CN104465900A - Structured arrangement manometer coarsened sapphire substrate and preparation method - Google Patents
Structured arrangement manometer coarsened sapphire substrate and preparation method Download PDFInfo
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- CN104465900A CN104465900A CN201410724538.7A CN201410724538A CN104465900A CN 104465900 A CN104465900 A CN 104465900A CN 201410724538 A CN201410724538 A CN 201410724538A CN 104465900 A CN104465900 A CN 104465900A
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- 239000000758 substrate Substances 0.000 title claims abstract description 108
- 229910052594 sapphire Inorganic materials 0.000 title claims abstract description 91
- 239000010980 sapphire Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000005484 gravity Effects 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 104
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 62
- 239000000377 silicon dioxide Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 36
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 230000003628 erosive effect Effects 0.000 claims description 16
- 230000007704 transition Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 238000000605 extraction Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 238000009616 inductively coupled plasma Methods 0.000 description 24
- 235000012239 silicon dioxide Nutrition 0.000 description 23
- 239000002105 nanoparticle Substances 0.000 description 18
- 238000001312 dry etching Methods 0.000 description 16
- 238000001039 wet etching Methods 0.000 description 16
- 238000005530 etching Methods 0.000 description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 5
- 229960000909 sulfur hexafluoride Drugs 0.000 description 5
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/20—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
- H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers
-
- 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
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention relates to a structured arrangement manometer coarsened sapphire substrate and a preparation method. The sapphire substrate is provided with composite patterns formed by combining micron order patterns and nanometer order patterns, the nanometer order patterns are distributed on the micron order patterns, and the nanometer order patterns are distributed on the radiuses or the connecting lines of the gravity centers and the corners of the upper surfaces of the micron order patterns. The central points of the lower surfaces of the nanometer order patterns coincide with the central points of the radiuses or the centers of the connecting lines of the gravity centers and the corners of the upper surfaces of the micron order patterns. The nanometer order patterns on each micron order pattern are distributed symmetrically. The method comprises the steps that firstly, the micron order patterns are prepared on the sapphire substrate, and then the nanometer order patterns are prepared on the micron order patterns. By means of the structured arrangement manometer coarsened sapphire substrate and the preparation method, the propagation direction of light can be effectively changed, the probability of light overflow is increased, a light path can be effectively emitted out, the reflection of the patterns to light is enhanced, so that the propagation direction of the light is changed, and the light extraction efficiency and the light output power of a GaN-based LED with the sapphire substrate are improved.
Description
Technical field
The present invention relates to and a kind ofly for epitaxial growth GaN crystal, there is Sapphire Substrate of nanometer alligatoring compound pattern and preparation method thereof, belong to semiconductor crystal preparing technical field.
Background technology
GaN has the characteristics such as wide direct band gap, high electron saturation velocities, high breakdown electric field and high heat conductance, has very large application potential at photoelectron and microelectronic.GaN and other III group nitride (InN, AlN) can form ternary or quaternary solid solution, and its energy gap is from 0.7eV to 6.28eV, and emission wavelength, from infrared adjustable to ultraviolet, obtains extensive use at blue green light and ultraviolet band opto-electronic device.
Owing to lacking large scale GaN substrate, current GaN film is generally grown by heteroepitaxy on the substrates such as sapphire, carborundum and silicon.Sapphire is due to low price, and transparency is high, chemical stability and Heat stability is good, is the most frequently used substrate of current commercialization GaN base LED.
The lattice mismatch about 16% of GaN film and Sapphire Substrate, therefore the GaN film of Sapphire Substrate Epitaxial growth has higher dislocation density.The refractive index of GaN about 2.4 in addition, much larger than the refractive index of air, therefore total reflection effect can reduce the light extraction efficiency of LED.
Prepare the figure of nanometer or micron dimension on a sapphire substrate, can make GaN that horizontal extension occurs, improve the crystal mass of GaN film.Figure can change the direction of propagation of light in addition, suppresses total reflection effect, improves the light extraction efficiency of GaN base LED.
