CN117199208A - Composite patterned substrate with inflection points on side walls, preparation method and LED epitaxial wafer - Google Patents
Composite patterned substrate with inflection points on side walls, preparation method and LED epitaxial wafer Download PDFInfo
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- CN117199208A CN117199208A CN202311059266.9A CN202311059266A CN117199208A CN 117199208 A CN117199208 A CN 117199208A CN 202311059266 A CN202311059266 A CN 202311059266A CN 117199208 A CN117199208 A CN 117199208A
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- 239000000758 substrate Substances 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 47
- 229920002120 photoresistant polymer Polymers 0.000 claims description 50
- 238000005530 etching Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 20
- 238000001312 dry etching Methods 0.000 claims description 16
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000059 patterning Methods 0.000 claims description 7
- 229910018503 SF6 Inorganic materials 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 4
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 4
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 abstract description 13
- 239000007789 gas Substances 0.000 description 25
- 125000005842 heteroatom Chemical group 0.000 description 17
- -1 fluoride ions Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 4
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 3
- 229910002601 GaN Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The embodiment of the invention discloses a composite patterned substrate with a side wall containing an inflection point, a preparation method and an LED epitaxial wafer, wherein the composite patterned substrate with the side wall containing the inflection point comprises a base and a plurality of raised microstructures, the raised microstructures are positioned on the surface of one side of the base, and at least part of the raised microstructures are prepared from heterogeneous materials; the convex microstructure comprises a first part and a second part, wherein the side walls of the first part and the second part are provided with radians, the included angle between a first auxiliary line of the first part and the first direction is alpha, the included angle between a second auxiliary line of the second part and the first direction is beta, alpha is smaller than 90 degrees, beta is smaller than 90 degrees, and alpha is larger than beta in any section passing through the central axis of the convex microstructure; the first auxiliary line is a line connecting a top edge point and a bottom edge point of the first portion, the second auxiliary line is a line connecting a top edge point and a bottom edge point of the second portion, and the first direction is parallel to a plane where the substrate is located. The embodiment of the invention can effectively improve the emergent direction of light and the light extraction efficiency.
Description
Technical Field
The embodiment of the invention relates to the technical field of semiconductor manufacturing, in particular to a composite patterned substrate with inflection points on side walls, a preparation method and an LED epitaxial wafer.
Background
The patterned sapphire substrate can effectively improve the epitaxial crystal quality and the light extraction efficiency of a gallium nitride (GaN) -based Light Emitting Diode (LED), but has a certain limit, and along with the diversification of application scenes, the requirements on the light efficiency and the light emitting direction modulation of the LED are higher and higher.
On the one hand, the refractive index of the material of the patterned composite substrate can influence the light emergent direction and the light extraction efficiency, and the angle of total reflection at the interface of the patterned composite substrate and the epitaxial layer is larger by adopting the material with low refractive index, so that the light extraction efficiency is further improved, and meanwhile, the light emergent line can be changed due to the difference of the refractive indexes, so that the axial light emergent ratio of the patterned composite substrate is higher. On the other hand, the radian (R value) of the side wall of the conical pattern on the patterned composite substrate also affects the light emergent direction and the light extraction efficiency, and in the dry etching process of the conical pattern, the radian (R value) of the side wall of the conical pattern and the inclination angle of the bottom of the conical pattern are both large, so that part of light becomes heat energy loss due to multiple reflection or refraction.
Disclosure of Invention
The embodiment of the invention provides a composite patterned substrate with inflection points on the side walls, a preparation method and an LED epitaxial wafer, which are used for reducing the radian (R value) of the side walls of a convex microstructure and the inclination angle of the bottoms of the convex microstructure, further improving the emergent direction of light and improving the light extraction efficiency.
In a first aspect, an embodiment of the present invention provides a composite patterned substrate having a sidewall with an inflection point, including:
a substrate;
a plurality of raised microstructures, the raised microstructures being located on one side surface of the substrate, at least a portion of the raised microstructures being made of a heterogeneous material;
the convex microstructure comprises a first part and a second part, wherein the side walls of the first part and the second part are provided with radians, in any section passing through the central axis of the convex microstructure, the included angle between a first auxiliary line of the first part and a first direction is alpha, the included angle between a second auxiliary line of the second part and the first direction is beta, alpha is less than 90 degrees, beta is less than 90 degrees, and alpha is more than beta; the first auxiliary line is a line connecting a top edge point and a bottom edge point of the first portion, the second auxiliary line is a line connecting a top edge point and a bottom edge point of the second portion, and the first direction is parallel to a plane where the substrate is located.
Optionally, the height of the first portion is smaller than the height of the second portion in a direction perpendicular to the substrate.
Optionally, the second portion includes a first sub-portion and a second sub-portion, where the first sub-portion is integrally formed with the first portion and is made of a heterogeneous material, and the second sub-portion is integrally formed with the substrate.
Optionally, the total height of the first and second portions in a direction perpendicular to the substrate ranges from 1 μm to 2 μm.
Optionally, the height of the second sub-portion in a direction perpendicular to the substrate ranges from 0 to 1 μm.
Optionally, the shape of the raised microstructure includes cones, pyramids, truncated cones, truncated pyramids, and polygonal pyramids.
