CN113066908A - Graph complementary composite substrate, preparation method and LED epitaxial wafer - Google Patents
Graph complementary composite substrate, preparation method and LED epitaxial wafer Download PDFInfo
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- CN113066908A CN113066908A CN202110276193.3A CN202110276193A CN113066908A CN 113066908 A CN113066908 A CN 113066908A CN 202110276193 A CN202110276193 A CN 202110276193A CN 113066908 A CN113066908 A CN 113066908A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/20—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
- H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers
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Abstract
The embodiment of the invention discloses a graph complementary composite substrate, a preparation method and an LED epitaxial wafer. The preparation method of the figure complementary composite substrate comprises the following steps: providing a flat substrate; patterning the flat substrate by using a first mask plate, and forming a plurality of first pattern microstructures on the first surface of the flat substrate; forming a heterogeneous material layer on the first surface of the flat substrate; patterning the heterogeneous material layer by using a second mask to form a plurality of second pattern microstructures; the first pattern microstructure and the second pattern microstructure are respectively a convex microstructure or a concave microstructure; the vertical projections of the first pattern microstructure and the second pattern microstructure on the first surface of the flat substrate do not overlap. The invention can solve the problem that the existing patterned substrate can not meet the requirements of the LED chip, can reduce the stress of the epitaxial layer and improve the growth quality of the epitaxial crystal; meanwhile, the light emitting efficiency of light is increased, and the internal quantum efficiency and the external quantum extraction rate of the LED chip are improved.
Description
Technical Field
The embodiment of the invention relates to the technical field of semiconductors, in particular to a graph complementary composite substrate, a preparation method and an LED epitaxial wafer.
Background
As is known, in the current Patterned Substrate production, a pattern with periodic arrangement is manufactured on the surface of an epitaxial Substrate by a Patterned Sapphire Substrate (PPS) process technology, a yellow light station is exposed through a mask once, and then etched through Inductively Coupled Plasma (ICP), the mask pattern is transferred to the surface of a wafer, so that a pattern corresponding to the mask arrangement is obtained on the surface of the Substrate, and epitaxial growth parameters are controlled to grow the gan with higher quality by controlling the pattern specification of the Substrate surface. However, with the rapid development of the LED display industry, the requirements of the consumer market on the product quality and brightness are higher and higher, and the conventional method for controlling the specification of the micro-nano patterned substrate is difficult to meet the requirements of the LED chip.
Disclosure of Invention
The invention provides a graph complementary composite substrate, a preparation method and an LED epitaxial wafer, which are used for realizing novel graphical combination, reducing epitaxial stress, improving the internal quantum efficiency and the external quantum extraction rate of an LED and improving the quality of the graphical substrate.
In a first aspect, an embodiment of the present invention provides a method for preparing a composite substrate with complementary patterns, including:
providing a flat substrate;
patterning the flat substrate by using a first mask plate, and forming a plurality of first pattern microstructures on the first surface of the flat substrate;
forming a heterogeneous material layer on the first surface of the flat substrate;
patterning the heterogeneous material layer by using a second mask to form a plurality of second pattern microstructures; the first pattern microstructure and the second pattern microstructure are respectively a convex microstructure or a concave microstructure; the first pattern microstructure and the second pattern microstructure do not overlap with each other in vertical projection on the first surface of the flat substrate.
Optionally, patterning the flat substrate by using a first mask to form a plurality of first pattern microstructures on a first surface of the flat substrate, including:
forming a first photoresist layer on the first surface of the flat substrate;
exposing and developing the first photoresist layer by using the first mask plate to form a first photoresist mask;
etching the first surface of the flat substrate through the first photoresist mask to form a plurality of first pattern microstructures;
patterning the heterogeneous material layer by using a second mask to form a plurality of second pattern microstructures, wherein the second pattern microstructures comprise:
forming a second photoresist layer on the second surface of the heterogeneous material layer;
exposing and developing the second photoresist layer by using the second mask plate to form a second photoresist mask;
etching the heterogeneous material layer through the second photoresist mask to form a plurality of second pattern microstructures;
the first photoresist layer and the second photoresist layer are respectively positive photoresist or negative photoresist, and the first mask plate and the second mask plate respectively comprise a plurality of shading patterns or a plurality of opening patterns.
Optionally, both the first photoresist layer and the second photoresist layer adopt positive photoresist or negative photoresist; the first pattern microstructure and the second pattern microstructure are both a convex microstructure or a concave microstructure; multiplexing the first mask plate into the second mask plate;
exposing and developing the second photoresist layer by using the second mask to form a second photoresist mask, comprising:
shifting the first mask plate relative to the flat substrate;
and exposing and developing the second photoresist layer by using the shifted first mask plate to form a second photoresist mask.
Optionally, patterning the flat substrate by using a first mask, and after forming a plurality of first pattern microstructures on the first surface of the flat substrate, the method further includes:
and cleaning and drying the first surface of the patterned flat sheet substrate in sequence by using a mixed solution of concentrated sulfuric acid and hydrogen peroxide and deionized water.
Optionally, the second pattern microstructure is a convex microstructure; the bottom surface of the second pattern microstructure and the bottom surface of the first pattern microstructure are positioned on the same plane.