Chinese patent literature CN102064088B disclosed " a kind of dry etching and wet etching are mixed with the method for sapphire pattern substrate ", make mask by silicon dioxide or silicon nitride, first utilize ICP dry etching silicon dioxide or silicon nitride mask, the triangle of formation rule and ring-shaped figure, then adopt the mixed solution wet etching sapphire of sulfuric acid and phosphoric acid, prepare sapphire pattern substrate.The CN102184842B disclosed method of graphic sapphire " a kind of wet etching combine with dry etching " deposits layer of silicon dioxide film on a sapphire substrate; Utilize photoetching technique on described silicon dioxide film, prepare the photoresist mask of band figure; Litho pattern is etched on silicon dioxide film; With patterned silicon dioxide film for mask, adopt wet etching in conjunction with the method for short time dry etching, by pattern etching in Sapphire Substrate; Wet etching removes silicon dioxide film, and Sapphire Substrate is cleaned up, and completes the preparation of graphical sapphire substrate.
CN102790150A disclosed " manufacture method of the bowl-shape sapphire pattern substrate of a kind of nanometer ", it is cvd silicon dioxide film on cesium chloride nano island, cesium chloride nano island is removed afterwards by ultrasonic method, silicon dioxide becomes etch mask, adopts the preparation of ICP technology to have the Sapphire Substrate of the bowl-shape figure of nanometer.
CN102881791A disclosed " a kind of sapphire LED graph substrate and preparation method thereof ", deposit DBR on a sapphire substrate in advance, then inductively coupled plasma (ICP) dry etching technology is adopted to prepare figure, finally obtain the Sapphire Substrate with graphical DBR, be actually the novel graphic substrate depositing DBR reflector on a sapphire substrate in advance.
Graphical sapphire substrate in above-mentioned document all just has the figure of single micron dimension, and its structure as shown in Figure 1, is prepare micron dimension figure 2 in Sapphire Substrate 1.The light that GaN base LED active area sends reflects through the figure of micron-scale, the direction of propagation can be changed, increase escape probability, but still have very most of light to be limited in GaN film and Sapphire Substrate inside because of total reflection effect, cause optical output power on the low side.
Summary of the invention
The present invention is directed to the problem lower at the light extraction efficiency of the GaN base LED prepared with it (light-emitting diode) that existing graphical sapphire substrate exists, a kind of regular arrangement nanometer alligatoring Sapphire Substrate and the preparation method that can obtain high light extraction efficiency GaN base LED are provided, a kind of preparation method of this Sapphire Substrate is provided simultaneously.
Regular arrangement nanometer alligatoring Sapphire Substrate of the present invention, it has the compound pattern that micron dimension figure and nanometer scale figure combine, each micron dimension figure is distributed with nanometer scale figure, and nanometer scale graphical distribution is on the radius (when upper surface is circular) of micron dimension figure upper surface or the line at center of gravity and each angle (when upper surface is polygon).
The central point of described nanometer scale figure lower surface overlaps with the mid point of the line at each angle with the mid point of the radius of described micron dimension figure upper surface or center of gravity.
Nanometer scale graphical distribution on each micron dimension figure is symmetrical.
Described micron dimension figure is round platform or the terrace with edge of micron dimension.The height of described micron dimension figure is 1 μm-20 μm, basal diameter (basal diameter of terrace with edge is its most long-diagonal) 1 μm-25 μm.
Described nanometer scale figure is pyramid, terrace with edge, hemisphere or other any irregular figure.The height of described nanometer scale figure is 10nm-700nm, and bottom width is 1nm-900nm.
The preparation method of the Sapphire Substrate of above-mentioned nanometer alligatoring compound pattern, prepares micron dimension figure first on a sapphire substrate, and then prepare nanometer scale figure on micron dimension figure; Specifically comprise the following steps:
(1) figure of micron dimension is prepared on a sapphire substrate;
Adopt ICP or wet etching method preparation.
