KR101660637B1 - Method for producing nano-structure of gallium nitride based semiconductor using charge patterning - Google Patents
Method for producing nano-structure of gallium nitride based semiconductor using charge patterning Download PDFInfo
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- KR101660637B1 KR101660637B1 KR1020150055497A KR20150055497A KR101660637B1 KR 101660637 B1 KR101660637 B1 KR 101660637B1 KR 1020150055497 A KR1020150055497 A KR 1020150055497A KR 20150055497 A KR20150055497 A KR 20150055497A KR 101660637 B1 KR101660637 B1 KR 101660637B1
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- Prior art keywords
- gallium nitride
- etching
- pattern
- nanostructure
- self
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- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 33
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 25
- 239000004065 semiconductor Substances 0.000 title claims abstract description 23
- 238000000059 patterning Methods 0.000 title abstract description 4
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 45
- 238000001259 photo etching Methods 0.000 claims abstract description 16
- 238000005530 etching Methods 0.000 claims abstract description 13
- 239000002801 charged material Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002094 self assembled monolayer Substances 0.000 claims description 20
- 239000013545 self-assembled monolayer Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000813 microcontact printing Methods 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 229910002704 AlGaN Inorganic materials 0.000 claims description 3
- 238000001749 colloidal lithography Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000025 interference lithography Methods 0.000 claims description 2
- -1 InGaN Inorganic materials 0.000 claims 2
- 125000000524 functional group Chemical group 0.000 claims 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 3
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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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
-
- 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
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
Abstract
The present invention relates to a method of forming a regular nanostructure on the surface of gallium nitride using patterning of a charged material.
The method according to the present invention includes the steps of forming a pattern of a substance charged on the surface of a gallium nitride semiconductor and etching the surface of the gallium nitride semiconductor having a pattern of the charged substance using a photochemical etching method .
Description
The present invention relates to a method of forming a nanostructure on the surface of a gallium nitride semiconductor, and more particularly, to a method of forming a regular nanostructure on the surface of a gallium nitride semiconductor using patterning of a charged material .
Since the gallium nitride semiconductor is a semiconductor having a wide band gap, it is widely used as a high-output, high-cycle element. However, in order to realize a high efficiency light emitting diode, it is necessary to overcome the internal reflection phenomenon occurring at the interface between gallium nitride having a high refractive index and air having a low refractive index.
There is a refractive index grading method which reduces the refractive index difference with air or a method of overcoming the critical angle of the internal reflection by giving a roughness to the surface.
Accordingly, the PCE method of forming a cone on the surface of gallium nitride by photochemical etching occupies an important part in the LED process.
The left side of FIG. 1 is for explaining the mechanism of photochemical etching using ultraviolet light in an aqueous solution containing OH - ions, and the right SEM photograph shows the result.
As shown in FIG. 1, on the gallium nitride surface, OH - ions stick to the Ga atoms to separate the Ga atoms, and the underlying n-face is exposed, so that etching continues. At this time, due to the polarity of the gallium nitride, the OH - ions of the basic solution used as the etching solution adhere to the gallium nitride and start etching. Since the beginning of such etching starts at an arbitrary point, As shown, irregular nanostructures are produced in which the cone size is not constant and the period is not constant.
This irregular and different size PCE cone structure not only causes irregular device efficiency but also causes a decrease in device efficiency. Therefore, there is a need for a technique for making nanostructures having a regular and uniform size in PCE etching.
An object of the present invention is to provide a method of forming a nanostructure that can be regulated and controlled in size on the surface of a gallium nitride semiconductor in order to realize a high-efficiency device.
According to an aspect of the present invention, there is provided a method for manufacturing a gallium nitride semiconductor device, comprising the steps of: forming a pattern of a charged material on a surface of a gallium nitride semiconductor; And etching the surface of the nanostructure.
According to the present invention, a nanostructure having a predetermined periodicity and controlled size can be formed on the surface of a gallium nitride semiconductor. When a gallium nitride semiconductor having such a controlled pattern is applied to a light emitting diode device, It is possible to further improve the efficiency of the apparatus.
FIG. 1 is a view for explaining a mechanism of photochemical etching using ultraviolet light in an aqueous solution containing OH - ions, and a photograph of the result.
Figure 2 shows an example of a positively or negatively charged self-assembled monolayer material that can be used in an embodiment of the present invention.
Figure 3 shows an example of a hard mold that can be used for microcontact printing.
4 is a process diagram of a method of forming a nanostructure according to an embodiment of the present invention.
Hereinafter, the present invention will be described in detail with reference to the preferred embodiments of the present invention with reference to the accompanying drawings.