Optionally, the first pattern microstructure is a convex microstructure; and enabling a first plane to be vertical to the first surface of the flat substrate, enabling a first direction to be vertical to the first surface of the flat substrate, and enabling the vertical projection of the first pattern microstructure and the second pattern microstructure on the first plane to at least partially overlap in the first direction.
Optionally, the first patterned microstructures and the second patterned microstructures are periodically arranged along rows and/or columns in a perpendicular projection on the first surface of the flat substrate.
Optionally, the vertical projections of the plurality of first pattern microstructures on the first surface of the flat substrate are uniformly arranged, and/or the vertical projections of the plurality of second pattern microstructures on the first surface of the flat substrate are uniformly arranged.
Optionally, the shapes of the protruding microstructures and the recessed microstructures include at least one of a cylinder, a cone, a truncated cone, a polygon prism, a polygon pyramid, a polygon frustum, and a segment, or the protruding microstructures and the recessed microstructures are respectively strip-shaped protrusions and strip-shaped recesses.
Optionally, the maximum size of the perpendicular projection of each of the first pattern microstructure and the second pattern microstructure on the first surface of the flat substrate ranges from 0.1 um to 6um, and the height of each of the first pattern microstructure and the second pattern microstructure ranges from 0.1 um to 3 um.
In a second aspect, an embodiment of the present invention further provides a composite substrate with complementary patterns, which is prepared by the preparation method according to any one of the first aspect, and the composite substrate with complementary patterns includes:
the first surface of the substrate is integrally connected with a plurality of first graphic microstructures;
a plurality of second pattern microstructures formed on the first surface of the substrate;
the first pattern microstructure and the second pattern microstructure are respectively a convex microstructure or a concave microstructure; the first pattern microstructure and the second pattern microstructure do not overlap with each other in vertical projection on the first surface of the flat substrate.
In a second aspect, the embodiment of the present invention further provides an LED epitaxial wafer, which includes the composite substrate with complementary patterns as described in the second aspect, and further includes an epitaxial layer on the composite substrate with complementary patterns.
In the embodiment of the invention, a flat substrate is patterned by utilizing a first mask plate to form a plurality of first pattern microstructures, then a heterogeneous material layer is formed on the flat substrate, and then the heterogeneous material layer is patterned by utilizing a second mask plate to form a plurality of second pattern microstructures; and the vertical projections of the first pattern microstructure and the second pattern microstructure on the first surface of the flat substrate are not overlapped with each other, so that the first pattern microstructure and the second pattern microstructure are complementary on the surface of the flat substrate to form a novel pattern combination of the two pattern microstructures, and the quality of the patterned substrate can be improved by reasonably designing the material, shape, size, arrangement mode, arrangement density and the like of the first pattern microstructure and the second pattern microstructure. The embodiment of the invention can solve the problem that the existing patterned substrate can not meet the requirements of the LED chip, provides a new way for improving the quality of the patterned substrate, can reduce the stress of the epitaxial layer, reduces the lattice defect and improves the growth quality of the epitaxial crystal; the propagation direction of light in the substrate can be improved through the combination of the two patterns, and the light-emitting efficiency of the light is increased, so that the internal quantum efficiency and the external quantum extraction rate of the LED chip are improved, and the light-emitting brightness of the LED chip is further improved.
Drawings
FIG. 1 is a flow chart of a method for fabricating a composite substrate with complementary patterns according to an embodiment of the present invention;
FIG. 2 is a flow chart of a structure of a method of fabricating the complementary composite substrate shown in FIG. 1;
FIG. 3 is a top view of a patterned complementary composite substrate formed by the fabrication method of FIG. 2;
FIG. 4 is a flow chart of another embodiment of a method for fabricating a composite substrate with complementary patterns;
FIG. 5 is a schematic cross-sectional view of another complementary patterned composite substrate and its mask according to an embodiment of the present invention;
FIG. 6 is a schematic cross-sectional view of another complementary patterned composite substrate and its mask according to an embodiment of the present invention;
FIG. 7 is a cross-sectional view of another complementary patterned composite substrate and its reticle according to an embodiment of the present invention;
FIGS. 8 and 9 are top views of two further complementary patterned composite substrates provided by embodiments of the present invention;
FIGS. 10 and 11 are top views of two further complementary patterned composite substrates provided by embodiments of the present invention;
FIG. 12 is a perspective view of another embodiment of a complementary composite substrate with patterns according to the present invention;
FIG. 13 is a schematic diagram illustrating another exemplary method for fabricating a complementary patterned composite substrate according to embodiments of the present invention;
fig. 14 is a structural flow chart of a method of making the pattern complementary composite substrate shown in fig. 13.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention. It should be further noted that, for the convenience of description, only some of the structures related to the present invention are shown in the drawings, not all of the structures.
Fig. 1 is a flowchart of a method for manufacturing a composite substrate with complementary patterns according to an embodiment of the present invention, fig. 2 is a flowchart of a structure of the method for manufacturing the composite substrate with complementary patterns shown in fig. 1, fig. 3 is a top view of the composite substrate with complementary patterns manufactured by the method for manufacturing shown in fig. 2, and referring to fig. 1 to fig. 3, the method for manufacturing the composite substrate with complementary patterns includes:
s110, providing a flat substrate 10;
referring to fig. 2 a), the flat substrate 10 is a sapphire flat, or may be a substrate formed of silicon, silicon carbide, or the like. The flat substrate surface needs to be polished and cleaned before subsequent steps are performed to ensure surface flatness and cleanliness.