(2) figure of the micron dimension formed in step (1) deposits the silica membrane of a layer thickness 50nm-1000nm;
(3) on the silica membrane of step (2), deposit the Ag films of a layer thickness 50nm-500nm again;
(4) substrate that step (3) is formed is annealed in air or oxygen, annealing temperature 100-2050 DEG C, 30 seconds-6000 seconds time, Ag films is made to be agglomerated into the particle of nanoscale, the figure (namely the particle of nanoscale is nanometer scale figure) of described nanometer scale is pyramid, terrace with edge, hemisphere or other any irregular figure, the height of the figure of described nanometer scale is 10nm-700nm, and bottom width is 1nm-900nm;
(5) by silver nano-grain Graphic transitions on silica membrane;
Shifted by the method for dry etching or wet etching:
ICP dry etch step: load in ICP etching apparatus by the Sapphire Substrate with silver nano-grain figure, setting ICP etching apparatus technological parameter, transfers to photoetching offset plate figure in Sapphire Substrate.
Wet etch step: the Sapphire Substrate with acid solution corrosion with silver nano-grain figure, by its Graphic transitions in Sapphire Substrate, rinsing dries.
(6) silver nano-grain is eroded;
Corrosive liquid is the mixed solution of ammoniacal liquor, hydrogen peroxide and water, and the volume ratio of ammoniacal liquor and hydrogen peroxide is 1:3-3:1, and the volume ratio of ammoniacal liquor, hydrogen peroxide mixed liquor and water is 1:10-1:0.2;
(7) erosion removal earth silicon mask layer, corrosive liquid is the mixed solution of hydrofluoric acid and water, and the volume ratio of hydrofluoric acid and water is 2:9-1:1;
(8) adopt acetone, ethanol and deionized water to clean step (7) gained substrate respectively, finally obtain the Sapphire Substrate with micron and nano combined figure.
The present invention prepares the compound pattern of micron dimension figure and nanometer scale figure on a sapphire substrate, nanometer scale pattern arrangement is on the central point of micron dimension figure and the connecting line at each angle, and the point coincides of the central point of nanometer scale figure and described connecting line.Nanometer alligatoring is carried out to the figure of micron-scale, effectively can change the direction of propagation of light, improve the probability of light effusion.Nanometer scale figure simultaneously on setting unit micron dimension figure, nanometer scale figure on same diagonal is symmetric figure, the nanometer scale figure of Formation rule on micron dimension figure, make light path outgoing effectively, more enhance the reflection of figure for light, thus change the direction of propagation of light, and then strengthen light extraction efficiency and the optical output power of Sapphire Substrate GaN base LED.Under identical LED growth conditions, nanometer alligatoring compound pattern Sapphire Substrate prepared by the present invention compares other patterned substrate, and its light extraction efficiency is high by 10%.
Accompanying drawing explanation
Fig. 1 is the generalized section of Conventional patterning Sapphire Substrate.
Fig. 2 is the generalized section of regular arrangement nanometer alligatoring Sapphire Substrate of the present invention.
Fig. 3 is the schematic diagram in embodiment 1 with nanometer alligatoring compound pattern.
Fig. 4 is the schematic diagram in embodiment 2 with nanometer alligatoring compound pattern.
Fig. 5 is the end view of figure described in Fig. 4.
Fig. 6 is the schematic diagram in embodiment 3 with nanometer alligatoring compound pattern.
In figure: 1, Sapphire Substrate; 2, micron dimension figure; 3, there is the micron figure of nanometer alligatoring; 4, nanometer scale figure
Embodiment
As shown in Figure 2, regular arrangement nanometer alligatoring Sapphire Substrate of the present invention has the compound pattern 3 of micron dimension figure 2 and nanometer scale figure 4 combination, micron dimension figure 2 is arranged nanometer scale figure 4.Nanometer scale figure 4 is distributed on the radius (upper surface be circular time) of the upper surface of micron dimension figure 2 or the line at center of gravity and each angle (when upper surface is polygon), and the mid point of the central point of nanometer scale figure 2 and described radius or center of gravity overlap with the mid point of the line at each angle.The nanometer scale pattern symmetrical that each micron dimension figure distributes.
The preparation method of the present invention's regular arrangement nanometer alligatoring Sapphire Substrate can be undertaken by described in following examples.
