KR20110053645A - Patterned substrate for gan-based semiconductor light emitting diode and manufacturing method - Google Patents
Patterned substrate for gan-based semiconductor light emitting diode and manufacturing method Download PDFInfo
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- KR20110053645A KR20110053645A KR1020090110263A KR20090110263A KR20110053645A KR 20110053645 A KR20110053645 A KR 20110053645A KR 1020090110263 A KR1020090110263 A KR 1020090110263A KR 20090110263 A KR20090110263 A KR 20090110263A KR 20110053645 A KR20110053645 A KR 20110053645A
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Abstract
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nitride-based semiconductor device and a method for manufacturing a substrate, wherein a wet-etched nano-sized ITO sphere is formed, and used as an etching mask for forming a nano-sized pattern on the substrate surface of the nitride-based semiconductor device. By forming a nano-sized pattern on the surface of the substrate, light generated in the nitride semiconductor element can be scattered at the interface between the nitride semiconductor and the substrate, thereby providing excellent external light emission efficiency.
Substrate, transparent conductive film, oxide film, wet etching, nitride semiconductor light emitting device
Description
The present invention relates to a nitride-based semiconductor device and a method for manufacturing a substrate, using a wet etching to form a nano-sized ITO sphere, using this as an etching mask for forming a nano-size pattern on the substrate surface of the nitride-based semiconductor device In addition, the present invention relates to a nitride-based semiconductor light emitting device having excellent external light emission efficiency and a method of manufacturing a substrate by forming a nano-sized pattern on the surface of a substrate so that light generated from the nitride-based semiconductor device can be scattered at an interface between the nitride-based semiconductor and the substrate. .
The III-V nitride semiconductor has a wide band spacing of 1.9 eV (InN) to 6.2 eV (AlN), so that light can be emitted even in the blue and green light and ultraviolet regions, thereby providing high brightness laser diode (LD) and light emitting diode (LED). ), And are attracting attention in the field of use, such as optoelectronic devices such as PD (photo diode) and high-output electrical devices. As the device is developed and used for the first time, it will be used more effectively in interior and exterior lighting as well as electronic devices such as watches, cars, traffic lights, etc. do. In order to meet such demands, high efficiency and high output power of LEDs are required, and there are many problems to be improved, such as internal quantum efficiency, light extraction efficiency, packaging efficiency, and thermal problems. Such nitride semiconductors do not have a lattice matched substrate, unlike other III-V compounds, against various advantages and applicability. Sapphire (Al 2 O 3 ), silicon carbide (SiC), gallium arsenide (GaAs), etc. are used so far, but gallium nitride (GaN) has good crystallinity due to very large lattice constant and thermal expansion coefficient. It is hard to grow thin film. The gallium nitride epitaxy, which is currently mainly studied, uses a gallium nitride buffer layer grown at low temperature using a sapphire substrate to reduce the difference in lattice matching, and to grow the gallium nitride epitaxy layer at high temperature again. It is carried out in a number of research groups, and research on lattice matching substrates continues. In addition, to reduce the TDD (Threading Dislocation Density) to increase the internal quantum efficiency, it first deposits an insulating material (SiO 2 , SiNx, etc.) on the sapphire substrate to prevent potential from rising from the bottom to prevent the potential above the insulating material Research using Lateral epitaxial overgrowth (LEO), which reduces TDD by growing non-existing gallium nitride thin films, and recombines electron-holes by changing the active layer structure of LEDs Methods to increase recombination efficiency have been studied, and the main focus has been on increasing internal quantum efficiency.
However, to increase the efficiency of the LED, it is necessary to increase the light extraction efficiency of the LED in addition to the increase of the internal quantum efficiency. In order to improve the light extraction efficiency by reducing the total reflection determined by the critical angle due to the refractive index difference between the nitride semiconductor and the air surrounding the nitride semiconductor, the refractive index difference between the nitride semiconductor and the air is reduced to increase the critical angle or increase the surface of the light emitting diode. It is important to roughen and change the internal path of the light to increase the escape probability of the light.