Optionally, the heterogeneous material comprises at least one of silicon dioxide, silicon nitride, and silicon carbide.
In a second aspect, an embodiment of the present invention further provides an LED epitaxial wafer, including a composite patterned substrate having a sidewall with an inflection point according to any one of the first aspect.
In a third aspect, an embodiment of the present invention further provides a method for preparing a composite patterned substrate having a sidewall with an inflection point, including:
providing a substrate;
forming a heterogeneous layer on the substrate;
forming a photoresist layer on the surface of the heterogeneous layer, and forming a photoresist column mask on the photoresist layer through a pattern transfer technology;
vertically etching the heterogeneous layer by adopting fluoride gas to form a plurality of heterogeneous layer columns; the heterogeneous layer columns and the photoresist column masks are the same in number and in one-to-one correspondence, and the height of the heterogeneous layer columns is smaller than that of the heterogeneous layer in the direction perpendicular to the substrate;
patterning the heterogeneous layer pillars and the rest of the heterogeneous layer between the heterogeneous layer pillars according to the photoresist pillar mask to form a plurality of raised microstructures; wherein the raised microstructure is positioned on one side surface of the substrate, and at least part of the raised microstructure is prepared from heterogeneous materials; the convex microstructure comprises a first part and a second part, wherein the side walls of the first part and the second part are provided with radians, in any section passing through the central axis of the convex microstructure, the included angle between a first auxiliary line of the first part and a first direction is alpha, the included angle between a second auxiliary line of the second part and the first direction is beta, alpha is less than 90 degrees, beta is less than 90 degrees, and alpha is more than beta; the first auxiliary line is a line connecting a top edge point and a bottom edge point of the first portion, the second auxiliary line is a line connecting a top edge point and a bottom edge point of the second portion, and the first direction is parallel to a plane where the substrate is located.
Optionally, the fluoride gas includes at least one of trifluoromethane, sulfur hexafluoride, and carbon tetrafluoride;
and vertically etching the heterogeneous layer by adopting fluoride gas to form a plurality of heterogeneous layer columns, wherein the method comprises the following steps:
and vertically etching the heterogeneous layer by adopting the fluoride gas at a preset time and a preset etching rate so as to enable the height of the heterogeneous layer column to reach a target height range.
Optionally, patterning the heterogeneous layer pillars and the rest of the heterogeneous layer between the heterogeneous layer pillars according to the photoresist pillar mask, to form a plurality of raised microstructures, including:
etching the heterogeneous layer pillars and the rest heterogeneous layers among the heterogeneous layer pillars by dry etching according to the photoresist pillar mask to form a plurality of raised microstructures; wherein the raised microstructure comprises the first portion and the second portion, all of which are made of the heterogeneous material;
or etching the heterogeneous layer pillars, the rest heterogeneous layers among the heterogeneous layer pillars and the substrate by dry etching according to the photoresist pillar mask to form a plurality of raised microstructures; the protruding microstructure comprises a first portion and a second portion, the second portion comprises a first sub-portion and a second sub-portion, the first sub-portion and the first portion are integrally formed and are made of heterogeneous materials, and the second sub-portion and the substrate are integrally formed.
The embodiment of the invention provides a composite patterned substrate with a side wall containing an inflection point, a preparation method and an LED epitaxial wafer, wherein the composite patterned substrate with the side wall containing the inflection point comprises a base and a plurality of raised microstructures, the raised microstructures are positioned on the surface of one side of the base, and at least part of the raised microstructures are prepared from heterogeneous materials; the convex microstructure comprises a first part and a second part, wherein the side walls of the first part and the second part are provided with radians, the included angle between a first auxiliary line of the first part and the first direction is alpha, the included angle between a second auxiliary line of the second part and the first direction is beta, alpha is smaller than 90 degrees, beta is smaller than 90 degrees, and alpha is larger than beta in any section passing through the central axis of the convex microstructure; the first auxiliary line is a line connecting a top edge point and a bottom edge point of the first portion, the second auxiliary line is a line connecting a top edge point and a bottom edge point of the second portion, and the first direction is parallel to a plane where the substrate is located. The convex microstructure of the embodiment of the invention comprises a first part with an included angle alpha between the first auxiliary line and the first direction and a second part with an included angle beta between the second auxiliary line and the first direction, and alpha is larger than beta, so that the side wall of the convex microstructure contains an inflection point.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing a composite patterned substrate with a side wall containing an inflection point, which is provided by the embodiment of the invention;
FIG. 2 is a structural flow chart of a method for preparing the composite patterned substrate with inflection points on the side walls shown in FIG. 1;
FIG. 3 is a schematic structural diagram of a composite patterned substrate with inflection points on the sidewalls according to an embodiment of the present invention;
FIGS. 4 and 5 are schematic cross-sectional views of two M regions shown in FIG. 2;
FIG. 6 is a schematic cross-sectional view of a prior art composite patterned substrate;
FIG. 7 is a schematic cross-sectional view of the region L shown in FIG. 2;
FIG. 8 is a schematic flow chart of another method for preparing a composite patterned substrate with inflection points on the side walls according to an embodiment of the present invention;
FIG. 9 is a structural flow chart of a method of fabricating a composite patterned substrate having inflection points on the sidewalls shown in FIG. 8;
FIG. 10 is a schematic structural diagram of another composite patterned substrate with inflection points on the sidewalls according to an embodiment of the present invention;
FIG. 11 is a schematic cross-sectional view of the N region shown in FIG. 9;
fig. 12 is a schematic structural diagram of an LED epitaxial wafer according to an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting thereof. It should be further noted that, for convenience of description, only some, but not all of the structures related to the present invention are shown in the drawings.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. It should be noted that, the terms "upper", "lower", "left", "right", and the like in the embodiments of the present invention are described in terms of the angles shown in the drawings, and should not be construed as limiting the embodiments of the present invention. In addition, in the context, it will also be understood that when an element is referred to as being formed "on" or "under" another element, it can be directly formed "on" or "under" the other element or be indirectly formed "on" or "under" the other element through intervening elements. The terms "first," "second," and the like, are used for descriptive purposes only and not for any order, quantity, or importance, but rather are used to distinguish between different components. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The term "comprising" and variants thereof as used herein is intended to be open ended, i.e., including, but not limited to. The term "based on" is based at least in part on. The term "one embodiment" means "at least one embodiment".