Embodiment 1
(1) layer of silicon dioxide mask is deposited on a sapphire substrate; Mask layer is coated with last layer photoresist, utilizes ICP equipment etching mask layer, form mask pattern, with sulfuric acid and phosphoric acid mixed solution wet etching sapphire.Prepare micron dimension figure 1; Micron dimension figure is round platform, and the height of round platform is 1.5 μm, and basal diameter is 2 μm.
(2) substrate is cleaned, then the silica membrane of deposit thickness 200nm on micron dimension figure 1.
(3) clean substrate, then the Ag films of deposit thickness 100nm on silica membrane, anneals in atmosphere, temperature 250 degree, 1000 seconds time, and Ag films is reunited in nano particle.
(4) by ICP dry etching figure transfer method by nano particle Graphic transitions on silica membrane, employing etching gas is sulphur hexafluoride.
(5) erosion removal silver nano-grain, described solution is the mixture of ammoniacal liquor, hydrogen peroxide and water, and the volume ratio of ammoniacal liquor and hydrogen peroxide is 1:3, and the volume ratio of ammoniacal liquor, hydrogen peroxide mixed liquor and water is 1:10.
(6) ICP dry etching Sapphire Substrate, micron figure carries out nanometer alligatoring.
(7) substrate described in step (6) is put into mixed solution (volume ratio of hydrofluoric acid and water is 1:1) the erosion removal silicon dioxide etch mask of hydrofluoric acid and water, acetone, ethanol and deionized water is adopted to clean gained substrate respectively, obtain the Sapphire Substrate with nanometer alligatoring compound pattern, as shown in Figure 3.
Embodiment 2
(1) layer of silicon dioxide mask is deposited on a sapphire substrate; Mask layer is coated with last layer photoresist, utilizes ICP equipment etching mask layer, form mask pattern; With sulfuric acid and phosphoric acid mixed solution wet etching sapphire.Prepare micron dimension figure 1; Micron dimension figure is corner terrace with edge, and the height of figure is 10 μm, and basal diameter (i.e. the most long-diagonal in bottom surface) is 10 μm, and the most short diagonal in bottom surface is 6 μm.
(2) substrate is cleaned, then the silica membrane of deposit thickness 1000nm on micron dimension figure 1.
(3) on the silica membrane of step (2), deposit the Ag films of a layer thickness 200nm again; Anneal in oxygen, temperature 900 degree, time 5000s, makes Ag films reunite in nano particle.
(4) by wet etching graph transfer method by nano particle Graphic transitions on silica membrane, specifically adopt the aqueous solution of hydrofluoric acid (volume ratio of hydrofluoric acid and water is 1:5) by nano particle Graphic transitions on silica membrane.
(5) erosion removal silver nano-grain, described solution is the mixture of ammoniacal liquor, hydrogen peroxide and water, and the volume ratio of ammoniacal liquor and hydrogen peroxide is 1:2, and the volume ratio of ammoniacal liquor, hydrogen peroxide mixed liquor and water is 2:3.
(6) adopt the mixed solution (volume ratio of sulfuric acid and phosphoric acid is 1:1) of sulfuric acid and phosphoric acid to corrode Sapphire Substrate, micron figure carries out nanometer alligatoring.Silver nano-grain is reunited on the terrace with edge of micron dimension corner, and under test proof employing this kind of condition manufacture method, silver nano-grain is jiao terrace with edge of five shown in Fig. 44, five jiaos of terrace with edges are arranged on the diagonal central point of corner terrace with edge, and both central spot overlap, up and down, symmetric figure centered by five jiaos of terrace with edges of left and right.
(7) substrate described in step (6) is put into mixed solution (volume ratio of hydrofluoric acid and water is 1:2) the erosion removal silicon dioxide etch mask of hydrofluoric acid and water, acetone, ethanol and deionized water is adopted to clean gained substrate respectively, obtain the Sapphire Substrate with nanometer alligatoring compound pattern, as shown in Figure 4 and Figure 5.
