CN117373903A - Graphical sapphire substrate and preparation method and application thereof - Google Patents
Graphical sapphire substrate and preparation method and application thereof Download PDFInfo
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- CN117373903A CN117373903A CN202311187683.1A CN202311187683A CN117373903A CN 117373903 A CN117373903 A CN 117373903A CN 202311187683 A CN202311187683 A CN 202311187683A CN 117373903 A CN117373903 A CN 117373903A
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- 239000000758 substrate Substances 0.000 title claims abstract description 71
- 229910052594 sapphire Inorganic materials 0.000 title claims abstract description 55
- 239000010980 sapphire Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 84
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011161 development Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000003292 glue Substances 0.000 description 5
- 201000002161 intrahepatic cholestasis of pregnancy Diseases 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/76—Patterning of masks by imaging
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02019—Chemical etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- 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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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to a preparation method of a patterned sapphire substrate, which comprises the following steps: s1, coating photoresist on a sapphire substrate and drying; s2, paving a soft photomask on the photoresist, exposing and developing, and forming a photoresist mask pattern on the photoresist; the soft photomask is provided with a plurality of grooves which are arrayed on one side facing the photoresist, and the bottom surface of each groove is provided with a metal aluminum shading layer; s3, etching the sapphire substrate with the photoresist mask pattern; the etching comprises a first etching stage and a second etching stage, the etchingThe etching gas in the first etching stage is BCl 3 The etching gas in the second etching stage is Cl 2 And BCl 3 Is a mixed gas of (a) and (b). By the technical scheme, the purpose of rapidly manufacturing the patterned sapphire substrate can be achieved, and the process can be shortened when the patterned sapphire substrate is manufactured by using the soft photomask.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a patterned sapphire substrate, and a preparation method and application thereof.
Background
The existing Patterning Sapphire Substrate (PSS) is manufactured by using a step-by-step lithography machine or an imprinting method as two main methods, and the purpose is to manufacture photoresist or imprinting glue with a cylindrical pattern as a mask, and then etch with boron trichloride gas (or boron trichloride added with trifluoromethane) plasma. In the etching process, the photoresist (or the imprinting glue) is etched by plasma, and the shape of the photoresist (or the imprinting glue) is changed from an initial cylindrical shape into a round boss, then into a pointed cone, and finally completely etched by the plasma.
However, stepper lithography machines have various disadvantages: the method has the advantages that (1) the productivity is low, (2) the equipment is old, (3) the pattern splicing problem needs to be continuously monitored and controlled by manpower, (4) the exposure is easily influenced by the uneven wafer to cause defocusing, and the mass production yield is low by 80-90%.
Although the imprinting mode has improved the conventional problems of low productivity, graphic splicing defocus and the like, the imprinting mode has the following disadvantages: (1) A large amount of silica gel soft film materials are required to be consumed, one soft film can only be stamped for 20-35 times, and then the soft film must be scrapped, (2) residual glue remains on the bottom layer of the graph after stamping, and the residual glue thickness cannot be uniformly distributed on the whole wafer due to stamping mode from middle pasting and diffusion to the periphery of the wafer, so that the next stage of ICP etching requires one more step of oxygen plasma treatment to clean the residual bottom film, the process is increased, and even the bottom film is cleaned, the high uniformity of the finished product PSS is inferior to that of a traditional stepping photoetching machine.
The key to overcoming the above-mentioned drawbacks is how to provide a photomask for manufacturing a patterned sapphire substrate, which can solve the problems existing in the two main process flows at the same time, so as to shorten the process and improve the production efficiency.