It should be noted that the terms "first," "second," and the like herein are merely used for distinguishing between corresponding contents and not for defining a sequential or interdependent relationship.
It should be noted that references to "one", "a plurality" and "a plurality" in this disclosure are intended to be illustrative rather than limiting, and those skilled in the art will appreciate that "one or more" is intended to be construed as "one or more" unless the context clearly indicates otherwise.
Fig. 1 is a schematic flow chart of a method for preparing a composite patterned substrate with a side wall having an inflection point according to an embodiment of the present invention, fig. 2 is a structural flow chart of the method for preparing a composite patterned substrate with a side wall having an inflection point shown in fig. 1, and fig. 3 is a schematic flow chart of the method for preparing a composite patterned substrate with a side wall having an inflection point according to an embodiment of the present invention, as shown in fig. 1, fig. 2 and fig. 3, the method for preparing a composite patterned substrate with a side wall having an inflection point includes:
s110, providing a substrate.
Specifically, referring to fig. 2 a), a substrate 10 is provided, and the substrate 10 is a substrate with a smooth polished surface, i.e., the substrate 10 has a C-plane with a perfect quality, which can help the epitaxial crystal form nuclei and grow into an epitaxial layer. The base 10 may be, for example, a sapphire substrate, and is not limited herein. Illustratively, sulfuric acid (H 2 SO 4 ) Solution and hydrogen peroxide (H) 2 O 2 ) The surface of the substrate 10 is cleaned by a mixed solution of solutions, in which sulfuric acid (H 2 SO 4 ) Solution and hydrogen peroxide (H) 2 O 2 ) The ratio of the solution is between 3:1 and 7:1.
S120, forming a heterogeneous layer on the substrate.
Specifically, referring to fig. 2 b), a hetero layer 20 is formed on the substrate 10, the hetero layer 20 is a film layer made of a hetero material substantially opposite to the substrate 10 and an epitaxial layer material such as gallium nitride, that is, a material different from the substrate 10 and the epitaxial material, and the hetero layer 20 may be formed by chemical vapor deposition, physical vapor deposition, magnetron sputtering, or the like, and the thickness of the hetero layer 20 may be 1.5 μm to 3 μm, for example. Because of the difficulty in growing epitaxial materials on the dissimilar materials, the dissimilar materials have the effect of inhibiting the growth of the epitaxial materials. And, the heterogeneous layer 20 may be a film layer formed on the substrate 10 by one material, or may be a plurality of film layers formed on the substrate 10 sequentially by a plurality of materials. It will be appreciated that, in order to achieve sequential graded or abrupt changes in refractive index in the subsequently fabricated composite patterned substrate, multiple layers of heterogeneous materials of different refractive indices may be disposed in the heterogeneous layer 20, which is not limited herein. Alternatively, the hetero-material employed for the hetero-layer 20 includes at least one of silicon dioxide, silicon nitride, and silicon carbide.
S130, forming a photoresist layer on the surface of the heterogeneous layer, and enabling the photoresist layer to form a photoresist column mask through a pattern transfer technology.
Specifically, referring to fig. 2 c), a photoresist layer is formed on the surface of the heterogeneous layer 20, and the photoresist layer is formed into a photoresist column mask 30 by a pattern transfer technique, which may be, for example, a photolithography exposure or a nanoimprint technique, etc., by which the photoresist layer is exposed through a photolithography exposure process, and then the photoresist layer is patterned by a developing step, i.e., the pattern of the photoresist mask is transferred onto the photoresist layer, to form the photoresist column mask 30. The photoresist column mask 30 is a pattern mask for patterning the photoresist layer, and the pattern of the photoresist column mask 30 corresponds to the pattern of the microstructure finally formed on the composite patterned substrate.
S140, vertically etching the heterogeneous layer by adopting fluoride gas to form a plurality of heterogeneous layer columns; the heterogeneous layer columns and the photoresist column masks are the same in number and in one-to-one correspondence, and the height of the heterogeneous layer columns is smaller than that of the heterogeneous layer in the direction perpendicular to the substrate.