Embodiment 3
(1) layer of silicon dioxide mask is deposited on a sapphire substrate; Mask layer is coated with last layer photoresist, utilizes ICP equipment etching mask layer, form mask pattern; With sulfuric acid and phosphoric acid mixed solution wet etching sapphire.Prepare micron dimension figure 1; Micron dimension figure is five jiaos of terrace with edges, and the height of figure is 10 μm, and basal diameter is 25 μm (basal diameter of terrace with edge, i.e. its most long-diagonals).
(2) figure of the micron dimension formed in step (1) deposits the silica membrane of a layer thickness 500nm;
(3) on the silica membrane of step (2), deposit the Ag films of a layer thickness 300nm again; Anneal in atmosphere, temperature 2000 degree, time 200s, makes Ag films reunite in nano particle.Test proves, adopt silver nano-grain prepared by this kind of condition, the height of figure is 500nm, and basal diameter is 20nm.
(4) by ICP dry etching figure transfer method by nano particle Graphic transitions on silica membrane, employing etching gas is sulphur hexafluoride.
(5) erosion removal silver nano-grain, described solution is the mixture of ammoniacal liquor, hydrogen peroxide and water, and the volume ratio of ammoniacal liquor and hydrogen peroxide is 3:1, and the volume ratio of ammoniacal liquor, hydrogen peroxide mixed liquor and water is 1:0.2.
(6) ICP dry etching Sapphire Substrate, micron figure carries out nanometer alligatoring.The nano particle figure 4 obtained is round platform.
(7) substrate described in (6) is put into mixed solution (volume ratio of ammoniacal liquor, hydrogen peroxide and water is 1:1:2) the erosion removal silicon dioxide etch mask of ammoniacal liquor, hydrogen peroxide and water, acetone, ethanol and deionized water is adopted to clean gained substrate respectively, obtain the Sapphire Substrate with nanometer alligatoring compound pattern, as shown in Figure 6, the symmetry axis of nano particle figure 4 is any center of gravity of micron dimension figure lower surface and the connecting line at angle).
Embodiment 4
(1) layer of silicon dioxide mask is deposited on a sapphire substrate; Mask layer is coated with last layer photoresist, utilizes ICP equipment etching mask layer, form mask pattern; With sulfuric acid and phosphoric acid mixed solution wet etching sapphire.Prepare micron dimension figure 1; Micron dimension figure is five jiaos of terrace with edges, and the height of figure is 1 μm, and basal diameter is 1 μm (basal diameter of terrace with edge, i.e. its most long-diagonal).
(2) figure of the micron dimension formed in step (1) deposits the silica membrane of a layer thickness 1000nm;
(3) on the silica membrane of step (2), deposit the Ag films of a layer thickness 500nm again; Anneal in atmosphere, temperature 100 degree, time 6000s, makes Ag films reunite in nano particle.Test proves, adopt silver nano-grain prepared by this kind of condition, the height of figure is 10nm, and basal diameter is 900nm.
(4) by ICP dry etching figure transfer method by nano particle Graphic transitions on silica membrane, employing etching gas is sulphur hexafluoride.
(5) erosion removal silver nano-grain, described solution is the mixture of ammoniacal liquor, hydrogen peroxide and water, and the volume ratio of ammoniacal liquor and hydrogen peroxide is 1:3, and the volume ratio of ammoniacal liquor, hydrogen peroxide mixed liquor and water is 1:10.
(6) ICP dry etching Sapphire Substrate, micron figure carries out nanometer alligatoring.
(7) substrate described in (6) is put into mixed solution (volume ratio of ammoniacal liquor, hydrogen peroxide and water is 1:1:2) the erosion removal silicon dioxide etch mask of ammoniacal liquor, hydrogen peroxide and water, adopt acetone, ethanol and deionized water to clean gained substrate respectively, obtain the Sapphire Substrate with nanometer alligatoring compound pattern.
Embodiment 5
(1) layer of silicon dioxide mask is deposited on a sapphire substrate; Mask layer is coated with last layer photoresist, utilizes ICP equipment etching mask layer, form mask pattern; With sulfuric acid and phosphoric acid mixed solution wet etching sapphire.Prepare micron dimension figure 1; Micron dimension figure is five jiaos of terrace with edges, and the height of figure is 20 μm, and basal diameter is 25 μm (basal diameter of terrace with edge, i.e. its most long-diagonals).
