KR0179143B1 - Blue luminous element - Google Patents
Blue luminous element Download PDFInfo
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- KR0179143B1 KR0179143B1 KR1019950043022A KR19950043022A KR0179143B1 KR 0179143 B1 KR0179143 B1 KR 0179143B1 KR 1019950043022 A KR1019950043022 A KR 1019950043022A KR 19950043022 A KR19950043022 A KR 19950043022A KR 0179143 B1 KR0179143 B1 KR 0179143B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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 system
- H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
- H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
- H01L33/12—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 stress relaxation structure, e.g. buffer layer
Abstract
본 발명은 LED 반도체 레이저 제작시의 청색 발광소자에서 기판과 질화물계 화합물간의 격자상수를 줄임으로서 질화물의 결정성을 높여 고휘도의 효율을 갖는 발광소자에 관한 것으로, 기판, 완충(buffer)층, 질화 화합물층이 순차적으로 적층된 것에 있어서, 기판 또는 기판과 버퍼층 사이에 불화합물(MF2: 여기서 M은 Ca, Sr, Ba) 또는 불화란탄(LaF3)층으로 이루어진 청색 발광소자에 관한 기술이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting device having a high luminance efficiency by reducing the lattice constant between a substrate and a nitride compound in a blue light emitting device for manufacturing a LED semiconductor laser. In the case where the compound layers are sequentially stacked, the technology relates to a blue light emitting device composed of a fluorine compound (MF 2 : M is Ca, Sr, Ba) or a lanthanum fluoride (LaF 3 ) layer between the substrate or the substrate and the buffer layer.
Description
제1도는 종래의 발광 다이오드 구조에 대한 단면도로서,1 is a cross-sectional view of a conventional light emitting diode structure,
(a)는 제1 실시예.(a) is the first embodiment.
(b)는 제2 실시예.(b) is a second embodiment.
(c)는 제3 실시예.(c) is a third embodiment.
제2도는 본 발명에 따른 발광소자의 단면도로서,2 is a cross-sectional view of a light emitting device according to the present invention.
(a)는 제1 실시예.(a) is the first embodiment.
(b)는 제2 실시예.(b) is a second embodiment.
(c)는 제3 실시예.(c) is a third embodiment.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
10, 10' : 기판 11 : MF2층10, 10 ': substrate 11: MF 2 layers
12, 12' : 질화물 완충층 13 : III-질화층12, 12 ': nitride buffer layer 13: III- nitride layer
본 발명은 청색 LED 등과 같은 청색 발광 디바이스에 관한 것으로, 불화 물질을 기판 또는 기판과 완충층 사이에 형성하므로서 질화물층의 결정성을 높여 고휘도의 발광 효율을 갖는 발광소자의 구조에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blue light emitting device such as a blue LED. The present invention relates to a structure of a light emitting device having a high luminous efficiency having high luminance by increasing the crystallinity of a nitride layer by forming a fluoride material between a substrate or a substrate and a buffer layer.
종래의 III-질화물(Nitride)계 발광소자(LED) 또는 반도체 레이져 제작시에는 격자상수 및 열팽창계수가 질화물과 유사한 기판 물질이 없어 대부분 사파이어(Sapphire) 또는 Sic, Si, MgO 등을 기판으로 사용하는데, 가장 일반적으로 사파이어를 사용한다.In the manufacture of conventional III-nitride-based light emitting devices (LEDs) or semiconductor lasers, since the lattice constant and thermal expansion coefficient do not have a substrate material similar to that of nitride, most of them use sapphire or Sic, Si, MgO, etc. as a substrate. Most commonly, sapphire is used.
이와 같은 물질을 기판으로 사용하여 III-질화물 박막을 성장시킬 때 III-질화물 박막의 결정성이 나쁘므로 기판과 III-질화물 박막 사이에 III-질화물완충층을 형성하여 이 완충층 위의 III-질화물 박막의 결정성을 높이는 연구가 많이 진행되었다.When the III-nitride thin film is grown using such a material as a substrate, the crystallinity of the III-nitride thin film is poor. Thus, a III-nitride buffer layer is formed between the substrate and the III-nitride thin film to form a III-nitride thin film on the buffer layer. Many studies have been conducted to increase the crystallinity.
이와 같은 사파이어 기판 위에 유기금속 화합물 기상성장법(Metalorganic Chemical Vapor Epitaxy)(이하, MOCVD 라 함) 또는 분자빔 적층성장(Moleculor Beam Epitaxy)(이하, MBE 라 함)기법으로 완충층, n-type III-질화물, P-type III-질화물층 등을 형성하여 발광소자를 만든다.A buffer layer, n-type III-, is formed on the sapphire substrate by an organometallic chemical vapor deposition method (hereinafter referred to as MOCVD) or a molecular beam epitaxy (hereinafter referred to as MBE) technique. A nitride, P-type III-nitride layer, etc. is formed to make a light emitting device.