Specifically, referring to d) of fig. 2, the step is a process of vertically etching the hetero layer 20 using a fluoride gas according to the photoresist column mask 30, which is also a chemical etching process, wherein fluoride ions are present in the fluoride gas, silicon ions are present in the hetero layer 20, and a silicon tetrafluoride gas is generated according to a chemical reaction of the fluoride ions and the silicon ions under a high temperature or the like, thereby etching a portion of the hetero layer 20 and forming the hetero layer column 21. Illustratively, by reasonably adjusting the parameters such as the gas flow rate, the etching temperature, the etching pressure and the like of the fluoride gas, the fluoride gas only chemically etches the heterogeneous layer 20 between the photoresist column masks 30, and the groove structure formed by the chemical etching has vertical and smooth side wall surfaces, that is, the heterogeneous layer column 21 formed by the chemical etching has vertical and smooth side wall surfaces. And by reasonably controlling parameters such as etching time of fluoride gas, the height H2 of the formed heterogeneous layer column 21 is changed, and in the direction vertical to the substrate 10, the height H2 of the heterogeneous layer column 21 is smaller than the height H1 of the heterogeneous layer 20, namely H2 is smaller than H1, so that the heterogeneous layer 20 cannot be completely etched in the vertical etching process. The heterogeneous layer pillars 21 formed by vertical etching and the photoresist pillar masks 30 have the same number and one-to-one correspondence, and the heterogeneous layer pillars 21 can be used as a part of the photoresist pillar masks 30, and the heterogeneous layer pillars 21 and the photoresist pillar masks 30 participate in the subsequent etching process together.
S150, patterning the heterogeneous layer columns and the rest heterogeneous layers among the heterogeneous layer columns according to the photoresist column mask to form a plurality of raised microstructures; wherein the raised microstructure is positioned on one side surface of the substrate, and at least part of the raised microstructure is prepared from heterogeneous materials; the convex microstructure comprises a first part and a second part, wherein the side walls of the first part and the second part are provided with radians, the included angle between a first auxiliary line of the first part and the first direction is alpha, the included angle between a second auxiliary line of the second part and the first direction is beta, alpha is smaller than 90 degrees, beta is smaller than 90 degrees, and alpha is larger than beta in any section passing through the central axis of the convex microstructure; the first auxiliary line is a line connecting a top edge point and a bottom edge point of the first portion, the second auxiliary line is a line connecting a top edge point and a bottom edge point of the second portion, and the first direction is parallel to a plane where the substrate is located.
Specifically, referring to e) of fig. 2 and fig. 3, this step is a process of performing pattern transfer on the heterogeneous layer pillars 21 and the remaining heterogeneous layer 20 between the heterogeneous layer pillars 21 according to the photoresist pillar mask 30. Illustratively, the heterogeneous layer pillars 21 and the remaining heterogeneous layer 20 between the heterogeneous layer pillars 21 may be patterned by etching using a dry or wet etching process, using boron trichloride (BCl) as an example 3 ) The gas was used as the main etching gas, boron trichloride (BCl) 3 ) The flow rate of the gas is 80sccm-200sccm, and trifluoromethane is adoptedCHF 3 ) Gas as an assist gas, trifluoromethane (CHF) 3 ) The flow rate of the gas is 5sccm-22sccm, the etching power of the etching upper electrode is 1000W-1600W, the etching power of the etching lower electrode is 300W-800W, the etching cavity pressure is 1.5mT-3mT, the etching cavity temperature is 10 ℃ to 20 ℃, and the etching time is 10min-45min.
The plurality of raised microstructures 40 formed by pattern transfer are located on one side surface of the substrate 10, at least a portion of the raised microstructures 40 are made of a heterogeneous material, and illustratively, the raised microstructures 40 may be made of a heterogeneous material throughout, or the raised microstructures 40 may be made of a heterogeneous material throughout, and the remainder may be made of a material corresponding to the substrate 10.
Fig. 4 and 5 are schematic cross-sectional views of two M regions shown in fig. 2, fig. 6 is a schematic cross-sectional view of a conventional composite patterned substrate, and as shown in fig. 4, 5 and 6, the raised microstructure 40 includes a first portion 41 and a second portion 42, the sidewalls of the first portion 41 and the second portion 42 have an arc shape, and the obtained sidewall arc R1 (the sidewall arc R value refers to the connection between the top edge point and the bottom edge point of the raised microstructure 40 and the maximum distance between the top edge point and the corresponding sidewall of the raised microstructure 40) of the first portion 41 is smaller than the sidewall arc R3 of the raised microstructure 40 shown in fig. 6, and the sidewall arc R2 of the second portion 42 is smaller than the sidewall arc R3 of the raised microstructure 40 shown in fig. 6.
And for the same light emitted from the active region, the larger the sidewall radian R3 of the raised microstructure 40 shown in fig. 6, the larger the angle between the incident light and the normal (or, the smaller the angle between the incident light and the sidewall of the raised microstructure 40), the larger the angle between the reflected light and the normal (or, the smaller the angle between the reflected light and the sidewall of the raised microstructure 40), and the reflected light tends to exit from the bottom of the raised microstructure 40, and is finally absorbed by the waveguide formed by multiple reflection. For the same light emitted from the active region, the smaller the sidewall radian R3 of the second portion 42 of the raised microstructure 40 shown in fig. 5, the smaller the angle between the incident light and the normal (or, the larger the angle between the incident light and the sidewall of the raised microstructure 40), the smaller the angle between the reflected light and the normal (or, the larger the angle between the reflected light and the sidewall of the raised microstructure 40), and the reflected light tends to exit from the top of the raised microstructure 40, effectively increasing the axial light extraction amount and improving the light extraction efficiency.
