CN101252158A - LED nanometer technology for improving external quantum efficiency - Google Patents
LED nanometer technology for improving external quantum efficiency Download PDFInfo
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- CN101252158A CN101252158A CNA2007103008043A CN200710300804A CN101252158A CN 101252158 A CN101252158 A CN 101252158A CN A2007103008043 A CNA2007103008043 A CN A2007103008043A CN 200710300804 A CN200710300804 A CN 200710300804A CN 101252158 A CN101252158 A CN 101252158A
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Abstract
The present invention relates to LED nanotechnology for improving external quantum efficiency, in particular to a method of utilizing the nanotechnology to form two-dimensional patterns on luminous elements. The method comprises the following steps that: a first substrate is formed on a luminous surface of a luminous element; a metal layer is formed on the first substrate; electrochemical anodic oxidation treatment is carried out to the metal layer, so as to form a porous metal oxide; the porous metal oxide is utilized as a shield for etching the first substrate; the porous metal oxide is removed, so as to form a two-dimensional pattern on the first substrate. According to the method disclosed by the present invention, a manufacturing method with low manufacturing cost and higher production efficiency can be provided. In addition, a luminous device manufactured by utilizing the method disclosed by the present invention can improve quantum efficiency, raise optical capture efficiency and improve the alignment of light extraction direction.
Description
Technical field
The present invention relates to a kind of method that forms two-dimensional pattern on the light-emitting component surface, particularly a kind of applied metal anodized is to form the method for two-dimensional pattern on the light-emitting component surface.
Background technology
Light-emitting diode is a kind of quite common photoelectric cell, generally speaking, the light-emitting diode that has the light-emitting diode of coarse surface or have a 2 D photon crystal rent land (Photonic crystal) has higher light than the light-emitting diode with smooth surface and takes out efficient.Usually, the technology that forms 2 D photon crystal at LED surface has following three kinds: electron beam lithography (Electron BeamLithography, EBL), nano imprint lithography (Nanoimprint Lithography, NIL) and the polymer photoetching technique (Copolymer Lithography, CPL).
Had many pieces of Patent publish at present and utilized the method for electron beam lithography, for example: U.S. Patent Publication No. No. 2006/0027815 and No. 2005/0285132 at light emitting diode base plate surface formation 2 D photon crystal.Generally speaking, prior art is coating one deck photoresist on a light emitting diode base plate, utilizes the photoresist in electron beam illuminated portion zone then.Photoresist part remaining after removing irradiated photoresist part can be taken as an etch mask, carrying out reactive ion etching (Reactive Ion Etching, RIE) and remove after the mask, on the substrate of light-emitting diode, form a two-dimensional pattern.The method of utilizing electron beam lithography to form two-dimensional pattern on the light emitting diode base plate surface has the advantage of pinpoint accuracy, its accuracy can reach the 1-2 nanometer, but shortcoming is that electron beam lithography equipment too expensive and manufacturing process are consuming time, makes production efficiency extremely low.
Utilizing nano imprint lithography to form the method for 2 D photon crystal at the substrate surface of light-emitting diode can be with reference to the relevant description of No. the 7074631st, No. the 2005/0173717th, U.S. Patent Publication No. and U.S. Patent number.Its key step is: at first utilize electron beam lithography to make the mould of an impression, then mould is pressed on the substrate that applies ultraviolet resist (UV curable resist) and irradiation ultraviolet radiation.After substrate is broken away from mould, can obtain having the substrate of imprinted pattern.The method of utilizing nano imprint lithography to form 2 D photon crystal can obtain nano level accuracy, but, shortcoming is that die cost is very expensive, and mould is through after repeatedly using, because pressure will cause mould to deform, thereby make the pattern dimension distortion, so the life cycle of mould is very short.In addition, in actual mechanical process, the interfacial characteristics of mould and polymer is a long-term intractable problem, polymer is difficult to flow in the groove of mould, therefore be difficult for forming meticulous pattern, and polymer is after pressurized is shaped, is not easy complete demoulding and do not deform.
U.S. Patent number the 6th, 468 has disclosed for No. 823 and to have utilized the electron beam lithography etching, and utilized chemically assisted ion beam etching or wet etching or other etching mode, and the patterned semiconductor layer is to form 2 D photon crystal.This Patent publish utilize photoresist to electron beam sensitive, for example PMMA defines two-dimensional photon crystal structure with electron beam lithography, or by other high resolution lithography technology, the ultraviolet light photoetching short as X ray, deep ultraviolet auroral poles, or nano impression, nanometer press back also can satisfy.After PMMA is graphical,, remove PMMA with acetone or oxygen electricity slurry etching more again by chemical assisting ion etching semiconductor layer.But the method still needs electron beam, X ray, the short equipment such as ultraviolet light photoetching of deep ultraviolet auroral poles of apparatus expensive, this manufacturing process is rather consuming time, even if make X-Y scheme with nano impression, nanometer press back, still need to face the die cost height, and problem such as easy deformation.