S120, patterning the flat substrate 10 by using a first mask 21, and forming a plurality of first pattern microstructures 11 on the first surface 101 of the flat substrate 10;
referring to fig. 2 b), the first patterned microstructure 11 is formed by patterning a flat substrate, and thus is structurally inseparable from the flat substrate 10. It can be understood that, as shown in b) of fig. 2, when the first patterned microstructure 11 is a raised microstructure, the material thereof is the same as that of the flat substrate. If the first patterned microstructure 11 is a recessed microstructure, the material of the first patterned microstructure 11 depends on the material filled therein.
S130, forming a heterogeneous material layer 30 on the first surface 101 of the flat substrate 10;
referring to c) of fig. 2, the heterogeneous material is substantially a material different from the substrate and the epitaxial layer, and may be an oxide, nitride, carbide, or simple substance, and illustratively, the oxide may be SiOx, ZnO, TiOx, TaOx, HfO2, ZrOx, AlOx, GaOx, MgOx, BaOx, InOx, SnO2, LiOx, CaOx, CuOx, IrOx, RhOx, CdGeO, InGaZnO, ZnRhO, GaIn2O4, LaO, laco, etc., the nitride may be SiNx, TiN, WN, CN, BN, LiN, TiON, SiON, CrN, CrNO, etc., the carbide may be SiC, HfC, ZrC, WC, TiC, CrC, etc., and the simple substance may be diamond, Si, Mo, Cu, Fe, Ag, Wu, Ni, Al, etc. The heterogeneous material layer 30 can be formed by different deposition processes such as chemical vapor deposition or physical vapor deposition, which are not limited herein. The thickness of the foreign material layer 30 ranges from 1.0 to 3.0 μm. It can be understood that, when the first patterned microstructure 11 in the step S120 is a recessed microstructure, the material thereof is the heterogeneous material filled therein.
S140, patterning the heterogeneous material layer 30 by using a second mask 22 to form a plurality of second pattern microstructures 12; the first pattern microstructure 11 and the second pattern microstructure 12 are respectively a convex microstructure or a concave microstructure; the first patterned microstructure 11 and the second patterned microstructure 12 do not overlap each other in perpendicular projection on the first surface 101 of the flat substrate 10.
Referring to fig. 2 d) and fig. 3, the second patterned microstructure 12 is patterned from the heterogeneous material layer 30, and thus, the material thereof depends on the shape of the second patterned microstructure 12 and the material filled thereon. Similarly, as shown in d) of fig. 2, when the second pattern microstructure 12 is a protruding microstructure, the material thereof is a heterogeneous material. If the second pattern microstructure 12 is a recessed microstructure, the material is filled therein.
The shapes and the arrangement of the first pattern microstructure 11 and the second pattern microstructure 12 formed in steps S120 and S140 mainly depend on the shapes and the arrangement of the light-shielding patterns or the opening patterns in the first mask 21 and the second mask 22, and a specific forming process of the first pattern microstructure 11 and the second pattern microstructure 12 will be described below. Fig. 4 is a structural flow chart of another method for manufacturing a complementary patterned composite substrate according to an embodiment of the present invention, and referring to fig. 2 and 4, in the manufacturing of the complementary patterned composite substrate, in step S120, a first mask is used to pattern a flat substrate, and a plurality of first patterned microstructures are formed on a first surface of the flat substrate, including:
s121, forming a first photoresist layer 41 on the first surface 101 of the flat substrate 10;
referring to b) of fig. 4, the first photoresist layer 41 may be formed using a positive photoresist or a negative photoresist by a coating process such as spray coating, spin coating, etc.
S122, exposing and developing the first photoresist layer 41 by using the first mask 21 to form a first photoresist mask 410;
in the above step, the thickness of the first photoresist layer 41 may be set to 0.5 to 3.0 μm, and the exposure time may be 50 to 500 msec.
S123, etching the first surface 101 of the flat substrate 10 through the first photoresist mask 410 to form a plurality of first pattern microstructures 11;
referring to fig. 4 c) and d), the first photoresist mask 410 is substantially a photoresist pattern formed on the flat substrate 10, and it can be understood by those skilled in the art that if a protruding microstructure is formed by etching using the first photoresist mask 410, the first photoresist mask 410 is substantially a plurality of photoresist columns; if the first photoresist mask 410 is used to etch a recessed microstructure, the first photoresist mask 410 is substantially a photoresist layer including a plurality of openings. In the present embodiment, the first mask 21 may include a plurality of light-shielding patterns or a plurality of opening patterns according to the positive and negative characteristics of the photoresist used for the first photoresist layer 41 and the roughness of the microstructure to be formed, which will not be described in detail herein.
With continued reference to fig. 2 and 4, in the preparation of the composite substrate with complementary patterns, step S140, patterning the heterogeneous material layer by using a second mask to form a plurality of second pattern microstructures, includes:
s141, forming a second photoresist layer 42 on the second surface 302 of the heterogeneous material layer 30;
referring to f) of fig. 4, similarly, the second photoresist layer 42 may also be formed by a coating process such as spray coating, spin coating, etc. using a positive photoresist or a negative photoresist.