With continued reference to fig. 4 and 5, the raised microstructure 40 comprises a first portion 41 and a second portion 42, wherein, in any cross-section passing through the central axis of the raised microstructure 40, the first auxiliary line 411 of the first portion 41 has an angle α with a first direction X, wherein the first auxiliary line 411 is a line connecting a top edge point and a bottom edge point of the first portion 41, the first direction X is parallel to the plane of the substrate 10, and α < 90 °. In any cross section passing through the central axis of the raised microstructure 40, the second auxiliary line 421 of the second portion 42 has an angle β with the first direction X, where the second auxiliary line 421 is a line connecting the top edge point and the bottom edge point of the second portion 42, and the first direction X is parallel to the plane of the substrate 10 and β is less than 90 °. The first auxiliary line 411 of the first portion 41 forms an angle α with the first direction X and the second auxiliary line 421 of the second portion 42 forms an angle β with the first direction X, that is, α > β, so as to regulate the light emitting direction, that is, for the same light emitted from the active region, the smaller β is the smaller the angle between the incident light and the normal (or the larger the angle between the incident light and the sidewall of the protruding microstructure 40 is), the smaller the angle between the reflected light and the normal (or the larger the angle between the reflected light and the sidewall of the protruding microstructure 40 is), the reflected light tends to exit from the top of the protruding microstructure 40, which effectively increases the amount of axial light and improves the light emitting efficiency. It will be appreciated that alternatively, in a direction perpendicular to the substrate 10, the height H4 of the first portion 41 is smaller than the height H5 of the second portion 42. Under the condition that the height H3 of the raised microstructure 40 and the width D of the bottom are ensured to be certain, the height H2 of the etched heterogeneous layer column 21 is appropriately adjusted so that the height H4 of the first portion 41 obtained by final etching is smaller than the height H5 of the second portion 42, that is, the height H4 of the first portion 41 is smaller than half of the height H3 of the raised microstructure 40, and thus, after the light emitted from the active region is reflected by the side wall of the second portion 42, the reflected light tends to exit toward the top of the raised microstructure 40. At the interface location of the first portion 41 and the second portion 42, there is an inflection point inward of the sidewalls of the raised microstructure 40, and the entire sidewalls of the raised microstructure 40 are not smoothly curved. Alternatively, the total height of the first and second portions 41 and 42 in a direction perpendicular to the substrate 10 ranges from 1 μm to 2 μm, i.e., the height H3 of the raised microstructure 40 ranges from 1 μm to 2 μm. The specific location of the inward inflection point at the interface location of the first portion 41 and the second portion 42 throughout the sidewall of the raised microstructure 40 may be controlled by appropriate control of the height H4 of the first portion 41.
With continued reference to fig. 3, the composite patterned substrate with inflection points on the sidewall, which is prepared by the method for preparing the composite patterned substrate with inflection points on the sidewall according to the embodiment of the present invention, includes a base 10 and a plurality of raised microstructures 40. Wherein the raised microstructure 40 is located on one side surface of the substrate 10, and at least part of the raised microstructure 40 is made of heterogeneous materials; the raised microstructure 40 comprises a first portion 41 and a second portion 42, wherein the side walls of the first portion 41 and the second portion 42 have radians, in any cross section passing through the central axis of the raised microstructure 40, an included angle between a first auxiliary line 411 of the first portion 41 and a first direction X is alpha, an included angle between a second auxiliary line 421 of the second portion 42 and the first direction X is beta, and alpha is less than 90 degrees, beta is less than 90 degrees, and alpha is more than beta; the first auxiliary line 411 is a line connecting a top edge point and a bottom edge point of the first portion 41, and the second auxiliary line 421 is a line connecting a top edge point and a bottom edge point of the second portion 42, and the first direction X is parallel to a plane of the substrate 10. Alternatively, the shape of the raised microstructure 40 includes cones, pyramids, truncated cones, pyramids, and polygonal pyramids, and the drawings corresponding to the embodiments of the present invention are given here by way of example only and not limitation.
According to the technical scheme, the composite graphical substrate with the side wall containing the inflection point comprises a base and a plurality of convex microstructures, wherein the convex microstructures are positioned on the surface of one side of the base, and at least part of the convex microstructures are made of heterogeneous materials; the convex microstructure comprises a first part and a second part, wherein the side walls of the first part and the second part are provided with radians, the included angle between a first auxiliary line of the first part and the first direction is alpha, the included angle between a second auxiliary line of the second part and the first direction is beta, alpha is smaller than 90 degrees, beta is smaller than 90 degrees, and alpha is larger than beta in any section passing through the central axis of the convex microstructure; the first auxiliary line is a line connecting a top edge point and a bottom edge point of the first portion, the second auxiliary line is a line connecting a top edge point and a bottom edge point of the second portion, and the first direction is parallel to a plane where the substrate is located. The convex microstructure of the embodiment of the invention comprises a first part with an included angle alpha between the first auxiliary line and the first direction and a second part with an included angle beta between the second auxiliary line and the first direction, and alpha is larger than beta, so that the side wall of the convex microstructure contains an inflection point.