Disclosure of Invention
The invention aims to provide a patterned sapphire substrate and a preparation method and application thereof, which are used for solving the problems that the stepping photoetching process has low productivity, exposure is easily affected by wafer unevenness to cause defocusing, and the imprinting process has the problems of large consumption of silica gel soft film materials, increased process manufacturing procedures and poor uniformity of the height of a finished product PSS.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a patterned sapphire substrate, the method comprising:
s1, coating photoresist on a sapphire substrate and drying;
s2, paving a soft photomask on the photoresist, exposing and developing, and forming a photoresist mask pattern on the photoresist; the soft photomask is provided with a plurality of grooves which are arrayed on one side facing the photoresist, and the bottom surface of each groove is provided with a metal aluminum shading layer;
s3, etching the sapphire substrate with the photoresist mask pattern; the etching comprises a first etching stage and a second etching stage, wherein the etching gas of the first etching stage is BCl 3 The etching gas in the second etching stage is Cl 2 And BCl 3 Is a mixed gas of (a) and (b).
Optionally, the soft photomask is prepared by a method comprising the following steps:
s1, pouring silica gel into a silicon plate with a plurality of cylindrical bulges arranged in an array, and then baking to solidify and demould the silica gel to obtain a soft substrate with grooves; the groove is of a cylindrical hole structure;
s2, depositing a metal aluminum layer on the flexible substrate, and then coating positive photoresist on the metal aluminum layer;
and S3, exposing and developing the positive photoresist, and then etching and cleaning the positive photoresist by using an aluminum etching solution to obtain the soft photomask.
Alternatively, the diameter of the cylindrical protrusion is 1-3 μm and the height is 2-4 μm; the distance between two adjacent cylindrical bulges is 2-5 mu m; the arrangement mode of the cylindrical protrusions is one of rectangular array arrangement, hexagonal closest packing arrangement and random arrangement.
Optionally, the thickness of the metal aluminum layer is 1-3 μm; the thickness of the positive photoresist is 1-3 mu m.
Optionally, the exposure energy is 20-30mJ, and the exposure time is 1-1.5s; the development time is 20-40s; the etching time is 1-5min; and/or the baking temperature is 60-75 ℃ and the baking time is 20-60min.
Optionally, in step S1, the photoresist is a positive photoresist, and the thickness of the positive photoresist is 2-5 μm; and/or, in the step S2, the exposure energy is 10-30mJ, and the exposure time is 1-1.5S; the development time is 20-40s.
Optionally, the parameters of the first etching stage are: BCl (binary coded decimal) 3 The inlet amount is 120-140sccm, the pressure is 2-4mTorr, the upper radio frequency power is 1900-2100W, the lower radio frequency power is 400-500W, and the etching is 25-30 minutes; and/or, the parameters of the second etching stage are as follows: BCl (binary coded decimal) 3 And Cl 2 The mixed gas is introduced into the reactor at 120-140sccm, the pressure is 2-4mTorr, the upper radio frequency power is 1800-2000W, the lower radio frequency power is 600-700W, and the etching is carried out for 8-10 minutes.
Optionally, the BCl 3 And Cl 2 The mixed gas inlet amount comprises BCl 3 The charging amount is 10-120sccm and Cl 2 The amount of the mixture is 10-120sccm.
The second aspect of the invention provides a patterned sapphire substrate, which is prepared by the method provided by the first aspect of the invention.
A third aspect of the present invention provides a use of the patterned sapphire substrate provided in the second aspect of the present invention for the manufacture of a semiconductor device.
Through the technical scheme, the purpose of rapidly manufacturing the patterned sapphire substrate can be achieved, meanwhile, equipment and clean room space required by production are saved, and production manpower is saved by at least 50%. The prepared patterned sapphire substrate is uniform in height, and the light emitting mode can be improved and the luminous efficiency of the LED device can be improved by reasonably carrying out patterning pretreatment on the substrate. Furthermore, the soft photomask is provided with the cylindrical hole-shaped structures which are arranged in an array manner, the bottom surface of the cylindrical hole-shaped structures is provided with the metal aluminum shading layer, and the structure is simple and does not need special design, so that the patterned sapphire substrate can be formed. In addition, when the patterned sapphire substrate is prepared by using the soft photomask, the process can be shortened, and the production efficiency can be improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a flow chart of a process for fabricating a flexible photomask according to the present invention;
FIG. 2 is a flowchart of the PSS fabrication of the soft mask of the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a preparation method of a patterned sapphire substrate, which comprises the following steps:
s1, coating photoresist on a sapphire substrate and drying;
s2, paving a soft photomask on the photoresist, exposing and developing, and forming a photoresist mask pattern on the photoresist; the soft photomask is provided with a plurality of grooves which are arrayed on one side facing the photoresist, and the bottom surface of each groove is provided with a metal aluminum shading layer;
s3, etching the sapphire substrate with the photoresist mask pattern; the etching comprises a first etching stage and a second etching stage, wherein the first etching stageThe etching gas is BCl 3 The etching gas in the second etching stage is Cl 2 And BCl 3 Is a mixed gas of (a) and (b).