(2) figure of the micron dimension formed in step (1) deposits the silica membrane of a layer thickness 50nm;
(3) on the silica membrane of step (2), deposit the Ag films of a layer thickness 50nm again; Anneal in atmosphere, temperature 2050 degree, time 30s, makes Ag films reunite in nano particle.Test proves, adopt silver nano-grain prepared by this kind of condition, the height of figure is 700nm, and basal diameter is 1nm.
(4) by ICP dry etching figure transfer method by nano particle Graphic transitions on silica membrane, employing etching gas is sulphur hexafluoride.
(5) erosion removal silver nano-grain, described solution is the mixture of ammoniacal liquor, hydrogen peroxide and water, and the volume ratio of ammoniacal liquor and hydrogen peroxide is 3:1, and the volume ratio of ammoniacal liquor, hydrogen peroxide mixed liquor and water is 1:0.2.
(6) ICP dry etching Sapphire Substrate, micron figure carries out nanometer alligatoring.
(7) substrate described in step (6) is put into mixed solution (volume ratio of hydrofluoric acid and water is 2:9) the erosion removal silicon dioxide etch mask of hydrofluoric acid and water, adopt acetone, ethanol and deionized water to clean gained substrate respectively, obtain the Sapphire Substrate with nanometer alligatoring compound pattern.
Embodiment 6
(1) layer of silicon dioxide mask is deposited on a sapphire substrate; Mask layer is coated with last layer photoresist, utilizes ICP equipment etching mask layer, form mask pattern, with sulfuric acid and phosphoric acid mixed solution wet etching sapphire.Prepare micron dimension figure 1; Micron dimension figure is round platform, and the height of round platform is 1.5 μm, and basal diameter is 2 μm.
(2) substrate is cleaned, then the silica membrane of deposit thickness 200nm on micron dimension figure 1.
(3) clean substrate, then the Ag films of deposit thickness 100nm on silica membrane, anneals in atmosphere, temperature 250 degree, 1000 seconds time, and Ag films is reunited in nano particle.
(4) by ICP dry etching figure transfer method by nano particle Graphic transitions on silica membrane, employing etching gas is sulphur hexafluoride.
(5) erosion removal silver nano-grain, described solution is the mixture of ammoniacal liquor, hydrogen peroxide and water, and the volume ratio of ammoniacal liquor and hydrogen peroxide is 1:3, and the volume ratio of ammoniacal liquor, hydrogen peroxide mixed liquor and water is 1:10.
(6) ICP dry etching Sapphire Substrate, micron figure carries out nanometer alligatoring.
(7) substrate described in step (6) is put into mixed solution (volume ratio of hydrofluoric acid and water is 1:1) the erosion removal silicon dioxide etch mask of hydrofluoric acid and water, acetone, ethanol and deionized water is adopted to clean gained substrate respectively, obtain the Sapphire Substrate with nanometer alligatoring compound pattern, as shown in Figure 3.
Embodiment 7
(1) layer of silicon dioxide mask is deposited on a sapphire substrate; Mask layer is coated with last layer photoresist, utilizes ICP equipment etching mask layer, form mask pattern; With sulfuric acid and phosphoric acid mixed solution wet etching sapphire.Prepare micron dimension figure 1; Micron dimension figure is corner terrace with edge, and the height of figure is 1 μm, and basal diameter (i.e. the most long-diagonal in bottom surface) is 25 μm, and the most short diagonal in bottom surface is 1 μm.
(2) substrate is cleaned, then the silica membrane of deposit thickness 1000nm on micron dimension figure 1.
(3) on the silica membrane of step (2), deposit the Ag films of a layer thickness 500nm again; Anneal in oxygen, temperature 2050 degree, time 6000s, makes Ag films reunite in nano particle.
(4) by wet etching graph transfer method by nano particle Graphic transitions on silica membrane, specifically adopt the aqueous solution of hydrofluoric acid (volume ratio of hydrofluoric acid and water is 1:1) by nano particle Graphic transitions on silica membrane.