S142, exposing and developing the second photoresist layer 42 by using the second mask 22 to form a second photoresist mask 420;
in the above step, the thickness of the second photoresist layer 42 is also in the range of 0.5-3.0 μm, and the exposure time is also 50-500 ms.
S143, etching the heterogeneous material layer 30 through the second photoresist mask 420 to form a plurality of second pattern microstructures 12;
referring to g) and h) of fig. 4, similarly, the second photoresist mask 420 may be a plurality of photoresist columns, or a photoresist layer including a plurality of openings, the photoresist pattern of which is a convex microstructure or a concave microstructure depending on the second pattern microstructure 12. In addition, the second mask 22 may also include a plurality of light-shielding patterns or a plurality of opening patterns according to actual situations.
It should be noted that the etching processes for the flat substrate 10 and the foreign material layer 30 in steps S123 and S143 may be implemented by using an ICP plasma etching process. The embodiment of the invention provides specific process parameters for the ICP plasma etching process. Specifically, the power of the upper electrode of the etching machine can be set to 200-3Flow rate of 30-150sccm, CHF3The flow is 0-25sccm, the etching temperature is-5-50 ℃, the helium pressure is 1-10mtorr, and the etching time is 5-60 minutes.
As can be seen from the above, in the embodiment of the present invention, the first mask is used to pattern the flat substrate to form a plurality of first pattern microstructures, then a heterogeneous material layer is formed on the flat substrate, and the second mask is used to pattern the heterogeneous material layer to form a plurality of second pattern microstructures; and the vertical projections of the first pattern microstructure and the second pattern microstructure on the first surface of the flat substrate are not overlapped with each other, so that the first pattern microstructure and the second pattern microstructure are complementary on the surface of the flat substrate to form a novel pattern combination of the two pattern microstructures, and the quality of the patterned substrate can be improved by reasonably designing the material, shape, size, arrangement mode, arrangement density and the like of the first pattern microstructure and the second pattern microstructure. Specifically, the embodiment of the invention can solve the problem that the existing patterned substrate cannot meet the requirements of an LED chip, provides a new way for improving the quality of the patterned substrate, and can provide various growth crystal orientation choices for epitaxial growth through the combination of two patterns, the growth rates of the epitaxy along the surface of the pattern are different, the dislocation density of the epitaxial layer is reduced, and the extension of defects to the epitaxial surface can be effectively inhibited, so that the stress of the epitaxial layer can be reduced, the lattice defects can be reduced, the growth quality of the epitaxial crystal can be improved, the non-radiative transition can be reduced, the non-radiative recombination center can be reduced, and the quantum efficiency in the LED chip can be improved; in addition, the propagation direction of light in the substrate can be improved through the combination of the two patterns, the light scattering effect of the substrate to light is effectively increased, and the light emitting efficiency of the light is increased, so that the external quantum extraction rate of the LED chip is improved, and the light emitting brightness of the LED chip is further improved.
As can be seen from the above specific preparation process, in the embodiment of the present invention, the shapes and the arrangement of the first pattern microstructure 11 and the second pattern microstructure 12 are determined by the first mask 21 and the second mask 22, and in the specific preparation process, the positive and negative polarities of the photoresist are also considered in the mask patterns of the first mask 21 and the second mask 22, so the mask patterns of the first mask 21 and the second mask 22 are exemplified below.
First, referring to fig. 3 and 4, taking an example that the first photoresist layer 41 and the second photoresist layer 42 in the manufacturing process both use positive photoresists, and the first pattern microstructure 11 and the second pattern microstructure 12 both use convex microstructures as examples, in the embodiment of the present invention, the first mask 21 includes a plurality of first light-shielding patterns 211, the second mask 22 includes a plurality of second light-shielding patterns 212, and when the first mask 21 and the second mask 22 are respectively aligned with the flat substrate 10, vertical projections of the plurality of first light-shielding patterns 211 and the plurality of second light-shielding patterns 212 on the plane of the flat substrate 10 do not overlap each other.
It can be understood that, when the photoresist is a positive photoresist, after the exposure and development step, the photoresist region blocked by the light-shielding pattern remains, a plurality of photoresist columns are formed on the flat substrate 10, and after the etching step, the flat substrate and the heterogeneous material layer respectively form the protruding microstructures. Obviously, the positions and shapes of the protruding first pattern microstructure 11 and the protruding second pattern microstructure 12 depend on the positions and shapes of the photoresist columns, that is, the positions and shapes of the light shielding patterns on the first mask and the second mask.
Fig. 5 is a schematic cross-sectional view of another complementary composite substrate with patterns and a mask thereof according to an embodiment of the present invention, and referring to fig. 5, in another embodiment of the present invention, a positive photoresist is used for both the first photoresist layer and the second photoresist layer in the manufacturing process, and both the first pattern microstructure 11 and the second pattern microstructure 12 are recessed microstructures, so that the first mask 21 includes a plurality of first opening patterns 201, the second mask 22 includes a plurality of second opening patterns 202, and when the first mask 21 and the second mask 22 are respectively aligned with the flat substrate 10, vertical projections of the plurality of first opening patterns 201 and the plurality of second opening patterns 202 on the plane of the flat substrate 10 do not overlap with each other.