According to the preparation method of the patterned sapphire substrate, the patterned sapphire substrate can be attached to the sapphire substrate by utilizing the soft characteristic of the soft photomask material, a cylindrical mask layer can be obtained by exposing and developing the soft photomask, and the patterned sapphire substrate can be manufactured after two-stage etching process. The manufacturing method of the patterned sapphire substrate solves various defects of the traditional step-by-step exposure and imprinting process, reduces the manufacturing cost of the patterned sapphire substrate, shortens the process, and improves the process yield of the patterned sapphire substrate. The prepared patterned sapphire substrate is uniform in height, and the process is simple and easy to operate, so that the patterned sapphire substrate is very suitable for mass production. Through carrying out reasonable graphical pretreatment to the sapphire substrate, the light emitting mode can be improved, and the luminous efficiency of the LED device is improved.
According to the invention, optionally, the patterned sapphire substrate comprises a sapphire substrate and a plurality of microstructures formed on the sapphire substrate and arranged in an array, wherein the microstructures are uniformly distributed on the sapphire substrate at intervals; the microstructure is one of conical protrusions, truncated cone-shaped protrusions, polygonal conical protrusions, polygonal truncated cone-shaped protrusions, elliptical protrusions, spherical protrusions and hemispherical protrusions; the microstructure is arranged in one of rectangular array arrangement, hexagonal closest packing array arrangement and random array arrangement. Compared with a non-structural flat sapphire substrate, the patterned sapphire substrate structure can reduce the phenomenon that the total reflection of a light source is limited in the sapphire substrate, so that the light extraction efficiency of an LED can be improved.
According to the invention, the microstructure may alternatively have a height of 1-3 μm and a bottom diameter of 2-4 μm; the distance between two adjacent microstructures may be 2-5 μm.
According to the present invention, optionally, the soft photomask is prepared by a method comprising the following steps:
s1, pouring silica gel into a silicon plate with a plurality of cylindrical bulges arranged in an array, and then baking to solidify and demould the silica gel to obtain a soft substrate with grooves; the groove is of a cylindrical hole structure;
s2, depositing a metal aluminum layer on the flexible substrate, and then coating positive photoresist on the metal aluminum layer;
and S3, exposing and developing the positive photoresist, and then etching and cleaning the positive photoresist by using an aluminum etching solution to obtain the soft photomask.
According to the present invention, alternatively, the diameter of the cylindrical protrusion may be 1-3 μm and the height may be 2-4 μm; the distance between two adjacent cylindrical protrusions may be 2-5 μm; the arrangement mode of the cylindrical protrusions is one of rectangular array arrangement, hexagonal closest packing arrangement and random arrangement. In a preferred embodiment, the cylindrical protrusions are arranged in a hexagonal closest packing arrangement.
According to the invention, alternatively, the diameter of the cylindrical hole-like structures can be 1-3 μm, the depth can be 2-4 μm, and the distance between two adjacent cylindrical hole-like structures can be 2-5 μm; the arrangement of the cylindrical hole-like structures may be one of rectangular array arrangement, hexagonal closest packing arrangement and random arrangement, and in a preferred embodiment, the cylindrical arrangement is hexagonal closest packing arrangement.
According to the present invention, alternatively, the thickness of the metallic aluminum layer may be 1-3 μm; the thickness of the positive photoresist may be 1-3 μm.