Can consult journal article Material Science and Engineering:B in the technology of patterning sapphire substrate (Patterned sapphire substrate) growth high-quality GaN epitaxial layer, V122, No.3, pp184-187 (2005) and IEEE Photonic Technology Letter:Vol.17, No.2, pp:288-290 (2005).Usually making this method with sapphire substrate of etching figure is with common exposure imaging technology, and the induction coupling gas ions reactive ion etching (ICP-RIE) with wet etching (330 ℃ of phosphoric acid) or chlorine-based gas environment forms then.Because what adopt is common exposure imaging technology, its dimension of picture is more than micron order (micron-scale), easily after building crystal to grow, because the out-of-flatness at PN interface makes element cause lock to flow effect (thyristor effect).
In sum, the complex manufacturing process of above-mentioned technology, consuming time and with high costs.Therefore, the utmost point needs a kind of simple and easy, quick and cost-effective method to form two-dimensional pattern on light-emitting component.
Summary of the invention
In order to improve the photonic crystal quantum efficiency effectively, the invention provides a kind of method that on light-emitting component, forms a two-dimensional pattern, it can improve light source and take out efficient, improves the light source collimation, and reduces cost of manufacture and promote production capacity.
One embodiment of the present of invention provide a kind of method that forms two-dimensional pattern on light-emitting component, and it is included on the light-emitting area of light-emitting component and forms first substrate; On this first substrate, form a metal level; Electrochemical anodic oxidation is handled this metal level, to form the porous metal oxide; Utilize the porous metal oxide as a shielding, this first substrate of etching; And remove this porous metal oxide, thereby on first substrate, form two-dimensional pattern.
Another embodiment of the present invention provides a kind of light-emitting component, and it comprises first kind semiconductor layer; The second type semiconductor layer is positioned at this first kind semiconductor top; And first substrate, being positioned at this second type semiconductor top, the surface of this first substrate has a two-dimensional pattern, and wherein this two-dimensional pattern is to make according to the following step: form a metal level on this first substrate; Electrochemical anodic oxidation is handled this metal level, to form the porous metal oxide; Utilize the porous metal oxide as a shielding, this first substrate of etching; And remove this porous metal oxide, on this first substrate, to form this two-dimensional pattern.
Description of drawings
Figure 1A-1E shows that the present invention forms the embodiment step of the method for two-dimensional pattern on light-emitting component;
Fig. 2 A-2E shows the embodiment step of the light-emitting component with two-dimensional pattern of the method made that discloses according to the present invention.
Embodiment
Figure 1A-1E shows that the present invention forms first preferred embodiment of the method for two-dimensional pattern on light-emitting component.Shown in Figure 1A, light-emitting area at light-emitting component 101 forms first substrate 102, and this first substrate 102 can be a light-transmitting substrate, this light-transmitting substrate comprises transparent conductive material at least, for example transparent conductive material carborundum of tin indium oxide (ITO) substrate, antimony tin (ATO), zinc oxide, zinc oxide, doped silicon carbide etc., or the transparent material of sapphire substrate, non-doped silicon carbide etc. or the like.In Figure 1B, metal level 103 of deposition on this first substrate 102 can be that thickness is about the aluminium of 0.2～2 micron (μ m) or other can form the metal of porous metal oxide in follow-up making at this metal level 103.Then, in Fig. 1 C this metal level 103 being carried out electrochemical anodic oxidation handles, it is approximately to be phosphoric acid, sulfuric acid or the oxalic acid of 0.3M at concentration of electrolyte that this electrochemical anodic oxidation is handled, and temperature approximately is that 2 ℃～15 ℃ and operating voltage range carry out under 40 volts to 220 volts.This electrochemical anodic oxidation is handled the electric field redistribution that can make in the metal level 103, thus the porous metal oxide that metal level 103 is formed than the nanoscale two-dimensional pattern of tool systematicness.Then, in Fig. 1 D, utilize the porous metal oxide as etch mask, carry out this first substrate 102 of vertical etching, this etching can utilize dry etching to carry out, generally be to carry out dry etching, thereby the systematicness nanoscale two-dimensional pattern of porous metal oxide is transferred on this first substrate 102 with ion etching.In a preferred embodiment, the aperture of two-dimensional pattern and the spacing between the aperture all are between about 80 nanometer to 500 nanometers, preferably, and generally all approximately less than 350 nanometers.