When the photoresist is a positive photoresist, after the exposure and development steps, the photoresist region exposed by the opening pattern is removed, a plurality of openings are formed on the photoresist layer and the flat substrate or the heterogeneous material layer is exposed, and after the etching step, a concave microstructure is formed on the surface of the flat substrate or the heterogeneous material layer. Similarly, the positions and the shapes of the first pattern microstructure and the second pattern microstructure of the recess depend on the positions and the shapes of the openings of the photoresist layer, namely the positions and the shapes of the patterns of the openings of the first mask and the second mask.
Fig. 6 is a schematic cross-sectional view of another complementary composite substrate and its mask according to an embodiment of the present invention, and referring to fig. 6, when both the first photoresist layer and the second photoresist layer in the manufacturing process use positive photoresists, the first pattern microstructure 11 is a convex microstructure, and the second pattern microstructure 12 is a concave microstructure, the first mask 21 includes a plurality of first light-shielding patterns 211, the second mask 22 includes a plurality of second opening patterns 202, and when the first mask 21 and the second mask 22 are respectively aligned with the flat substrate 10, vertical projections of the plurality of first light-shielding patterns 211 and the plurality of second opening patterns 202 on the plane of the flat substrate 10 do not overlap each other.
It can be understood that, after the exposure and development step, the region on the first photoresist layer 41 shielded by the first light-shielding pattern 211 on the first mask 21 is remained, a plurality of photoresist columns are formed on the flat substrate 10, and after the etching step, the protruding microstructure, i.e. the first pattern microstructure 11, is formed on the flat substrate 10; after the exposure and development step, the region of the second photoresist layer 42 exposed by the second opening pattern 202 on the second mask 22 is removed, a plurality of openings are formed on the second photoresist layer 42 to expose the heterogeneous material layer, and after the etching step, a recessed microstructure, i.e., the second pattern microstructure 12, is formed on the surface of the heterogeneous material layer. Therefore, the positions and shapes of the protruding first patterned microstructures 11 and the recessed second patterned microstructures 12 depend on the positions and shapes of the first light-shielding pattern 211 on the first mask 21 and the second opening pattern 202 on the second mask 22.
Fig. 7 is a cross-sectional view of another complementary composite substrate and a mask thereof according to an embodiment of the present invention, and referring to fig. 7, when both the first photoresist layer and the second photoresist layer in the manufacturing process use positive photoresists, the first pattern microstructures 11 are recessed microstructures, and the second pattern microstructures 12 are raised microstructures, the first mask 21 includes a plurality of first opening patterns 201, the second mask 22 includes a plurality of second light-shielding patterns 212, and when the first mask 21 and the second mask 22 are respectively aligned with the flat substrate 10, vertical projections of the plurality of first opening patterns 201 and the plurality of second light-shielding patterns 212 on the plane of the flat substrate 10 do not overlap each other.
It can be understood that, after the exposure and development step, the areas of the first photoresist layer 41 exposed by the first opening pattern 201 on the first mask 21 are removed, a plurality of openings are formed on the first photoresist layer 41 and the flat substrate is exposed, and after the etching step, the surface of the heterogeneous material layer forms a recessed microstructure, i.e., the first pattern microstructure 11; after the exposure and development step, the areas of the second photoresist layer 42 covered by the second light-shielding pattern 212 on the second mask 22 remain, and a plurality of photoresist columns are formed on the heterogeneous material layer, which forms a plurality of protruding microstructures, i.e., the second pattern microstructures 12, after the etching step. Therefore, the positions and shapes of the recessed first pattern microstructures 11 and the raised second pattern microstructures 12 depend on the positions and shapes of the first opening pattern 201 on the first mask 21 and the second light-shielding pattern 212 on the second mask 22.
Therefore, when the photoresist layer adopts the positive photoresist and the shading pattern is arranged on the mask plate, the convex microstructure can be formed on the flat substrate or the heterogeneous material layer; when the opening pattern is arranged on the mask plate, the concave microstructure can be formed on the flat substrate or the heterogeneous material layer. Based on the characteristics of the positive photoresist and the negative photoresist, the skilled person can understand that when the photoresist layer adopts the negative photoresist, and the shading graph is arranged on the mask, the concave microstructure can be formed on the flat substrate or the heterogeneous material layer; when the opening pattern is arranged on the mask plate, the raised microstructure can be formed on the flat substrate or the heterogeneous material layer. In summary, those skilled in the art can design the mask pattern according to the desired combination of the concave and convex patterns, and no limitation is made herein. In addition, as for the array in which the first pattern microstructure 11 and the second pattern microstructure 12 form a periodic arrangement, the positions of the first pattern microstructure 11 and the second pattern microstructure 12 are actually complementary, and it can be known from the contrary that the light-shielding pattern or the opening pattern on the first mask is complementary to the light-shielding pattern or the opening pattern on the second mask.
Based on the above, with continued reference to fig. 2 and fig. 7, in a further alternative embodiment of the present invention, the second patterned microstructure 12 may be configured as a protruding microstructure; the bottom surface of the second pattern microstructure 12 and the bottom surface of the first pattern microstructure 11 are positioned on the same plane.