제1도는 이와 같은 종래의 발광 다이오드 구조에 대한 실시예를 나타낸 단면도로서, (a)와 같이 사파이어 기판(1)에 AIN, GaN 또는 AlGaN 물질로된 질화물완충층(2), n-type III-질화물층(3), 활성층(4), P-type III-질화물층(5), 전극(6)(6')을 형성하거나, (b)와 같이 완충층 없는 n-type III-질화물층(3)과 P-type III-질화물층(5)을 형성하거나, (c)와 같이 사파이어 기판(1), AlGaN 등과 같은 질화물완충층(2), n+-type III-질화물층(7), n-type III-질화물층(3), 활성층(4), P-type III-질화물층(5), 전극(6)(6')을 형성한다. 상기한 구조의 경우 (b)나와 같이 완충층이 없을 때는 n-type 층과 P-type 층의 결정성이 나빠져 발광효율이 떨어짐으로, (a) 및 (c)와 같이 완충층(2)을 형성시킨다.1 is a cross-sectional view showing an embodiment of such a conventional light emitting diode structure, a nitride buffer layer (2), n-type III- nitride of an AIN, GaN or AlGaN material on the sapphire substrate (1) as shown in (a) A layer 3, an active layer 4, a P-type III-nitride layer 5, an electrode 6, 6 ', or an n-type III-nitride layer 3 without a buffer layer, such as (b) And P-type III-nitride layer 5, or a nitride buffer layer 2 such as sapphire substrate 1, AlGaN, etc., n + -type III-nitride layer 7, n-type III, as shown in (c). A nitride layer 3, an active layer 4, a P-type III-nitride layer 5, and electrodes 6 and 6 '. In the case of the above structure, when the buffer layer is not present as shown in (b), the crystallinity of the n-type layer and the P-type layer is deteriorated, so that the luminous efficiency is lowered. Thus, the buffer layer 2 is formed as shown in (a) and (c). .
이들 구조들의 형성 후 인가전류를 전극(6)(6')에 흘려 P-n 접합[(b)의 경우] 에서 또는 활성층(4)에서 빛을 얻는다.After formation of these structures, an applied current is passed through the electrodes 6, 6 'to obtain light at the P-n junction (in the case of (b)) or at the active layer 4.
그러나 상기한 구조들에서는 다음과 같은 문제점들이 있다.However, the above structures have the following problems.
즉, III-질화물과 사파이어 기판 사이에는 (표 1)에 나타낸 바와 같이 큰 격자상수의 차이로 인해 III-질화물 박막의 결정성이 저하하며, 이 결정성 저하는 발광효율을 저하시킨다.That is, the crystallinity of the III-nitride thin film is lowered due to the large lattice constant difference between the III-nitride and the sapphire substrate as shown in Table 1, and the decrease in crystallinity lowers the luminous efficiency.
또한, 열팽창 계수가 III-질화물의 경우는 αa〉αc 인 반면, 사파이어의 경우는 αa〈 αc이다.In addition, the coefficient of thermal expansion is α a > α c for III-nitride, while α a <α c for sapphire.
이 때문에 완충층 위의 박막에 많은 전위(dislocation)가 생기며, 이 전위는 역시 발광효율을 저하시킨다.This causes a lot of dislocations in the thin film on the buffer layer, which also lowers the luminous efficiency.
그리고, 기판물질인 사파이어 또는 SiC는 화학식각(Chemical etching)이 잘 되지 않으므로 소자의 구조 형성(Patterning)이 어렵고, 사파이어의 경우 벽개성결정(한문)(Clearing crystals)면이 없어 LD 제작시 거울면(mirror) 형성이 어려운 등의 문제점이 있다.In addition, sapphire or SiC, which is a substrate material, does not have good chemical etching, so patterning of the device is difficult, and in the case of sapphire, there is no clearing crystals surface, so the mirror surface of LD is manufactured. (mirror) is difficult to form.
본 발명은 상기한 종래의 문제점을 해결하기 위해 안출한 것으로, 기판 또는 기판과 버퍼층 사이에 불소화합물(Fluouride)을 사용하므로써, 질화층과 기판간의 격자상수를 줄여 질화층의 결정성을 향상시키고, 전위밀도의 줄임과 소자 제작시의 후공정이 용이하는 등의 특성을 갖는 청색 발광소자 구조를 제공하고자 하는 데 그 목적이 있다.The present invention has been made to solve the above-mentioned conventional problems, by using a fluorine compound between the substrate or the substrate and the buffer layer, by reducing the lattice constant between the nitride layer and the substrate to improve the crystallinity of the nitride layer, An object of the present invention is to provide a structure of a blue light emitting device having characteristics such as reduction of dislocation density and easy post-processing during device fabrication.