At last, in Fig. 1 E, this porous metal oxide is removed, to form two-dimensional pattern on this first substrate 102.
In a further advantageous embodiment, can another layer of additional deposition conductive material layer before forming metal level 103 on first substrate 102, this conductive metal material can be the titanium that thickness is about 300 dusts (), or tin indium oxide (ITO), stop layer in follow-up manufacturing process, to form one.In addition, this conductive material layer also is removed when the porous metal oxide is removed in the lump.
In another embodiment, after forming the porous metal oxide, can be then the porous metal oxide of formation rule two-dimensional pattern being carried out reaming handles, the etching liquid of handling is about 5% phosphoric acid, utilize the tropism that waits of wet etching, the porous metal oxide is carried out vertically and the side direction etching, make the hole of porous metal oxide widen and deepen.
In another embodiment, the method for the present invention's disclosure also can second substrate (as sapphire substrate) of additional application in light-emitting component.Like this, the light of whole light-emitting component takes out efficient and the light direction collimation can further be promoted.
The method that the present invention discloses goes for various light-emitting component, as light-emitting diode, vertical LED or inverted light-emitting diode (LED) etc.
The method that discloses according to the present invention, because the process of electrochemical anodic oxidation only needs electrolysis tank, cooler and power supply, making or impress making with conditional electronic bundle patterning compares, cost of manufacture significantly reduces, and electrochemical reaction has the characteristic of wet type batch making, and make efficiency also significantly improves.
Fig. 2 A-2E shows the different embodiment of the light-emitting component with two-dimensional pattern that the method for the disclosure according to the present invention is made.Shown in Fig. 2 A, this light-emitting component (as light-emitting diode) comprises first kind semiconductor layer 206; The second type semiconductor layer 207 is positioned at described first kind semiconductor layer 206 tops; With first substrate 204, be positioned at the described second type semiconductor layer 207 top, there is a two-dimensional pattern on the surface of described first substrate 204, and wherein the two-dimensional pattern on described first substrate 204 surfaces is that the method for utilizing the present invention to disclose forms.
Fig. 2 B shows another embodiment that discloses the made light-emitting component of method according to the present invention.This light-emitting component comprises a N type semiconductor 202, and a P type semiconductor 203 is arranged above it.Semiconductor layer is example with GaN in the present embodiment, be quantum well (MWQ) 208 between N layer GaN 202 and the P type GaN 203, first substrate 204 of a light transmission is arranged above P type GaN 203, and (light-transmitting substrate comprises transparent conductive material at least, as tin indium oxide substrate, antimony tin substrate, zinc oxide substrate, doped silicon carbide substrate, or the transparent material of sapphire substrate, non-doped silicon carbide etc.).The method that described first substrate 204 utilizes the present invention to disclose, formation has nano level systematicness two-dimensional pattern, thereby forms the light-emitting diode of 2 D photon crystal, and then improves external quantum efficiency, improve the light extraction efficiency of light-emitting diode, and improve the collimation that light source penetrates.And second substrate 201 below N type GaN202 can be sapphire substrate, tin indium oxide (ITO), copper, silver, gold, silicon, carborundum or aluminum oxide substrate etc.
(shown in Fig. 2 C) in another embodiment of the present invention, a light-emitting diode has P type GaN 203, N type GaN 202 is arranged above it, be quantum well (MWQ) 208 between P type GaN 203 and the N type GaN 202, between the P type GaN203 and second substrate 201, a specular layer 205 can be arranged, make from P type GaN 203, the source reflection that N type GaN 202 interfaces produce is after specular layer 205 reflections, direction by first substrate 204 on the N type GaN 202 penetrates, this first substrate is a light-transmitting substrate, described light-transmitting substrate comprises transparent conductive material at least, tin indium oxide (ITO) for example, antimony tin (ATO), zinc oxide, doped silicon carbide, or sapphire, the transparent material of non-doped silicon carbide etc. etc.Described first substrate 204 is to utilize method provided by the invention, the nanoscale two-dimensional pattern of formation rule, and second substrate 201 below specular layer, at least comprise a kind of in tin indium oxide (ITO), sapphire, copper, silver, gold, silicon, carborundum or the aluminum oxide substrate, thereby form the light-emitting diode of rectilinear 2 D photon crystal.