It can be understood that, at this time, the first pattern microstructure 11 and the second pattern microstructure 12 are located on the same side of the same plane or on two opposite sides of the same plane, that is, the first pattern microstructure 11 and the second pattern microstructure 12 are closer to each other in a direction perpendicular to the flat substrate, which can be simply understood as that the first pattern microstructure 11 and the second pattern microstructure 12 are arranged on the same plane. From the angle of reflected light, the surface of the substrate can be changed into a concave-convex shape by the single microstructure, so that the total reflection angle of the light is improved, and the total reflection probability is increased; and a plurality of first figure microstructures 11 and second figure microstructures 12 which are complementary in position on the same plane can avoid light leakage in the transverse direction, so that reflection of more light is realized, and the light extraction efficiency is improved.
With continued reference to fig. 2 and 6, optionally, the first patterned microstructure 11 is a raised microstructure; the first plane is vertical to the first surface 101 of the flat substrate 10, the first direction 1 is vertical to the first surface 101 of the flat substrate 10, and the perpendicular projection of the first pattern microstructure 11 and the second pattern microstructure 12 on the first plane at least partially overlaps in the first direction 1.
In both embodiments, the centers of the first patterned microstructure 11 and the second patterned microstructure 12 are closer in a direction perpendicular to the flat substrate, which can also be understood as the first patterned microstructure 11 and the second patterned microstructure 12 are arranged on the same plane. Therefore, the light can be prevented from leaking in the transverse direction by the position complementation of the first pattern microstructure 11 and the second pattern microstructure 12, so that the reflection of more light is realized, and the light extraction efficiency is improved.
Fig. 8 and 9 are top views of two patterns of complementary composite substrates according to an embodiment of the present invention, and referring to fig. 3, 8 and 9, in the pattern of complementary composite substrates according to the embodiment of the present invention, a plurality of first pattern microstructures 11 and a plurality of second pattern microstructures 12 are arranged in a periodic manner along rows and/or columns in a vertical projection of the first surface 101 of the flat substrate 10.
Further, with continued reference to fig. 3 and 8, in this embodiment, the plurality of second patterned microstructures 12 may be uniformly arranged in a vertical projection on the first surface 101 of the flat substrate 10. Of course, a person skilled in the art may also arrange a plurality of first pattern microstructures 11 in a uniform arrangement in the vertical projection on the first surface 101 of the flat substrate 10, and design the overall arrangement manner and the respective arrangement manner of the first pattern microstructures 11 and the second pattern microstructures 12 according to the angle considerations such as the reflection effect of the first pattern microstructures 11 and the second pattern microstructures 12 on light and the improvement effect on the crystal quality of the epitaxial layer.
Illustratively, the embodiment of the invention also provides two pattern complementary composite substrates. Fig. 10 and 11 are top views of two patterns of complementary composite substrates according to an embodiment of the present invention, and referring to fig. 10, in this embodiment, a first pattern microstructure row composed of a plurality of first pattern microstructures 11 and a second pattern microstructure row composed of a plurality of second pattern microstructures 12 are alternately arranged at row intervals. Referring to fig. 11, in this embodiment, the first pattern microstructures 11 and the second pattern microstructures 12 are alternately arranged in both the row direction and the column direction.
In an embodiment of the present invention, the shape of the optional protruding microstructure and the recessed microstructure includes at least one of a cylinder, a cone, a truncated cone, a polygonal prism, a polygonal pyramid, a polygonal frustum, and a segment. Specifically, in this embodiment, the ranges of the maximum sizes of the vertical projections of the first patterned microstructure and the second patterned microstructure on the first surface of the flat substrate are both 0.1-6um, and the ranges of the heights of the first patterned microstructure and the second patterned microstructure are both 0.1-3 um. Taking the first pattern microstructure 11 and the second pattern microstructure 12 as conical protrusions as an example, the diameters of the bottom surfaces of the first pattern microstructure 11 and the second pattern microstructure 12 can be set within the range of 0.1-6um, and the heights can be set within the range of 0.1-3 um. For the recessed microstructure, it can be understood that the height of the microstructure in this embodiment substantially represents the depth, and the depth of the conical pits can be set within a range of 0.1-3 um.
In addition, in the embodiment of the invention, the protruding microstructures and the recessed microstructures can be strip-shaped protrusions and strip-shaped recesses respectively. Fig. 12 is a perspective view of another complementary patterned composite substrate according to an embodiment of the present invention, and referring to fig. 12, the first patterned microstructure 11 and the second patterned microstructure 12 may be arranged as a plurality of prismatic strips arranged in a periodic manner.