Optionally, the fluoride gas comprises at least one of trifluoromethane, sulfur hexafluoride, and carbon tetrafluoride; adopt fluoride gas to carry out vertical etching to heterogeneous layer, form a plurality of heterogeneous layer posts, include: and vertically etching the heterogeneous layer by adopting fluoride gas at a preset time and a preset etching rate so as to enable the height of the heterogeneous layer column to reach a target height range.
Wherein the fluoride gas includes at least one of trifluoromethane, sulfur hexafluoride, and carbon tetrafluoride, i.e., fluoride ions are present in the fluoride gas, and the hetero-material includes at least one of silicon dioxide, silicon nitride, and silicon carbide, i.e., silicon ions are present in the hetero-material. The target height range may be determined according to the light extraction efficiency and the axial light extraction capability of the composite patterned substrate. Specifically, with continued reference to fig. 2 d), during the vertical etching of the hetero-layer 20, a silicon tetrafluoride gas is generated according to a chemical reaction of fluorine ions and silicon ions under conditions of high temperature and the like, so that a portion of the hetero-layer 20 is etched and a hetero-layer pillar 21 is formed. It should be noted that, the height H2 of the hetero-layer pillar 21 needs to be controlled, the height H2 of the hetero-layer pillar 21 should be smaller than the height H1 of the hetero-layer pillar 20, i.e. H2 < H1, so as to ensure that the hetero-layer pillar 20 will not be completely etched through during the vertical etching process, and the height H2 of the hetero-layer pillar 21 should be within the target height range, so as to ensure that the height H4 of the first portion 41 obtained by the final etching is smaller than the height H5 of the second portion 42, i.e. the height H4 of the first portion 41 is smaller than half of the height H3 of the raised microstructure 40, and the inward inflection point at the interface position of the first portion 41 and the second portion 42 is located at the upper position of the entire raised microstructure 40, so that the finally obtained raised microstructure 40 has higher light extraction efficiency and axial light extraction capability. Fig. 7 is a schematic cross-sectional view of the L region shown in fig. 2, and with continued reference to fig. 4, 5 and 7, if a portion of the hetero layer 20 is etched and a hetero layer pillar 21 is formed, an included angle between an auxiliary line of a sidewall of the formed bump microstructure 40 and the first direction X is β, tan β= Δh/Δw, and if the hetero layer 20 is not etched and the hetero layer pillar 21 is formed, an included angle between an auxiliary line of a sidewall of the formed bump microstructure 40 and the first direction X is λ, tan λ= (Δh+h2)/Δw=h1/Δw, and when H2 > 0, β < λ is obviously obtained, that is, an inclination angle of a sidewall radian (R value) of the bump microstructure 40 and an inclination angle of a bottom of the bump microstructure 40 can be controlled by a height H2 of the hetero layer pillar 21, and as the height H2 of the hetero layer pillar 21 increases, the inclination angle of the bottom of the bump microstructure 40 is smaller.
Fig. 8 is a flow chart of another method for preparing a composite patterned substrate with a side wall having an inflection point according to an embodiment of the present invention, fig. 9 is a structural flow chart of the method for preparing a composite patterned substrate with a side wall having an inflection point shown in fig. 8, and fig. 10 is a structural flow chart of another composite patterned substrate with a side wall having an inflection point according to an embodiment of the present invention, which is optimized on the basis of the above embodiment. Optionally, patterning the heterogeneous layer pillars and the remaining heterogeneous layer between the heterogeneous layer pillars according to a photoresist pillar mask to form a plurality of raised microstructures, including:
etching the heterogeneous layer columns and the rest heterogeneous layers among the heterogeneous layer columns by dry etching according to the photoresist column mask to form a plurality of raised microstructures; the convex microstructure comprises a first part and a second part, wherein the first part and the second part are all made of heterogeneous materials;
or etching the heterogeneous layer columns, the rest heterogeneous layers among the heterogeneous layer columns and the substrate by dry etching according to the photoresist column mask to form a plurality of raised microstructures; the protruding microstructure comprises a first part and a second part, the second part comprises a first sub-part and a second sub-part, the first sub-part and the first part are integrally formed and are made of heterogeneous materials, and the second sub-part and the substrate are integrally formed.
For details not yet described in this embodiment, please refer to the above embodiment, as shown in fig. 8, 9 and 10, the method for preparing the composite patterned substrate with the inflection point on the sidewall includes:
s210, providing a substrate.
S220, forming a heterogeneous layer on the substrate.
S230, forming a photoresist layer on the surface of the heterogeneous layer, and enabling the photoresist layer to form a photoresist column mask through a pattern transfer technology.
S240, vertically etching the heterogeneous layer by adopting fluoride gas to form a plurality of heterogeneous layer columns; the heterogeneous layer columns and the photoresist column masks are the same in number and in one-to-one correspondence, and the height of the heterogeneous layer columns is smaller than that of the heterogeneous layer in the direction perpendicular to the substrate.