In another embodiment of the present invention, shown in Fig. 2 D, light-emitting diode structure is as follows, first substrate 204 (as sapphire substrate) on N type GaN 202, the method that the application of the invention discloses is treated to the nanoscale two-dimensional pattern of systematicness, N type GaN 202 belows are P type GaN 203, and the electrode of light-emitting diode directly is attached to P type GaN 203 and N type GaN202 respectively, form the 2 D photon crystal inverted light-emitting diode (LED).In the present embodiment, the 2 D photon crystal ito substrate with nano-pattern can improve the external quantum efficiency of light-emitting diode, promotes light and takes out efficient, and improve the collimation of light direction.
Fig. 2 E shows an alternative embodiment of the invention.Second substrate 210 of light-emitting diode can be a sapphire substrate, the nanoscale two-dimensional pattern of the method formation rule that the application of the invention discloses, N type GaN 211 is formed on second substrate, 210 surfaces of patterning, there is P type GaN212 its top, between N type GaN 211 and P type GaN 212, be quantum well (MQW) 208, first substrate 213 on P type GaN 212 can be an ito substrate, the nanoscale two-dimensional pattern of the method formation rule that the application of the invention discloses.Because N type GaN 211 forms on regular nano-pattern, can improve internal quantum, and improve the reflection of light source on N type GaN 211 and second substrate, 210 interfaces, thereby improve luminous efficiency, and can not produce lock stream effect (thyristoreffect).And the 2 D photon crystal ITO of the systematicness nano-pattern of LED surface can further improve outside quantum effect, improves light and takes out efficient, and improve the collimation of light direction.
In sum, the present invention utilizes the electrochemical anodic oxidation of metal to handle, nanoscale two-dimensional pattern with formation rule, and the substrate formation 2 D photon crystal of this design transfer to light-emitting component, to improve the quantum efficiency of light-emitting component, improve light and take out efficient, improve the collimation of light direction.In addition, according to method provided by the invention, not only manufacture method is simple, and is with low cost, and can significantly promote production efficiency.
Though below described technology contents of the present invention and feature, yet those skilled in the art still can carry out many variations and modification under the situation of non-migration spirit of the present invention and disclosure content.Therefore, scope of the present invention is not to be subject to the embodiment that has disclosed, comprises of the present invention other of non-migration yet and changes and modification, and it belongs to the scope that contains as accessory claim.
Claims (27)
1. method that forms two-dimensional pattern on light-emitting component comprises following steps:
(a) on the light-emitting area of described light-emitting component, form first substrate;
(b) on described first substrate, form a metal level;
(c) the described metal level of electricity consumption chemical anode oxidation processes is to form the porous metal oxide;
(d) utilize described porous metal oxide as one deck mask, described first substrate of etching; With
(e) remove described porous metal oxide, thereby on described first substrate, form two-dimensional pattern.
2. method according to claim 1, wherein said step (a) also are included in the step that forms a conductive material layer on described first substrate.
3. method according to claim 2, the thickness of wherein said conductive material layer approximately are 300 dusts ().
4. method according to claim 2, wherein said conductive material layer are to be made by titanium or tin indium oxide (ITO).
5. method according to claim 1, the concentration of electrolyte of wherein said step (c) approximately is phosphoric acid, sulfuric acid or the oxalic acid of 0.3M, and temperature approximately is 2 ℃～15 ℃, and operating voltage range is greatly between 40 volts to 220 volts.
6. method according to claim 1, wherein said step (c) also comprises the step in the aperture that enlarges described porous metal oxide.
7. method according to claim 2, wherein said step (e) also comprises the step that removes described conductive material layer.
8. method according to claim 1, wherein said step (e) is a dry etching.
9. method according to claim 1, wherein said metal level is made of aluminum, described porous metal oxide is to be made by aluminium oxide.
10. method according to claim 1, described porous metal oxide has the two-dimensional pattern than systematicness.
11. method according to claim 1, wherein in the aperture of the described two-dimensional pattern on described first substrate and the spacing between the aperture all approximately between 80 nanometer to 500 nanometers.
12. method according to claim 1, wherein the aperture of the described two-dimensional pattern on described first substrate and the spacing between the aperture are all approximately less than 350 nanometers.
13. method according to claim 1, wherein said first substrate is a light-transmitting substrate, described light-transmitting substrate comprises the transparent conductive material of tin indium oxide (ITO), antimony tin (ATO), zinc oxide, doped silicon carbide etc. at least, or a kind of material in the transparent material of sapphire, non-doped silicon carbide etc.
14. method according to claim 1, wherein said light-emitting component comprise a kind of in light-emitting diode, vertical LED and upside-down mounting (flip-chip) light-emitting diode at least.