(5) erosion removal silver nano-grain, described solution is the mixture of ammoniacal liquor, hydrogen peroxide and water, and the volume ratio of ammoniacal liquor and hydrogen peroxide is 3:1, and the volume ratio of ammoniacal liquor, hydrogen peroxide mixed liquor and water is 1:10.
(6) adopt the mixed solution (volume ratio of sulfuric acid and phosphoric acid is 1:1) of sulfuric acid and phosphoric acid to corrode Sapphire Substrate, micron figure carries out nanometer alligatoring.
(7) substrate described in step (6) is put into mixed solution (volume ratio of hydrofluoric acid and water is 1:1) the erosion removal silicon dioxide etch mask of hydrofluoric acid and water, adopt acetone, ethanol and deionized water to clean gained substrate respectively, obtain the Sapphire Substrate with nanometer alligatoring compound pattern.
Claims (10)
1. a regular arrangement nanometer alligatoring Sapphire Substrate, it has the compound pattern that micron dimension figure and nanometer scale figure combine, it is characterized in that, each micron dimension figure is distributed with nanometer scale figure, and nanometer scale graphical distribution is on the radius of micron dimension figure upper surface or the line at center of gravity and each angle.
2. regular arrangement nanometer alligatoring Sapphire Substrate according to claim 1, it is characterized in that, the central point of described nanometer scale figure lower surface overlaps with the mid point of the line at each angle with the mid point of the radius of described micron dimension figure upper surface or center of gravity.
3. regular arrangement nanometer alligatoring Sapphire Substrate according to claim 1 or 2, is characterized in that, the nanometer scale graphical distribution on described each micron dimension figure is symmetrical.
4. regular arrangement nanometer alligatoring Sapphire Substrate according to claim 1, it is characterized in that, described micron dimension figure is round platform or terrace with edge.
5. regular arrangement nanometer alligatoring Sapphire Substrate according to claim 1 or 4, it is characterized in that, the height of described micron dimension figure is 1 μm-20 μm, and basal diameter is 1 μm-25 μm.
6. regular arrangement nanometer alligatoring Sapphire Substrate according to claim 1, it is characterized in that, described nanometer scale figure is pyramid, terrace with edge, hemisphere or other any irregular figure.
7. regular arrangement nanometer alligatoring Sapphire Substrate according to claim 1 or 6, it is characterized in that, the height of described nanometer scale figure is 10nm-700nm, and bottom width is 1nm-900nm.
8. a preparation method for regular arrangement nanometer alligatoring Sapphire Substrate described in claim 1, prepares micron dimension figure first on a sapphire substrate, and then prepare nanometer scale figure on micron dimension figure; It is characterized in that, comprise the following steps:
(1) figure of micron dimension is prepared on a sapphire substrate;
(2) figure of the micron dimension formed in step (1) deposits the silica membrane of a layer thickness 50nm-1000nm;
(3) on the silica membrane of step (2), deposit the Ag films of a layer thickness 50nm-500nm again;
(4) substrate that step (3) is formed is annealed in air or oxygen, annealing temperature 100-2050 DEG C, 30 seconds-6000 seconds time, Ag films is made to be agglomerated into the particle of nanoscale, the figure of described nanometer scale is pyramid, terrace with edge, hemisphere or other any irregular figure, the height of the figure of described nanometer scale is 10nm-700nm, and bottom width is 1nm-900nm;
(5) by silver nano-grain Graphic transitions on silica membrane;
(6) silver nano-grain is eroded;
(7) erosion removal earth silicon mask layer;
(8) adopt acetone, ethanol and deionized water to clean step (7) gained substrate respectively, finally obtain the Sapphire Substrate with micron and nano combined figure.
9. the preparation method of regular arrangement nanometer alligatoring Sapphire Substrate according to claim 8, it is characterized in that, the corrosive liquid that described step (6) adopts is the mixed solution of ammoniacal liquor, hydrogen peroxide and water, the volume ratio of ammoniacal liquor and hydrogen peroxide is 1:3-3:1, and the volume ratio of ammoniacal liquor, hydrogen peroxide mixed liquor and water is 1:10-1:0.2.