The critical angle of light can be expressed by Snell's law [θ C = sin -1 (n air / n GaN )], where the difference in refractive index between the inside of the LED (n GaN = 2.5) and the outside of the LED (n air = 1) Light incident from an angle greater than 23.5 ° is totally reflected inside the LED, so the light extraction efficiency of a general light emitting diode structure is very low.
The method of improving the light extraction efficiency of the light emitting diode is to change the structure of the light emitting diode to change the path of the light generated inside the light emitting diode to increase the probability of escape of light, or the intermediate refractive index between the nitride semiconductor and air There is a method to reduce the total reflection by inserting the material of the light to increase the critical angle of the light. In order to reduce the total reflection, research is being conducted to give irregularities to the surface of P-type gallium nitride, and the sidewall is tilted to form a structure in which photons easily escape from the LED, thereby increasing light extraction. The research is being actively conducted. In addition, research has been conducted to increase the light extraction efficiency of LEDs by suppressing internal multi-reflection of the emitted light by a patterned substrate formed by a simple photolithography process using an SiO 2 insulating film. In addition, research is being conducted to increase the external quantum efficiency by fabricating a patterned sapphire substrate (PSS) through sapphire dry etching. However, dry etching using ICP causes lattice damage and strain on sapphire, resulting in deterioration of device characteristics and reduction of internal quantum efficiency.
In addition, the PSS process using the conventional photolithography is possible only up to micro units, while the PSS process using the nickel mask is possible at the nano unit, but the process configuration is complicated and it is difficult to remove the nickel mask after the process is in progress. There was a problem that was not easy.
SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the method of manufacturing a nitride-based semiconductor light emitting device and substrate having an effect that can be processed in nano units, the process configuration is simple, and the mask used for etching after the process is easy to remove. The purpose is to provide.
The above object of the present invention is to prepare a bare substrate (bare substrate); Forming an oxide film on the bare substrate; Forming a transparent conductive film on the oxide film; Forming a nano-sized sphere by applying a first etching process to the transparent conductive film; Forming the oxide film on the bottom surface of the nanospheres as a nano-sized etching mask by applying a second etching process; It is achieved by providing a substrate manufacturing method of the nitride-based semiconductor light-emitting device comprising the step of forming a pattern on the bare substrate by applying a third etching process to the nano-sized etching mask. The oxide film may be a polycrystalline oxide film.
In addition, the transparent conductive film for forming the nano-sized sphere is any one of SnO x , In x O y , Al x O y , ZnO, ZrO x , HfO x , TiO x , Ta x O y , Ga x O and the like. Or two or more compositions.
In addition, the transparent conductive film may be ITO.
In addition, the first etching process is an acid solution such as hydrochloric acid (HCl), nitric acid (HNO 3 ), phosphoric acid (H 3 PO 4 ), oxalic acid (oxalic acid), sulfuric acid (H 2 SO 4 ), hydrofluoric acid (HF) One or more can be applied for etching.
In addition, the acidity (pH) of the acid solution may be 0.1 ~ 1.
In addition, the transparent conductive film is a polycrystalline state which is not subjected to heat treatment, has a grain boundary having a weak bonding force, and may form nano-sized spheres by active etching at an interface having a weak bonding force with the oxide film.
In addition, the thickness of the transparent conductive film is 50nm ~ 600nm, it is possible to adjust the average size of the nano-sized spheres generated by adjusting the thickness.
In addition, the oxide film is SiO x , Si x N y It may consist of one or two or more of such compositions.
In addition, a heat treatment curing step of the nano-sized sphere may be further included after the first etching process.
In addition, an ICP treatment step of changing the shape of the nano-sized sphere after the first etching process may be further included.
In addition, the second etching process may be wet etching.
In addition, the second etching process may be dry etching.
In addition, the third etching process may be etched using an acid solution in which sulfuric acid and phosphoric acid are mixed in a volume ratio of 3: 1.
In addition, the third etching process may have an etching temperature of 270 ~ 280 ℃.
In addition, the bare substrate may be one having irregularities formed on one surface.