According to the invention, alternatively, the exposure energy may be 20-30mJ and the exposure time may be 1-1.5s; the development time may be 20 to 40s; the etching time may be 1-5min. The exposure energy can fully expose the positive photoresist on the flexible substrate, but does not expose the positive photoresist on the bottom surface of the groove, the exposed positive photoresist is developed by using a developing solution, at the moment, only the metal aluminum layer is arranged on the plane of the flexible substrate, and the positive photoresist in the groove is covered on the metal aluminum layer; carrying out wet etching by using an aluminum etching liquid, wherein the metal aluminum layer in the groove can not be etched due to the protection of positive photoresist, and the metal aluminum layer on the plane of the flexible substrate can be etched cleanly; and then cleaning the positive photoresist in the groove by using acetone to obtain the soft photomask.
According to the invention, the baking temperature may be optionally 60-75 ℃ and the time may be 20-60min.
According to the present invention, optionally, in step S1, the photoresist may be a positive photoresist, and the thickness of the positive photoresist is suitable to make the resolution of the photoresist high, the contrast of the photoresist good, and the pattern uniformity of the photoresist good, for example, the thickness of the positive photoresist may be 2-5 μm.
According to the present invention, optionally, in step S2, the exposure energy may be 10-30mJ, and the exposure time may be 1-1.5S; the development time may be 20 to 40s. In a preferred embodiment, the exposure mode can adopt contact exposure, the soft photomask is directly contacted with the photoresist layer, the resolution of the exposed pattern is equivalent to that of the pattern on the soft photomask, the equipment is simple, and the problems that the stepper equipment is old, the exposure needs to be carried out in a partitioning multi-step scanning mode, the pattern splicing problem needs to be controlled by manpower continuously, the exposure is easy to lose focus, and the mass production yield is low are avoided.
According to the present invention, optionally, the parameters of the first etching stage are: BCl (binary coded decimal) 3 The inlet amount is 120-140sccm, the pressure is 2-4mTorr, the upper radio frequency power is 1900-2100W, the lower radio frequency power is 400-500W, and the etching is 25-30 minutes; the parameters of the second etching stage are as follows: BCl (binary coded decimal) 3 And Cl 2 The mixed gas is introduced into the reactor at 120-140sccm, the pressure is 2-4mTorr, the upper radio frequency power is 1800-2000W, the lower radio frequency power is 600-700W, and the etching is carried out for 8-10 minutes. In the invention, chlorine is introduced in the second etching stage to accelerate the etching speed of the mask, and the high-down radio frequency power in the second etching stage can help the pattern to be quickly shaped, so that the pattern is modified from a shell shape to a conical shape, and the process is shortened. The ICP dry etching is adopted in the etching, the etching efficiency of the ICP dry etching is high, the etching damage is small, excellent etching uniformity control is realized, the inter-chip uniformity and the process repeatability in mass production are ensured, and the ICP dry etching process can be more realizedThe luminous efficiency of the LED chip is greatly improved.
According to the invention, optionally, the BCl 3 And Cl 2 The mixed gas inlet amount comprises BCl 3 The charging amount is 10-120sccm and Cl 2 The amount of the mixture is 10-120sccm. In the invention, BCl with arbitrary proportion 3 And Cl 2 The etching speed of the mask can be increased, and the total etching time is shortened.
The second aspect of the invention provides a patterned sapphire substrate, which is prepared by the method provided by the first aspect of the invention.