이와 같은 목적 달성을 위한 본 발명은, 기판, 질화버퍼층, 질화물층이 형성된 것에 있어서, 불화물질(MF2)(M : Ca, Sr, Ba 중에서 선택) 또는 불화란탄(LaF3)으로 조성된 기판 또는 상기한 MF2또는 LaF3기판과 질화버퍼층 사이에 MF2층 또는 LaF3층이 형성된 청색 발광소자로 구성된다.In order to achieve the above object, the present invention provides a substrate, a substrate formed of fluoride material (MF 2 ) (M: Ca, Sr, Ba) or lanthanum fluoride (LaF 3 ) in which a substrate, a nitride buffer layer, and a nitride layer are formed. Or a blue light emitting device in which an MF 2 layer or a LaF 3 layer is formed between the MF 2 or LaF 3 substrate and the nitride buffer layer.
본 발명에 이용되는 MF2물질에 대한 격자상수 및 열팽창계수는 (표 2)에 나타내었다.The lattice constants and thermal expansion coefficients for the MF 2 materials used in the present invention are shown in (Table 2).
MF2물질은 면심입장(Face Centered Cubic) 결정구조는 가지며 (111)면에서는 조밀한 구조로 III-질화물 구조 중 가장 일반적인 섬유 아연석(Wurtzite) 구조의 (0001)면에서의 적층형태와 같아서 박막 형성시 결정성이 좋아진다.The MF 2 material has a face centered cubic crystal structure and is dense at the (111) plane, which is the same as the lamination on the (0001) plane of the most common III-nitride structure of the wurtzite structure. Good crystallinity when formed.
이와 같이 MF2들의 격자상수는 가장 널리 사용되는 Al2O3보다 GaN의 격자상수는 근접하다.Thus, the lattice constant of the MF 2 is the most widely used of the GaN lattice constant than Al 2 O 3 which is close-up.
따라서, GaN 박막의 결정성이 향상된다.Thus, the crystallinity of the GaN thin film is improved.
또는 MF2는 산성용액에 쉽게 식각되므로 소자 제작 후 공정에서 이점이 많으며, 특히 절단면이 (111)으로서 존재하므로 LD 제작시 거울면을 만들기 쉽다.Alternatively, since MF 2 is easily etched in an acidic solution, there are many advantages in the post-device fabrication process. In particular, since the cut surface exists as (111), it is easy to make a mirror surface during LD fabrication.
더욱이 LaF3는 육방정(hexagonal) 구조를 가졌기 때문에 GaN 박막성장이 용이해진다.Furthermore, LaF 3 has a hexagonal structure, which makes GaN thin film growth easier.
제2도는 본 발명에 따른 여러 형태의 구조를 나타낸 실시에로서 이에 따라 설명된다.2 is an embodiment showing various types of structures according to the present invention and thus described.
(a)구조는, MF2또는 LaF2로 된 기판(10)을 트리크로로에틸렌(Trichloroethylen), 메탄올(Methanol), 아세톤(Aceton) 등의 용매(Solvent)로 산성용액(HCL : H2O = 1 : 9)으로 식각한 뒤 MOCVD 또는 MBE 반응기로 넣은 후 1000℃(MOCVD 경우), 850℃(MBE 경우)의 온도에서 열처리한다.(a) The structure of the substrate 10 made of MF 2 or LaF 2 is an acidic solution (HCL: H 2 O = 1) with a solvent such as trichloroethylen, methanol, acetone, etc. 9) After etching into MOCVD or MBE reactor, heat treatment is performed at 1000 ℃ (MOCVD) and 850 ℃ (MBE).
이렇게 처리한 기판(10)상에, GaN, AlN 또는 GaAlN로 된 질화물완충층(12)을 증착한 후 주(main) III-질화물층(13) 박막을 성장시킨다.On the substrate 10 thus treated, a nitride buffer layer 12 made of GaN, AlN or GaAlN is deposited, and then a thin film of the main III-nitride layer 13 is grown.
본 발명에서는 MOCVD인 경우 트리메틸갈륨(Trimethylgallium), 트리메틸인디윰(Trimethylindium), 트리메틸알루미늄(Trimethylaluminum)을 III 족의 전구체(Precusor)로 암모니아 V족의 전구체(Precusor)로 사용하였다.In the present invention, in the case of MOCVD, trimethylgallium, trimethylindium, and trimethylaluminum were used as precursors of group III as precursors of ammonia group V.