S250, etching the heterogeneous layer columns and the rest heterogeneous layers among the heterogeneous layer columns by dry etching according to the photoresist column mask to form a plurality of raised microstructures; the convex microstructure comprises a first part and a second part, wherein the first part and the second part are all made of heterogeneous materials; or etching the heterogeneous layer columns, the rest heterogeneous layers among the heterogeneous layer columns and the substrate by dry etching according to the photoresist column mask to form a plurality of raised microstructures; the protruding microstructure comprises a first part and a second part, the second part comprises a first sub-part and a second sub-part, the first sub-part and the first part are integrally formed and are made of heterogeneous materials, and the second sub-part and the substrate are integrally formed.
Specifically, referring to e) of fig. 9 and fig. 3, this step is a process of performing pattern transfer on the heterogeneous layer pillars 21 and the remaining heterogeneous layer 20 between the heterogeneous layer pillars 21 by dry etching according to the photoresist pillar mask 30. A plurality of raised microstructures 40 formed by pattern transfer are located on one side surface of the substrate 10, and the raised microstructures 40 include a first portion 41 and a second portion 42, and the first portion 41 and the second portion 42 are all made of heterogeneous materials. Alternatively, the total height of the first and second portions 41 and 42 in a direction perpendicular to the substrate 10 ranges from 1 μm to 2 μm, i.e., the height H3 of the raised microstructure 40 ranges from 1 μm to 2 μm. In other words, the sidewall of the composite patterned substrate having an inflection point shown in fig. 3, when the dry etching process is stopped at the interface between the base 10 and the hetero layer 20. Alternatively, referring to e) of fig. 9 and fig. 10, this step is a process of performing pattern transfer on the hetero-layer pillars 21, the remaining hetero-layer 20 between the hetero-layer pillars 21, and the substrate 10 by dry etching according to the photoresist pillar mask 30. The plurality of raised microstructures 40 formed by pattern transfer are located on one side surface of the substrate 10, the raised microstructures 40 include a first portion 41 and a second portion 42, the second portion 42 includes a first sub-portion 422 and a second sub-portion 423, the first sub-portion 422 is integrally formed with the first portion 41 and is made of a heterogeneous material, and the second sub-portion 423 is integrally formed with the substrate 10. Alternatively, the height of the second sub-portion 423 in the direction perpendicular to the substrate 10 may range from 0 to 1 μm. In other words, in order to ensure that the height H3 of the raised microstructure 40 and the width D of the bottom are constant, when the dry etching process is stopped at the interface between the substrate 10 and the hetero layer 20, the resulting height H3 of the raised microstructure 40 and the width D of the bottom do not meet the target requirement, the substrate 10 may be over-etched, and the dry etching process is stopped at the position inside the substrate 10.
Fig. 11 is a schematic cross-sectional view of the N region shown in fig. 9, and as shown in fig. 11, the raised microstructure 40 includes a first portion 41 and a second portion 42, the raised microstructure 40 has a height H3, the first portion 41 has a height H4, and the second portion 42 has a height H5, in a direction perpendicular to the substrate 10, and h3=h4+h5. If the over-etching occurs, the second portion 42 includes a first sub-portion 422 and a second sub-portion 423, where the first sub-portion 422 has a height H6 and the second sub-portion 423 has a height H7, h5=h6+h7. And the first sub-portion 422 and the first portion 41 are integrally formed and made of heterogeneous materials, and the second sub-portion 423 and the substrate 10 are integrally formed.
According to the technical scheme, two conditions of forming a plurality of protruding microstructures by etching a heterogeneous layer column and a residual heterogeneous layer between heterogeneous layer columns by dry etching according to a photoresist column mask are described in detail, wherein the protruding microstructures comprise a first part and a second part, and the first part and the second part are all made of heterogeneous materials; or, the protruding microstructure comprises a first part and a second part, the second part comprises a first sub-part and a second sub-part, the first sub-part and the first part are integrally formed and are made of heterogeneous materials, and the second sub-part and the substrate are integrally formed. By utilizing the method, the height and the width of the bottom of the raised microstructure are ensured to meet the target requirements, and on the premise that the size of the raised microstructure is the same as or similar to that of the conventional raised microstructure, the composite patterned substrate with the inflection point on the side wall can effectively improve the light emergent direction, improve the light extraction efficiency and increase the light emergent efficiency from the substrate to the epitaxial layer direction.
Based on the same inventive concept, the embodiment of the invention also provides an LED epitaxial wafer. Fig. 12 is a schematic structural diagram of an LED epitaxial wafer according to an embodiment of the present invention, and as shown in fig. 12, the LED epitaxial wafer includes a composite patterned substrate 1 with a side wall containing an inflection point according to any one of the embodiments of the present invention, and further includes an epitaxial layer 2 formed on the composite patterned substrate 1 with a side wall containing an inflection point.
For forming epitaxial layers on patterned substrates of different materials, different LED epitaxial wafer growth techniques are required, and for the composite patterned substrate provided by the embodiment of the present invention, the epitaxial layer 2 in the LED epitaxial wafer may be a GaN epitaxial layer, an AlGaN epitaxial layer, or the like. The LED epitaxial wafer adopts the composite patterned substrate 1 with the side wall containing the inflection point provided in the above embodiment, so that the LED epitaxial wafer has the same or similar beneficial effects as the composite patterned substrate 1 with the side wall containing the inflection point, and will not be described herein.