15. method according to claim 1 also is included in the step that forms described two-dimensional pattern on second substrate of described light-emitting component.
16. method according to claim 15, wherein said second substrate is a sapphire substrate.
17. a light-emitting component comprises:
First kind semiconductor layer;
The second type semiconductor layer is positioned at the semi-conductive top of the described first kind; With
First substrate is positioned at the top of described second type semiconductor, and there is a two-dimensional pattern on the surface of described first substrate, and the two-dimensional pattern on wherein said first substrate surface is to be formed by following steps:
(a) on described first substrate, form a metal level;
(b) electrochemical anodic oxidation is handled described metal level, to form the porous metal oxide;
(c) utilize described porous metal oxide as one deck mask, described first substrate of etching;
(d) remove described porous metal oxide, thereby on described first substrate, form described two-dimensional pattern.
18. light-emitting component according to claim 17, wherein said first substrate is a light-transmitting substrate, described light-transmitting substrate comprises the transparent conductive material of tin indium oxide (ITO), antimony tin (ATO), zinc oxide, doped silicon carbide etc. at least, or a kind of material in the transparent material of sapphire, non-doped silicon carbide etc.
19. light-emitting component according to claim 17, wherein said first kind semiconductor layer is a P type semiconductor, and the described second type semiconductor layer is a N type semiconductor.
20. light-emitting component according to claim 17, wherein said first kind semiconductor layer is a N type semiconductor, and the described second type semiconductor layer is a P type semiconductor.
21. light-emitting component according to claim 17 also comprises second substrate, it is adjacent with described first kind semiconductor layer.
22. light-emitting component according to claim 21 also comprises a specular layer, it is between described second substrate and described first kind semiconductor layer.
23. light-emitting component according to claim 21, wherein said second substrate comprise a kind of in tin indium oxide (ITO), sapphire, copper, silver, gold, silicon, carborundum or the aluminum oxide substrate at least.
24. light-emitting component according to claim 21, wherein said second substrate surface has described two-dimensional pattern.
25. light-emitting component according to claim 17, wherein said light-emitting component comprise a kind of in light-emitting diode, vertical LED and the inverted light-emitting diode (LED) at least.
26. light-emitting component according to claim 17, wherein in the aperture of the described two-dimensional pattern on described first substrate and the spacing between the aperture all approximately between 80 nanometer to 500 nanometers.
27. light-emitting component according to claim 17, wherein the aperture of the described two-dimensional pattern on described first substrate and the spacing between the aperture are all approximately less than 350 nanometers.
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| CNA2007103008043A CN101252158A (en) | 2007-12-18 | 2007-12-18 | LED nanometer technology for improving external quantum efficiency |
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| CNA2007103008043A CN101252158A (en) | 2007-12-18 | 2007-12-18 | LED nanometer technology for improving external quantum efficiency |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157642A (en) * | 2011-03-23 | 2011-08-17 | 华中科技大学 | Nanoimprint based preparation method of LED with high light-emitting efficiency |
| CN102185061A (en) * | 2011-04-06 | 2011-09-14 | 北京大学 | LED (Light-Emitting Diode) structure and manufacturing method thereof |
| CN101667629B (en) * | 2009-09-30 | 2011-11-02 | 四川虹视显示技术有限公司 | Led device and manufacturing method thereof |
| CN111223967A (en) * | 2018-11-26 | 2020-06-02 | 山东浪潮华光光电子股份有限公司 | Manufacturing method for coarsening side wall of GaAs-based red light LED tube core |
| CN111785763A (en) * | 2020-07-29 | 2020-10-16 | 北海惠科光电技术有限公司 | Display panel and manufacturing method thereof |
-
2007
- 2007-12-18 CN CNA2007103008043A patent/CN101252158A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101667629B (en) * | 2009-09-30 | 2011-11-02 | 四川虹视显示技术有限公司 | Led device and manufacturing method thereof |
| CN102157642A (en) * | 2011-03-23 | 2011-08-17 | 华中科技大学 | Nanoimprint based preparation method of LED with high light-emitting efficiency |
| CN102185061A (en) * | 2011-04-06 | 2011-09-14 | 北京大学 | LED (Light-Emitting Diode) structure and manufacturing method thereof |
| CN111223967A (en) * | 2018-11-26 | 2020-06-02 | 山东浪潮华光光电子股份有限公司 | Manufacturing method for coarsening side wall of GaAs-based red light LED tube core |
| CN111785763A (en) * | 2020-07-29 | 2020-10-16 | 北海惠科光电技术有限公司 | Display panel and manufacturing method thereof |
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