It should also be understood that the terms or words used in the present specification and claims should not be construed in a conventional and dictionary sense and that the inventors may properly define the concept of the term to best describe its invention And should be construed in accordance with the principles and meanings and concepts consistent with the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely preferred embodiments of the present invention and do not represent all the technical ideas of the present invention, so that various equivalents And the scope of the present invention is not limited to the following embodiments.
While 'GaN' is emphasized throughout this specification, the technology according to the present invention is also applicable to other III-nitride based semiconductors, such as InGaN. Thus, the term 'GaN' should be interpreted to include any III-nitride material such as InGaN, AlGaN, and the like.
A method of forming a nanostructure according to the present invention includes the steps of forming a pattern of a substance charged on a surface of a gallium nitride semiconductor and a step of forming a pattern of the charged substance on the surface of the gallium nitride semiconductor using a photochemical etching method And etching.
The present invention forms a pattern of a material having a positive or negative charge on the surface of a gallium nitride semiconductor, wherein a material having a positive charge or a negative charge attracts or excludes OH - ions contained in an etchant used in photochemical etching. Thus, it is possible to obtain a pattern of a periodic and size-controlled nanostructure by creating an etching site in which a photochemical etching is actively performed in a specific portion that is controlled.
The gallium nitride-based semiconductor includes not only GaN but also III-nitride-based semiconductors such as InGaN and AlGaN.
The chargeable material is not particularly limited as long as it is a material capable of controlling the density of OH - ions used for photochemical etching including charge. Preferably, a self assembled monolayer (SAM) material can be used. As shown in FIG. 2, positively charged self-assembled monolayer materials include NH 2 terminated materials such as cysteamine and APTES (3-aminopropyl triethoxysilane), and negatively charged Self-assembled monolayer materials include COOH terminated materials such as carboxy alkanethiols and dithiodibutyric acid.
A method of forming a pattern of a charged material may be, for example, a micro contact printing method. However, if it is a method capable of forming a pattern of a charged material on the surface of a gallium nitride semiconductor, It is not limited to the microcontact printing method.
The microcontact printing can be performed through a soft mold in which a regular pattern is transferred by applying a polymer material such as PDMS having flexibility to a hard mold in which periodic and regular nanostructure patterns are formed, followed by curing.
A hard mold having a periodic and regular nanostructure pattern can be formed by using an aluminum anodized oxide (AAO), a laser interference lithography (LIL), a colloidal lithography such as colloidal lithography, metal assisted Si etching, or the like.
The nanostructure of the hard mold may be variously formed. For example, the nanostructure may have a width of 100 nm to 10 μm and a height of 100 nm to 10 μm.
As shown in FIG. 3, a soft mold can be obtained by applying a polymer-based material such as PDMS to a hard mold having a regular and periodic micro or nano structure, followed by curing.
By immersing the obtained soft mold in a material to be printed (for example, a self-assembled monolayer) and removing the soft mold, the material to be printed is regularly and periodically coated on the surface of the structure. As a method of applying the printing material to the mold, other methods such as a spray method may be used in addition to the above-described immersion method.
The photochemical etching method is performed using an aqueous solution containing OH - ions. The aqueous solution may preferably include KOH, NaOH, or H 2 O 2.
The concentration of KOH or NaOH contained in the aqueous solution is preferably 1M to 24M. When the concentration is less than 1M, it takes a long time to form the nanostructure. When the concentration exceeds 24M, This is because the reaction is disturbed.
The photochemical etching uses ultraviolet rays, and the wavelength of ultraviolet rays used may be 400 nm or less. The photochemical etching time may be 1 minute to 30 minutes.
4 is a process diagram of a method of forming a nanostructure according to an embodiment of the present invention.
As shown in FIG. 4A, a soft contact mold having the nano structure transferred thereon is fabricated by PDMS softened in a hard mold having regular periodic nanostructures.
Subsequently, as shown in FIG. 4B, the soft contact mold is coated with a self-assembled monolayer having a positive charge or a negative charge.
Then, as shown in FIG. 4C, a self-assembled monolayer material having a positive charge or a negative charge is printed on the GaN surface to form a pattern of self-assembled monolayer on the GaN surface. The pattern includes a portion coated with a self-assembled monolayer film and a portion not coated with the self-assembled monolayer film.
FIG. 4d shows a photochemical etching process in which ultraviolet light is irradiated after immersing GaN in which a pattern of a self-assembled monolayer having a positive or negative charge is formed in an aqueous KOH solution containing OH- ions.