According to another aspect of the present invention, the above object of the present invention is a nitride-based laminated on the substrate by the method of manufacturing a substrate of the light emitting device, including an n-type nitride-based semiconductor layer, an active layer, a p-type nitride-based semiconductor layer It is achieved by providing a semiconductor light emitting element.
In addition, the bare substrate of the light emitting device may be used that the irregularities formed on one surface.
In the method of manufacturing the nitride-based semiconductor light emitting device and the substrate of the present invention, nano-sized spheres can be used as an etching mask, and the process can be performed in nano units, the process configuration is simple, and the etching mask can be easily removed after the etching process. have.
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings by the embodiments.
1A to 1F are diagrams sequentially illustrating a method of manufacturing a substrate of a nitride semiconductor light emitting device according to a first embodiment of the present invention, and FIGS. 2A to 2E are nitride semiconductors of the present invention when the thickness of ITO is 100 nm. 3D to 3E illustrate a substrate manufacturing method of a light emitting device in a dotted line, and FIGS. 3A to 3E sequentially illustrate a method of manufacturing a substrate of the nitride-based semiconductor light emitting device of the present invention having an ITO thickness of 200 nm. 4A to 4F are diagrams sequentially illustrating a method of manufacturing a substrate of a nitride-based semiconductor light emitting device according to a second exemplary embodiment of the present invention, and FIG. 5 is a nitride system according to a third embodiment of the present invention. Fig. 6 is a SEM photograph of a nano-sized sphere of the present invention, and Fig. 7 shows ITO of 100 nm. SEM image of the pattern formed on the substrate by 1500 times magnification, FIG. 8 is an SEM image of 45000 times magnification of the pattern formed on the substrate using 100 nm ITO, and FIG. 9 on the substrate using 200 nm ITO. SEM image of the pattern formed on the substrate at 1500 times magnification, FIG. 10 is a SEM image at 45000 times the pattern formed on the substrate using 200 nm ITO, and FIG. 11 is a pattern formed on the substrate using 100 nm ITO. Is a SEM photograph at 10000 times magnification, FIG. 12 is an SEM photograph at 25000 times magnification of a pattern formed on a substrate using 100 nm of ITO, and FIG. 13 is 80000 at a pattern formed on a substrate using 100 nm of ITO. SEM
1A to 1F, a method of manufacturing a substrate of a nitride based semiconductor light emitting device according to a first embodiment of the present invention includes preparing a bare substrate; Forming a polycrystalline oxide film on the bare substrate; Forming a transparent conductive film on the polycrystalline oxide film; Forming a nano-sized sphere by applying a first etching process to the transparent conductive film; Forming the polycrystalline oxide film on the lower surface of the nanospheres as a nano-sized etching mask by applying a second etching process; And forming a pattern on the bare substrate by applying a third etching process to the nano-sized etching mask.
As shown in FIG. 1A, preparing the
As shown in FIG. 1B, the forming of the
As shown in FIG. 1C, the step of forming the transparent
As shown in FIG. 1D, forming the
Wet etching is performed by controlling the etching time using BOE (buffered oxide echant), hydrochloric acid (HCl), nitric acid (HNO 3 ), phosphoric acid (H 3 PO 4 ), oxalic acid, sulfuric acid ( H 2 SO 4 ), hydrofluoric acid (HF) may be an etching solution containing one or two or more. At this time, the acidity (pH) of the acidic solution is preferably 0.1 ~ 1. Etching with a high concentration acid solution with a pH less than 0.1 does not form nanospheres and removes the transparent conductive film.Etching rate with a low concentration acid solution with a pH greater than 1 As a result, it is not etched in the form of a sphere, and the density of the nano-sized sphere is lowered.
FIG. 18 shows the relationship between the% concentration of the etching solution and the density of ITO nanosized spheres. The density decreases as the% concentration increases within the range of 5% to 10%.
Dry etching is performed using ICP (Inductively Coupled Plasma) equipment, and the etching gas is selected as the optimal etching gas according to the material of the transparent conductive film. For example, when the transparent conductive film is ITO, the main etching gas is CH 4 and the additive gas is O 2 and HBr.