Note that the above is only a preferred embodiment of the present invention and the technical principle applied. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, and that various obvious changes, rearrangements, combinations, and substitutions can be made by those skilled in the art without departing from the scope of the invention. Therefore, while the invention has been described in connection with the above embodiments, the invention is not limited to the embodiments, but may be embodied in many other equivalent forms without departing from the spirit or scope of the invention, which is set forth in the following claims.
Claims (11)
1. A composite patterned substrate having a sidewall with an inflection point, comprising:
a substrate;
a plurality of raised microstructures, the raised microstructures being located on one side surface of the substrate, at least a portion of the raised microstructures being made of a heterogeneous material;
the convex microstructure comprises a first part and a second part, wherein the side walls of the first part and the second part are provided with radians, in any section passing through the central axis of the convex microstructure, the included angle between a first auxiliary line of the first part and a first direction is alpha, the included angle between a second auxiliary line of the second part and the first direction is beta, alpha is less than 90 degrees, beta is less than 90 degrees, and alpha is more than beta; the first auxiliary line is a line connecting a top edge point and a bottom edge point of the first portion, the second auxiliary line is a line connecting a top edge point and a bottom edge point of the second portion, and the first direction is parallel to a plane where the substrate is located.
2. The inflection point-containing composite patterned substrate of claim 1 wherein the height of said first portion is less than the height of said second portion in a direction perpendicular to said base.
3. The composite patterned substrate with inflection points on the sidewalls of claim 1, wherein the second portion comprises a first sub-portion and a second sub-portion, the first sub-portion being integrally formed with the first portion and being made of heterogeneous materials, the second sub-portion being integrally formed with the base.
4. The inflection point containing composite patterned substrate of claim 1 wherein the total height of said first and second portions in the direction perpendicular to said base is in the range of 1 μm to 2 μm.
5. A composite patterned substrate having inflection points on its sidewalls as claimed in claim 3, wherein the height of the second sub-portion is in the range of 0-1 μm in a direction perpendicular to the base.
6. The inflection point-containing composite patterned substrate of claim 1 wherein the shape of the raised microstructure comprises cones, pyramids, and polygonal pyramids.
7. The inflection point containing composite patterned substrate of claim 1 wherein the heterogeneous material comprises at least one of silicon dioxide, silicon nitride and silicon carbide.
8. An LED epitaxial wafer comprising a composite patterned substrate having inflection points on the sidewalls as claimed in any one of claims 1 to 7.
9. The preparation method of the composite patterned substrate with the inflection point on the side wall is characterized by comprising the following steps of:
providing a substrate;
forming a heterogeneous layer on the substrate;
forming a photoresist layer on the surface of the heterogeneous layer, and forming a photoresist column mask on the photoresist layer through a pattern transfer technology;
vertically etching the heterogeneous layer by adopting fluoride gas to form a plurality of heterogeneous layer columns; the heterogeneous layer columns and the photoresist column masks are the same in number and in one-to-one correspondence, and the height of the heterogeneous layer columns is smaller than that of the heterogeneous layer in the direction perpendicular to the substrate;
patterning the heterogeneous layer pillars and the rest of the heterogeneous layer between the heterogeneous layer pillars according to the photoresist pillar mask to form a plurality of raised microstructures; wherein the raised microstructure is positioned on one side surface of the substrate, and at least part of the raised microstructure is prepared from heterogeneous materials; the convex microstructure comprises a first part and a second part, wherein the side walls of the first part and the second part are provided with radians, in any section passing through the central axis of the convex microstructure, the included angle between a first auxiliary line of the first part and a first direction is alpha, the included angle between a second auxiliary line of the second part and the first direction is beta, alpha is less than 90 degrees, beta is less than 90 degrees, and alpha is more than beta; the first auxiliary line is a line connecting a top edge point and a bottom edge point of the first portion, the second auxiliary line is a line connecting a top edge point and a bottom edge point of the second portion, and the first direction is parallel to a plane where the substrate is located.
10. The production method according to claim 9, wherein the fluoride gas includes at least one of trifluoromethane, sulfur hexafluoride, and carbon tetrafluoride;
and vertically etching the heterogeneous layer by adopting fluoride gas to form a plurality of heterogeneous layer columns, wherein the method comprises the following steps:
and vertically etching the heterogeneous layer by adopting the fluoride gas at a preset time and a preset etching rate so as to enable the height of the heterogeneous layer column to reach a target height range.
11. The method of manufacturing of claim 9, wherein patterning the heterogeneous layer pillars and the remaining heterogeneous layer between the heterogeneous layer pillars according to the photoresist pillar mask forms a plurality of raised microstructures, comprising:
etching the heterogeneous layer pillars and the rest heterogeneous layers among the heterogeneous layer pillars by dry etching according to the photoresist pillar mask to form a plurality of raised microstructures; wherein the raised microstructure comprises the first portion and the second portion, all of which are made of the heterogeneous material;
or etching the heterogeneous layer pillars, the rest heterogeneous layers among the heterogeneous layer pillars and the substrate by dry etching according to the photoresist pillar mask to form a plurality of raised microstructures; the protruding microstructure comprises a first portion and a second portion, the second portion comprises a first sub-portion and a second sub-portion, the first sub-portion and the first portion are integrally formed and are made of heterogeneous materials, and the second sub-portion and the substrate are integrally formed.
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