbon nanotube layer; 100112869 Form No. A0101 Page 38 of 51 1002021432-0 201239948 12 . G 13 . 14 . G 15 100112869 Setting the surface of the continuous first epitaxial layer a second carbon nanotube layer; vertically growing on the surface of the continuous first epitaxial layer - a second epitaxial layer, the second epitaxial layer being a discontinuous epitaxial spacer separated by a carbon nanotube in the carbon nanotube layer And removing the first carbon nanotube layer disposed on the surface of the continuous first epitaxial layer to obtain a substrate having a nano microstructure. The method for preparing a nano-micro structure substrate according to claim 11, wherein the material of the second epitaxial layer is SGI, LiGa〇2, LiA102, Al2〇3, Si, GaAs, GaN, GaSb. , InN, InP, InAs, InSb, A1P, AlAs, AlSb, A1N, GaP, Sic, SiGe, GaMnAs, GaAlAs, GalnAs, GaA1N, GaInN, AlInN, GaAsP, InGaN, AlGalnN, AlGalnP, GaP: Zn or GaP: N . The method of fabricating a nano-microstructure substrate according to claim 11, wherein the first epitaxial layer is a hetero-epitaxial layer, and the second epitaxial layer is a homoepitaxial layer. The method for preparing a nano-micro structure substrate according to claim 11, wherein the method for growing the first epitaxial layer comprises the following steps: nucleating along an epitaxial growth surface substantially perpendicular to the substrate And epitaxially growing to form a plurality of epitaxial grains; the plurality of epitaxial grains are epitaxially grown along a direction substantially parallel to an epitaxial growth surface of the substrate to form a continuous epitaxial film; and the epitaxial film is substantially perpendicular to the The epitaxial growth plane of the substrate grows to form a continuous first epitaxial layer. A method for fabricating a nano-microstructured substrate, comprising the steps of: Form No. A0101, Page 39/51, 1002021432-0 201239948, providing a substrate having an epitaxial growth surface supporting epitaxial layer growth on the substrate a carbon nanotube layer is disposed on the epitaxial growth surface; a continuous epitaxial layer is grown on the epitaxial growth surface of the substrate and covers the carbon nanotube layer; and a carbon nanotube layer is disposed on the surface of the continuous epitaxial layer Forming an epitaxial layer perpendicularly on a surface of the continuous epitaxial layer, the epitaxial layer being a discontinuous epitaxial layer separated by a carbon nanotube in the carbon nanotube layer; removing the surface of the continuous epitaxial layer a carbon nanotube layer; peeling off the substrate and the carbon nanotube layer provided on the epitaxial growth surface of the substrate to obtain a substrate having a nano-micro structure. The method for producing a nano-microstructured substrate according to claim 15, wherein the method of peeling off the substrate is a laser irradiation method, a corrosion method or a temperature difference separation method. The method for producing a nano-microstructure substrate according to claim 15, wherein the laser lift-off method comprises the steps of: polishing and cleaning a surface of the substrate on which the epitaxial layer is not grown; The substrate is placed on a platform and the substrate is scanned by laser; the laser-irradiated substrate is immersed in a solution for etching to peel the substrate from the continuous epitaxial layer. 100112869 Form No. A0101 Page 40 of 51 1002021432-0