In other embodiments of the present invention, when both the first photoresist layer and the second photoresist layer are made of positive photoresist or negative photoresist, and both the first pattern microstructure and the second pattern microstructure are raised microstructures or recessed microstructures, the first mask can be further configured to be reused as the second mask. Fig. 13 is another method for manufacturing a complementary patterned composite substrate according to an embodiment of the present invention, and fig. 14 is a structural flow chart of the method for manufacturing a complementary patterned composite substrate shown in fig. 13, and referring to fig. 13 and fig. 14, the method specifically includes:
s110, providing a flat substrate 10;
s121, forming a first photoresist layer 41 on the first surface 101 of the flat substrate 10;
s122, exposing and developing the first photoresist layer 41 by using the first mask 21 to form a first photoresist mask 410;
s123, etching the first surface 101 of the flat substrate 10 through the first photoresist mask 410 to form a plurality of first pattern microstructures 11;
s130, forming a heterogeneous material layer 30 on the first surface 101 of the flat substrate 10;
s141, forming a second photoresist layer 42 on the second surface 302 of the heterogeneous material layer 30;
s1421, shifting the first mask 21 relative to the flat substrate 10;
s1422, exposing and developing the second photoresist layer 42 by using the shifted first mask 21 to form a second photoresist mask 420;
s143, etching the heterogeneous material layer 30 through the second photoresist mask 420 to form a plurality of second pattern microstructures 12; the first pattern microstructure 11 and the second pattern microstructure 12 are respectively a convex microstructure or a concave microstructure; the first patterned microstructure 11 and the second patterned microstructure 12 do not overlap each other in perpendicular projection on the first surface 101 of the flat substrate 10.
It can be understood that, when the first photoresist layer and the second photoresist layer adopt the same positive photoresist or negative photoresist, and the first pattern microstructure and the second pattern microstructure are similar convex microstructures or concave microstructures, the mask patterns in the first mask and the second mask are both light-shielding patterns or opening patterns. Based on this, the first pattern microstructure and the second pattern microstructure can be set to have the same shape and arrangement mode, at this time, when the second pattern microstructure is prepared and formed, the first mask can be reused, and in order to realize the position complementation of the first pattern microstructure and the second pattern microstructure, the first mask can be shifted. It can be understood that the displacement distance of the first mask determines the position of the whole second pattern microstructure, and the arrangement of the light-shielding patterns or the opening patterns in the first mask determines the position of each second pattern microstructure.
In addition, in each of the above embodiments, after patterning the flat substrate by using the first mask and forming a plurality of first pattern microstructures on the first surface of the flat substrate, the method further includes:
and cleaning and drying the first surface of the patterned flat substrate in sequence by using a mixed solution of concentrated sulfuric acid and hydrogen peroxide and deionized water.
In particular, concentrated H at 140 ℃ may be used2SO4And H2O2Cleaning for 10-15 minutes in a mixed solution with a volume ratio of 5:1, cleaning for 5-10 minutes by using deionized water at 25 ℃, and finally spin-drying for 3-10 minutes at a high speed to clean the surface of the substrate.
Based on the same inventive concept, the embodiment of the invention also provides a composite substrate with complementary patterns. Referring to fig. 2 and fig. 3, the composite substrate with complementary patterns according to the embodiment of the present invention is prepared by any one of the preparation methods provided in the above embodiments, and specifically includes: the flat substrate comprises a flat substrate 10, wherein a plurality of first graphic microstructures 11 are integrally connected to a first surface 101 of the flat substrate 10; a plurality of second pattern microstructures 12 formed on the first surface 101 of the flat substrate 10; wherein, the first pattern microstructure 11 and the second pattern microstructure 12 are respectively a convex microstructure or a concave microstructure; the first patterned microstructure 11 and the second patterned microstructure 12 do not overlap each other in the perpendicular projection on the first surface 101 of the flat substrate 10.
According to the composite substrate with the complementary pattern, which is provided by the embodiment of the invention, the plurality of first pattern microstructures and the plurality of second pattern microstructures are integrally connected on the flat substrate, and the vertical projections of the first pattern microstructures and the second pattern microstructures on the first surface of the flat substrate are not overlapped with each other, so that the first pattern microstructures and the second pattern microstructures are complementary on the surface of the flat substrate, a novel pattern combination of two pattern microstructures is formed, and the improvement of the quality of the patterned substrate can be realized by reasonably designing the materials, the shapes, the sizes, the arrangement modes, the arrangement density and the like of the first pattern microstructures and the second pattern microstructures. The embodiment of the invention can solve the problem that the existing patterned substrate can not meet the requirements of an LED chip, provides a new way for improving the quality of the patterned substrate, can provide various growth crystal orientation choices for epitaxial growth by combining two patterns, has different growth rates of epitaxy along the surface of the pattern, reduces the dislocation density of the epitaxy layer, and can effectively inhibit the extension of defects to the epitaxy surface, thereby reducing the stress of the epitaxy layer, reducing lattice defects, improving the growth quality of an epitaxy crystal, reducing non-radiative transition, reducing non-radiative recombination centers and improving the quantum efficiency in the LED chip; in addition, the propagation direction of light in the substrate can be improved through the combination of the two patterns, the light scattering effect of the substrate to light is effectively increased, and the light emitting efficiency of the light is increased, so that the external quantum extraction rate of the LED chip is improved, and the light emitting brightness of the LED chip is further improved.
Fig. 13 is a schematic structural diagram of an LED epitaxial wafer according to an embodiment of the present invention, and referring to fig. 13, the LED epitaxial wafer includes any one of the complementary patterned composite substrates 100 according to an embodiment of the present invention and an epitaxial layer 200 formed on the complementary patterned composite substrate 100.