Through the first etching process as described above, as shown in the SEM image of Figure 6, a nano-sized sphere is formed. Heat treatment for hardening the nano-
As shown in FIG. 1E, the step of forming the
As shown in FIG. 1F, the forming of the pattern on the
17 shows the relationship between the sulfuric acid solution and the etching rate. As the concentration increases, the etching rate increases.
In the case where the third etching process is performed by wet etching, it is preferable to use an acid solution as a mixture of sulfuric acid and phosphoric acid in a volume ratio of 3: 1. As shown in FIG. 17, when the ratio of sulfuric acid to phosphoric acid is etched with an acid solution (75% sulfuric acid solution) of 3: 1, it is easy to control the etching time by adjusting the etching rate.
In addition, the wet etching is preferably etched at a temperature of 270 ~ 280 ℃.
It is easy to adjust the etching rate at a temperature of 270 ~ 280 ℃ as above in the boiling point of the
As described above, when the sulfuric acid and phosphoric acid is mixed at a volume ratio of 3: 1 by using a mixed solution at 270 to 280 ° C., the etching solution has an etching rate of about 100 nm / min and is preferably etched for 5 minutes under the above conditions. Do.
In addition, when the third etching process is performed by dry etching, dry etching is performed using an ICP (Inductively Coupled Plasma) equipment, and as an etching gas, fluorine such as SF 6 , CF 4 , CHF 3 , C 2 F 6 , etc. Use fluorine-based gas.
Hereinafter, the relationship between the triangular pyramid pattern formed on the
Referring to FIGS. 2A to 2E and 3A to 3E, when the thickness of the ITO layer is 100 nm and the thickness of 200 nm, as shown in FIGS. 2A to 2E, the thickness of the
On the other hand, as shown in FIGS. 3A to 3E, when the thickness of the
As such, when the size of the nano-sized sphere is adjusted by adjusting the thickness of the transparent conductive film ITO, the size of the opening of the etching mask formed of the polycrystalline oxide film is adjusted to change the distribution and shape of the triangular pyramid pattern formed on the substrate. 9 and 10 are SEM images of a pattern formed on a substrate when a 200 nm-thick ITO layer is applied, and it can be seen that a flat C plane is present on an upper portion of the triangular pyramid pattern. 14 and 15 are plan views of the substrate on which the pattern is formed, as viewed from above, to identify a triangular pyramid shape having a C surface.
Since the distribution and shape of the triangular pyramid affects the light extraction efficiency, it is preferable to adjust the distribution and shape of the triangular pyramid according to the wavelength of light of the LED to emit light using the substrate on which the pattern is formed. .
The second and third embodiments of the present invention are characterized in that the concave-
4A to 4F illustrate a case in which an uneven substrate on which micro-units of irregularities are formed in advance is used as a bare substrate. The transparent
FIG. 5 illustrates a third embodiment, wherein a triangular pyramid shape 120 'is formed on an upper portion of the substrate 110' by using a bare substrate having a flat surface formed between the irregularities and the irregularities of the uneven substrate. Since each process goes through the same steps as in the second embodiment, the repeated description is omitted.
As such, when the pattern is formed on the bare substrate on which the micro unity of concavities and convexities is formed in advance, a nano-sized pattern is formed on the microunity concavity and convexity, thereby obtaining a higher light extraction efficiency on the substrate.
On the substrate made by the embodiment of the present invention, a nitride-based semiconductor light emitting device may be formed by including an n-type nitride-based semiconductor layer, an active layer, and a p-type nitride-based semiconductor layer.
As described above, the present invention has been described with reference to specific embodiments, but is not necessarily limited thereto, and modifications and variations may be made without departing from the scope of the technical idea of the present invention.
1A to 1F are diagrams sequentially illustrating a method of manufacturing a substrate of a nitride-based semiconductor light emitting device according to a first embodiment of the present invention.
2A through 2E are diagrams sequentially illustrating a method of manufacturing a substrate of the nitride-based semiconductor light emitting device according to the first embodiment of the present invention.