A third aspect of the present invention provides a use of the patterned sapphire substrate provided in the second aspect of the present invention for the manufacture of a semiconductor device. For example, patterned sapphire substrates may be used to fabricate LED chips.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
Example 1
S1, manufacturing a soft photomask shown in FIG. 1, namely designing cylinders with the diameter of 2 mu m and the height of 2.2 mu m on a silicon plate by using a master plate silicon plate, arranging adjacent cylinders in a hexagonal closest packing mode, pouring silica gel (PDMS) on the silicon plate, baking at 70 ℃ for 45min to solidify and demolding to obtain a soft substrate;
s2, depositing a 2 mu m thick aluminum metal layer on the flexible substrate by using sputtering equipment through a sputtering method, wherein the sputtering power is 1300W, and the moving speed of the carrier is 1m/min. Coating positive photoresist with the thickness of 2 mu m on an aluminum metal layer by using a spin speed of 2000rpm of a spin coater, then selectively exposing the positive photoresist for 1s at the moving speed of 0.1m/min by using a UV LED linear exposure machine under the energy of 25mJ, fully exposing the upper part of a soft substrate plane, developing the positive photoresist above the soft substrate plane by using a developing solution for 30s to develop the exposed positive photoresist, wherein only the metal aluminum layer is arranged on the soft substrate plane, and the positive photoresist in the groove is covered on the metal aluminum layer;
s3, carrying out wet etching for 3min through an aluminum etching liquid, wherein the metal aluminum layer in the groove can not be etched due to the protection of positive photoresist, and the metal aluminum layer on the plane of the flexible substrate can be etched cleanly; then cleaning the positive photoresist in the groove by using acetone to obtain the soft photomask;
s4, as shown in FIG. 2, directly paving a soft photomask on the sapphire substrate coated with the photoresist with the thickness of 2.5 mu m, carrying out full-face exposure for 1S by using energy of 20mJ, and developing for 30S by using a developing solution after exposure to obtain cylinders with the diameter of 2 mu m and the height of 2.5 mu m, wherein the distance between two adjacent cylinders is 3 mu m;
s5, performing ICP dry etching, wherein the etching stage is divided into a first etching stage and a second etching stage, and the technological parameters of the first etching stage are as follows: BCl (binary coded decimal) 3 The input amount is 130sccm, the pressure is 3mTorr, the upper radio frequency power is 2000W, the lower radio frequency power is 450W, the etching is carried out for 30 minutes, and the technological parameters of the second etching stage are as follows: BCl (binary coded decimal) 3 110sccm and Cl 2 And the taper patterns with the height of 1.8 mu m and the diameter of 2.8 mu m are obtained by etching for 10 minutes under the conditions that the input quantity is 20sccm, the pressure is 3mTorr, the upper radio frequency power is 2000W, the lower radio frequency power is 650W, and the distance between two adjacent taper patterns is 3 mu m. After etching, 98% sulfuric acid and 30% hydrogen peroxide are adopted for 4: and 1, washing the mixed washing liquid for 10min to obtain a final patterned sapphire substrate finished product.
Example 2
The preparation method of this example is the same as that of example 1, except that the thickness of the photoresist is 3.5 μm, the exposure energy is 30mJ, and the exposure time is 1.5s; developing with developing solution for 40s after exposure; the technological parameters of the second etching stage are as follows: BCl (binary coded decimal) 3 The amount of the mixture to be introduced is 90sccm and Cl 2 The total etching time is 35 minutes with the feeding amount of 40sccm, the pressure of 3mTorr, the upper radio frequency power of 2000W and the lower radio frequency power of 650W, and the cone with the period of 3 μm, the diameter of 3.5 μm and the height of 2.5 μm is obtained.
Comparative example 1
The preparation method of this comparative example is identical to that of example 1, except that the process parameters of the first etching stage are: BCl (binary coded decimal) 3 Introducing 130sccm, pressure 3mTorr, upper radio frequency power 2000W, lower radio frequency power 450W, etching for 30 min, and second etchingThe technological parameters of the etching stage are as follows: BCl (binary coded decimal) 3 130sccm of pressure, 3mTorr of upper radio frequency power, 2000W of lower radio frequency power and 600W of lower radio frequency power are introduced, and etching is carried out for 20 minutes, so that a cone with a period of 3 μm, a diameter of 2.5 μm and a height of 1.5 μm is obtained.