As shown in FIG. 4 (d), when a self-assembled monolayer having a negative charge is applied, the negative charge imparts a repulsive force to the OH- ions included in the aqueous solution so that the portion where the self- assembled monolayer is coated is not photochemically etched , And the portion where the self-assembled monolayer film is not applied is photochemically etched, so that a periodic and regular cone shape as shown in FIG. 4E is produced.
In addition, when a positively charged self-assembled monolayer film is applied, a positive charge imparts attraction to OH - ions contained in the aqueous solution, and a portion where the self-assembled monolayer film is applied is actively photochemically etched, Since the uncoated portion is mostly photochemical etched, a periodic and regular cone shape as shown in FIG. 4E is made.
Claims (14)
Etching the gallium nitride semiconductor surface on which the pattern of the charged material is formed by using a photochemical etching method,
Wherein the charged material comprises a self-assembled monolayer.
Wherein the gallium nitride-based semiconductor includes GaN, InGaN, or AlGaN.
Wherein the pattern of the charged material is formed by a microcontact printing method.
The mold for microcontact printing may be formed using an aluminum anodized oxide (AAO), a laser interference lithography (LIL), a colloidal lithography, or a metal assisted Si etching metal assisted Si etching), and a method of forming a nanostructure using the soft mold manufactured using the hard mold.
Wherein the nanostructure of the hard mold has a width of 100 nm to 10 탆 and a height of 100 nm to 10 탆.
Wherein the soft mold is made of PDMS (polydimethylsiloxane).
Wherein the self-assembled monolayer material comprises a positively charged material comprising an NH 2 functional group.
Wherein the self-assembled monolayer material comprises a negatively charged material having a COOH functional group.
The photochemical etching method uses an aqueous solution containing OH - ions to form a nanostructure.
Wherein the aqueous solution comprises KOH, NaOH, or H 2 O 2 .
Wherein the concentration of KOH or NaOH contained in the aqueous solution is 1M to 24M.
Wherein the photochemical etching uses ultraviolet light and the wavelength of ultraviolet light used is 400 nm or less.
Wherein the photochemical etching time is from 1 minute to 30 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150055497A KR101660637B1 (en) | 2015-04-20 | 2015-04-20 | Method for producing nano-structure of gallium nitride based semiconductor using charge patterning |
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| KR1020150055497A KR101660637B1 (en) | 2015-04-20 | 2015-04-20 | Method for producing nano-structure of gallium nitride based semiconductor using charge patterning |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040090465A (en) | 2003-04-15 | 2004-10-25 | 마츠시타 덴끼 산교 가부시키가이샤 | Semiconductor light emitting device and method for fabricating the same |
| KR20120012554A (en) * | 2010-08-02 | 2012-02-10 | 광주과학기술원 | Fabricating method of nano structure for antireflection and fabricating method of photo device integrated with antireflection nano structure |
| KR20120084839A (en) * | 2011-01-21 | 2012-07-31 | 포항공과대학교 산학협력단 | Method of manufacturing vertical light emitting diode using light emitting diode epilayer growthed on patterned sappaire substrate and vertical light emitting diode manufactured by the method |
| WO2014036400A1 (en) * | 2012-08-30 | 2014-03-06 | The Regents Of The University Of California | Pec etching of { 20-2-1 } semipolar gallium nitride for light emitting diodes |
| KR20150027770A (en) * | 2012-06-01 | 2015-03-12 | 코닌클리케 필립스 엔.브이. | Improved light extraction using feature size and shape control in led surface roughening |
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2015
- 2015-04-20 KR KR1020150055497A patent/KR101660637B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040090465A (en) | 2003-04-15 | 2004-10-25 | 마츠시타 덴끼 산교 가부시키가이샤 | Semiconductor light emitting device and method for fabricating the same |
| KR20120012554A (en) * | 2010-08-02 | 2012-02-10 | 광주과학기술원 | Fabricating method of nano structure for antireflection and fabricating method of photo device integrated with antireflection nano structure |
| KR20120084839A (en) * | 2011-01-21 | 2012-07-31 | 포항공과대학교 산학협력단 | Method of manufacturing vertical light emitting diode using light emitting diode epilayer growthed on patterned sappaire substrate and vertical light emitting diode manufactured by the method |
| KR20150027770A (en) * | 2012-06-01 | 2015-03-12 | 코닌클리케 필립스 엔.브이. | Improved light extraction using feature size and shape control in led surface roughening |
| WO2014036400A1 (en) * | 2012-08-30 | 2014-03-06 | The Regents Of The University Of California | Pec etching of { 20-2-1 } semipolar gallium nitride for light emitting diodes |
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