3A to 3E are views sequentially showing a method of manufacturing a substrate of a nitride-based semiconductor light emitting device according to another embodiment of the present invention.
4A to 4F are diagrams sequentially illustrating a method of manufacturing a substrate of a nitride-based semiconductor light emitting device according to a second embodiment of the present invention.
5 is a nitride semiconductor light emitting device according to the method of manufacturing a substrate of the nitride semiconductor light emitting device according to a third embodiment of the present invention.
6 is a SEM photograph of a nano-sized sphere of the present invention.
FIG. 7 is a SEM photograph at 1500 times magnification of a pattern formed on a substrate using 100 nm of ITO. FIG.
FIG. 8 is an SEM photograph at 45000 times magnification of a pattern formed on a substrate using 100 nm of ITO. FIG.
9 is a SEM photograph at 1500 times magnification of a pattern formed on a substrate using 200 nm of ITO.
FIG. 10 is an SEM photograph at 45000 times magnification of a pattern formed on a substrate using 200 nm of ITO. FIG.
FIG. 11 is an SEM photograph at 10000 times magnification of a pattern formed on a substrate using 100 nm of ITO. FIG.
12 is an SEM photograph at 25000 times magnification of a pattern formed on a substrate using 100 nm of ITO.
FIG. 13 is an SEM photograph at 80000 times magnification of a pattern formed on a substrate using 100 nm of ITO. FIG.
FIG. 14 is a SEM photograph at 10000 times magnification of a pattern formed on a substrate using 200 nm of ITO. FIG.
FIG. 15 is a SEM photograph at 25000 times magnification of a pattern formed on a substrate using 200 nm of ITO. FIG.
FIG. 16 is a SEM photograph sequentially photographing the density change of the nano-sized sphere according to the thickness change of the transparent conductive film. FIG.
17 is a chart showing the relationship between the concentration of the acidic solution and the etching rate.
18 is a chart showing the density change of the sphere of the nano-size according to the change in the concentration of the acid solution.
Explanation of symbols on the main parts of the drawings
10, 100; Bare board
20; Oxide film
30, 300; Transparent conductive film
31, 31 ', 31' ', 310; Nano-sized sphere
Claims (17)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140079111A (en) * | 2012-12-18 | 2014-06-26 | 엘지이노텍 주식회사 | Light Emitting device package |
| WO2017127461A1 (en) * | 2016-01-18 | 2017-07-27 | Sensor Electronic Technology, Inc. | Semiconductor device with improved light propagation |
| CN110087816A (en) * | 2016-11-09 | 2019-08-02 | 艾克斯特朗欧洲公司 | Use the method and corresponding equipment of the crystal nucleation layer of laser beam preparation structure |
| CN111243867A (en) * | 2020-01-20 | 2020-06-05 | 南昌航空大学 | Preparation method of acid-treated dye-sensitized solar cell photo-anode |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100593941B1 (en) | 2005-04-28 | 2006-06-30 | 삼성전기주식회사 | Method for manufacturing iii-nitride light emitting device |
| JP4852973B2 (en) | 2005-10-26 | 2012-01-11 | パナソニック電工株式会社 | Optical component manufacturing method and light emitting device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140079111A (en) * | 2012-12-18 | 2014-06-26 | 엘지이노텍 주식회사 | Light Emitting device package |
| WO2017127461A1 (en) * | 2016-01-18 | 2017-07-27 | Sensor Electronic Technology, Inc. | Semiconductor device with improved light propagation |
| US10461221B2 (en) | 2016-01-18 | 2019-10-29 | Sensor Electronic Technology, Inc. | Semiconductor device with improved light propagation |
| CN110087816A (en) * | 2016-11-09 | 2019-08-02 | 艾克斯特朗欧洲公司 | Use the method and corresponding equipment of the crystal nucleation layer of laser beam preparation structure |
| CN111243867A (en) * | 2020-01-20 | 2020-06-05 | 南昌航空大学 | Preparation method of acid-treated dye-sensitized solar cell photo-anode |
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