According to the invention, the soft photomask containing the metal aluminum layer is used for exposing the photoresist with proper thickness, the cylindrical mask layer can be obtained by developing after exposure, and the patterned sapphire substrate can be manufactured after two-stage etching process, so that the process is shortened, and the production efficiency is improved. The patterned sapphire substrate has high light-emitting efficiency, and further, the light extraction efficiency of the LED can be improved. In comparative example 1, no chlorine gas was introduced during the second etching stage, the etching mask speed was reduced, and the process was increased. Therefore, the manufacturing method of the invention reduces the manufacturing cost of the patterned sapphire substrate, shortens the process, improves the process yield of the patterned sapphire substrate, and is simple and easy to operate, thus being very suitable for mass production. Through carrying out reasonable graphical pretreatment to the sapphire substrate, the light emitting mode can be improved, and the luminous efficiency of the LED device is improved.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The preparation method of the patterned sapphire substrate is characterized by comprising the following steps of:
s1, coating photoresist on a sapphire substrate and drying;
s2, paving a soft photomask on the photoresist, exposing and developing, and forming a photoresist mask pattern on the photoresist; the soft photomask is provided with a plurality of grooves which are arrayed on one side facing the photoresist, and the bottom surface of each groove is provided with a metal aluminum shading layer;
s3, etching the sapphire substrate with the photoresist mask pattern; the etching comprises a first etching stage and a second etching stage, wherein the etching gas of the first etching stage is BCl 3 The etching gas in the second etching stage is Cl 2 And BCl 3 Is a mixed gas of (a) and (b).
2. The method of claim 1, wherein the soft mask is prepared by a method comprising:
s1, pouring silica gel into a silicon plate with a plurality of cylindrical bulges arranged in an array, and then baking to solidify and demould the silica gel to obtain a soft substrate with grooves; the groove is of a cylindrical hole structure;
s2, depositing a metal aluminum layer on the flexible substrate, and then coating positive photoresist on the metal aluminum layer;
and S3, exposing and developing the positive photoresist, and then etching and cleaning the positive photoresist by using an aluminum etching solution to obtain the soft photomask.
3. The manufacturing method according to claim 2, wherein the diameter of the cylindrical protrusion is 1-3 μm and the height is 2-4 μm; the distance between two adjacent cylindrical bulges is 2-5 mu m; the arrangement mode of the cylindrical protrusions is one of rectangular array arrangement, hexagonal closest packing arrangement and random arrangement.
4. The production method according to claim 2, wherein the thickness of the metallic aluminum layer is 1-3 μm; the thickness of the positive photoresist is 1-3 mu m.
5. The production method according to claim 2, wherein the exposure energy is 20 to 30mJ and the exposure time is 1 to 1.5s; the development time is 20-40s; the etching time is 1-5min; and/or the number of the groups of groups,
the baking temperature is 60-75deg.C, and the baking time is 20-60min.
6. The method according to claim 1, wherein in step S1, the photoresist is a positive photoresist having a thickness of 2 to 5 μm; and/or the number of the groups of groups,
in the step S2, the exposure energy is 10-30mJ, and the exposure time is 1-1.5S; the development time is 20-40s.
7. The method of manufacturing according to claim 1, wherein the parameters of the first etching stage are: BCl (binary coded decimal) 3 The inlet amount is 120-140sccm, the pressure is 2-4mTorr, the upper radio frequency power is 1900-2100W, the lower radio frequency power is 400-500W, and the etching is 25-30 minutes; and/or, the parameters of the second etching stage are as follows: BCl (binary coded decimal) 3 And Cl 2 The mixed gas is introduced into the reactor at 120-140sccm, the pressure is 2-4mTorr, the upper radio frequency power is 1800-2000W, the lower radio frequency power is 600-700W, and the etching is carried out for 8-10 minutes.
8. The method of claim 7, wherein the BCl 3 And Cl 2 The mixed gas inlet amount comprises BCl 3 The charging amount is 10-120sccm and Cl 2 The amount of the mixture is 10-120sccm.
9. A patterned sapphire substrate prepared by the method of any of claims 1-8.
10. Use of the patterned sapphire substrate of claim 9 for the manufacture of a semiconductor device.
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| CN202311187683.1A CN117373903A (en) | 2023-09-13 | 2023-09-13 | Graphical sapphire substrate and preparation method and application thereof |
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| CN202311187683.1A CN117373903A (en) | 2023-09-13 | 2023-09-13 | Graphical sapphire substrate and preparation method and application thereof |
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