For forming epitaxial layers on heterogeneous microstructures of different materials, different LED epitaxial wafer growth techniques are required, and for the complementary pattern composite substrate 100 provided in the embodiment of the present invention, the epitaxial layer 200 on the LED epitaxial wafer may be a GaN or AlGaN epitaxial layer. The LED epitaxial wafer has the same advantageous effects as the pattern complementary composite substrate 100, because the pattern complementary composite substrate 100 provided in the above embodiment is used.
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious modifications, rearrangements, combinations and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.
Claims (12)
1. A preparation method of a pattern complementary composite substrate is characterized by comprising the following steps:
providing a flat substrate;
patterning the flat substrate by using a first mask plate, and forming a plurality of first pattern microstructures on the first surface of the flat substrate;
forming a heterogeneous material layer on the first surface of the flat substrate;
patterning the heterogeneous material layer by using a second mask to form a plurality of second pattern microstructures; the first pattern microstructure and the second pattern microstructure are respectively a convex microstructure or a concave microstructure; the first pattern microstructure and the second pattern microstructure do not overlap with each other in vertical projection on the first surface of the flat substrate.
2. The method of claim 1, wherein patterning the flat substrate with a first mask to form a plurality of first patterned microstructures on the first surface of the flat substrate comprises:
forming a first photoresist layer on the first surface of the flat substrate;
exposing and developing the first photoresist layer by using the first mask plate to form a first photoresist mask;
etching the first surface of the flat substrate through the first photoresist mask to form a plurality of first pattern microstructures;
patterning the heterogeneous material layer by using a second mask to form a plurality of second pattern microstructures, wherein the second pattern microstructures comprise:
forming a second photoresist layer on the second surface of the heterogeneous material layer;
exposing and developing the second photoresist layer by using the second mask plate to form a second photoresist mask;
etching the heterogeneous material layer through the second photoresist mask to form a plurality of second pattern microstructures;
the first photoresist layer and the second photoresist layer are respectively positive photoresist or negative photoresist, and the first mask plate and the second mask plate respectively comprise a plurality of shading patterns or a plurality of opening patterns.
3. The method for preparing the figure complementary composite substrate according to claim 2, wherein the first photoresist layer and the second photoresist layer are both positive photoresist or negative photoresist; the first pattern microstructure and the second pattern microstructure are both a convex microstructure or a concave microstructure; multiplexing the first mask plate into the second mask plate;
exposing and developing the second photoresist layer by using the second mask to form a second photoresist mask, comprising:
shifting the first mask plate relative to the flat substrate;
and exposing and developing the second photoresist layer by using the shifted first mask plate to form a second photoresist mask.
4. The method for preparing a composite substrate with complementary patterns according to claim 2, wherein the step of patterning the flat substrate by using a first mask and the step of forming a plurality of first pattern microstructures on the first surface of the flat substrate further comprises:
and cleaning and drying the first surface of the patterned flat sheet substrate in sequence by using a mixed solution of concentrated sulfuric acid and hydrogen peroxide and deionized water.
5. The method of claim 1, wherein the second patterned microstructure is a raised microstructure; the bottom surface of the second pattern microstructure and the bottom surface of the first pattern microstructure are positioned on the same plane.
6. The method of manufacturing a pattern complementary composite substrate according to claim 1, wherein the first pattern microstructure is a convex microstructure; and enabling a first plane to be vertical to the first surface of the flat substrate, enabling a first direction to be vertical to the first surface of the flat substrate, and enabling the vertical projection of the first pattern microstructure and the second pattern microstructure on the first plane to at least partially overlap in the first direction.
7. The method of claim 1, wherein the first pattern microstructures and the second pattern microstructures are periodically arranged in rows and/or columns in a perpendicular projection on the first surface of the flat substrate.
8. The method of claim 1, wherein the first patterned microstructures are uniformly arranged in a vertical projection onto the first surface of the flat substrate, and/or wherein the second patterned microstructures are uniformly arranged in a vertical projection onto the first surface of the flat substrate.
9. The method for preparing the figure complementary composite substrate according to claim 1, wherein the shapes of the protruding microstructures and the recessed microstructures comprise at least one of cylindrical shapes, conical shapes, truncated cone-shaped polygonal prisms, polygonal pyramid shapes, polygonal frustum shapes and spherical segment shapes, or the protruding microstructures and the recessed microstructures are strip-shaped protrusions and strip-shaped recesses respectively.
10. The method of claim 1, wherein the first pattern microstructure and the second pattern microstructure both have a maximum dimension in the range of 0.1-6um in a perpendicular projection on the first surface of the flat substrate, and the first pattern microstructure and the second pattern microstructure both have a height in the range of 0.1-3 um.
11. A pattern-complementary composite substrate produced by the production method according to any one of claims 1 to 10, comprising:
the first surface of the substrate is integrally connected with a plurality of first graphic microstructures;
a plurality of second pattern microstructures formed on the first surface of the substrate;
the first pattern microstructure and the second pattern microstructure are respectively a convex microstructure or a concave microstructure; the first pattern microstructure and the second pattern microstructure do not overlap with each other in vertical projection on the first surface of the flat substrate.
12. An LED epitaxial wafer comprising the patterned complementary composite substrate of claim 11, further comprising an epitaxial layer on the patterned complementary composite substrate.
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