또한, 전자 사이클은 공명(Electro Cyclon Resonance) N2와 Ga, Al, In 금속을 MBE에서 사용하였다.In addition, the electron cycle used the resonance (Electro Cyclon Resonance) N 2 and Ga, Al, In metal in MBE.
2㎛ 두께의 주(main) III-질화물층(13) 위에 P-N 접합을 형성하여 소자의 구조를 형성한다.The structure of the device is formed by forming a P-N junction on the main III-nitride layer 13 having a thickness of 2 m.
이와 같이 기판을 MF2 또는 LaF3로 함께 따라 격자상수의 차이가 사파이어보다 줄어든다.In this way, the difference in the lattice constant is reduced than that of sapphire by joining the substrate together with MF2 or LaF3.
따라서, 사파이어 사용시보다 III-V 질화층 물질의 결정성이 향상된다.Thus, the crystallinity of the III-V nitride layer material is improved than when using sapphire.
(b)의 경우는, 상기한 (a)의 구조의 질화물완충층(12)과 기판(10) 사이에 MF2층(11) 또는 LaF3층을 형성하여 기판 표면의 품질을 향상시켰으며 또한 GaN 등의 완충층(12) 성장시 많은 결정성장씨드(Crystal growth seed)가 MF2층(11)에서 제공되므로 주(main) III-질화물층(13)의 결정성이 향상된다.In the case of (b), the MF2 layer 11 or LaF 3 layer was formed between the nitride buffer layer 12 and the substrate 10 of the structure (a) described above to improve the quality of the surface of the substrate. Since many crystal growth seeds are provided in the MF 2 layer 11 when the buffer layer 12 is grown, the crystallinity of the main III-nitride layer 13 is improved.
여기서 기판의 재질은 (a)와 같고, 기타의 제조수단 역시 (a)와 동일하게 하였다.Herein, the material of the substrate was the same as in (a), and other manufacturing means were also the same as in (a).
(c)의 경우는, 기판(10')을 Si 또는 Ge을 사용하므로서, 기판의 세척을 용이하게 하기 위한 것으로, Si 또는 Ge로 완충층(12')과 III-질화물완충층(12) 사이에 MF2 또는 LaF3 층(11) 형성하고 III-질화물완충층(12)상에 III-질화물층(13)을 형성시킨다.In the case of (c), the substrate 10 'is made of Si or Ge to facilitate the cleaning of the substrate, and MF2 is formed between the buffer layer 12' and the III-nitride buffer layer 12 by Si or Ge. Or LaF3 layer 11 is formed and III-nitride layer 13 is formed on III-nitride buffer layer 12.
이와 같은 구조에서는 박막 성장 후 온도를 내릴 때 생기는 III-질화물층(12)(13)들의 압축응력상태이다.In such a structure, the compressive stress state of the III-nitride layers 12 and 13 generated when the temperature is lowered after the thin film is grown.
압축응력을 받은 박막은 균열(Crack)의 밀도가 적어져 III-질화물(12)(13)층의 결정성이 더욱 향상된다.The thin film subjected to the compressive stress has a smaller crack density, which further improves the crystallinity of the III-nitride 12 (13) layer.
본 구조에 따른 기타 제조수단은 상기한 (a)와 동일하다.Other manufacturing means according to the present structure are the same as in (a) above.
이상에서와 같은 본 발명은 종래 III-V 질화물질을 이용해서 청색 발광소자 도는 자외선 탐지기(UV detector) 등을 제작할 때 문제가 되었던 결정성을 높여 고휘도의 청색 LED를 만들었으며, 또한 불화물의 강한 분자해리 에너지(moleculor dissociation energy)에 의한 동일조성유지 승화로 (comgruent Subimation) 버퍼층 제작시 조성조절이 쉬웠다.As described above, the present invention improves crystallinity, which is a problem when fabricating a blue light emitting device or an ultraviolet detector using a III-V nitride material, and makes a high brightness blue LED, and also a strong molecule of fluoride. It was easy to control the composition when fabricating the comgruent subimation buffer layer by dissociation energy.
또한, 높은 III-V 질화물질의 결정성은 고위도 LED와 LD 제작을 가능하게 하였다.In addition, the crystallinity of high III-V nitrides made it possible to fabricate high-level LEDs and LDs.
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| KR1019950043022A KR0179143B1 (en) | 1995-11-22 | 1995-11-22 | Blue luminous element |
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