10. the preparation method of regular arrangement nanometer alligatoring Sapphire Substrate according to claim 8, it is characterized in that, the corrosive liquid that described step (7) adopts is the mixed solution of hydrofluoric acid and water, and the volume ratio of hydrofluoric acid and water is 2:9-1:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104992900A (en) * | 2015-06-24 | 2015-10-21 | 哈尔滨工业大学 | Method for manufacturing alpha-Al2O3 monocrystal surface SiO2 mask |
| CN105304775A (en) * | 2015-11-16 | 2016-02-03 | 河北工业大学 | Preparation method of LED patterned substrate with low refractive index micro-nano structure layer |
| CN106469769A (en) * | 2015-08-17 | 2017-03-01 | 南通同方半导体有限公司 | A kind of micro-nano graph Sapphire Substrate and preparation method thereof |
| CN113097357A (en) * | 2021-03-25 | 2021-07-09 | 福建晶安光电有限公司 | Patterned substrate of light emitting diode, light emitting diode and preparation method thereof |
| CN115020563A (en) * | 2022-06-01 | 2022-09-06 | 淮安澳洋顺昌光电技术有限公司 | Preparation method of graphic substrate with micro-nano structure and epitaxial structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623590A (en) * | 2012-03-31 | 2012-08-01 | 中国科学院半导体研究所 | Method for producing nanometer gallium nitride light-emitting diode (LED) |
| US20120280243A1 (en) * | 2011-05-06 | 2012-11-08 | Nanocrystal Asia Inc. | Semiconductor substrate and fabricating method thereof |
| CN103035806A (en) * | 2012-12-28 | 2013-04-10 | 湘能华磊光电股份有限公司 | Preparation method of nano graphic substrate for nitride epitaxial growth |
-
2014
- 2014-12-03 CN CN201410724538.7A patent/CN104465900A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120280243A1 (en) * | 2011-05-06 | 2012-11-08 | Nanocrystal Asia Inc. | Semiconductor substrate and fabricating method thereof |
| CN102623590A (en) * | 2012-03-31 | 2012-08-01 | 中国科学院半导体研究所 | Method for producing nanometer gallium nitride light-emitting diode (LED) |
| CN103035806A (en) * | 2012-12-28 | 2013-04-10 | 湘能华磊光电股份有限公司 | Preparation method of nano graphic substrate for nitride epitaxial growth |
Non-Patent Citations (2)
| Title |
|---|
| 于威 等: "热退火诱导纳米银膜形貌变化对表面等离激元共振特性的影响", 《光谱学与光谱分析》 * |
| 李宁 等: "银纳米颗粒的制备及其光散射特性", 《电源技术》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104992900A (en) * | 2015-06-24 | 2015-10-21 | 哈尔滨工业大学 | Method for manufacturing alpha-Al2O3 monocrystal surface SiO2 mask |
| CN104992900B (en) * | 2015-06-24 | 2018-01-30 | 哈尔滨工业大学 | α‑Al2O3Single-crystal surface SiO2The preparation method of mask |
| CN106469769A (en) * | 2015-08-17 | 2017-03-01 | 南通同方半导体有限公司 | A kind of micro-nano graph Sapphire Substrate and preparation method thereof |
| CN105304775A (en) * | 2015-11-16 | 2016-02-03 | 河北工业大学 | Preparation method of LED patterned substrate with low refractive index micro-nano structure layer |
| CN105304775B (en) * | 2015-11-16 | 2017-12-15 | 河北工业大学 | The preparation method of LED patterned substrates with low-refraction micro-nano structure layer |
| CN113097357A (en) * | 2021-03-25 | 2021-07-09 | 福建晶安光电有限公司 | Patterned substrate of light emitting diode, light emitting diode and preparation method thereof |
| CN115020563A (en) * | 2022-06-01 | 2022-09-06 | 淮安澳洋顺昌光电技术有限公司 | Preparation method of graphic substrate with micro-nano structure and epitaxial structure |
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